(19)

TEPZZ _95¥49B_T
(11) EP 2 195 349 B1
(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) Int Cl.:

of the grant of the patent: C08F 10/00 (2006.01) C08F 2/01 (2006.01)
11.07.2012 Bulletin 2012/28 C08J 3/18 (2006.01)

(21) Application number: 08830948.9 (86) International application number:

PCT/US2008/010517
(22) Date of filing: 09.09.2008
(87) International publication number:
WO 2009/035580 (19.03.2009 Gazette 2009/12)

(54) IN-LINE PROCESS FOR PRODUCING PLASTICIZED POLYMERS AND PLASTICIZED POLYMER
BLENDS
IN-LINE-VERFAHREN ZUR HERSTELLUNG VON WEICHGEMACHTEN POLYMEREN UND
WEICHGEMACHTEN POLYMERBLENDS
PROCEDE DE PRODUCTION EN LIGNE DE POLYMERES PLASTIFIES ET MELANGES DE
POLYMERES PLASTIFIES

(84) Designated Contracting States: • GALUSKA, Alan, A.

AT BE BG CH CY CZ DE DK EE ES FI FR GB GR Glen Gardner
HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT NJ 08826 (US)
RO SE SI SK TR • DATTA, Sudhin
Houston
(30) Priority: 13.09.2007 US 993647 P TX 77007 (US)
• CHAPMAN, Bryan, R.
(43) Date of publication of application: Annandale
16.06.2010 Bulletin 2010/24 NJ 08801 (US)
• BRANT, Patrick
(73) Proprietor: ExxonMobil Research and Seabrook
Engineering Company TX 77586 (US)
Annandale, NJ 08801-0900 (US)
(74) Representative: Mareschal, Anne
(72) Inventors: ExxonMobil Chemical Europe Inc.
• KISS, Gabor IP Law Shared Services
Hampton Hermeslaan 2
NJ 08827 (US) 1831 Machelen (BE)
• CHU, John, W.
Neshanic Station (56) References cited:
NJ 08853 (US) WO-A1-2008/082511 US-A- 4 252 911
• REYNOLDS, Robert, P., Jr. US-A- 6 066 762 US-A1- 2005 234 217
Clinton US-A1- 2006 189 744 US-A1- 2006 189 763
NJ 08809 (US) US-A1- 2006 293 474
EP 2 195 349 B1

Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent
Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the
Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been
paid. (Art. 99(1) European Patent Convention).

Printed by Jouve, 75001 PARIS (FR)

 EP 2 195 349 B1

Description

FIELD

5 [0001] The present disclosure relates to the field of polymer blending. It more particularly relates to a process for in-
line blending of polyolefin-based polymers and plasticizers in the fluid phase. Still more particularly, the present disclosure
relates to a process for fluid-phase in-line blending of high molecular weight olefin polymers low molecular weight, low
glass transition temperature polyolefins acting as plasticizers in the product-feed separator section of an integrated
polymerization plant operating with two or more parallel reactor trains.
10
BACKGROUND

[0002] Polyolefins, such as polyethylene or polypropylene, are widely used in a number of everyday articles, machines,
consumer goods, and the like. Polyolefins are relatively inexpensive to produce and are capable of providing a number
15 of useful functions. Polyolefins may be formed into various shapes, films, laminates, and the like. Polyolefins may be
coated on, or co-extruded with various substrates. Polyolefins may also be combined with other materials to form a
structure having a plurality of layers, each layer having a specific purpose. Laminates, for example, may comprise a
plurality of layers, such as a configurationally rigid core layer, an outer liquid-tight layer, an oxygen gas barrier such as
a mid-layer of aluminum foil, and/or other layers depending on application needs. However, polyolefins may be too rigid
20 and hard for the target applications, or cannot be extended without tear, or difficult to process due to their high viscosity
at the processing temperature, or become brittle at colder temperatures due to their relatively high glass transition
temperatures. These properties may render various polyolefins brittle, hard, inflexible, and thus unsuitable for particular
uses, particularly uses at lower temperatures or may lead to slower processing speeds and/or excessive rejects during
processing. Many applications of polyolefins would benefit from a polyolefin having useful properties over a wide range
25 of temperatures, and under a variety of conditions. It would also be beneficial if the viscosity of melts could be reduced
affording better and higher speed processability in common polymer processing plants, such as extruders, melt blowers,
etc. Such useful properties may include both high- and low-temperature performance in the areas of impact strength,
toughness, flexibility, and the like. The ability to adjust the stiffness-toughness balance and processability of polyolefins
is important to meeting the needs of a broad range of applications at a lower cost and thus to expanding the potential
30 of polyolefins in delivering desired performance at a reduced cost.
[0003] In some instances, the stiffness-toughness balance may be tailored by changing the molecular structure of
polymers or by changing their composition (i.e. making copolymers), stereoregularity, molecular weight, etc. The stiffness-
toughness balance may also be readily shifted by making blends of polymers with different stiffness and toughness or
by blending polymers and plasticizing agents, such as polyolefin fluids and low molecular weight polymers, particularly
35 low glass transition temperature polyolefin fluids and polymers. A plasticizer added to high molecular weight, highly
crystalline stiff polyolefins softens the structure to improve the toughness of such materials. Plasticizers with low glass
transition temperature also extend the flexibility of plastics to lower temperatures by lowering the glass transition tem-
perature of the polymer-plasticizer blend. Plasticizers are also beneficial during polymer processing due to improvements
in a number of characteristics, such as lubricity, viscosity, ease of fusion, etc. The concept of plasticization, the benefits
40 of using plasticizers, and the different methods of using plasticizers are discussed in detail in J.K. Sears, J.R. Darby,
THE TECHNOLOGY OF PLASTICIZERS, Wiley, New York, 1982. Although this monograph focuses on the plasticization
of poly(vinyl chloride), PVC, the concepts and benefits are analogous to those applicable to plasticized polyolefins.
[0004] Since the plasticizers are often fluids at ambient temperature, plasticized polymer blends are sometimes also
referred to herein as fluid-enhanced polyolefins or fluid-enhanced polymers. These plasticized polymers may be made
45 by a variety of methods. Plasticized polyolefins are traditionally made by starting with polyolefin polymers and plasticizer
fluids made in separate plants. Since the polymer is in its essentially pure, fully recovered solid state, it is difficult and
expensive to blend it with a plasticizer fluid. A flexible but expensive process of making them starts with the high molecular
weight polymer resin component in its solid, essentially pure, fully recovered state. In one prior art process, the one or
more solid polymers are first melted and then blended with the plasticizing fluid or low molecular weight resin, which is
50 commonly referred to as a melt-blending process. In another prior art process, the one or more solid polymers are put
into solution with a suitable solvent before being blended with the plasticizing fluid or low molecular weight resin, which
is commonly referred to as an off-line solution blending process. Off-line blending to produce plasticized polyolefins has
numerous issues in that it increase processing cost. For example, melt blending is difficult requiring high-performance
blenders or extruders due to the high viscosity of polymers and the low viscosity of the plasticizing fluid. Off-line solution
55 blending is also an expensive process due to the need for redissolving the polymer and possibly the plasticizer blend
components and also due to the cost of solvent handling. Also, as mentioned before, handling plasticizers requires
additional special equipment.
[0005] As described above, polymer blends may be made by a variety of ways. A flexible but expensive off-line process

2
 EP 2 195 349 B1

of making polymer blends uses solid polymers as starting materials, typically outside the polymerization process that
produced the polymer blend components. The polymer blend components are typically first melted or dissolved in a
solvent and then blended. These processes are known as melt-blending and off-line solution blending, respectively. In
melt blending, the solid, often pelletized or baled, polymer blend components are first melted and then blended together
5 in their molten state. One of the difficulties presented by melt blending is the high viscosity of molten polymers, which
makes blending of two or more polymers difficult and often imperfect on the molecular level. In solution off-line blending,
the solid, often pelletized, polymer blend components are first dissolved in a suitable solvent to form a polymer solution,
and then two or more polymer solutions are blended together. After blending, solution blending requires the extraction
of solvent from the blend and drying of the blended polymer. Solution blending can overcome the viscosity issue asso-
10 ciated with melt blending, but is expensive due to the need for redissolving the polymer blend components and due to
the cost of solvent handling.
[0006] The common feature of both melt blending and off-line solution blending is that the polymer blending components
are made in separate plants and the solid polymers then are reprocessed either in a molten or in a dissolved state to
prepare the final polymer blend. In fact, these off-line blending processes are often operated by so-called compounders,
15 generally independent of the manufacturers of the polymer blend components. These processes add considerable cost
to the cost of the final polymer blend. The production and full polymer recovery in separate plants and subsequent
reprocessing increases the costs of producing such blends because of the need for duplicate polymer recovery lines
and because of the need for separate blending facilities and the energy associated with their operations. Off-line solution
blending also requires extra solvent, and facilities for polymer dissolution and solvent recovery-recycle. Handling plas-
20 ticizers for blending them with the base polymer represents a further challenge, since plasticizers are typically low
molecular weight, low melting point fluids or soft materials. Compounding plants are typically equipped for handling free-
flowing pelletized components, thus are not equipped for receiving, storing, and blending fluids and/or soft, baled sub-
stances. The disclosed processes blend the plasticizer fluids and/or soft polymers in the polymerization plant producing
plasticized polymers for final use, or plasticized polymer masterbatches for further compounding in stable pelletized
25 forms, thus afford their handling in downstream processing plants without the need for special handling and without the
associated investment costs. For the above-outlined reasons, substantial reprocessing costs could be saved if the
polymer blends could be made in one integrated polymerization plant in-line, i.e. before the recovery and pelletizing of
the solid polymer blend components. In some instances, especially when the plasticizer is liquid at ambient temperature,
significant cost savings can also be achieved even if the plasticizer was produced in a separate plant by blending the
30 liquid plasticizer with the polymer in its diluted state, i.e., before the viscosity-reducing components of the polymerization
system, such as monomer and the optional inert solvent/diluent, are removed from the product polymer or polymer blend.
[0007] The disadvantages of a separate polyolefin blending plant associated with the melt blending and off-line solution
blending processes is alleviated with the prior art method of in-line solution blending of polymers using a series reactor
configuration. Utilizing the series reactor configuration, product blending may be accomplished in the solution polymer-
35 ization reactor itself when the effluent of the first solution polymerization reactor is fed into the second reactor operating
at different conditions with optionally different catalyst and monomer feed composition. Referring to the two-stage series
reactor configuration of FIG. 1, the two different polymers made in the first and second reactor stages are blended in
the second stage yielding a blended polymer product leaving the second reactor. Such reactor series configuration may
be further expanded into more than a two-stage series configuration (three or more reactors in series). Generally, a
40 series of n reactors may produce a blend with as many as n components or even more present in the effluent of the last
reactor. Note that in principle, more than n components may be produced and blended in n reactors by, for example,
using more than one catalyst or by utilizing multiple zones operating at different conditions in one or more reactors of
the series reactor cascade. While mixing in the downstream reactor(s) provides good product mixing, particularly when
the reactors are equipped with mixing devices, e.g., mechanical stirrers, such series reactor configuration and operation
45 presents a number of practical process and product quality control problems due to the close coupling of the reactors
in the cascade. One of the most important difficulties in commercial practice is ensuring proper blend and monomer
ratios to deliver consistent blend quality. Additional complications arise when the blend components have different
monomer compositions, particularly when they have different monomer pools, such as in the case of blending different
copolymers or in the case of blending homo- and copolymers. As will be shown later in the detailed description of the
50 disclosed processes, this is often the case in the production of plasticized polyolefins. In such instances, either some
monomers need to be converted completely before passing the effluent to the downstream stages or need to be removed
between the reactor stages. In many cases, such solutions are not practical. Also, since the monomer streams are
blended, there is no option for their separate recovery and recycle mandating costly monomer separations in the monomer
recycle lines.
55 [0008] The above-outlined issues with series reactor operations are apparent to those skilled in the art of polymer
reactor engineering. These difficulties are particularly significant in polymerization because unlike in small-molecule
synthesis, reactor conditions determine not only reactor productivities related to blend ratio, but also product properties
related to controlling the quality of the polymer blend components. For example, FIGS. 2 and 3 show how reactor

3
 EP 2 195 349 B1

temperature and pressure affect polymer properties of fundamental importance, such as molecular weight (MW) and
melting behavior. Surprisingly, we found that monomer conversion in the reactor also influences these critical product
attributes (see FIG. 4). Since in a series reactor cascade, the effluent of an upstream reactor flows into the next down-
stream member of the reactor cascade, the residence time, catalyst concentration, and monomer composition and thus
5 monomer conversion in the downstream reactor cannot be adjusted independently of the operating conditions (particularly
of the flow rate) of the upstream reactor. Because of this close and inherent coupling of operating regimes in the reactors
of the series cascade, the correlations depicted in Figures 2, 3, and 4 further reduce the controllability, flexibility, and
thus the usefulness of the in-line blending method in a series reactor configuration. Ultimately, this greatly reduces the
number of blend products that can be made in such a series reactor cascade and makes the blend quality difficult to control.
10 [0009] Applying parallel reactors can overcome the disadvantages related to the direct coupling of the polymerization
reactors in an in-line polymer blending applying series reactors. While production flexibility is increased, a parallel reactor
arrangment necessitates the installation of blending vessels increasing the cost of the process. A need thus exists for
an improved and cost-effective method of in-line blending of polymers and plasticizers to avoid the issues associated
with the prior-art methods, such as melt blending and off-line solution blending. More particularly, a need exists for an
15 improved in-line method of blending polymers and plasticizers, especially for an improved in-line method of blending
polyolefins and plasticizers, where the residence time, monomer composition, catalyst choice, and catalyst concentration
can be independently controlled in the polymer reactor(s) and the optional plasticizer reactor(s) prior to the blending
step. There is also a need for a simplified and cost-effective polymer-plasticizer blending process to reduce the number
of process steps and the associated investment and operating costs in an integrated polymer and plasticizer production
20 and blending process employing parallel reactor trains for producing the polymer-plasticizer blend components in-line,
i.e. without recovering the polymer component(s) in its/(their) solid state. Embodiments of the present invention, which
follow, meet these needs.

SUMMARY
25
[0010] Provided is a process for fluid phase in-line blending of polymers and plasticizers.
[0011] According to the present disclosure, an advantageous process for in-line blending of plasticized polymers
includes: (a) providing two or more reactor trains configured in parallel and a high-pressure separator downstream fluidly
connected to the two or more reactor trains configured in parallel, wherein one or more of the reactor trains produces
30 one or more polymers and one or more of the reactor trains produces one or more plasticizers; (b) contacting in the two
or more reactor trains configured in parallel 1) olefin monomers having two or more carbon atoms 2) one or more catalyst
systems, 3) optional one or more comonomers, 4) optional one or more scavengers, and 5) optional one or more diluents
or solvents, wherein at least one of the reactor trains configured in parallel is at a temperature above the solid-fluid
phase transition temperature of the polymerization system and a pressure no lower than 10 MPa below the cloud point
35 pressure of the polymerization system and less than 1500 MPa, wherein the polymerization system for each reactor
train is in its dense fluid state and comprises the olefin monomers, any comonomer present, any diluent or solvent
present, any scavenger present, and the polymer product, wherein the catalyst system for each reactor train comprises
one or more catalyst precursors, one or more activators, and optionally, one or more catalyst supports, wherein the one
or more catalyst systems are chosen from Ziegler-Natta catalysts, metallocene catalysts, nonmetallocene metal-cen-
40 tered, heteroaryl ligand catalysts, late transition metal catalysts, and combinations thereof; (c) forming an unreduced
polymer or unreduced plasticizer reactor effluent including a homogeneous fluid phase polymer-monomer mixture in
one or more parallel reactor trains and a homogeneous fluid phase plasticizer-monomer mixture in one or more parallel
reactor trains; (d) passing the reactor effluents comprising the homogeneous fluid phase polymer-monomer mixture and
plasticizer-monomer mixture from each parallel reactor train through the high-pressure separator for product blending
45 and product-feed separation; (e) maintaining the temperature and pressure within the high-pressure separator above
the solid-fluid phase transition point but below the cloud point pressure and temperature to form a fluid-fluid two-phase
system comprising a plasticized polymer-rich blend phase and a monomer-rich phase; and (f) separating the monomer-
rich phase from the plasticized polymer-rich blend phase in the high pressure separator to form a plasticized polymer
blend and a separated monomer-rich phase.
50 [0012] A further aspect of the present disclosure relates to an advantageous process for in-line blending of plasticized
polymers including: (a) providing two or more reactor trains configured in parallel and two or more high-pressure sepa-
rators fluidly connected to the two or more reactor trains configured in parallel, wherein one or more of the reactor trains
produces one or more polymers and one or more of the reactor trains produces one or more plasticizers; (b) contacting
in the two or more reactor trains configured in parallel 1) olefin monomers having two or more carbon atoms 2) one or
55 more catalyst systems, 3) optional one or more comonomers, 4) optional one or more scavengers, and 5) optional one
or more diluents or solvents, wherein at least one of the reactor trains configured in parallel is at a temperature above
the solid-fluid phase-transition temperature of the polymerization system and a pressure no lower than 10 MPa below
the cloud point pressure of the polymerization system and less than 1500 MPa, wherein the polymerization system for

4
 EP 2 195 349 B1

each reactor train is in its dense fluid state and comprises the olefin monomers, any comonomer present, any diluent
or solvent present, any scavenger present, and the polymer product, wherein the catalyst system for each reactor train
comprises one or more catalyst precursors, one or more activators, and optionally, one or more catalyst supports,
wherein the one or more catalyst systems are chosen from Ziegler-Natta catalysts, metallocene catalysts, nonmetallocene
5 metal-centered, heteroaryl ligand catalysts, late transition metal catalysts, and combinations thereof; (c) forming an
unreduced polymer or unreduced plasticizer reactor effluent including a homogenous fluid phase polymer-monomer
mixture or plasticizer-monomer mixture in each parallel reactor train; (d) passing the reactor effluents from one or more
of the parallel reactor trains through one or more high-pressure separators, maintaining the temperature and pressure
within the one or more high-pressure separators above the solid-fluid phase transition point but below the cloud point
10 pressure and temperature to form one or more fluid-fluid two-phase systems with each two-phase system comprising
a polymer-enriched phase or plasticizer-enriched phase and a monomer-rich phase, and separating the monomer-rich
phase from the polymer-enriched phase or plasticizer-enriched phase in each of the one or more high-pressure separators
to form one or more separated monomer-rich phases, one or more polymer-enriched phases and one or more plasticizer-
enriched phases; (e) passing the one or more polymer-enriched phases and one or more plasticizer-enriched phases
15 from the one or more high-pressure separators of (d), any unreduced polymer reactor effluents from one or more parallel
reactor trains through another high-pressure separator for product blending and product-feed separation; (f) maintaining
the temperature and pressure within the another high pressure separator of (e) above the solid-fluid phase transition
point but below the cloud point pressure and temperature to form a fluid-fluid two-phase system comprising a plasticized
polymer-rich blend phase and a monomer-rich phase; and (g) separating the monomer-rich phase from the plasticized
20 polymer-rich blend phase in the high pressure separator to form a plasticized polymer blend and a separated monomer-
rich phase.
[0013] Another aspect of the present disclosure relates to an advantageous process for in-line blending of plasticized
polymers including: (a) providing two or more reactor trains configured in parallel, a high- pressure separator downstream
fluidly connected to the two or more reactor trains configured in parallel, and one or more storage tanks, wherein the
25 two or more reactor trains produce one or more polymers and the one or more storage tanks store one or more off-line
produced plasticizers; (b) contacting in the two or more reactor trains configured in parallel 1) olefin monomers having
two or more carbon atoms 2) one or more catalyst systems, 3) optional one or more comonomers, 4) optional one or
more scavengers, and 5) optional one or more diluents or solvents, wherein at least one of the reactor trains configured
in parallel is at a temperature above the solid-fluid phase transition temperature of the polymerization system and a
30 pressure no lower than 10 MPa below the cloud point pressure of the polymerization system and less than 1500 MPa,
wherein the polymerization system for each reactor train is in its dense fluid state and comprises the olefin monomers,
any comonomer present, any diluent or solvent present, any scavenger present, and the polymer product, wherein the
catalyst system for each reactor train comprises one or more catalyst precursors, one or more activators, and optionally,
one or more catalyst supports, wherein the one or more catalyst systems are chosen from Ziegler-Natta catalysts,
35 metallocene catalysts, nonmetallocene metal-centered, heteroaryl ligand catalysts, late transition metal catalysts, and
combinations thereof; (c) forming an unreduced polymer reactor effluent including a homogeneous fluid phase polymer-
monomer mixture in each parallel reactor train; (d) passing the polymer reactor effluent comprising the homogeneous
fluid phase polymer-monomer mixture from each parallel reactor train through the high-pressure separator for product
blending and product-feed separation; (e) maintaining the temperature and pressure within the high-pressure separator
40 above the solid-fluid phase transition point but below the cloud point pressure and temperature to form a fluid-fluid two-
phase system comprising a polymer-rich blend phase and a monomer-rich phase; (f) separating the monomer-rich phase
from the polymer-rich blend phase in the high pressure separator to form a polymer blend and a separated monomer-
rich phase; and (g) feeding the one or more off-line produced plasticizers from the one or more storage tanks to the
process after (c) to form a plasticized polymer blend.
45 [0014] A still further aspect of the present disclosure relates to an advantageous process for in-line blending of plasticized
polymers including: (a) providing two or more reactor trains configured in parallel and two or more high-pressure separators
fluidly connected to the two or more reactor trains configured in parallel, and one or more storage tanks, wherein two or
more of the reactor trains produce one or more polymers and the one or more storage tanks store one or more off-line-
produced plasticizers; (b) contacting in the two or more reactor trains configured in parallel 1) olefin monomers having two
50 or more carbon atoms 2) one or more catalyst systems, 3) optional one or more comonomers, 4) optional one or more
scavengers, and 5) optional one or more diluents or solvents, wherein at least one of the reactor trains configured in parallel
is at a temperature above the solid-fluid phase-transition temperature of the polymerization system and a pressure no
lower than 10 MPa below the cloud point pressure of the polymerization system and less than 1500 MPa, wherein the
polymerization system for each reactor train is in its dense fluid state and comprises the olefin monomers, any comonomer
55 present, any diluent or solvent present, any scavenger present, and the polymer product, wherein the catalyst system for
each reactor train comprises one or more catalyst precursors, one or more activators, and optionally, one or more catalyst
supports, wherein the one or more catalyst systems are chosen from Ziegler-Natta catalysts, metallocene catalysts, non-
metallocene metal-centered, heteroaryl ligand catalysts, late transition metal catalysts, and combinations thereof; (c)

5
 EP 2 195 349 B1

forming an unreduced polymer reactor effluent including a homogenous fluid phase polymer-monomer mixture in each
parallel reactor train; (d) passing the reactor effluents from one or more of the parallel reactor trains through one or more
high-pressure separators, maintaining the temperature and pressure within the one or more high-pressure separators
above the solid-fluid phase transition point but below the cloud point pressure and temperature to form one or more fluid-
5 fluid two-phase systems with each two-phase system comprising a polymer-enriched phase and a monomer-rich phase,
and separating the monomer-rich phase from the polymer-enriched phase in each of the one or more high-pressure
separators to form one or more separated monomer-rich phases and one or more polymer-enriched phases; (e) passing
the one or more polymer-enriched phases from the one or more high-pressure separators of (d), any unreduced polymer
reactor effluents from one or more parallel reactor trains through another high-pressure separator for product blending
10 and product-feed separation; (f) maintaining the temperature and pressure within the another high pressure separator of
(e) above the solid-fluid phase transition point but below the cloud point pressure and temperature to form a fluid-fluid two-
phase system comprising a polymer-rich blend phase and a monomer-rich phase; (g) separating the monomer-rich phase
from the polymer-rich blend phase in the high pressure separator to form a polymer blend and a separated monomer-rich
phase; and (h) feeding the one or more off-line produced plasticizers from the one or more storage tanks to the process
15 after (c) to form a plasticized polymer blend.
[0015] These and other features and attributes of the disclosed processes for in-line blending of plasticized polymers
and their advantageous applications and/or uses will be apparent from the detailed description that follows, particularly
when read in conjunction with the figures appended hereto.

20 BRIEF DESCRIPTION OF THE DRAWINGS

[0016] To assist those of ordinary skill in the relevant art in making and using the subject matter hereof, reference is
made to the appended drawings, wherein:
[0017] FIG. 1 presents the process for the production of polymer blends in a two-stage series reactor configuration
25 (prior art);
[0018] FIG. 2 presents the effect of polymerization temperature on the molecular weight and melting point of polypro-
pylene made in supercritical polypropylene using MAO-activated (m-dimethylsilyl)bis(2-methyl-4-phenylindenyl)zirconi-
um dichloride (Q-Zr-MAO) catalyst at 207 MPa (30 kpsi);
[0019] FIG. 3 presents the effect of polymerization pressure on the molecular weight and melting point of polypropylene
30 made in supercritical propylene using MAO-activated (m-dimethylsilyl)bis(2-methyl-4-phenylindenyl)zirconium dichloride
(Q-Zr-MAO) catalyst at 120 and 130˚C;
[0020] FIG. 4 presents the effect of propylene conversion in the polymerization of supercritical propylene using MAO-
activated (m-dimethylsilyl)bis(2-methyl-4-phenylindenyl)zirconium dichloride (Q-Zr-MAO) at 130˚C and 69 and 138 MPa
(10 or 20 kpsi, respectively);
35 [0021] FIG. 5 presents the effect of temperature on the activity of MAO-activated (m-dimethylsilyl)bis(2-methyl-4-
phenylindenyl)zirconium dichloride (Q-Zr-MAO) catalyst in the polymerization of supercritical propylene;
[0022] FIG. 6 presents an exemplary in-line plasticized polymer blending process schematic with a single separation
vessel;
[0023] FIG. 7 presents an exemplary in-line plasticized polymer blending process schematic with multiple separation
40 vessels;
[0024] FIG. 8 presents an exemplary in-line plasticized polymer blending process schematic with product effluent
buffer tanks for improved blend ratio control;
[0025] FIG. 9 presents an exemplary in-line plasticized polymer blending process schematic with product effluent
buffer tanks that also serve as monomer/product separators for improved blend ratio control;
45 [0026] FIG. 10 presents an exemplary in-line plasticized polymer blending process schematic with one slurry reactor
train.
[0027] FIG. 11 presents an exemplary in-line plasticized polymer blending process schematic with buffer tanks for
improved blend ratio control and with the option for additive/polymer blending component;
[0028] FIG. 13 presents cloud point isotherms for Polymer Achieve™ 1635;
50 [0029] FIG. 14 presents cloud point isotherms for Polymer PP 45379 dissolved in bulk propylene;
[0030] FIG. 15 presents cloud point isotherms for Polymer PP 4062 dissolved in bulk propylene;
[0031] FIG. 16 presents cloud point isotherms for Polymer Achieve™ 1635 dissolved in bulk propylene;
[0032] FIG. 17 presents cloud point isotherms for Polymer PP 45379 dissolved in bulk propylene;
[0033] FIG. 18 presents cloud point isotherms for Polymer PP 4062 dissolved in bulk propylene;
55 [0034] FIG. 19 presents a comparison of isopleths for PP 45379, Achieve™ 1635, and PP 4062 dissolved in bulk
propylene;
[0035] FIG. 20 presents a comparison of isopleths for Achieve™ 1635 and literature data as described in J. Vladimir
Oliveira, C. Dariva and J. C. Pinto, Ind. Eng, Chem. Res. 29, 2000, 4627;

6
 EP 2 195 349 B1

[0036] FIG. 21 presents a comparison of isopleths for PP 45379 and literature data as described in J. Vladimir Oliveira,
C. Dariva and J. C. Pinto, Ind. Eng, Chem. Res. 29 (2000), 4627;
[0037] FIG. 22 presents a comparison of isopleths for PP 4062 and literature data as described in J. Vladimir Oliveira,
C. Dariva and J. C. Pinto, Ind. Eng, Chem. Res. 29, 2000, 4627;
5 [0038] FIG. 23 presents a basic phase diagram for mixture of propylene monomer with selected polymers (isotactic
polypropylene - iPP, syndiotactic polypropylene - sPP, atactic polypropylene - aPP, or propylene-ethylene copolymer);
[0039] FIG. 24 presents a comparison of the density of supercritical propylene at 137.7˚C. with liquid propylene at
54.4˚C;
[0040] FIG. 25 presents an operating regime in accordance with the process disclosed herein for a reactor operating
10 in a single liquid phase;
[0041] FIG. 26 presents an operating regime in accordance with the process disclosed herein for a reactor operating
in a liquid-liquid phase; and
[0042] FIG. 27 presents an operating regime in accordance with the process disclosed herein for a gravity separator.
[0043] FIG. 28 presents a graphical depiction of the thermodynamic definition of binodal and spinodal boundaries.
15 [0044] FIG. 29 presents a phase diagram for a typical polymerization medium of the current invention.

DEFINITIONS

[0045] For the purposes of this disclosure and the claims thereto:
20 [0046] A catalyst system is defined to be the combination of one or more catalyst precursor compounds and one or
more activators. Any part of the catalyst system can be optionally supported on solid particles, in which case the support
is also part of the catalyst system.

Critical Properties Of Pure Substances And Mixtures:

25
[0047] Pure substances, including all types of hydrocarbons, can exist in either a subcritical, or supercritical state,
depending on their temperature and pressure. Substances in their supercritical state possess interesting physical and
thermodynamic properties, which are exploited in this invention. Most notably, as supercritical fluids undergo large
changes in pressure, their density and solvency for polymers changes over a wide range. To be in the supercritical state,
30 a substance must have a temperature above its critical temperature (Tc) and a pressure above its critical pressure (Pc).
Mixtures of hydrocarbons, including mixtures of monomers, polymers, and optionally solvents, have pseudo-critical
temperatures (Tc) and pseudo-critical pressures (Pc), which for many systems can be approximated by mole-fraction-
weighted averages of the corresponding critical properties (Tc or Pc) of the mixture’s components. Mixtures with a
temperature above their pseudo-critical temperature and a pressure above their pseudo-critical pressure will be said to
35 be in a supercritical state or phase, and the thermodynamic behavior of supercritical mixtures will be analogous to
supercritical pure substances.

Phase Behavior:

40 [0048] The phase of a hydrocarbon, or mixture of hydrocarbons, is a key thermodynamic property. A mixture’s phase
may be either solid, vapor, liquid, or a supercritical fluid. For purposes of this invention, the supercritical fluid phase may
at times simply be referred to as the fluid phase. A mixture is determined to be in the fluid phase when its temperature
exceeds its critical, or pseudo-critical temperature (Tc) and when its pressure exceeds its critical, or pseudo-critical
pressure (Pc).
45 [0049] When mixtures change their phase by virtue of changes in temperature, pressure, and/or composition, they
are said to cross phase boundaries, which may be represented as a locus of points (curves) on temperature-pressure
diagrams, where said curves apply to a mixtures of a given composition. For purposes of this invention, the phase
boundaries between fluid and liquid phases will be called fluid-liquid phase boundaries, or cloud point curves, and
transitions of temperatures or pressures that cross these boundaries may be referred to as fluid-liquid transitions. A
50 given point on the cloud point curve will be referred to by its cloud point pressure. The cloud point pressure can be
experimentally determined as the pressure at which, and below which, at a given temperature, the polymerization system
becomes turbid as described in J. Vladimir Oliveira, C. Dariva and J. C. Pinto, Ind. Eng, Chem. Res. 29 (2000) 4627.
For purposes of this invention and the claims thereto, the cloud point is measured by shining a laser through the selected
polymerization system in a cloud point cell onto a photocell and recording the pressure at the onset of rapid increase in
55 light scattering for a given temperature. For purposes of illustration, the fluid-liquid phase boundary (cloud point curve)
of a typical polymerization medium is depicted in Fig. 29. The critical temperatures (Tc) and critical pressures (Pc) are
those that are found in the Handbook of Chemistry and Physics, David R. Lide, Editor-in-Chief, 82nd edition 2001-2002,
CRC Press, LLC. New York, 2001. In particular, the Tc and Pc of selected molecules are:

7
 EP 2 195 349 B1

Name Tc (K) Pc (MPa) Name Tc (K) Pc (MPa)

Hexane 507.6 3.025 Propane 369.8 4.248
5 Isobutane 407.8 3.64 Toluene 591.8 4.11
Ethane 305.3 4.872 Methane 190.56 4.599
Cyclobutane 460.0 4.98 Butane 425.12 3.796
Cyclopentane 511.7 4.51 Ethylene 282.34 5.041
10
1-Butene 419.5 4.02 Propylene 364.9 4.6
1-pentene 464.8 3.56 Cyclopentene 506.5 4.8
Pentane 469.7 3.37 Isopentane 460.4 3.38
15 Benzene 562.05 4.895 Cyclohexane 553.8 4.08
1-hexene 504.0 3.21 Heptane 540.2 2.74
273.2 K = 0 ˚C.

20
[0050] Phase boundaries between solids and liquids (or solids and fluids) will be called solid-liquid (or solid-fluid)
phase boundaries. Crossing solid-liquid (or solid-fluid) phase boundaries will be called solid-liquid (or solid-fluid) tran-
sitions. A single point on a solid-liquid (or solid-fluid) phase boundary may be referred to as solid-liquid (or solid-fluid)
transition temperature. However, many of mixtures referred to in this invention exhibit two different solid-liquid (or solid-
25 fluid) phase boundaries, depending on the direction of the phase change. One is for melting, ie. when the direction of
phase change is from solid to liquid (or fluid), and the other is for crystallization, ie. when the direction of phase change
is from liquid (or fluid) to solid. When it is necessary to differentiate between these two types of transitions, the terms
melting and crystallization will be used, and a single point on the phase boundary will be referred to by its melting
temperature or its crystallization temperature. For purposes of this invention and the claims thereto, solid-liquid (or solid-
30 fluid) phase transitions of either type are determined by shining a laser through the selected polymerization medium in
a cell onto a photocell and recording the temperature at the onset of rapid increase in light scattering indicating the
formation of a solid phase (crystallization), or at the onset of a rapid decrease in light scattering indicating the disap-
pearance of a solid phase (melting). For purposes of illustration, solid-liquid (or solid-fluid) phase boundaries of both
the crystallization and melting types for a typical polymerization medium are depicted in Fig. 29.
35
Phase Densities:

[0051] As described above, the measurement of phase boundaries is determined by making cloud point pressure
measurements at a variety of temperatures for a given composition mixture, using the experimental methods described
40 in J. Vladimir Oliveira, C. Dariva and J. C. Pinto, Ind. Eng, Chem. Res. 29 (2000) 4627. These phase boundary data
are all that is needed to fit Equation of State (EOS) models to predict the thermodynamic and physical properties of the
individual phases, ie. fluid, liquid, solid, and/or vapor over a range of temperature and pressure. For the experimental
work supporting the current invention, a version of the Statistically Associating Fluid Theory (SAFT) EOS called SAFT1
(Adidharma and Radosz, 1998) has been used for this purpose. Because phase separation experiments must be run
45 at high temperatures and pressures, it is usually impractical to sample individual phases in multi-phase mixtures to
determine their composition or physical properties, and thus the predicted properties of these phases have been used
in lieu of directly measured values in support of the current invention. This approach has been validated in other instances,
where material balances from pilot plants and commercial plants have been used to validate SAFT1 EOS predictions.
As an example, SAFT1 EOS models of the polymerization systems and liquid-liquid separation systems described in
50 US Patents 6,881,800(B2) and No. 7,163,989(B2), which include polymers, monomers, and catalysts similar to the
current invention, but which include relatively large amounts of alkane solvents in the polymerization medium, and are
operated at lower pressures than the current invention, have been verified by these types of material balances.

Spinodal Decomposition:
55
[0052] Phase boundaries of mixtures, such as a polymerization medium, may be depicted as T, P diagrams for a
constant composition mixture as illustrated in Figure 2, or alternatively, they may be depicted as T,c diagrams for mixtures
at constant pressure (as illustrated conceptually by the binodal curve in Fig. 28), or P,c diagrams for mixtures at constant

8
 EP 2 195 349 B1

temperature, where the symbol c is used to denote composition. For multi-component mixtures the composition must
be designated by a series of composition variables ci, where i refers to each component in the mixture, but for a binary
mixture, a single variable c will adequately denote the composition. In general, the polymerization medium of the current
invention is a multi-component mixture, but for our current purposes of illustration, there is no generality lost by considering
5 the polymerization medium to be a binary mixture of polymer and a single low molecular weight hydrocarbon, and the
composition variable c can be taken to denote polymer concentration. If we take by way of example a phase boundary
depicted by T,c at constant P as depicted in Fig. 28, then the fluid-liquid phase boundary appears as a curve (which,
following terminology commonly used in the art, we have designated as a binodal curve) where a minimum value of
temperature (which is also commonly called the Lower Critical Solution Temperature, or LCST) exists at a concentration
10 called the critical polymer concentration (crit). This binodal curve, which represents the two-phase (fluid-liquid) phase
boundary, is a locus of points where the single phase polymerization medium is in equilibrium with a two-phase mixture
of monomer-rich and polymer-rich phases. From Fig. 28, it is apparent that for any given T & P, which is represented
by horizontal line at T1, there are two mixture compositions that are in equilibrium with the Polymerization medium, and
thus in equilibrium with each other. One of these mixture compositions is a monomer-rich composition, and the other a
15 polymer-rich composition (these two compositions are designated as c’ and c" on Fig. 28). The bottom part of Fig. 28
illustrates a curve representing the chemical potential (∆m1]) of the binary mixture as a function of c at a temperature
equal to T1 (note that a similar curve could be constructed for all other values of T). Note also that ∆m1(c’) = ∆m1(c"),
since for two mixtures to be in equilibrium, their chemical potentials must be equal. At other values of c on this curve,
∆m1 assumes other values, since these other compositions are not in equilibrium with c’ and c". Along this ∆m1. curve,
20 there are two other special points, where the first partial derivative of ∆m1 with respect to composition is zero (∂∆m1/∂c
= 0). This is the thermodynamic criterium that defines the spinodal boundary, as is illustrated by the graphical construction
in Fig. 28. For compositions on, or inside, the spinodal boundary, the compositions of the monomer-rich and polymer-
rich phases differ sufficiently from equilibrium to form a thermodynamically unstable two-phase mixture, which tends to
form a co-continuous morphology rather than a morphology where one of the two phases is dispersed as droplets in a
25 continuum of the other phase. Inside the cross-hatched area in Fig. 28, the mixture tends to form a morphology where
one of the two phases is dispersed in a continuum of the other phase. When the polymer concentration in the polymer-
ization medium is higher than ccrit , the polymer-rich phase is continuous, and when the polymer concentration in the
polymerization medium is lower than ccrit, the monomer-rich phase is continuous. In many embodiments of the current
invention, the polymerization medium is a single phase fluid, such that its thermodynamic state (T,P,c) would place it in
30 the single phase region outside the binodal boundary on Fig. 28. The process of spinodal decomposition refers to a
process by which a rapid change in the temperature or pressure is effected to move the thermodynamic state of the
system across both the binodal and spinodal boundaries to a point inside the spinodal boundary. For this change to be
effective in producing the desired co-continuous morphology, the time that the thermodynamic state of the system resides
in the area between the binodal and spinodal boundaries (cross-hatched area of Fig. 28) must be short enough that the
35 undesired morphology does not have sufficient time to become established. The exact value of time that satisfies this
criterium must be determined empirically for each polymerization medium. Spinodal boundaries may also be depicted
on phase diagrams which plot P vs. T at constant composition, as illustrated in Fig. 29. A full treatment of this concept
may be found in the paper "A Low-Energy Solvent Separation Method", T.G. Gutowski et. al., Polymer Engineering and
Science, March 1983, v. 23, No. 4.
40 [0053] Dense fluids are defined as fluid media in their liquid or supercritical state with densities greater than 300 kg/m3.
[0054] Solid-fluid phase transition temperature is defined as the temperature at and below which a solid polymer
phase separates from the polymer-containing fluid medium at a given pressure. The solid-fluid phase transition temper-
ature can be determined by temperature reduction starting from temperatures at which the polymer is fully dissolved in
the fluid reaction medium.
45 [0055] Solid-fluid phase transition pressure is defined as the pressure at and below which a solid polymer phase
separates from the polymer-containing fluid medium at a given temperature. The solid-fluid phase transition pressure
can be determined by pressure reduction at constant temperature starting from pressures at which the polymer is fully
dissolved in the fluid reaction medium.
[0056] A higher α-olefin or higher alpha-olefin is defined as an α-olefin having five or more carbon atoms.
50 [0057] The new numbering scheme for the Periodic Table Groups is used as published in CHEMICAL AND ENGI-
NEERING NEWS, 63(5), 27 (1985).
[0058] The term "polymer" describes chain-like molecules synthesized from one or more repeat units, or monomers,
and is meant to encompass homopolymers and copolymers, and includes any polymer having two or more different
monomers in the same chain, including random copolymers, statistical copolymers, interpolymers, and block copolymers.
55 [0059] Polymerization encompasses any polymerization reaction such as homopolymerization and copolymerization.
Copolymerization encompasses any polymerization reaction of two or more monomers.
[0060] When a polymer is referred to as comprising an olefin, the olefin present in the polymer is the polymerized
form of the olefin. A "polyolefin" is a polymer comprising at least 50 mol % of one or more olefins. Advantageously, a

9
 EP 2 195 349 B1

polyolefin comprises at least 60 mol %, or at least 70 mol %, or at least 80 mol %, or at least 90 mol %, or at least 95
mol %, or 100 mol % of one or more olefins, preferably 1-olefins, having carbon numbers of 2 to 20, preferably 2 to 16,
or 2 to 10, or 2 to 8, or 2 to 6.
[0061] A "high molecular weight" polymer has a Mw of 30 kg/mol or more. Advantageously, a high molecular weight
5 polymer has a weight-averaged molecular weight (Mw) of 50 kg/mol or more, or 75 kg/mol or more, or 100 kg/mol or
more, or 125 kg/mol or more, or 150 kg/mol or more.
[0062] An "oligomers" or "low molecular weight" polymer is a polymer having a Mw of less than 30 kg/mol. Advanta-
geously, oligomers have a Mw of less than 20 kg/mol, or less than 10 kg/mol, or less than 5 kg/mol, or less than 4 kg/mol,
or less than 3 kg/mol, or less than 2 kg/mol, or less than 1 kg/mol. A "polyolefin oligomers" is a polyolefin that meets the
10 definition of an oligomer.
[0063] A "high crystallinity" polymer has a heat of fusion (Hf) of greater than 70 J/g. Advanatgeously, a high crystallinity
polymer has a Hf of greater than 80 J/g, or greater than 90 J/g, or greater than 100 J/g, or greater than 110 J/g, or greater
than 120 J/g.
[0064] A "low crystallinity" polymer has a Hf of 70 J/g or less. Advanatgeously, a low crystallinity polymer has a Hf of
15 60 J/g or less, or 50 J/g or less, or 40 J/g or less, or 30 J/g or less, or 20 J/g or less, or 10 J/g or less, or 5 J/g or less,
or an Hf that is too small to meaure reliably.
[0065] A "base polymer" or "base resin" is a polyolefin or polyolefin blend the properties of which are modified by
blending them with one or more plasticizers. Typically, a base polymer is a high crystallinity, high molecular weight
polyolefin.
20 [0066] A "soft" polymer is a low crystallinity high molecular weight polymer. Typically, a soft polymer has a glass
transition temperature (Tg) of less than 0˚C. Preferably, a soft polymer has a Tg of less than -10˚C, or less than -20˚C,
or less than -30˚C, or less than -40˚C. A "soft polyolefin" is a polyolefin that meets the definition of a soft polymer.
Examples of soft polyolefins include "plastomers" which comprise a majority of ethylene (ethylene plastomers) or a
majority of propylene (propylene plastomers) with crystallizable sequences of the majority monomer, and "elastomers"
25 which have a Mw of 100 kg/mol or more (such as EP elastomers which comprise ethylene, propylene, and optionally
one or more dienes).
[0067] Plasticizers are defined as per J.K. Sears, J.R. Darby, THE TECHNOLOGY OF PLASTICIZERS, Wiley, New,
York, 1982, stating that "Plasticizer is a material incorporated in a plastic to increase its workability and its flexibility or
distensibility (elongation). Addition of the plasticizer may lower the melt viscosity, temperature or the second-order
30 transition, or the elastic modulus of the plastic." Plasticizers have a lower glass transition temperature and/or lower
modulus and/or lower crystallinity and/or lower Mw than the base polymer. They may be oligomers, soft polymers, or
other fluids.
[0068] A series reactor cascade includes two or more reactors connected in series, in which the effluent of an upstream
reactor is fed to the next reactor downstream in the reactor cascade. Besides the effluent of the upstream reactor(s),
35 the feed of any reactor can be augmented with any combination of additional monomer, catalyst, scavenger, or solvent
fresh or recycled feed streams.
[0069] Reactor train or reactor branch or reactor leg refers to a polymerization reactor or to a group of polymerization
reactors of the in-line blending process disclosed herein that produces a single blend component. If the reactor train
contains more than one reactor, the reactors are arranged in a series configuration within the train. The need for having
40 more than one reactor in a reactor train may, for example, arise when an in-line blend component cannot be produced
at the desired rate economically in a single reactor but there could be also reasons related to blend component quality,
such as molecular weight or composition distribution, etc. Since a reactor train can comprise multiple reactors and/or
reactor zones in series, the single blend component produced in a reactor train may itself be a polymer blend of polymeric
components with varying molecular weights and/or compositions. However, in order to simplify the description of different
45 embodiments of the in-line blending processes disclosed herein, the polymeric product of a reactor train is referred to
simply as blend component or polymeric blend or plasticizer blend component regardless of its molecular weight and/or
compositional dispersion. For the purpose of defining the process of the present invention, parallel reactors will be always
considered as separate reactor trains even if they produce essentially the same in-line blend component. Also, spatially
separated, parallel reaction zones that do not exchange or mix reaction mixtures by, for example, pump-around loops,
50 or by other recirculation methods, will be considered as separate parallel reactor trains even when those parallel zones
are present in a common shell and fall within the in-line blending process disclosed herein.
[0070] Reactor bank refers to the combination of all polymerization reactors in the polymerization section of the in-
line polymer blending process disclosed herein.
[0071] A parallel reactor configuration includes two or more reactors or reactor trains connected (also referred to as
55 fluidly connected) in parallel. A reactor train, branch, or leg may include one reactor or alternatively more than one
reactor configured in a series configuration. For example, a reactor train may include two, or three, or four, or more
reactors in series. The entire parallel reactor configuration of the polymerization process disclosed herein, i.e., the
combination of all parallel polymerization reactor trains forms the reactor bank.

10
 EP 2 195 349 B1

[0072] Monomer recycle ratio refers to the ratio of the amount of recycled monomer fed to the reactor divided by the
total (fresh plus recycled) amount of monomer fed to the reactor.
[0073] Polymerization system is defined to be monomer(s) plus optional comonomer(s) plus polymer(s) plus optional
inert solvent(s)/diluent(s) plus optional scavenger(s). Note that for the sake of convenience and clarity, the catalyst
5 system is always addressed separately in the present discussion from other components present in a polymerization
reactor. In this regard, the polymerization system is defined here narrower than customary in the art of polymerization
that typically considers the catalyst system as part of the polymerization system. By the current definition, the mixture
present in the polymerization reactor and in its effluent is composed of the polymerization system plus the catalyst
system. Dense fluid polymerization systems have greater than 300 kg/m3 fluid phase density, all of their components
10 listed above, i.e., the monomer(s) plus optional comonomer(s) plus polymer(s) plus optional inert solvent(s)/diluent(s)
plus optional scavenger(s), are in fluid state, or stating differently, none of their components is in solid state. Note that
these qualifications may be different for the catalyst system since it is not part of the polymerization system.
[0074] A homogeneous polymerization system contains all of its components dispersed and mixed on a molecular
scale. In our discussions, homogeneous polymerization systems are meant to be in their dense fluid (liquid or supercritical)
15 state. Note that our definition of the polymerization system does not include the catalyst system, thus the catalyst system
may or may not be homogeneously dissolved in the polymerization system. A homogeneous system may have regions
with concentration gradients, but there would be no sudden, discontinuous changes of composition on a micrometer
scale within the system. In practical terms, a homogeneous polymerization system has all of its components in a single
dense fluid phase. Apparently, a polymerization system is not homogeneous when it is partitioned to more than one
20 fluid phase or to a fluid and a solid phase. The homogeneous fluid state of the polymerization system is represented by
the single fluid region in its phase diagram.
[0075] A homogeneous polymerization process operates with a homogeneous polymerization system. Note that the
catalyst system is not part of the polymerization system, thus it is not necessarily dissolved homogeneously in the
polymerization system. A reactor in which a homogeneous polymerization process is carried out will be referred to as
25 homogeneous polymerization reactor.
[0076] The following abbreviations are used: Me is methyl, Ph is phenyl, Et is ethyl, Pr is propyl, iPr is isopropyl, n-Pr
is normal propyl, Bu is butyl, iBu is isobutyl, tBu is tertiary butyl, p-tBu is para-tertiary butyl, TMS is trimethylsilyl, TIBA
is tri-isobutylaluminum, MAO is methylaluminoxane, pMe is para-methyl, flu is fluorenyl, cp is cyclopentadienyl.
[0077] By continuous is meant a system that operates (or is intended to operate) without interruption or cessation.
30 For example, a continuous process to produce a polymer would be one where the reactants are continually introduced
into one or more reactors and polymer product is continually withdrawn.
[0078] Slurry polymerization refers to a polymerization process in which particulate, solid polymer (e.g., granular)
forms in a dense fluid or in a liquid/vapor polymerization medium. The dense fluid polymerization medium can form a
single or two fluid phases, such as liquid, supercritical fluid, or liquid/liquid, or supercritical fluid/supercritical fluid, po-
35 lymerization medium. In the liquid/vapor polymerization medium, the polymer resides in the liquid (dense) phase.
[0079] Solution polymerization refers to a polymerization process in which the polymer is dissolved in a liquid polym-
erization system in which the solvent for the polymeric product is an inert solvent(s) or the monomer(s) or their blends.
Solution polymerization comprises a liquid polymerization system. Solution polymerization may be performed at condi-
tions where a vapor and a liquid phase are present, in which case the polymerization system comprises the liquid phase.
40 Advantageously, solution polymerization is performed with liquid-filled reactors, in the substantial absence of a vapor
phase. Liquid-filled reactor operations are characterized by reactor pressures that are at or above the bubble point of
the polymerization system. Bubble point is defined as the pressure at which a liquid starts forming vapor bubbles at a
given temperature. Bubble point pressures of hydrocarbon blends can be readily determined by standard techniques
known in the art of chemical engineering. Methods suitable for conducting such calculations are equation of state
45 methods, such as Peng Robinson or Suave Redlich Kwong. Bubble point of liquids can be also readily measured by
methods such as disclosed in T. Tsuji et al., Fluid Phase Equilibria 219 (2004) 87-92 or in R.W. et al., US Pat. 6,223,588
(2001). The bubble point of a liquid can be conveniently determined by reducing the pressure at constant temperature
of a compressed fluid until the first vapor bubble is formed. Solution polymerization typically performed in a single
homogeneous liquid phase, but solution polymerization comprising two liquid phases are also known. In the latter case,
50 the polymerization system is below of its cloud point pressure but above of its solid-fluid phase transition pressure and
temperature. In these two-phase liquid polymerizations systems, the polymerization system is typically partitioned into
two liquid phases, a polymer-lean and a polymer-rich liquid phase. In a well-stirred polymerization reactor, these two
phases are finely dispersed. Note, however, that these two-phase liquid polymerizations systems have none of their
components in solid state.
55 [0080] Supercritical polymerization refers to a polymerization process in which the polymerization system is in its
dense supercritical state, i.e. when the density of the polymerization system is above 300 g/L and its temperature and
pressure are above the corresponding critical values. Supercritical polymerization is typically performed in a single
homogeneous supercritical phase, but supercritical polymerization comprising two supercritical fluid phases is also

11
 EP 2 195 349 B1

contemplated. In the latter case, the polymerization system is below of its cloud point pressure but above of its solid-
fluid phase transition pressure and temperature. In these two-phase supercritical fluid polymerizations systems, the
polymerization system is typically partitioned into two fluid phases, a polymer-lean and a polymer-rich fluid phase. In a
well-stirred polymerization reactor, these two phases are finely dispersed. Note, however, that these two-phase super-
5 critical fluid polymerizations systems have none of their components in solid state.
[0081] Bulk polymerization refers to a polymerization process in which the dense fluid polymerization system contains
less than 40 wt %, or less than 30 wt %, or less than 20 wt %, or less than 10 wt %, or less than 5 wt %, or less than 1
wt % of inert solvent or diluent. The product polymer may be dissolved in the dense fluid polymerization system or may
form a solid phase. In this terminology, slurry polymerization, in which solid polymer particulates form in a dense fluid
10 polymerization system containing less than 40 wt % of inert solvent or diluent, will be referred to as a bulk slurry
polymerization process or bulk heterogeneous polymerization process. The polymerization process in which the poly-
meric product is dissolved in a single-hase dense fluid polymerization system containing less than 40 wt % of inert
solvent or diluent will be referred to as bulk homogeneous polymerization process. The polymerization process in which
the polymeric product is dissolved in a liquid polymerization system containing less than 40 wt %, or less than 30 wt %,
15 or less than 20 wt %, or less than 10 wt %, or less than 5 wt %, or less than 1 wt % of inert solvent or diluent will be
referred to as bulk solution polymerization process. The polymerization process in which the polymeric product is dis-
solved in a single-phase supercritical polymerization system containing less than 40 wt %, or less than 30 wt %, or less
than 20 wt %, or less than 10 wt %, or less than 5 wt %, or less than 1 wt % of inert solvent or diluent will be referred to
as bulk homogeneous supercritical polymerization process.
20 [0082] Homogeneous supercritical polymerization refers to a polymerization process in which the polymer is dissolved
in a single-phase dense supercritical fluid polymerization medium, such as an inert solvent or monomer or their blends
in their supercritical state. As described above, when the supercritical fluid polymerization system contains less than 40
wt %, or less than 30 wt %, or less than 20 wt %, or less than 10 wt %, or less than 5 wt %, or less than 1 wt % of inert
solvent and the polymer is dissolved in the dense supercritical fluid, the process is referred to as a bulk homogeneous
25 supercritical polymerization process. Homogeneous supercritical polymerization should be distinguished from hetero-
geneous supercritical polymerizations, such as for example, supercritical slurry processes, the latter of which are per-
formed in supercritical fluids but form solid polymer particulates in the polymerization reactor. Similarly, bulk homoge-
neous supercritical polymerization should be distinguished from bulk solution polymerization, the latter of which is per-
formed in a liquid as opposed to in a supercritical polymerization system.
30 [0083] Single-pass conversion of monomer i in reactor train j is defined by the following formula: Single pass conversion
of monomer i in reactor train j (%) = 100 x [(reactor train j effluent flow rate in weight per hour) x (polymer product
concentration in the effluent of reactor train j in weight fraction) x (monomer i concentration in the polymer product made
in reactor train j in weight fraction)] / [(reactor train j feed flow rate, including fresh and recycled, in weight per hour) x
(monomer i concentration in the feed of reactor train j, including fresh and recycled, in weight fraction)].
35 [0084] Overall conversion of monomer i in reactor train j is defined by the following formula: Overall conversion of
monomer i in reactor train j (%) = 100 x [(reactor train j effluent flow rate in weight per hour) x (polymer product concentration
in the effluent of reactor train j in weight fraction) x (monomer i concentration in the polymer product made in reactor
train j in weight fraction)] / [(reactor train j fresh feed flow rate, excluding recycled, in weight per hour) x (monomer i
concentration in the fresh feed of reactor train j, excluding recycled, in weight fraction)].
40 [0085] The total monomer feed rate of a given train is equal to the sum of fresh (make up) monomer feed rate plus
recycled monomer feed rate in weight per hour.
[0086] The flow (feed, effluent, recycle, purge etc. flow) rate of monomer component i in weight per hour is equal to
the total flow (feed, effluent, recycle, purge etc. flow) rate in weight per hour multiplied by the weight fraction of monomer
component i.
45 [0087] Conversion rate of monomer i in reactor train j expressed in weight per hour is equal to [(reactor train j effluent
flow rate in weight per hour) x (polymer product concentration in the effluent of reactor train j in weight fraction) x
(monomer i concentration in the polymer product made in reactor train j in a single pass in weight fraction)].
[0088] Unreduced reactor effluent refers to the whole effluent stream emerging from a reactor train, leg, or branch
that has yet to undergo phase separation in one or more high pressure separators., i.e., it contains the entire unreduced
50 polymerization system as it emerges from the reactor train, leg, or branch. As opposed to unreduced reactor effluents,
reduced reactor effluents are the polymer-containing streams derived from the unreduced reactor effluents. Reduced
reactor effluents contain less than the entire, unreduced polymerization system as it emerges from the reactor train, leg,
or branch. In practical terms, reduced effluents are formed by separating and removing a part of the monomer and the
optional inert solvent/diluent content in the form of a monomer-rich stream. In the practice of the present disclosure, the
55 separation of the said monomer-rich effluent and thus the reduction of the unreduced reactor effluent is performed by
phase separation that generates the said monomer-rich stream and the said reduced reactor effluent, the latter of which
in the form of a polymer-enriched stream. Stating it yet another way, the unreduced reactor effluent is the whole reactor
effluent before any split of that effluent occurs, while a reduced effluent is formed after at least one split in which some

12
 EP 2 195 349 B1

of the light components (monomers and the optional inert solvents/diluents) are removed from the whole, unreduced
reactor effluent.
[0089] Base polymers, base polymer components or base resins are polyolefins the properties of which are modified
by blending them with one or more plasticizers and optionally other additives, such as waxes, antioxidants, nucleating
5 and clarifying agents, slip agents, flame retardants, heat and UV stabilizers, antiblocking agents, fillers, reinforcing fibers,
antistatic agents, lubricating agents, coloring agents, foaming agents, etc.
[0090] An in-line blending process disclosed herein refers to one where the polymerization and the polymer blending
processes are integrated in a single process and at least one of the polymerization trains operates under solution or
homogeneous supercritical conditions. Although in-line blending processes typically employ polymerization trains using
10 solution or homogeneous supercritical polymerization systems, one or more of the polymerization trains may employ
slurry polymerization systems, particularly bulk slurry polymerization systems. When the polymerization bank includes
one or more slurry polymerization trains, the effluents of those slurry trains are always heated above their solid-fluid
transition points and optionally pressurized before mixing them with the effluents of other trains to enable fluid-phase
mixing.
15 [0091] In-line polymer blend or in-line blend disclosed herein refers to a mixture of two or more polymeric components,
at least one of which is produced under either homogeneous supercritical polymerization conditions or homogeneous
solution polymerization conditions. The said polymeric in-line blend components are produced internally in the in-line
blending process and are mixed in the same process without recovering them in their solid state, i.e., the polymeric in-
line blend components are produced and blended in-line. Optionally, the in-line blends may also contain common polymer
20 additives which are used to impart certain desirable properties and are produced outside the invention process, such
as UV stabilizers, antioxidants, nucleating agents, cross-linking agents, fillers, etc. Such additives are described in
PLASTICS ADDITIVE HANDBOOK, 5th Ed.; H. Zweifel, Ed. (Hanser-Gardner, 2001) and may be present at any effective
concentration but typically at less than 10 wt %, or even less than 1 wt %, by weight. The in-line blends may also contain
polymeric additives/modifiers produced outside the invention process (i.e. off-line). They are typically added in minor
25 amounts, i.e., less than 50 wt %, or less than 40 wt %, or less than 30 wt %, or less than 20 wt %, or less than 10 wt %,
or less than 5 wt %, or less than 1 wt % by weight. These optional additives may advanatgeously be blended in-line,
i.e., before the plasticizer-polymer blend is recovered in their solid state, such as in the finishing equipment that converts
the molten polymer-plasticizer blend into formulated granules, pellets, bales, or the like.
[0092] In-line polymer-plasticizer blend, or in-line-plasticized polymer or in-line-plasticized polymer blend disclosed
30 herein refers to a mixture of one or more polymeric components (base polymer) with one or more plasticizers, wherein
at least one of the polymeric components of the base polymer is produced in-line (i.e., in one or more of the reactor
trains of the disclosed in-line blending processes) under either supercritical polymerization conditions or solution po-
lymerization conditions and the one or more plasticizer components are blended with the base polymer also in-line, i.e.,
before the base polymer is recovered in its essentially pure, solid form. The one or more plasticizers blended in-line with
35 the base polymer may be produced in-line, i.e., in one of the reactor trains of the reactor bank of the disclosed processes,
or may be produced in a separate plant and added to a stream comprising the base polymer or a combination thereof.
When none of the plasticizers comprising the in-line-plasticized polymer or in-line-plasticized polymer blend are produced
in-line, the base polymer is an in-line polymer blend of two or more polymer components. When one or more plasticizer
components are produced in-line, the base polymer may be either a single component or an in-line blend of two or more
40 polymer components. Note that the one or more polymeric components constituting the base polymer are produced and
mixed internally in the disclosed in-line blending processes. Furthermore, the disclosed blending processes blend the
plasticizers and the base polymer in-line, i.e., before the base polymer is recovered in its essentially pure, solid form.
Finally, note that the base polymer may itself be an in-line blend of polymers or alternatively may be a single polymer
component. In the latter case, one or more of the plasticizer components of the in-line-plasticized polymer are also
45 produced in-line. The blending point for combining the polymer- and plasticizer-containing streams may be anywhere
downstream of the reactor bank of the disclosed in-line polymer blending processes. Advantageously, the one or more
plasticizers are blended with a base polymer containing stream that still contains at least some of the low molecular
weight components, such as the monomers and the optional inert solvents/diluents of the polymerization system, to
facilitate the blending process by the virtue of reduced viscosity. The said advantageous mixing points of the disclosed
50 in-line blending processes exist downstream of the reactors and upstream of the extruder or devolatizing extruder of
the product finishing section of the processes disclosed herein, particularly, downstream of the reactors and upstream
of or in the low-pressure separator deployed just before the said extruder or devolatizing extruder of the finishing section.
[0093] The term plasticized polyolefin masterbatch, or plasticized polymer masterbatch, is defined as a blend of one
or more high molecular weight base polymer(s) and one or more plasticizer(s) made primarily for further compounding,
55 i.e., for further blending with high molecular weight polymer to produce plasticized polymeric product. The purpose of
making plasticized masterbatches essentially is to deliver plasticizers in a pelletized form and thus enable compounding
in the traditional compounding facilities equipped to handle pelletized polymers but typically not equipped to handle
fluids and or bales. Pelletization is afforded by blending one or more high molecular weight base polymer with one or

13
 EP 2 195 349 B1

more plasticizers, wherein the base polymer creates a matrix providing for proper processability and pellet stability.
Masterbatches typically have high concentration of plasticizers for efficient delivery of the plasticizer package. The
compounders blend these masterbatches in appropriate ratios with additional amounts of base polymers to adjust their
properties for final use. When the plasticized polyolefin masterbatch is made in-line, i.e., when the plasticizer is blended
5 with the base polymer in-line, the plasticized masterbatch is also referred to as in-line-plasticized polyolefin masterbatch,
or in-line-plasticized polymer masterbatch.
[0094] The term mineral oil includes any fluid derived from petroleum crude oil that has been subjected to refining
steps (such as distillation, solvent processing, hydroprocessing, and/or dewaxing). This also includes petroleum-based
oils that are extensively purified and/or modified through severe processing treatments. It excludes synthetic oils, which
10 have been manufactured by combining monomer units using catalysts and/or heat. In the polymer processing art, mineral
oils are often called process oils, extender oils, white oils, technical oils, or food grade oils. Such fluids typically have a
viscosity index less than 120, most have a viscosity index less than 110, and many have a viscosity index of 100 or less.
[0095] The American Petroleum Institute categorizes mineral oils as Group I, II, or III basestocks based upon saturates
content, sulfur content, and Viscosity Index (VI). Group I basestocks are solvent-refined mineral oils. They contain the
15 most unsaturates and sulfur of the three groups, and have the lowest viscosity indices. Group II and Group III basestocks
are hydroprocessed mineral oils. The Group III basestocks contain less unsaturates, less sulfur, and have higher VIs
compared to Group II basestocks. Even in cases where a mineral oil is not identified by an API Group classification, it
is still possible, for purposes of this invention, to define two classes of mineral oils based on Viscosity Index: "Group I/II
mineral oils" which have VI less than 120; and "Group III mineral oils" which have VI of 120 or more.
20 [0096] As used herein, the following terms have the indicated meanings: "naphthenic" describes cyclic (mono-ring
and/or multi-ring) saturated hydrocarbons (i.e., cycloparaffins) and branched cyclic saturated hydrocarbons; "aromatic"
describes cyclic (mono-ring and/or multi-ring) unsaturated hydrocarbons and branched cyclic unsaturated hydrocarbons
as described in J. March, ADVANCED ORGANIC CHEMISTRY Fourth ed., Wiley, New York, 1992; "hydroisomerized"
describes a catalytic process in which normal paraffins and/or slightly branched isoparaffins are converted by rearrange-
25 ment into more branched isoparaffins (also known as "isodewaxing"); "wax" is a hydrocarbonaceous material existing
as a solid at or near room temperature, with a melting point of 0˚C or above, and consisting predominantly of paraffinic
molecules, most of which are normal paraffins; "slack wax" is the wax recovered from petroleum oils such as by solvent
dewaxing, and may be further hydrotreated to remove heteroatoms.
[0097] The term paraffin includes all isomers such as normal paraffins (n-paraffins), branched paraffins, isoparaffins,
30 cycloparaffins, and may include cyclic aliphatic species, and blends thereof.
[0098] The term isoparaffin means that the paraffin chains possess C1 to C18 (more commonly C1 to C10) alkyl
branching along at least a portion of each paraffin chain, and may include cycloparaffins with branched side chains as
a minor component (advantageously less than 30%, or less than 20%, or less than 10%, or 0% of carbons are in
cycloparaffins structures). More particularly, isoparaffins are saturated aliphatic hydrocarbons whose molecules have
35 at least one carbon atom bonded to at least three other carbon atoms or at least one side chain (i.e., a molecule having
one or more tertiary or quaternary carbon atoms); various isomers of each carbon number (i.e. structural isomers) will
typically be present. Isoparaffins with multiple alkyl branches may include any combination of regio and stereo placement
of those branches.
[0099] By heterogeneous composition is meant a composition having two or more morphological phases. For example
40 a blend of two polymers where one polymer forms discrete domains dispersed in a matrix of another polymer is said to
be heterogeneous in the solid state. Heterogeneous blends also include co-continuous blends where the blend compo-
nents are separately visible, but it is unclear which is the continuous phase and which is the discontinuous phase. Such
heterogeniety in the composition and mophology of the blend occurs in phase of dimensions of 100 mm to less than 0.1
mm, as determined using optical microscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), or
45 in some cases by dynamic mechanical thermal analysis (DMTA); in the event there is disagreement among the methods,
then the SEM data shall be used. By continuous phase is meant the matrix phase in a heterogeneous blend. By dis-
continuous phase is meant the dispersed phase in a heterogeneous blend.
[0100] By homogeneous composition is meant a composition having substantially one morphological phase in the
same state. For example, a blend of two polymers where one polymer is miscible with another polymer is said to be
50 homogeneous in the solid state. Such morphology is determined using optical microscopy, SEM, AFM, or in some cases
by DMTA; in the event there is disagreement among the methods, then the SEM data shall be used.
[0101] Unless noted otherwise:
[0102] Percents express a weight percent (wt %), based on the total amount of the material or component at issue;
[0103] Physical and chemical properties described are measured using the following test methods:
55
Kinematic Viscosity (KV) ASTM D 445
Viscosity Index (VI) ASTM D 2270

14
 EP 2 195 349 B1

(continued)
Pour Point ASTM D 97
Specific Gravity and Density ASTM D 4052 (15.6/15.6 ˚C)
5 Flash Point ASTM D 92
Distillation range, initial boiling point, and final boiling point ASTM D 86
Glass Transition Temperature (Tg) ASTM E 1356 (10˚C/min, midpoint convention)
Saturates Content ASTM D 2007
Sulfur Content ASTM D 2622
10
Melt Index (MI) ASTM D 1238 (190˚C/2.16 kg)
Melt Flow Rate (MFR) ASTM D 1238 (230˚C/2.16 kg)
Mooney Viscosity ASTM D 1646
Density ASTM D 4052
15 Injection Molding ASTM D 4101
DMTA Properties ASTM D 4065
Tensile Properties ASTM D 638 (Type I bar, 5 cm/min)
1% Secant Flexural Modulus ASTM D 790 (A, 1.3 mm/min)
Heat Deflection Temperature ASTM D 648 (0.45 MPa)
20
Vicat Softening Temperature ASTM D 1525 (200 g)
Gardner Impact Strength ASTM D 5420 (GC)
Notched Izod (NI) Impact Strength ASTM D 256 (Method A, or Method E if "reverse notch"
noted, RNI)
25
Notched Charpy Impact Strength ASTM D 6110
Multi-Axial Impact Strength ASTM D 3763 (15 MPH)
Shore (Durometer) Hardness ASTM D 2240 (A or D, 15 sec delay)

[0104] For polymers and oligomers have a KV 100˚C of greater than 10 cSt, the weight-averaged molecular weight
30 (Mw), number-averaged molecular weight (Mn), and z-averaged molecular weight (Mz) are each determined utilizing
gel permeation chromatography (GPC) based on calibration using polystyrene standards; Mn for oligomers having a
KV 100˚C of 10 cSt or less is determined by gas chromatography with a mass spectrometer detector;
[0105] Branched Paraffin to n-paraffin ratio, % mono-methyl species, and % side chains with X number of carbons
are determined by 13C-NMR;
35 [0106] Composition Distribution Breadth Index (CDBI) is a measure of the composition distribution of monomer within
the polymer chains and is measured by the procedure described in PCT publication WO 93/03093, published Feb. 18,
1993 including that fractions having a weight average molecular weight (Mw) below 15,000 are ignored when determining
CDBI. For purposes of this invention a homopolymer is defined to have a CDBI of 100%.
[0107] Heat of fusion, Hf, is measured between the temperatures of 21 and 230˚C by differential scanning calorimetry
40 (DSC) second melt;
[0108] Molecular weight distribution (MWD) is defined as the weightaverage molecular weight divided by the number-
average molecular weight (Mw/Mn); and
[0109] When melting or crystallization point is referred to and there is a range of melting or crystallization temperatures,
the melting or crystallization point is defined to be the peak melting or crystallization temperature from a DSC trace, and,
45 unless noted otherwise, when there is more than one melting or crystallization peak, it refers to the peak melting or
crystallization temperature for the largest peak among principal and secondary melting peaks, as opposed to the peak
occurring at the highest temperature, thereby reflecting the largest contribution to the calorimetric response of the material.

DETAILED DESCRIPTION
50
[0110] As disclosed in U.S. Patent Application No. 60/876,193 filed on December 20, 2006, an improved in-line process
for blending polymers has been developed to improve blend quality and reduce the capital and operating costs associated
with a combined polymerization and blending plant. The present disclosure expands the scope of U.S. Patent Application
No. 60/876,193 to an in-line blending process with two or more parallel reactor trains for producing plasticized polyolefins,
55 plasticized polyolefin blends, and plasticized polyolefin masterbatches. These plasticized polyolefin products are also
referred to herein as plasticized polymers, or plasticized polymer blends, or plasticized polymer masterbatches, or in-
line-plasticized polyolefins/polymers or in-line-plasticized polyolefin/polymer blends, or plasticized polyolefin/polymer
masterbatches.

15
 EP 2 195 349 B1

[0111] Disclosed herein are novel in-line blending processes for producing plasticized polymers in polymerization
processes in which at least one of the reactor trains, advantageously each reactor train, operates with a fluid phase,
advantageously with a homogeneous fluid phase (i.e., with a homogeneous liquid phase or homogeneous supercritical
phase) polymerization system and the polymerization system in at least one of the polymerization reactor trains includes
5 an olefin monomer that has two or more carbon atoms. More particularly, the present disclosure is related to making in-
line-plasticized polymers or in-line-plasticized polymer blends when one or more of the blending components is a suitable
plasticizer, such as, for example, oligomers, polymers, and copolymers of C5 to C20 alpha olefins and mixtures thereof
(also called poly(alpha-olefin)s) or PAOs), oligomers and copolymers of ethylene and propylene, oligomers and copol-
ymers of ethylene and C4-C20 olefins, oligomers and copolymers of propylene and C4-C20 olefins, paraffin oils and
10 waxes, mineral oils, synthetic oils, synthetic and mineral lube base stocks, elastomers, plastomers, etc., acting as a
plasticizer within a high molecular weight polyolefin base resin (also referred to as base polymer). The plasticizer com-
ponents may be made within the same plant or may be produced off-line or combination thereof and blended in-line
before the high molecular weight polyolefin base polymer component is recovered in its essentially pure solid state. The
blending point for combining the polymer- and plasticizer-containing streams may be anywhere downstream of the
15 reactor bank of the disclosed in-line polymer blending processes. Advantageously, the one or more plasticizers are
blended with a base polymer containing stream that still contains at least some of the low molecular weight components,
such as the monomers and the optional inert solvents/diluents of the polymerization system, to facilitate the blending
process by the virtue of reduced viscosity. The said advantageous mixing points of the disclosed in-line blending proc-
esses exist downstream of the reactors and upstream of the extruder or devolatizing extruder of the product finishing
20 section of the processes disclosed herein, particularly, downstream of the reactors and upstream of or in the low-pressure
separator deployed just before the said extruder or devolatizing extruder of the finishing section, which is also referred
to as the separator section of the disclosed processes. All embodiments of the disclosed processes blend the plasticizers
and the base polymer (the latter may be a polymer blend itself) in-line in the separator section of the in-line blending
process, i.e., before the base polymer is recovered in its essentially pure, solid form. The polyolefin-plasticizer-rich phase
25 from the separator section of the in-line blending process is then conveyed to a downstream finishing stage for further
monomer stripping, drying and/or pelletizing to form the plasticized polyolefin blend product of the in-line blending
process. Plasticized polyolefin blends may be made cheaper, easier, and with improved mixing if the high molecular
weight polyolefin component is present in a solution state and blended with a plasticizer also in a solution state. For
example, when a supercritical polymerization process is employed to produce the base polyolefin, the blending may be
30 performed in the production plant before the supercritical monomer acting as solvent is removed and the high molecular
weight base resin is recovered.
[0112] In some embodiments of the disclosed processes, the one or more polyolefin effluent streams from the one or
more parallel base polymer reactor trains and the plasticizer feed streams (produced either in-line or off-line or combi-
nation thereof) are combined downstream of the reactor bank and upstream of or in a high-pressure phase separator
35 that simultaneously provides blending of the in-line blend components and separation of the monomer(s) and inert
diluents(s) or solvents(s) from the base polyolefin blend component(s) and plasticizer blend component(s) by bringing
the combined reactor effluent and plasticizer feed streams below the cloud point of the mixture while maintaining said
mixed streams above the solid-fluid phase transition point by adjusting the temperature and pressure of the effluent
streams individually (i.e., before the mixing point), or combined (i.e., after the mixing point); when the reactor effluents
40 are combined upstream of a phase separator, optionally passing the mixed reactor effluent streams through one or more
static mixers before entering the said separator to enhance mixing; maintaining the pressure within the separator vessel
below the cloud point pressure to form two fluid phases comprising a polyolefin-plasticizer-rich fluid phase and a monomer-
rich fluid phase; maintaining the temperature in the separator above the solid-fluid phase transition temperature to allow
the settling to the bottom and the formation of a continuous layer at the bottom of a denser well-mixed fluid polyolefin-
45 plasticizer-rich blend phase and allowing the rising to the top and the formation of a continuous layer of a lower-density
monomer-solvent-rich phase at the top; separating a monomer-rich phase from a polyolefin-plasticizer-rich blend phase
and recycling the separated monomer-rich phase directly or after further treatment to the polymerization trains; optionally,
further reducing the pressure of the said first polyolefin-plasticizer-rich blend phase upstream of or in a low-pressure
separator to achieve another fluid-fluid separation into a more concentrated polyolefin-plasticizer-rich fluid phase and
50 another monomer-rich phase while maintaining the temperature above the solid-fluid phase transition temperature by
optionally further heating the first polyolefin-plasticizer rich blend stream; optionally, adding catalyst killer(s), and/or
polymer modifier(s) and/or additive(s) in their dense fluid state (i.e., liquid, supercritical fluid, molten, or dissolved state)
to the base polyolefin- and/or plasticizer-containing effluent stream(s) at any desired point downstream of the first
pressure letdown valves in any of the individual or combined effluent streams of the reactor trains in the reactor bank
55 of the disclosed processes. The polyolefin-plasticizer-rich phase from the separator section of the in-line blending process
is then conveyed to a downstream finishing stage for further monomer stripping, drying and/or pelletizing to form the
plasticized polyolefin blend product of the in-line blending process.
[0113] Another embodiment of the novel in-line blending processes for plasticized polyolefins includes providing two

16
 EP 2 195 349 B1

or more reactor trains configured in parallel wherein one or more of the reactor trains produce one or more high molecular
weight polyolefins (base polymers) and one or more of the reactor trains produce one or more plasticizers. For the one
or more parallel reactor trains producing the one or more high molecular weight polyolefins, the process includes con-
tacting olefin monomer(s) with catalyst systems, optional comonomer(s), optional scavenger(s), and optional diluent(s)
5 or solvent(s). At least one of the said parallel reactor trains producing the one or more high molecular weight polyolefins,
and advantageously each of them, operates at a temperature above the solid-fluid phase transition temperature of the
polymerization system and at a pressure no lower than the solid-fluid phase transition pressure and no lower than 10
MPa below, or no lower than 5 MPa below, or no lower than 1 MPa below, or no lower than 0.1 MPa below, or no lower
than 0.01 MPa below the cloud point pressure of the polymerization system and less than 1500 MPa, particularly between
10 1 and 300 MPa, still more particularly between 1 and 250 MPa, wherein the polymerization system comprises the
monomer, any comonomer(s), any scavenger(s), any diluent(s) or solvent(s) present, and the polyolefin-based polymer
product and where the catalyst system comprises catalyst precursor compound(s), activator(s), and optional support
(s); and forming a polyolefin/polymer reactor effluent stream including a polyolefin blend component (base polymer blend
component) dissolved in the effluent dense fluid polymerization system. For the one or more of the reactor parallel trains
15 producing a plasticizer, the process includes contacting olefin monomer(s) with catalyst systems, optional comonomer
(s), optional scavenger(s), and optional diluent(s) or solvent(s) at an effective reactor temperature and pressure of the
plasticizer system to create a plasticizer, wherein the plasticizer system comprises the monomer, any comonomer(s),
any scavenger(s), any diluent(s) or solvent(s) present, and the plasticizer product and where the catalyst system com-
prises catalyst precursor compound(s), activator(s), and optional support(s); and forming a plasticizer reactor effluent
20 stream including a plasticizer blend component dissolved in the monomer and optional diluent(s) or solvent(s). Note
that other aspects of the blending and separation methods and the location of advantageous blending points are not
effected, and thus are the same as in other embodiments.
[0114] In some other embodiments, one or more plasticizers produced in-line, i.e., in one or more reactor trains of
the disclosed processes, are fully recovered before blending them with the one or more effluent streams comprising the
25 one or more high molecular weight polymer components of the base polymer. By fully recover, we mean to recover them
in their essentially pure, solvent- and monomer-free, liquid form. Fully recovering in-line-produced plasticizer fluids before
blending them with the base polymer containing streams is particularly advantageous when the combined monomer
pool of the one or more plasticizer trains producing plasticizer fluids has monomer members that are not part of the
combined monomer pool of the one or more polymer trains producing the base polymer due to reduced complexity and
30 thus reduced cost of monomer recycle. Such separate recovery of the monomers and optional solvents of the one or
more plasticizer trains may allow the direct recycle of the plasticizer monomers to the one or more plasticizer reactor
trains. Since many plasticizers have relatively low viscosity at the blending conditions even in the absence of low
molecular weight diluents, such as monomers and optional solvents present in the plasticizer reactor train effluents,
they can be blended with the effluent streams comprising the high molecular weight polymer components without neg-
35 atively impacting the efficiency of the blending process. Such full recovery may not be always advantageous, particularly
for plasticizers with high viscosity at the blending conditions, such as in the case of some plastomers and elastomers.
As for any embodiment with in-line produced plasticizers, these embodiments may optionally also employ off-line-
produced plasticizers after proper conditioning, i.e., after bringing them into fluid phase by dissolving them in a proper
solvent or by melting them. Note that other aspects of the blending and separation methods and the location of advan-
40 tageous blending points are not effected, and thus are the same as in other embodiments employing only off-line-
produced plasticizers or as in embodiments that do not fully recover any of the in-line-produced plasticizers.
[0115] Yet another embodiment of the novel in-line blending processes for plasticized polyolefins includes providing
two or more reactor trains configured in parallel wherein the two or more reactor trains produce two or more high molecular
weight polyolefin (base polymer) blend components and all plasticizer components are made off-line but blended in-
45 line. For the two or more parallel reactor trains producing the two or more high molecular weight polyolefin(s), the process
includes contacting olefin monomer(s) with catalyst systems, optional comonomer(s), optional scavenger(s), and optional
diluent(s) or solvent(s); the polymerization performed in at least one of the two or more reactor trains, and advantageously
in all reactor trains, at a temperature above the solid-fluid phase transition temperature of the polymerization system
and at a pressure no lower than the solid-fluid phase transition pressure and no lower than 10 MPa below the cloud
50 point pressure of the polymerization system and less than 1500 MPa, particularly between 10 and 300 MPa, still more
particularly between 20 and 250 MPa; wherein the polymerization system comprises the monomer, any comonomer(s),
any scavenger(s), any diluent(s) or solvent(s) present, and the polyolefin-based polymer product and where the catalyst
system comprises catalyst precursor compound(s), activator(s), and optional support(s); and forming a polyolefin/polymer
reactor effluent stream including a polyolefin blend component (base polymer blend component) dissolved in the effluent
55 dense fluid polymerization system. The one or more off-line-produced plasticizers are pumped in their liquid, molten, or
dissolved state into one or more polymer-containing effluent streams to produce an in-line-plasticized polymer blend.
The blending point for combining the polymer- and plasticizer-containing streams may be anywhere downstream of the
reactor bank of the disclosed in-line polymer blending processes. Advantageously, the one or more plasticizers are

17
 EP 2 195 349 B1

blended with a base polymer containing stream that still contains at least some of the low molecular weight components,
such as the monomers and the optional inert solvents/diluents of the polymerization system, to facilitate the blending
process by the virtue of reduced viscosity. The said advantageous mixing points of the disclosed in-line blending proc-
esses exist downstream of the reactors and upstream of the extruder or devolatizing extruder of the product finishing
5 section of the processes disclosed herein, particularly, downstream of the reactors and upstream of or in the low-pressure
separator deployed just before the said extruder or devolatizing extruder of the finishing section. Thus, this embodiment
of the disclosed processes blend the plasticizers and the base polymer in-line, i.e., before the base polymer is recovered
in its essentially pure, solid form but do not produce any of the employed plasticizers in-line. In some embodiments, the
two or more polyolefin effluent streams from the two or more parallel reactor trains and the one or more off-line-produced
10 plasticizer feed streams are combined downstream of the reactor bank and upstream of or in a phase separator that
simultaneously provides blending of the in-line blend components and separation of the monomer(s) and inert diluents
(s) or solvents(s) from the base polyolefin blend component(s) and plasticizer blend component(s) by bringing the
combined reactor effluent and plasticizer feed streams below the cloud point of the mixture while maintaining said mixed
streams above the solid-fluid phase transition point by adjusting the temperature and pressure of the effluent streams
15 individually (i.e., before the mixing point), or combined (i.e., after the mixing point); when the reactor effluents are
combined upstream of a phase separator, optionally passing the mixed reactor effluent streams through one or more
static mixers before entering the said separator to enhance mixing; maintaining the pressure within the separator vessel
below the cloud point pressure to form two fluid phases comprising a polyolefin-plasticizer-rich fluid phase and a monomer-
rich fluid phase; maintaining the temperature in the separator above the solid-fluid phase transition temperature to allow
20 the settling to the bottom and the formation of a continuous layer at the bottom of a denser well-mixed fluid polyolefin-
plasticizer-rich blend phase and allowing the rising to the top and the formation of a continuous layer of a lower-density
monomer-solvent-rich phase at the top; separating a monomer-rich phase from a polyolefin-plasticizer-rich blend phase
and recycling the separated monomer-rich phase directly or after further treatment to the polymerization trains; optionally,
further reducing the pressure of the said first polyolefin-plasticizer-rich blend phase upstream of or in a low-pressure
25 separator to achieve another fluid-fluid separation into a more concentrated polyolefin-plasticizer-rich fluid phase and
another monomer-rich phase while maintaining the temperature above the solid-fluid phase transition temperature by
optionally further heating the first polyolefin-plasticizer-rich blend stream; optionally, adding catalyst killer(s), and/or
polymer modifier(s) and/or additive(s) in their dense fluid state (i.e., liquid, supercritical fluid, molten, or dissolved state)
to the base polyolefin- and/or plasticizer-containing effluent stream(s) at any desired point downstream of the first
30 pressure letdown valves in any of the individual or combined effluent streams of the reactor trains in the reactor bank
of the disclosed processes. The polyolefin-plasticizer-rich phase from the separator section of the in-line blending process
is then conveyed to a downstream finishing stage for further monomer stripping, drying and/or pelletizing to form the
plasticized polyolefin blend product of the in-line blending process.
[0116] Note that the in-line blending processes disclosed herein comprise a polymerization section or polymerization
35 reactor bank or reactor bank and at least one monomer-polymer separator vessel, called the separator-blending vessel,
or separator-blender, or high-pressure separator or high-pressure separator-blender. In some embodiments, one or
more reactor trains produce plasticizers. In those embodiments, the plasticizer-producing reactor trains also belong to
the polymerization section, i.e., those reactors are also part of the polymerization reactor bank or reactor bank even if
they are referred to as plasticizer trains in order to differentiate them from the reactor trains producing the high molecular
40 weight base polymer blending components (the latter trains are sometimes referred to as polymer trains). The separator-
blender serves as both a separator and a blender for the reactor effluents of the two or more parallel reactor trains in
the reactor bank in which at least one of the reactor trains employs a homogeneous fluid polymerization system (i.e.,
defined as a homogeneous supercritical or a solution polymerization process). It is also beneficial to the proper operation
of the in-line blending processes disclosed herein to bring the polymerization system in each reactor train effluent into
45 a homogeneous state upstream of the separator-blending vessel. Thus, when one or more in-line blending components
is/are produced in a particle-forming polymerization process, such as, for example bulk propylene slurry polymerization
with Ziegler-Natta or supported metallocene catalysts, the so-produced solid polymer pellets need to be homogeneously
dissolved in the reactor effluent before entering the separator-blending vessel. This can be accomplished by, for example,
pumping the reactor effluent slurry into a higher-temperature/higher-pressure dissolution zone that brings the reactor
50 effluent above the solid-fluid phase transition temperature creating a stream in which the reaction product is homoge-
neously dissolved. Although any and all combinations of reactor operation modes may be included in the in-line blending
processes disclosed herein, it is advantageous that at least one reactor train operates in a homogeneous fluid phase
and more advantageous if all reactor operations operate in the homogenous fluid phase for economic and process
simplicity reasons. Bulk homogeneous fluid phase polymerizations such as bulk homogeneous supercritical or bulk
55 solution polymerizations are particularly advantageous.
[0117] The methods of fluid phase in-line-plasticized polymer blending disclosed herein offer significant advantages
relative to prior art methods of blending polymers and plasticizers. One or more of the advantages of the dislosed method
of in-line plasticized polymer blending include, but are not limited to, improved polymer-plasticizer blend homogeneity

18
 EP 2 195 349 B1

because of molecular-level mixing of blend components, improved cost of manufacture because of savings from avoid-
ance of the reprocessing cost associated with conventional off-line blending processes that start with the separately
produced solid, pelletized polymer and plasticizer blend components, and because of the ease and simplicity of blending
polymers at substantially reduced viscosities due to the presence of substantial amounts of mononomers and optionally
5 solvents in the blending step; flexibility of adjusting blend ratios and therefore blend properties in-line; flexibility in adjusting
production rates of the blend components; flexibility in independently controlling for each reactor the residence time,
monomer composition and conversion, catalyst choice, catalyst concentration, temperature and pressure; improved
blend quality; flexibility in making a broader slate of plasticized polymer products in the same plant; reduced process
cost by utilizing the monomer-polymer separator(s) for product blending and, in some embodiments, for product buffering
10 to allow better control of blend ratio.

In-line Blending Process Overview:

[0118] Polyolefins are used in a large number of different applications. Each of these applications requires a different
15 balance between the stiffness, elasticity, and toughness of the polymer. Ideally, polymers would be custom-tailored to
the different needs of each customer. One of the methods enabling product tailoring involves the blending of individual
polymer components. The ability to adjust the stiffness-elasticity-toughness balance of polyolefins provides for the ability
to meet the needs of a broad range of applications and thus to expand the potential of polyolefins in delivering desired
performance at reduced cost. The stiffness-elasticity-toughness balance may be altered by changing the molecular
20 structure of polymers by changing their composition (i.e. making copolymers), stereoregularity, molecular weight, etc.
The stiffness elasticity-toughness may also be readily shifted by making blends of polymers, blends of polymers and
plasticizers or by producing composites. The in-line blending processes disclosed herein relate to making polymer-
plasticizer blends, also referred to as plasticized polymers. The one or more base polymer components for blending
with one or more plasticizers are generally high molecular weight polyolefin resins, such as polypropylenes (particularly
25 isotactic and syndiotactic polypropylenes), polyethylene, ethylene-propylene copolymers, copolymers of propylene and
C4 to C20 olefins (particularly C5 to C20 linear alpha-olefins), copolymers of ethylene and C4 to C20 olefins (particularly
C5 to C20 linear alpha-olefins), polymers with long-chain branching (LCB), and cyclic olefin copolymers (COC’s) made
of ethylene and a cyclic olefin, such as norbomene, cyclopentene, cyclohexene, and the like. When the base polymer
comprises soft copolymer components, they are always used in combination with high molecular weight high crystallinity
30 base polymer components, such as polypropylene or polyethylene. The one or more plasticizer components that are
either produced in-line and/or off-line but always blended in-line include polyolefin oligomers, mineral oils, lubricant
basestocks, and soft polyolefins.. The one or more externally-produced plasticizers may be optionally used in connection
with the one or more in-line-produced plasticizers. Alternatively, the one or more externally-produced plasticizers may
be used for in-line blending to produce in-line-plasticized polymers without employing in-line-produced plasticizers.
35 [0119] Plasticizers conducive to off-line production and in-line blending include all types of useful plasticizers listed
above. Plasticizers conducive to in-line production and in-line blending, on the other hand, typically represent a shorter
list. Thus, for example, plasticizers produced by separation from natural resources, such as, paraffin oils and waxes, Group
I, II, and III lube base stocks, etc. made from crude oil, would obviously not be produced in-line. Some synthetic plasticizers,
made primarily for other markets, like phthalates, mellitates, adipates, etc. made for PVC applications, would be also
40 produced off-line. There are also instances, when the in-line production of plasticizers is impractical for compatibility
reasons due to potential cross-contamination. For example, in-line processes to make plasticizers involving superacids,
and oxygen-containing compounds are typically not practical when the one or more base polymers are produced by using
highly poison-sensitive single-site catalysts, such as metallocenes, Ziegler-Natta catalysts, etc., due to the high potential
for catalyst poisoning and consequentially, due to the need for expensive purification methods in the feed recycle lines.
45 Other practical reasons, for example retrofitting existing plants, or unfavorable economics in certain locations due to
feedstock cost structure, etc., may also favor in-line blending of off-line-produced plasticizers even if they could be eco-
nomically produced in-line at other locations. For the above reasons, the disclosed processes for in-line blending of
plasticizers with base polymers to produce in-line-plasticized polymers offer three options: (1) in-line production of all
employed plasticizer blending components; (2) in-line production of one or more plasticizer blending components employed
50 in combination with one or more off-line-produced plasticizer blending components; (3) all plasticizer blending components
employed produced off-line. It should be also noted that the in-line blending processes disclosed herein are deployed in
combination with two or more parallel polymerization reactor trains. Consequently, by our definitions of parallel polymer-
ization reactor trains (vide supra), the number of base polymer components may be one or more for options (1) and (2)
and may be two or more for option (3). Furthermore, when all in-line-blended plasticizers are produced off-line (option (3)),
55 the base polymer comprise two or more high molecular weight in-line polymer blending components. The processes
described by options (1) and (2), on the other hand, may comprise one or more high molecular weight in-line polymer
blending components. When two or more high molecular weight in-line polymer blending components are produced, these
blending components may essentially be the same or may be different. The utility of making essentially the same high

19
 EP 2 195 349 B1

molecular weight in-line polymer blending components in more than one reactor trains could be increased capacity.
[0120] One of the important functions of plasticizers is their ability to reduce the glass transition temperature of polymer-
plasticizer blends. They perform this function by themselves having significantly lower glass transition temperatures as
compared to that of the base polymer. Another important function of plasticizers is to reduce blend viscosity during
5 processing. Again, they perform this function by themselves having significantly lower viscosity as compared to that of
the base polymers. Both of these properties strongly influenced by molecular weight. Namely, lower molecular weight
lowers both and thus is advantageous. For that reason, plasticizers are advantageously low molecular weight (<30
kg/mol Mw) oligomers (i.e., have less than 76 monomer units) that are liquid at ambient conditions although for increased
permanence/lower volatility, polymers are also used as plasticizers commercially.
10 [0121] Disclosed herein are advantageous processes for direct in-line polymer blend production in an integrated
parallel multi-reactor polymerization wherein the in-line blending step of combining one or more polyolefin base polymers
with one or more plasticizers is achieved downstream of the reactors and upstream of the extruder or devolatalizing
extruder of the finishing section of the process and wherein at least one, advantageously all, reactor trains operate with
a homogeneous polymerization system. The production of plasticized polymer blends in the polymerization plant is
15 facilitated when the polymer and plasticizer blend components, particularly when the highly viscous polymer blend
components, are dissolved in the polymerization system since the small-molecule components, such as monomers and
optional solvents/diluents of the polymerization system reduce viscosity thus allowing molecular level blending in a
lower-shear/lower-energy process. The presence of low molecular weight diluents also lowers the solid-fluid phase
transition temperature allowing lower-temperature blending operations. Hence, using the reactor effluents wherein the
20 polymer and plasticizer blending components are present in a dissolved dense fluid state may be advantageous to
downstream blending operations. Thus, the polymerization reactors for the high molecular weight polymer and/or plas-
ticizer advantageously may be of the homogeneous supercritical process, the solution process type, or a combination
thereof in order to provide the base polymer and the plasticizer for blending in a dense fluid state in the direct reactor
effluents suitable for the in-line blending process. Bulk homogeneous supercritical and bulk solution polymerization
25 processes are particularly useful for producing base polymer and plasticizer blend components due to the simplicity of
the monomer recycle loop and due to the enhancements in reactor productivity and base polymer properties, such as
molecular weight and melting behavior, as will become apparent from the following discussions. The processes disclosed
herein can also utilize certain other polymerization reactors making base polymer blend components, for example, in
the form of a slurry, wherein the polymers form solid pellets in a dense fluid polymerization system (for an exemplary
30 process configuration comprising a slurry, polymerization reactor train see FIG. 10). In such instances, a dissolution
stage is added between the polymerization reactor train and the separator-blending vessel. This dissolution stage
typically consists of a pump followed by a heater to bring the reactor effluent above the solid-fluid phase transition
conditions affording a stream that contains the polymer blending component homogeneously dissolved in the dense
fluid polymerization system. In order to facilitate the dissolution of the polymer pellets, increased shearing may be applied,
35 which typically is provided by stirring or by pumping. Because of the added processing and investment costs of such
reactor operations, homogeneous polymerization processes, such as homogeneous supercritical or solution polymeri-
zation, are typically cost-advantaged and thus advantageous to produce the in-line polymer blending components. At
least some fraction of the low molecular weight components, such as unused monomers and the optional inert solvents/
diluents are separated for recycle from the product polymers and plasticizers in one or more phase separators. Other
40 separation methods, such as distillation, vacuum drying, etc. may also be deployed, particularly in the plasticizer pro-
duction trains and in the product finishing section of the disclosed processes. At least one of the one or more phase
separators also serves as a blending vessel to form a polymer-plasticizer-rich phase to ultimately yield the in-line-
plasticized polyolefin final product. Advantageous configurations and operation modes for the feed-product phase sep-
aration section are disclosed in U.S. Patent Application No. 60/876,193 filed on December 20, 2006.
45 [0122] One or more plasticizers for in-line blending may be produced in-line using the homogeneous fluid-phase
synthesis processes disclosed herein. In particular, homogeneous dense supercritical phase or solution phase process-
ing may be utilized to synthesize selected plasticizers disclosed herein in one or more of the parallel reactor trains of
the disclosed in-line polymerization and blending processes. Advantageously, all parallel trains, i.e., both the base
polymer and plasticizer trains, run with single-site catalysts as described in the section titled "Catalyst System Overview"
50 (vide infra) but other catalyst types may also be used if so desired. When the catalyst systems of the plasticizer and
base polymer reactor trains have incompatible components and/or the monomer pools of the plasticizer and base polymer
reactor trains have no common monomer members, it may be advantageous to recover the one or more plasticizers in
essentially pure form before blending them with the base polymer containing streams. The full recovery of the one or
more plasticizer components is particularly advantageous when one of more of the above-stated conditions are met and
55 the fully recovered plasticizer blending component is a liquid. Note, however, that in order to facilitate the in-line blending,
it is always performed in a fluid phase diluted by low molecular weight components, such as unreacted monomers and
optional one or more inert solvents/diluents. Therefore, it is advantageous to blend the plasticizer-containing streams
before the said low molecular weight components of the polymerization system of the base polymer containing effluents

20
 EP 2 195 349 B1

are fully removed. The disclosed processes often blend the effluents of the base polymer producing reactor trains before
any of the low-molecular weight components, such as the unreacted monomers and the optional inert solvents/diluents,
are removed from the said base polymer containing straight reactor effluents. As stated before, at least some fraction
of the low molecular weight components, such as unused monomers and the optional inert solvents/diluents, are sep-
5 arated for recycle from the product polymers and plasticizers in one or more phase separators. Other separation methods,
such as distillation, vacuum drying, etc. may also be deployed, particularly in the plasticizer production trains and in the
product finishing section of the disclosed processes. At least one of the one or more phase separators also serves as
a blending vessel to form a polymer-plasticizer-rich phase to ultimately yield the in-line-plasticized polyolefin final product.
Advantageous configurations and operation modes for the feed-product phase separation section are disclosed in U.S.
10 Patent Application No. 60/876,193 filed on December 20, 2006.
[0123] Optionally, other plasticizers that are not conducive to in-line reacting, but are conductive to in-line blending
may be further added to the polymer-plasticizer blend. These other plasticizers may be stored in one or more polymer
additive storage tanks. Non-limiting exemplary plasticizers that are not conducive to in-line production, but are conducive
to in-line blending include paraffin oils and waxes (n-paraffins, isoparaffins, paraffin blends), mineral oils, process oils,
15 high purity hydrocarbon fluids, lubricant basestocks, and other synthetic or natural oils. Off-line-produced liquid plasti-
cizers can be directly pumped to the mixing point of the in-line blending process. Solid plasticizers are typically dissolved
before delivering them to the mixing point advantageously using a solvent and/or monomer that is also used in the
polymerization bank. Before bringing them to the mixing point, the plasticizer feeds are typically heated to the temperature
of the polymerization product stream to be blended with the plasticizer feed.
20 [0124] As described herein before, the disclosed in-line blending process for plasticized polymers comprises a po-
lymerization process that provides one or more of the high molecular weight base polymers and in some embodiments
one or more of the plasticizers in a homogeneous fluid state used for in-line blending. Therefore, if the polymerization
reaction is carried out at conditions that form solid polymer particles, such as, for example, slurry polymerization, an
additional step is required to bring the solid in-line polymer blending component into a dissolved fluid state before feeding
25 the polymer-containing stream to the separator-blender section of the disclosed polymer-plasticizer blending process
(for an exemplary process configuration comprising a slurry polymerization reactor train see FIG. 10). This can be
accomplished by, for example, heating the reactor effluent comprising the solid polymeric product, unused monomer
(s), and optional inert diluent(s)/solvent(s) above the solid-liquid phase transition temperature. However, for simpler and
thus lower cost operations, the polymerization reaction is typically carried out at conditions where the product polymer
30 (s) is/are dissolved in the dense fluid polymerization system comprising one or more monomers, the polymeric product
(s), and - optionally - one or more inert solvents, and - optionally - one or more scavengers. Fluid-phase operations have
some further advantages from certain product quality and operation stability perspectives since they do not require
supported catalysts that significantly increase the ash level of the products and can cause fouling and excessive wear
of downstream process hardware. The fluid reaction medium may form one single fluid phase or two fluid phases in the
35 reactor. For more robust and simpler reactor operations, conditions affording a single fluid phase in the reactor, i.e.
operating above the cloud point conditions, are advantageous.
[0125] In one embodiment of the plasticized polymer blending processes disclosed herein, the blending of the one or
more polymer reactor effluent streams with the one or more plasticizer effluent streams occurs simultaneously with
product separation in a single downstream separator-blending vessel. The separator-blender operates at conditions
40 that lead to the formation of two fluid phases: the upper one essentially consisting of the low-molecular weight components
of the polymerization systems, predominantly the monomer(s) and the optional solvent(s) of the polymer and plasticizer
reaction processes, while the lower one is a plasticized polymer-rich phase. In order to create the conditions that lead
to the formation of two fluid phases in the separator-blender, the temperatures of the reactor effluents are often first
increased to provide the heat for staying above the solid-fluid phase transition temperature of the to-be-formed plasticized
45 polymer-rich fluid phase. After adjusting the heat contents of the reactor effluents, their pressures are typically reduced
to bring the temperature and pressure of the combined effluent stream to a condition that corresponds to two fluid (liquid-
liquid or supercritical fluid-supercritical fluid) phases in the phase diagram. The blending process may be aided by
optional static mixer(s) downstream of the mixing point of the polymer-containing and plasticizer-containing effluents
but upstream of the separator-blending vessel. The homogeneous fluid blending of the individual polymer and plasticizer
50 components and the separation of the monomer- and plasticized-polymer-rich phases are accomplished in the same
vessel eliminating the need for a separate blending vessel and blending process step. The bulk of the monomer(s) and
the optional solvent(s) separated from the polymer and plasticizer is then recycled back into the polymer and plasticizer
polymerization reactor bank of the plant.
[0126] In another embodiment of the in-line blending processes disclosed herein, one or more reactor effluent streams
55 containing the dissolved polymer or plasticizer blend components are fed to independent separators or separation
vessels (also referred to as single-stream high-pressure separators) upstream of the separator-blending vessel for
separation of a polymer-enriched or plasticizer-enriched stream from some fraction of the monomer and the optional
solvent/diluent content of the said streams. Such single-stream high-pressure separators deployed upstream of the

21
 EP 2 195 349 B1

separator-blending vessel (high-pressure separator) in essence afford a partial recovery of the monomer and the optional
solvent present in the reactor effluent thus allowing their recovery and recycle before being mixed with monomers and
optional solvents used in other reactor trains. Such processes may be advantageous by eliminating the need for sepa-
rating mixed monomer and optional solvent streams before recycling them to the appropriate reactor trains for polymer
5 and plasticizer of the reactor bank as disclosed in US Pat. Appl. No. 60/905,247 filed on March 6, 2007. The polymer-
enriched streams and plasticizer-enriched streams from each of these single-stream separators are blended in one
separator vessel that serves both as a separator for one of the reactor trains and as a blender for the entire reactor bank
(separator-blending vessel). In this embodiment, the operation conditions of one or more single-stream separators
upstream of the separator-blending vessel may be adjusted to yield one or more polymer-enriched streams and/or one
10 or more plasticizer-enriched streams that still contain enough low molecular weight components, such as monomers
and optional inert solvents to keep the viscosity of these streams much below that of the essentially pure molten polymers
or plasticizers thus facilitating the mixing of the polymer and plasticizer components in the separator-blender. The one
or more separators feeding the separator-blending vessel may also serve as buffer vessels affording an improved control
of the blend ratio by compensating for the small but inevitable fluctuations in the production of the individual in-line
15 polymer and plasticizer blend components. The buffer capacity of these vessels is defined by the volume between the
maximum and minimum levels of the separated polymer-enriched or plasticizer-enriched lower phase.
[0127] The blending processes disclosed herein provide for the individual components of the plasticized polymer blend
to be made in a bank of parallel reactors. One or more of the parallel reactor trains produce one or more polymer blend
components and one or more of the parallel reactor trains produce one or more plasticizer blend components for
20 subsequent downstream in-line blending. Such direct blend production may be advantageously achieved in polymeri-
zation processes that operate in a homogeneous dense fluid phase, i.e. above the fluid-solid phase transition limits.
The in-line blending process disclosed has at least one reactor train making a high molecular weight base polymer blend
component that operates in a homogeneous dense fluid phase. Advantageously, all reactor trains in the reactor bank
of the disclosed processes operate in a homogeneous dense fluid phase. Polymerization processes that operate in a
25 homogenous dense fluid phase use either inert solvent(s) or monomer(s) or their mixtures as a solvent/diluent in their
liquid or supercritical state. Hence, such parallel reactors operate with polymerization systems in their homogeneous
supercritical or in their liquid state. In both the supercritical and liquid operation modes, the process may be a bulk
polymerization process operating with less than 40 wt %, or less than 30 wt %, or less than 20 wt % or less than 10 wt
% or less than 5 wt % of inert solvent present in the reactor, and in some embodiments, essentially free (less than 1 wt
30 %) of inert solvents. In one embodiment of the disclosed process, the one or more polymer reactors and one or more
plasticizer reactors operate at bulk homogeneous supercritical conditions as has been disclosed in U.S. Patent Application
Nos. 11/433,889 and 11/177,004.
[0128] In another embodiment, one or more polymer reactor trains and one or more plasticizer reactor trains operate
at conditions where the polymer and plasticizer dissolution is substantially aided by an inert solvent (solution process
35 where the polymerization medium contains more than 40 wt % solvent, typically more than 60 wt % solvent) as has
been disclosed in PCT Publication No. WO 2006/044149. In yet another embodiment, one or more of the polymer or
plasticizer reactors included in the parallel bank of reactors operate in the homogeneous supercritical state and one or
more of the polymer or plasticizer reactors included in the parallel bank of reactors operate in the solution state (com-
bination of solution process and homogeneous supercritical process reactors). Both homogenous solution and homo-
40 geneous supercritical polymerization processes provide polymers dissolved in a fluid state, which is required for the
downstream in-line blending of plasticized polymers. Both homogenous solution and homogeneous supercritical proc-
esses providing polymers and plasticizers in a homogeneous fluid state may be performed in a bulk monomer phase
using essentially pure monomer(s) as solvent or may keep the polymer or plasticizer in the homogeneous fluid state by
employing an inert solvent in substantial concentrations (i.e., 60 wt % or more). The homogenous solution process
45 provides for a polymer- or plasticizer-containing liquid phase either in an inert solvent or in the essentially neat monomer
or in their mixture in their liquid state. The homogeneous supercritical process provides for the fluid state by dissolving
the polymeric base polymer or plasticizer product either in an inert solvent or in the essentially neat monomer or in their
mixture in their supercritical state.
[0129] In another embodiment, one or more polymer or plasticizer reactors included in the parallel reator bank operate
50 in homogeneous supercritical or solution mode and one or more polymer reactor trains operate in the slurry mode
(combination of slurry and homogeneous supercritical or combination of slurry and solution processes). The dense fluid
phase(s) of the slurry polymerization process(es) deployed in one or more polymer trains of the disclosed in-line blending
process can be either in its/their liquid or in its/their supercritical state. Before bringing the effluent(s) of the slurry train
(s) to the separator-blending vessel (high-pressure separator) of the in-line blending process, the effluents are treated
55 to fully dissolve the slurried polymer blend component. Aside this dissolution step, the other aspects of the in-line blending
process disclosed herein are not affected by having a particle-forming polymerization reactors in the reactor bank. This
embodiment may provide product advantages in certain applications due to the ability of the slurry process to produce
certain highly crystalline homopolymer blend components, such as isotactic polypropylene made with Ziegler-Natta

22
 EP 2 195 349 B1

catalysts. It is, however, typically more expensive due to the added processing and investment cost. The optimal choice
between the different reactor configurations of the disclosed process depends on the target product slate or even on
some production site-specific issues, like, for example, the utilization of existing polymerization facilities. The optimal
configuration can be determined by standard techniques well known in the art of chemical engineering.
5 [0130] The parallel reactor configuration disclosed herein permits for flexibility in independently controlling for each
polymer and plasticizer reactor, the residence time, monomer composition and conversion, catalyst choice, solvent/
diluent composition and concentration, and catalyst concentration. It also makes the independent control of reaction
temperature and pressure easier thus enhancing the control of the synthesis processes yielding the individual in-line
polymer and plasticizer blend components.
10 [0131] U.S. Patent Application Nos. 11/433,889 and 11/177,004 disclose a flexible polymerization platform for the
supercritical propylene polymerization process (also referred to herein as the "supercritical process"). In the referred
supercritical propylene polymerization process, polymerization is carried out in a substantially supercritical monomer
medium, thus it is a bulk supercritical polymerizations process. The polymer is in a dissolved state in the reactor and in
the reactor effluent thus making the reactor effluent suitable for a direct downstream blending operation prior to recovering
15 the polymeric products in their solid pelletized or baled form. U.S. Patent Application Nos. 11/433,889 and 11/177,004
also teach that the supercritical polymerization process provides an advantageous means to the so-called solution
processes in its ability to produce highly crystalline, high molecular weight (i.e. low melt-flow rate) isotactic propylene
homopolymers. Unlike gas phase and slurry polymerization processes, the supercritical process may also produce
ethylene-propylene copolymers and propylene homopolymers with reduced tacticity, and thus reduced polymer melting
20 point without fouling. As previously referenced, U.S. Patent Application Nos. 11/433,889 and 11/177,004.
[0132] Advantageous plasticized polymer blends are often composed of a blend of (a) high molecular weight highly
crystalline polymer component(s) and (a) low molecular weight low crystallinity oligomer/polymer component(s). Slurry
and gas phase polymerization processes may provide for high molecular weight, highly crystalline polymers, but not for
low crystallinity products because the polymer pellets stick together causing fouling of the reactor. In contrast, solution
25 polymerization processes may provide for low crystallinity products because the polymer is present in solution in the
reactor, and therefore cannot foul it. However, the solution process has limitations in producing highly crystalline, high
molecular weight products with higher melting point. One limitation of the solution process is that it typically cannot
produce high MW products that also have high melting point, and if it could, such products tend to crystallize in the
reactor and cause fouling. In contrast, the homogeneous supercritical process may provide for both high crystallinity/
30 high melting point and low crystallinity/low melting point polymers without fouling. These products can also be made
with any desired, low or high, molecular weight. It also generates the polymer blend components in a dissolved state in
the polymerization system allowing direct blending without the need for a dissolution step. These attributes make it a
particularly advantageous polymerization process for the in-line blending processes disclosed herein. Notwithstanding,
any combination of polymerization processes operating with dense polymerization systems may be deployed in the in-
35 line blending processes disclosed herein as long as at least one of the polymer and plasticizer reactor trains operates
with a homogeneous polymerization system. Homogeneous operation is ensured by operating above the solid-fluid
phase transition point, advantageously not lower than 10 MPa below the cloud point of the polymerization system.
[0133] The monomers for use in the bank of parallel reactors disclosed herein may be any olefinic compounds con-
taining at least one aliphatic double bond. The olefin group may be unsubstituted or substituted by one or more aliphatic
40 or aromatic group(s) and may be part of an open chain or a non-aromatic ring. Exemplary, but not limiting, olefins include
alpha and internal linear or branched olefins and their blends, such as ethylene, propylene, butenes, pentenes, hexenes,
heptenes, octenes, nonenes, decenes, dodecenes, styrenes, non-conjugated dienes, cyclohexene, norbornene, and
the like. Exemplary, but not limiting, non-polymerizing (inert) fluid components serving as diluents/solvents include light
paraffinic and aromatic hydrocarbons and their blends, such as butanes, pentanes, hexanes, heptanes, octanes, toluene,
45 xylenes, cyclopentane, cyclohexane, fluorocarbons, hydrofluorocarbons, etc.
[0134] The conditions in the polymerization reactors of the aforementioned olefin polymerization process may be
established such that the entire reactor content, including the monomer(s), optional non-polymerizing fluid, catalyst
system(s), optional scavenger(s) and polymeric products, is in a homogeneous fluid, and advantageously in a single
homogeneous fluid state. In certain embodiments, the conditions in the reactors of the aforementioned process may be
50 set such that the reactor contents are in their supercritical fluid state, and advantageously in a single homogeneous
supercritical fluid state.
[0135] The upper limit for temperature is determined by the product properties that are strongly influenced by the
reaction temperature (for an example, see FIG. 2). Since polymers with higher molecular weights and/or higher melting
points are desired for the base polymer blend components, high polymerization temperatures (>250˚C) are generally
55 not advantageous. Increased temperatures can also degrade most known catalytic systems, providing another reason
for avoiding excessive polymerization temperatures. However, high polymerization termperatures (>250˚C) may be
advantageous for producing plasticizer components because of the desirability for low molecular weight. FIG. 5 provides
an example of how catalytic activity is impacted by increasing polymerization temperature. At the current state of the

23
 EP 2 195 349 B1

art of polymerization, polymerization temperatures above 350˚C are not recommended. For the slurry polymerization
processes, the upper temperature limits of polymerization are also influenced by the solid-fluid phase transition conditions
since running near the solid-fluid phase transition line leads to fouling. For that reason, slurry operations not higher than
5˚C below the solid-fluid phase transition are advantageous, not higher than 10˚C below the solid-fluid phase transition
5 are particularly advantageous.
[0136] The lower limits of reaction temperature are determined by the desired polymer and/or plasticizer properties.
Lower temperatures generally favor higher crystallinity and higher molecular weight (for an example, see FIG. 2). For
homogeneous polymerization processes, the lower limits of reaction temperature are also determined by the solid-fluid
phase transtion temperature. Running the reactors below the solid-fluid phase transtion temperature of the reaction
10 mixture may lead to operation problems due to fouling. For the production of highly crystalline polypropylenes (melting
peak temperatures >150˚C) in bulk homogeneous supercritical propylene polymerization processes, the minimum op-
erating temperature is about 95-100˚C. In the production of lower melting copolymers, such as ethylene-propylene and
ethylene-hexene-1 copolymers, significantly lower reactor temperatures, e.g., 90˚C or even lower, may be readily used
without fouling. The application of certain inert solvents may further reduce the minimum operation temperature of the
15 fouling-free operation regime, although, as discussed earlier, the substantial presence of inert solvents also tends to
limit the product molecular weight and often the melting peak temperature. It also increseases production cost due to
the need for solvent handling.
[0137] The critical temperature and pressure of the polymerization systems are different from the critical values of
pure components, and thus supercritical operations at temperatures lower than the critical temperature of pure propylene
20 and C4 plus monomers (e.g., 92˚C for propylene) are possible and disclosed herein. Additionally, near-amorphous and
amorphous materials with low melting points may be produced without fouling even below the critical temperature of
the reactor blends, i.e., at temperatures that correspond to the condensed liquid state of the polymerization system in
the reactor. In these instances, the operation temperature may be below the bubble point of the reaction mixture and
thus the reactor operates at what is often referred to as liquid-filled conditions. In some instances, such operation mode
25 could be desired to achieve high molecular weight (MW) and thus low melt flow rate (MFR), particularly in the manufacture
of high molecular weight copolymers, such as propylene-ethylene or ethylene-higher olefin or propylene-higher olefin
copolymers. Thus, reactor operations under conditions at which the polymeric products are dissolved in the monomer
or monomer blend present in its liquid state, also known as bulk solution polymerization, are also disclosed herein.

30 Reaction Temperature for Homogeneous Fluid Phase Polymerizations:

[0138] The reaction process temperature should be above the solid-fluid phase transition temperature of the polymer-
containing and (when the plasticizer is a solid at ambient temperature) the plasticizer-containing fluid reaction systems
at the reactor pressure, or at least 2˚C above the solid-fluid phase transition temperature of the polymer-containing and
35 plasticizer-containing fluid reaction system at the reactor pressure, or at least 5˚C above the solid-fluid phase transition
temperature of the polymer-containing and plasticizer-containing fluid reaction system at the reactor pressure, or at least
10˚C above the solid-fluid phase transformation point of the polymer-containing and plasticizer-containing fluid reaction
system at the reactor pressure. In another embodiment, the reaction process temperature should be above the cloud
point of the single-phase fluid reaction system at the reactor pressure, or 2˚C or more above the cloud point of the fluid
40 reaction system at the reactor pressure. In still another embodiment, the reaction process temperature should be between
40 and 350˚C, or between 50 and 250˚C, or between 60 and 250˚C, or between 70 and 250˚C, or between 80 and
250˚C, or between 90 and 220˚C, or between 93 and 220˚C. Exemplary lower reaction temperature limits are 40, or 50,
or 60, or 70, or 80, or 90, or 95, or 100, or 110, or 120˚C. Exemplary upper reaction temperature limits are 350, or 250,
or 240, or 230, or 220, or 210, or 200˚C.
45 [0139] In certain embodiments, polymerization is performed in a supercritical polymerization system. In such embod-
iments, the reaction temperature is above the critical temperature of the polymerization system. In some embodiments,
some or all reactors operate at homogeneous supercritical polymerization conditions Said homogeneous supercritical
polymerizations of the in-line blending processes disclosed herein may be carried out at the following temperatures: In
one embodiment, the temperature is above the solid-fluid phase transition temperature of the polymer-containing and
50 plasticizer-containing fluid reaction medium at the reactor pressure or at least 5˚C above the solid-fluid phase transition
temperature of the polymer-containing and plasticizer-containing fluid reaction medium at the reactor pressure, or at
least 10˚C above the solid-fluid phase transformation point of the polymer-containing and plasticizer-containing fluid
reaction medium at the reactor pressure. In another embodiment, the temperature is above the cloud point of the single-
phase fluid reaction medium at the reactor pressure, or 2˚C or more above the cloud point of the fluid reaction medium
55 at the reactor pressure.

24
 EP 2 195 349 B1

Reaction Pressure for Homogeneous Fluid Phase Polymerizations:

[0140] The maximum reactor pressure may be determined by process economics, since both the investment and
operating expenses increase with increasing pressure. The minimum pressure limit for the production of the individual
5 polymer and plasticizer blend components disclosed herein is set by the desired product properties, such as molecular
weight (MW) and melt flow rate (MFR) (see, for example, FIG. 3).
[0141] Reducing process pressures in homogeneous polymerizations may lead to phase separation creating a poly-
mer-rich or plasticizer-rich and a polymer-lean or plasticizer-lean fluid phase. In well-stirred reactors, where mass trans-
port is sufficiently high due to efficient mixing of the two phases, product qualities may not be impacted by such fluid-
10 fluid phase separation. Therefore, polymerization process conditions under which there is a polymer-rich or plasticizer-
rich and a polymer-lean or plasticizer-lean phase are provided herein as long as both phases are above the solid-fluid
phase separation limit thus preventing fouling and are well mixed thus preventing substantial mass transfer limitation
leading to poorly controlled increasees in molecular weight and/or compositional distributions. Generally, however,
operating in a single-phase dense fluid polymerization is advantageous because it is less prone to fouling and provides
15 better heat transfer properties..
[0142] Exemplary, but not limiting, process pressures, are between 1 MPa (0.15 kpsi) to 1500 MPa (217 kpsi), and
more particularly between 1 and 500 MPa (0.15 and 72.5 kpsi). In one embodiment, the polymerization process pressure
should be no lower than the solid-fluid phase transition pressure of the polymer-containing or plasticizer-containing fluid
polymerization system at the reactor temperature. In another embodiment, the polymerization process pressure should
20 be no lower than 10, or 5, or 1, or 0.1, or 0.01 MPa below the cloud point of the fluid polymerization system at the reactor
temperature and less than 1500 MPa. In still another embodiment, the polymerization process pressure should be
between 10 and 500 MPa, or between 10 and 300 MPa, or between 20 and 250 MPa. Exemplary lower pressure limits
are 1,10, 20, and 30 MPa (0.15, 1.45, 2.9, 4.35 kpsi, respectively). Exemplary upper pressure limits are 1500, 1000,
500, 300, 250, and 200 MPa (217, 145, 72.5, 43.5, 36.3, and 29 kpsi, respectively).
25 [0143] In certain embodiments, polymerization is performed in a supercritical polymerization system. In such embod-
iments, the reaction pressure is above the critical the pressure of the polymerization system. In some embodiments,
some or all reactors operate at homogeneous supercritical polymerization conditions The supercritical polymerization
process of the in-line blending processes disclosed herein may be carried out at the following pressures. In one em-
bodiment, the pressure is no lower than the crystallization phase transition pressure of the polymer-containing and
30 plasticizer containing fluid reaction medium at the reactor temperature or no lower than 10, or 5, or 1, or 0.1, or 0.01
MPa below the cloud point of the fluid reaction medium at the reactor temperature. In another embodiment, the pressure
is between 10 and 500 MPa, between 10 and 300 MPa, or between 20 and 250 MPa. In one form, the pressure is above
10, 20, or 30 MPa. In another form, the pressure is below 1500, 500, 300, 250, or 200 MPa. In another form, the cloud
point pressure is between 10 and 500 MPa, between 10 and 300 MPa, or between 20 and 250 MPa. In yet another
35 form, the cloud point pressure is above 10, 20, or 30 MPa. In still yet another form, the cloud point pressure is below
1500, 500, 300, 250, or 200 MPa.

Total Monomer Conversion for Homogeneous Fluid Phase Reactions:

40 [0144] Increasing the conversion of the total monomer feed in a single-pass in the individual reactor trains of the
parallel reactor bank can reduce the monomer recycle ratio thus can reduce the cost of monomer recycle. Increasing
monomer recycle ratios (i.e., the ratio of recycled/total monomer feed to the reactor train) require the treatment and
recycle of larger monomer volumes per unit polymer production, which increases production cost. Therefore, higher
monomer conversion (lower recycle ratios) often provides for improved process economics. However, because high
45 polymer content in the polymerization system, particularly in homogeneous polymerization systems, yields high viscos-
ities, which correspondingly may make reactor mixing, heat transfer, and downstream product handling difficult, the
monomer conversion in a single pass has practical operation limits. The viscosity of monomer-polymer blends and thus
the practical conversion limits can be readily established by standard engineering methods known in the art (M. Kinzl,
G. Luft, R. Horst, B.A. Wolf, J. Rheol. 47 (2003) 869). Single-pass conversions also depend on operating conditions
50 and product properties. For example, FIG. 4 shows how increasing conversion reduces the polymer molecular weight.
Therefore, monomer conversion may also be constrained by the desire to increase the molecular weight of the blend
component made in the given reactor train, particularly in the reactor trains producing the high molecular weight base
polymer in-line blending components. Exemplary, but not limiting, total monomer single pass conversions are below
90%, more particularly below 80% and still more particularly below 60%. Total monomer conversion is defined as the
55 weight of polymer or plasticizer made in a reactor or in a reactor train divided by the combined weight of monomers and
comonomers in the feed to the reactor or reactor train. It should be understood that while high total monomer conversion
is often limited by product viscosity or by product property targets, the conversion of some highly reactive monomer
components present in some monomer feed blends may be higher than 90%. For example, the single-pass conversion

25
 EP 2 195 349 B1

of ethylene in ethylene-propylene or in ethylene-higher olefin feed blends may be nearly complete (approaching 100%)
and is disclosed herein.
[0145] As mentioned above, another factor limiting the total monomer conversion is the MW-decreasing effect of
conversion (see FIG. 4). Therefore, the production of the base polymer blend components with high MW requires the
5 moderation of monomer conversion in a single pass beyond that of what viscosity and other practical operation consid-
erations would dictate. Hence, for the production of base polymer blend components with high molecular weight (par-
ticularly those with higher than >200 kg/mol weight-averaged molecular weight - Mw), the total monomer conversion
may need to be below 30%. Again, the conversion of some highly reactive components in a monomer feed blend may
be higher, and may even approach 100%.
10 [0146] The single-pass conversion in the reactors disclosed herein may be adjusted by the combination of catalyst
concentration and total feed flow rate. The total feed rate determines the average residence time (in a back-mixed reactor
equal to the reactor volume divided by the total volumetric flow rate of the effluent). The same conversion may be
achieved at lower residence time by increasing the catalyst concentration in the feed and vice versa. Lower catalyst
concentration may reduce catalyst cost, but may also reduce volumetric productivity thus requiring higher residence
15 times, and ultimately a larger reactor and thus higher investment cost for the same polymer production capacity. The
optimum balance between residence time/reactor volumes and catalyst concentration may be determined by standard
engineering methods known in the art. A wide-range of polymer and plasticizer blend components may be produced in
the reactors disclosed herein at reactor residence times ranging from 1 sec to 120 min, particularly from 1 sec to 60
min, more particularly from 5 sec to 30 min, still more particularly from 30 sec to 30 min, and yet still more particularly
20 from 1 min to 30 min. In yet another form of the in-line blending process embodiments disclosed herein, the residence
time in the reactors disclosed herein may be less than 120, or less than 60, or less than 30, or less than 20, or less than
10, or less than 5, or less than 1 minute(s).
[0147] In certain embodiments, one or more of the polymer blend component and/or one or more of the plasticizer
blend component reactor trains of the in-line blending process disclosed herein operate at supercritical conditions
25 advantageously at homogeneous supercritical conditions, or more advantageously at bulk homogeneous supercritical
conditions. The residence times in the supercritical polymerization reactors, particularly in the bulk homogeneous su-
percritical reactors disclosed herein are generally lower than the residence times in solution, gas phase, and slurry
processes due to the high reaction rates achieved at the conditions of the supercritical polymerization process. In-line
blending processes disclosed herein applying bulk homogeneous supercritical polymerizaton often choose residence
30 times between 1 and 60 min, and more particularly between 1 and 30 min.
[0148] The reactors in the individual trains and in the entire bank can be of any type useful for making polymers (for
a review of different polymerization reactors see Reactor Technology by B.L. Tanny in the ENCYCLOPEDIA OF POL-
YMER SCI. AND ENG., Vol. 14, H.F. Mark et al., Eds., Wiley, New York, 1988, and J.B.P. Soares, L.C. Simon in the
HANDBOOK OF POLYMER REACTION ENGINEERING, T. Meyer and J. Keurentjes, Eds., Wiley-VCH, Weinheim,
35 2005, p. 365-430.) and can be constructed the same way or can be different. The optimal reactor type and configuration
can be determined by standard techniques well known in the art of polymer reactor engineering.
[0149] It should be recognized that the catalytic activity and thus the volumetric productivity in the individual reactors
may be different. If the reactor effluents for in-line blending are directly blended, the catalytic activity and the volumetric
productivity may determine the reactor sizes required for the production of the individual polymer and plasticizer blend
40 components. In order to reduce cost, a single plant may need to produce several plasticized polymer blends with different
polymer and plasticizer components blended over a range of blend ratios. Consequently, a parallel reactor bank will
often have reactors of different sizes allowing for a flexible and thus more cost effective configuration for the production
of different plasticized polymer blend grades. The optimal reactor volumes may be determined from the combination of
the composition of the target plasticized polymer blends and the volumetric reactor productivity data using optimization
45 methods known in the art of chemical engineering.
[0150] In commercial practice, reactor productivity tends to vary to some degree, which in turn may lead to the cor-
responding level of variability in polymer-plasticizer blend ratios. In one embodiment, buffer tanks may be added to the
process downstream of the reactors comprising the bank of parallel reactors, but before the polymer-plasticizer mixing
or blending point to compensate for the fluctuations of the volumetric productivity in each reactor train producing the
50 individual polymer and plasticizer blend components (see for example FIG. 8). The buffer tanks may improve the com-
positional control of the final product blends by homogenizing the individual reactor effluents and by allowing a more
independent metering of the plasticized polymer blend components. When an individual reactor train effluent is stored
in the buffer tank in its liquid state at a pressure below its bubble point, essentially the entire volume of the buffer tank
is available for compensating for the differences in the blending and production rates. However, when the individual
55 reactor effluent is stored in the buffer tank in its supercritical state or in its liquid state but at pressures above its bubble
point, the dense liquid or supercritical fluid fills the entire tank. In such operation modes, the buffering capacity, i.e. the
capacity to deviate from the instant reactor flow rate, is more limited and is associated with the pressure/density changes
allowed in the buffer tank and with the size of the buffer tank. In the latter case, the process streams may be driven by

26
 EP 2 195 349 B1

a gradual pressure drop downstream of the reactor to avoid the cost of installing and operating booster pumps. However,
booster pumps may be alternatively installed and operated within the process to increase the pressure range and thus
the buffering capacity of the system. When no booster pumps are deployed, the pressure of the buffer tank should be
lower than that of the reactor, but higher than that of the lines downstream of the blending point.
5 [0151] Apparently, while feasible, controlling this kind of buffer system is difficult and it is not very efficient. Thus, in
another embodiment, when the individual reactor effluent is stored in the buffer tank in its supercritical state or in its
liquid state but at pressures above its bubble point, the conditions in the buffer tanks may be set to achieve fluid-fluid
phase separation (separator-buffer tank operation). Buffering in this mode can be achieved by allowing the fluid level
of the denser polymer-rich and/or plasticizer-rich phase to move up and down between the minimum and maximum
10 levels allowed for the desired level of separation while taking the monomer-rich upper phase out of the separator buffer
via a pressure control valve. One skilled in the art can see that this operation mode is analogous to the operation of a
buffer tank filled with a liquid phase containing the polymeric or plasticizer product and a vapor phase containing the
more volatile components, such as monomer(s) and solvent(s). In the supercritical regime, the upper phase is a monomer-
rich supercritical fluid, while the lower phase is a polymer-rich or plasticizer-rich supercritical fluid, the latter of which
15 can be withrawn for blending at a controlled rate required for making a constant blend ratio, independent of the short-
term fluctuations in the production ratios of the individual blend components. A similar analogy may be derived for liquid-
filled operations. The polymer or plasticizer content, and thus the viscosity of the polymer-rich or plasticizer-rich phase
can be controlled by properly adjusting the temperature at constant pressure or by adjusting the pressure at constant
temperature in the separator-buffer tank(s). In this embodiment, the polymer-rich and/or plasticizer-rich effluent(s) of
20 the separator-buffer tank(s) are combined with the direct, unseparated effluent of one of the reactor trains upstream of
the separator-blending vessel that recovers the monomer of the direct reactor effluent as a supernatant and the in-line
plasticized polymer blend as the bottom phase. In this particular embodiment, one of the separators serves as a separator-
blender, while the rest of the separators serve as separator-buffers. Advantageously, the separator-blender is connected
to a reactor train making a polymer blending component while the separator-buffer vessels are connected to a plasticizer
25 train. This configuration allows the recovery and recycle of a significant portion of plasticizer monomer without the need
for separation from monomer from the polymer train.
[0152] As described before, certain embodiments recover the one or more in-line produced plasticizer blend compo-
nents in their essentially pure liquid form before blending them with streams comprising the one or more high molecular
weight base polymer components. In these embodiments, the disclosed processes may employ one or more storage
30 tanks for storing and buffering the plasticizer blend components to increase blending flexibility and to improve composition
control. These embodiments may include plasticizer export from the disclosed in-line blending plants further increasing
their versatility and the value they may offer.
[0153] In another embodiment of the processes disclosed herein, polymer additives may be added to the in-line-
produced plasticized polymer blends at ratios of up to 40 wt %, or up to 30 wt % , or up to 20 wt %, or up to 10 wt %, or
35 up to 5 wt % to further improve product quality and product properties. Exemplary, but not limiting polymer additives,
include specialty polymers including polar polymers, waxes, antioxidants, clarifiers, slip agents, flame retardants, heat
and uv stabilizers, antiblocking agents, fillers, reinforcing fibers, antistatic agents, lubricating agents, coloring agents,
foaming agents, tackifiers, organically modified clays such as are available from Southern Clay, etc. and masterbatches
containing the above components. Hence, one or more polymer additive storage tanks containing liquid, molten, dis-
40 solved, or dispersed polymer components and polymer additives may be added to the processes disclosed herein. If
solvent(s) is used in these polymer additive storage tanks, it may be advantageously the same as used in the polymer-
ization and plasticizer reactors previously described in order to avoid an increase in separation costs in the solvent
recovery and recycle section of the process. For example, when the polymer synthesis process is performed in super-
critical propylene, the off-line produced polymer additives may also be advantageously dissolved in supercritical pro-
45 pylene. However, other solvent(s) or solvent-free introduction may be used with the polymer additives. Solvent-free
introduction of the polymer additive components may be used when the additive component is brought into its molten
state or when the additive component is a liquid at ambient temperatures.
[0154] The homogeneous supercritical polymerization and the solution polymerization processes are particularly suit-
able for providing both the product base polymer component(s) and the plasticizer component(s) of the plasticized
50 polymer blend in a dissolved fluid state. In one particular embodiment, the supercritical polymerization process is per-
formed in the substantial absence of an inert solvent/diluent (bulk homogeneous supercritical polymerization) and pro-
vides the product in a dissolved supercritical state for the downstream in-line separation-blending process. More par-
ticularly, the supercritical polymerization of propylene is performed in the substantial absence of an inert solvent/diluent
(bulk homogeneous supercritical propylene polymerization) and provides the product in a dissolved supercritical state
55 for the downstream in-line separation-blending process.
[0155] The total amount of inert solvents is generally not more than 80 wt % in the reactor feeds of the polymer and
plasticizer reactor trains. In some embodiments, where the feed essentially comprises the monomer or monomer blend,
like for example, bulk slurry, or bulk supercritical, or bulk solution polymerizations, the minimization of solvent use is

27
 EP 2 195 349 B1

desired to reduce the cost of monomer recycling. In these cases, the typical solvent concentration in the reactor feed
is often below 40 wt %, or below 30 wt %, or below 20 wt %, or below 10 wt %, or below 5 wt % or even below 1 wt %.
In one form disclosed herein, the polymerization system of the polymer and plasticizer reactor trains comprise less than
20 wt % aromatic hydrocarbons and advantageously less than 20 wt % toluene. In another form disclosed herein, the
5 polymerization system of the polymer and plasticizer reactor trains comprise less than 40 wt % saturated aliphatic
hydrocarbons and advantageously less than 40 wt % of hexanes, or pentanes, or butanes, and propane, or their mixtures.

Fluid Phase In-Line Blending Process Configuration:

10 [0156] The disclosed fluid phase in-line blending processes for making in-line-plasticized polyolefins may have different
detailed process configurations. For example, the number of parallel reactor trains and their configurations in the parallel
reactor bank may be varied. Typically, each reactor train serves to produce a single in-line polymer or plasticizer blend
component. A given train of the parallel reactor bank may be configured as a single reactor or two or more reactors in
series. From a practical commercial plant design standpoint, however, there should be a minimum number of reactors
15 for a given train of the parallel reactor bank in order to make a given polymer or plasticizer blend component. Generally,
not more than ten series reactors are utilized and more particularly not more than three series reactors are generally
utilized in a given reactor train. The number of parallel trains in the parallel reactor bank may be two, three, four or five
or more. The number of reactors in the parallel reactor bank may be any number, although for economic reasons the
number of reactors should be maintained as low as the desired product grade slate and plant capacity allows. The
20 optimum number of parallel reactor trains (also referred to as legs of the reactor bank) may be determined by standard
chemical engineering optimization methods well known in the art. Most typically, the polymerization-blending plant will
have two or three parallel polymerization reactor trains or legs in the reactor bank producing product blends with the
corresponding number of in-line polymer blend components. However, more than three parallel reactors/legs may be
employed if the production of the target product blends so requires. Besides the in-line base polymer and plasticizer
25 blend components, the final plasticized polymer blends often contain additives and modifiers that are not produced within
the same polymerization process. Therefore, it should be understood that the number of components in the final product
blend typically is higher than the number of reactor trains or the number of in-line plasticized polymer blend components.
[0157] Based on the source of the in-line blend components, the disclosed in-line blending processes producing in-
line-plasticized polyolefins may be grouped into three options: (1) all plasticizer blending components produced in-line,
30 i.e., in the reactor bank of the in-line blending process, (2) one or more plasticizer blending components produced in-
line and one or more additional plasticizer blending components produced off-line, and (3) all plasticizer blending com-
ponents produced off-line. Furthermore, the processes falling under options (1) and (2), may deliver the one or more
in-line-produced plasticizer blend components to the blending point with the base polymer containing stream (a) without
removing any of the light components from the one or more plasticizer reactor effluents, such as the unreacted monomers
35 and optional inert solvents/diluents (unreduced reactor effluent), (b) after partial recovery of the said light components
from the said one or more plasticizer-containing reactor effluents (reduced reactor effluent), and (c) after full recovery
of the essentially pure plasticizer blending component, i.e., after removing essentially all of the said light components
from the said plasticizer-containing one or more reactor effluents (fully recovered plasticizer). As stated before, the
plasticized polyolefin product may contain one or more high molecular weight base polymer components for options (1)
40 and (2), and may contain two or more high molecular weight base polymer components for option (3).
[0158] The fluid phase in-line blending processes disclosed herein may also optionally incorporate other polymers,
other plasticizers and other polymer additives that were produced outside the reactor bank of the processes disclosed
herein. The optional other polymer, other plasticizer, and polymer additive components may first be transferred into
solution or molten fluid state before being blended with the in-line produced polymer and plasticizer blend components.
45 These other polymer, other plasticizer, and polymer additive components may be stored in polymer additive storage
tanks containing liquid, molten, or dissolved polymer components, plasticizer components and polymer additives prior
to being transferred and metered to the separation-blending vessel or to a mixing point upstream or downstream of the
separation-blending vessel. Other polymer, other plasticizer, and polymer additive components may be accurately me-
tered to the blending vessel or to another mixing point by one or more pumps or if the downstream pressure is lower,
50 through the use of one or more pressure letdown valves. The optional other polymer, other plasticizer, and polymer
additives and modifiers can be mixed into the product upstream of or directly in the separator-blending vessel or down-
stream of the separator-blending vessel of the processes disclosed herein. In order to simplify monomer treatment in
the monomer recycle train and thus to reduce the cost of monomer recycle, it may be advantageous to add the other
polymer, other plasticizer and polymer additives and modifiers downstream of the separator-blending vessel. In such
55 embodiments, the additives and modifiers may be mixed with the in-line produced plasticized polymer blend in dedicated
pieces of equipment or in the hardware of the product finishing section of the processes disclosed herein, for example,
in a low-pressure separator or in a devolatizer extruder.
[0159] Referring to FIG. 6, in one exemplary embodiment of the fluid phase in-line blending process disclosed herein,

28
 EP 2 195 349 B1

the effluents of all parallel reactor trains in the reactor bank are brought into a single high-pressure separator-blending
vessel (also referred to as separator-blender or high-pressure separator). One or more of the parallel reactor trains
produce polymer blend components and optionally (as in options (1) and (2) described earlier) one or more of the parallel
reactor trains produce plasticizer blend components. The separator-blender separates some or most of the low molecular
5 weight components, such as monomer(s), optional solvent(s), and product lights (monomer-rich phase) from the (mon-
omer-lean) polymer-rich phase, but also blends the polymeric and optional plasticizer blend components made in different
reactor trains of the in-line process forming a polymer-rich blend effluent that also comprise the optional in-line produced
plasticizer. In some embodiments (not shown in Fig. 6), one or more off-line-produced plastizizers may also be blended
at the same point of the process, i.e., in which case the polymer-rich blend effluent will also carry the one or more off-
10 line-produced plasticizer blend components. This mode is also referred to as single separation vessel operation even
if the process employs one or more low-pressure separators. The number of reactor trains in the parallel bank may be
2, 3, 4, and up to n. The effluents of the different reactor trains and thus the individual polymer and the optionally in-
line-produced plasticizer blend components are combined upstream of the separation vessel after individual pressure
let down valves, which function to bring the reactor train effluents to the common pressure of the separator-blending
15 vessel. Catalyst killing agent(s), may be optionally introduced prior to or into the separator-blending vessel to minimize
further polymerization outside the polymerization reactors. Optionally, one or more static mixers positioned before the
separator-blending vessel, but downstream of the mixing point, may also be utilized to enhance mixing between the
reactor train effluents. Optionally, some or all reactor train effluents may be heated before the pressure letdown (not
shown in FIG. 6) in order to maintain the temperature in the downstream lines and in the separation-blending vessel at
20 the desired value, i.e., above the solid-fluid phase transition temperature of the polymer-rich phase and plasticizer-rich
phase of the separator-blender, but below the cloud point of the combined effluents entering the separator-blending
vessel to allow the formation of a plasticized polymer-rich denser fluid phase and a monomer-rich lighter fluid phase.
[0160] After the combined reactor train effluent streams enter the separator-blending vessel, monomer recycle (mon-
omer-rich phase) emerges from the top of the separator-blending vessel and an optionally plasticized (as in the afore-
25 mentioned options (1) and (2) and when optional off-line-produced plasticizers introduced) polymer-rich blend emerges
from the bottom of the vessel. The optionally plasticized polymer-rich blend may then be conveyed to a downstream
finishing stage for further monomer stripping, drying and/or pelletizing. As described earlier, modifiers and additives (i.e.
other polymers, other plasticizers, and polymer additives) may also be introduced either before or into the separator-
blending vessel or downstream of it. However, a downstream introduction of these modifiers and additives typically
30 simplifies monomer recycle, and is thus advantageous. In this embodiment, the single separator-blending vessel serves
as both a separator and a blender. One advantage of this exemplary embodiment is the utilization of a single separator-
blending vessel, which provides for process simplicity because it functions for both separation and blending purposes.
One disadvantage of this exemplary embodiment is that because all reactor train effluent streams are combined, the
recovered monomer stream from the separator-blending vessel may need to be separated prior to recycle to the individual
35 reactor trains in the bank of parallel reactors. In summary, this embodiment may be simpler and thus lower cost in the
separator section, but may be more costly in the monomer separation and recycling loop section of the process.
[0161] FIG. 7 depicts an alternative exemplary embodiment of the fluid phase in-line blending process disclosed herein
in which each reactor train has a dedicated separator vessel with the exception of one reactor effluent train where all
polymer-rich and the optional plasticizer-rich phases (as in the aforementioned options (1) and (2)) from the other reactors
40 are combined in a high-pressure separator that also serves as a blending vessel (also referred to as multiple separation
vessel operation). In this embodiment, for all but one of the reactor trains (all but train n in FIG. 7), the single-stream
high-pressure separator serves as a separator to separate a polymer-enriched phase or plasticizer-enriched phase from
a monomer-rich phase in the reactor effluent stream. In order to keep the content of low molecular weight components
higher and thus to keep the viscosity of the optionally plasticized polymer-enriched phase lower, the single-stream high-
45 pressure separators dedicated to the individual reactor trains often operate at a somewhat higher pressure than the one
downstream high-pressure separator that serves both as a separator and as a blender (separator-blender). Therefore,
there is an optional pressure letdown between these separators and the separator-blender. For the one high-pressure
separator (separator-blender) where the other polymer-rich phases and plasticizer-rich phases are combined and the
reactor train effluent from one of the reactor trains is introduced (reactor train n in FIG. 7), the separator serves both
50 product blending and product-feed separating functions. Catalyst killing agent may be optionally introduced prior to or
into each separator vessel, including the separator-blender to minimize further polymerization outside the polymerization
reactors. One or more off-line-produced plasticizers, and other additives may optionally also be blended in at the same
mixing point (not shown in Fig. 7). Optionally, one or more static mixers positioned before the separator-blending vessel,
but downstream of the mixing point may be utilized to enhance mixing between the polymer-rich phases, the optional
55 plasticizer-rich phases of the reactor trains, the optional off-line-produced plasticizers and other optional additives, and
the reactor train effluent of the reactor train associated with the separator-blender. Optionally, some or all reactor train
effluents may be heated before the first pressure letdown (not shown in FIG. 7) in order to maintain the temperature in
the downstream lines and in the separators, including the separation-blending vessel, at the desired value, i.e., above

29
 EP 2 195 349 B1

the solid-fluid phase transition temperatures of the polymer-rich phases and plasticizer-rich phases but below the cloud
point of the streams entering the separators, including the separator-blender, to allow the formation of plasticized polymer-
rich denser fluid phase and monomer-rich lighter fluid phase. The optional off-line-produced plasticizer and other optional
additive feed streams may also be heated before their introduction for the same purpose. The process of this embodiment
5 may be advantageous in the production of plasticized polymer blends that include one or more in-line-produced plasti-
cizers and one or more high molecular weight polymers. In this embodiment, the plasticizer train(s) has/have its (their)
own separator(s) and the polymerization train to produce a high molecular weight polyolefin serves as a blender. The
process of this embodiment may also be advantageous in the production of plasticized polymer blends that include
different homopolymers or homopolymer(s) and copolymer(s) as blend components. In this embodiment, the homopo-
10 lymerization train(s) and the plasticizer train(s) has/have its (their) own separator(s) and the copolymerization train (or
one of the copolymerization trains in case of more than one copolymer trains used) serves as a blender. The monomer
(s) recovered in the separator(s) dedicated to individual reactor train(s) may be recycled to the corresponding reactor
train(s) without the complex separation from other monomers as was associated with single separation-blending vessel
operation previously described. Hence, one advantage of this embodiment is that monomer recycle is simplified and
15 thus affords lower cost in the monomer recycle loop. While multiple separation vessel operation increases cost in the
separator section, it adds flexibility in the monomer recycle loops. In summary, this embodiment may be more complicated
and higher cost in the separator section, but may be simpler in the monomer recycle loops.
[0162] In one particular embodiment similar to the process scheme depicted in Fig. 7, one or more of the in-line-
produced plasticizers may be fully recovered in their essentially pure form before blending them with the effluent streams
20 carrying the one or more high molecular weight base polymer in-line blending components. The full recovery of the one
or more plasticizer blend components may include one or more fluid-fluid phase separation, or distillative separations
comprising one or more liquid-vapor equilibrium conditions, and any combination thereof. The operation of fluid-fluid
phase separators is disclosed in details in U.S. Patent Application No. 60/876,193 filed on December 20, 2006. Distillative
separations comprising one or more liquid-vapor equilibrium conditions employing flash drums, knock-out pots, or dis-
25 tillation columns, or vacuum stripping, etc., are well-known in the art of chemical engineering. The full recovery of the
in-line-produced plasticizer blending component may be advantageous when in-line-produced plasticizer blending com-
ponent is a liquid at ambient temperature and/or when some fraction of it is exported from the in-line blending plant
disclosed herein since plasticizer liquids readily blend with the process streams comprising the high molecular weight
base polymer. Further advantages may arise from the full recovery of one or more in-line-produced plasticizers before
30 blending them with the effluent streams carrying the one or more high molecular weight base polymer in-line blending
components when the combined monomer pool of the one or more optional plasticizer reactor trains has no common
monomer members with the combined monomer pools of the reactor trains producing the high molecular weight base
polymer in-line blending components.
[0163] Since both embodiments of FIG. 6 and 7 serve the same function of product blending and separation of the
35 polymer-rich and plasticizer-rich phases from the monomer-rich phases, the choice between them is driven by the
economics of a given plant producing a given product slate and may be determined by standard engineering optimization
techniques known in the art.
[0164] FIG. 8 presents another alternative exemplary embodiment of the fluid phase in-line blending process disclosed
herein in which is provided a dedicated buffer tank in which no phase separation occurs for each reactor train and in
40 which the reactor train effluents are combined in a single separator-blending vessel (also referred to as single separation
vessel operation with buffer tanks). Each of the n parallel reactor trains in the reactor bank is provided with its own buffer
tank to enable the fine-tuning of the mixing ratio of the polymer and plasticizer blend components. Pressure let down
valves may be positioned on the inlet and outlet side of each buffer tank to control the in-line polymer or plasticizer blend
component flow. Optionally, the reactor effluents may be heated to maintain the desired temperature in the downstream
45 separator-blender as described above. Catalyst killing agent may be optionally introduced prior to or into each buffer
tank to minimize further polymerization outside the polymerization reactors. Optionally, one or more static mixers posi-
tioned after the mixing point but before the separation vessel for blending may be utilized to enhance mixing between
the reactor effluents being fed from the buffer tanks. In comparison to the single separation vessel operation of FIG. 6,
this alternative exemplary embodiment allows for more precise control of the blend ratio and quality but without the
50 benefit of dedicated monomer recovery provided by the configuration depicted in FIG. 7. As previously discussed, this
embodiment may improve the control of product blend ratio and hence product quaility, but its buffer capacity may be
limited, particularly when the reactor effluent is in its supercritical state or when its pressure is above its bubble point.
[0165] An alternative design employing buffering capability is depicted in FIG. 9. FIG. 9, a variation of the multiple
separation vessel operation depicted in FIG. 7, and an advantageous version of the buffer-only operation shown in FIG.
55 8, presents yet another alternative exemplary embodiment of the fluid phase in-line blending process disclosed herein.
In this exemplary embodiment the single-stream high-pressure separators dedicated to the individual reactor trains also
serve as buffer tanks. Referring to FIG. 9, for all reactor trains but n, the reactor train effluent is fed to a dual-purpose
separator-buffer for both separation of the polymer-rich phase or plasticizer-rich phase from the supernatant monomer-

30
 EP 2 195 349 B1

rich phase and storage of polymer-rich phase or the optional plasticizer-rich phase prior to conveyance to a downstream
blending separator. These single-stream separators dedicated to individual reactor trains afford buffering by allowing
the level of the denser polymer-rich and plasticizer-rich phases to move between an upper and a lower limit. This buffer
capacity allows for the correction in the potential fluctuations in the production rates of the individual in-line blend
5 components and thus provides a means for a more precise control of the polymer-plasticizer blend ratio. For reactor
train n, the high-pressure separator (separator-blender) functions to separate the polymer-rich phase from the monomer-
rich phase for the reactor effluent from reactor n and also to blend the polymer-rich phases and plasticizer-rich phases
from all reactors (1, 2, through n in FIG. 9). From a blend control point of view, there is no buffering for the in-line
component n, and thus all other blend component flows to the separator-blending vessel, and ultimately their production
10 rates, are controlled by the production rate in reactor train n in order to maintain the desired blend ratios. Catalyst killing
agent may be optionally introduced prior to or into each separator vessel to minimize further polymerization within the
separator. Optionally, one or more static mixers positioned before the separation vessel for blending may be utilized to
enhance mixing between polymer-rich phases of the reactors and the reactor effluent of the reactor associated with the
blending separator. For heat and pressure management, the same considerations, configurations, and controls may be
15 applied as described for the previous embodiments. As in all process configurations, optional modifiers and additives
may be introduced either prior or into the separator-blending vessel or downstream of it.
[0166] FIG. 10 presents yet another exemplary embodiment of the fluid-phase in-line blending process disclosed
herein in which one of the parallel polymerization trains (train 1 in FIG. 10) produces a high molecular weight base
polymer blending component in the form of solid pellets, i.e. operates in the slurry polymerization regime. Thus in order
20 to bring the polymer into a dissolved state before in-line blending, the reactor effluent is brought into a heated stirred
vessel. In order to keep the entire reactor effluent in a dense fluid phase, the pressure of the reactor effluent is increased
by a slurry pump. Slurry polymerization typically operates at lower temperatures than supercritical and solution polym-
erizations and thus may afford products with higher molecular weight and melting peak temperatures, which may provide
advantages in certain plasticized polymer blend applications. However, the dissolution of polymer pellets adds cost and
25 tends to be prone to fouling and other operational issues. Other aspects of the in-line blending process disclosed herein,
such as catalyst killing, additive blending, heat and pressure management, as described in the previously described
embodiments, apply hereto as well.
[0167] FIG. 11 presents still yet another exemplary embodiment of the fluid phase in-line blending process disclosed
herein in which one or more optional polymer, and/or plasticizer, and/or other polymer additive storage tanks may be
30 added to the process for the storage and metering of other fluid polymers and polymer additives to the blending vessel.
Optional pump(s) may be used to convey the one or more polymers, plasticizers or other polymer additives to the
separator vessel for blending. Note that FIG. 11 presents the particular embodiment wherein the one or more optional
polymer, and/or plasticizer, and/or more polymer additive storage tanks are added to the single separation-blending
vessel operation with buffer tanks configuration of FIG. 8. However, the one or more optional polymer, and/or plasticizer,
35 and/or one or more polymer additive storage tanks may be added to the processes depicted in FIG. 6, FIG. 7, and/or
FIG. 9 without deviating from the spirit of the fluid phase in-line blending process disclosed herein. Similarly, optional
off-line produced polymers, plasticizers, modifiers, and additives may be introduced in any part of the polymer finishing
section or in a dedicated section prior to the product finishing section of the process disclosed herein. Other aspects of
the in-line blending process disclosed herein, such as catalyst killing, additive blending, heat and pressure management,
40 as described in the previously described embodiments, apply hereto as well.
[0168] As will be appreciated by one skilled in the art of chemical engineering, the process schematic details of the
design of the fluid phase in-line blending process in terms of reactor configuration, separator configuration, valving, heat
management, etc. may be set differently without deviating from the spirit of the fluid-phase in-line blending process
disclosed herein. The choice between different embodiments of the processes disclosed herein will be driven by product
45 performance requirements and process economics, which can be readily determined by standard engineering tech-
niques. However, the in-line blending processes disclosed herein are advantageous relative to the prior art by the virtue
of reduced blending cost due to savings in investment and operation costs, and enabling well-controlled and cost-
effective molecular-level blending to yield enhanced plasticized polymer blend performance.
[0169] The processes disclosed herein provide an effective recycle pathway for monomer separation from the products.
50 They are particularly advantageous in homogeneous olefin polymerization processes such as, for example, bulk homo-
geneous supercritical propylene polymerization (SCPP), solution polymerization, and bulk solution polymerization. As
will be discussed in more detail below for bulk homogeneous polymerization processes, the efficient separation of
monomer and polymer is achieved by advantageously utilizing the cloud point pressure and temperature relationships
for the relevant (polymer/olefinic monomer) or (copolymer/olefinic monomer blend); e.g. (polypropylene/propylene mon-
55 omer), (ethylene-propylene copolymer/ethylene-propylene monomer blend), etc. mixtures.
[0170] For illustration, cloud point curves are shown in FIGS. 13-22 for three different polypropylene samples having
different molecular weights and crystallinities dissolved in propylene (at 18 wt %). (Achieve 1635 PP is a commercially
available metallocene-catalyzed isotactic polypropylene having a Melt Flow Rate, MFR, (I10/I2-ASTM 1238, 230 ˚C, 2.16

31
 EP 2 195 349 B1

kg) of 32 g/10 min available from ExxonMobil Chemical Company, Houston, Texas. ESCORENE PP 4062 is a com-
mercially available isotactic polypropylene having an MFR of 3.7 g/10 min, available from ExxonMobil Chemical Company,
Houston, Texas. PP 45379 is an isotactic polypropylene having an MFR of 300 g/10 min produced using a supported
metallocene in a slurry polymerization process.
5
Plasticized Polymer Blend Formulations and Products:

[0171] Many different types of plasticized polymer blends may be made by the fluid-phase in-line blending process
disclosed herein. A major fraction of a blend is defined as 50% or more by weight of the blend. A minor fraction of a
10 blend is defined as less than 50% by weight of the blend. The plasticized polymer blend formulation produced by the
in-line processes disclosed herein generally include a major fraction of one or more high molecular weight polymer
components and a minor fraction of one or more plasticizers.
[0172] Besides achiving plasticization, i.e., increasing softness and/or cold temperature flexibility and/or processability,
etc., by in-line blending of plasticizers, plasticized polymer blends produced by the fluid phase in-line blending process
15 disclosed herein may also be used to blend base polymer components and thus, for example, to provide bi- or multi-
modality to the distributions of the molecular characteristics of resins encompassed herein. Non-limiting examples of
such materials are blends with similar polymer components, but having different molecular weights, different levels of
incorporation of comonomers, different levels of molecular defects like stereo-and regio- defects, and the like. The result
of such bimodality is to produce an improved suite of properties in the blend as compared to any of the polymer components
20 alone. Processing ease and melt strength may be improved by such blending as well as the balance between stiffness-
toughness, heat resistance, tolerance of exposure to high energy radiation and other properties of the resins.
[0173] The weight fractions of the individual base polymer components in the blends made by the fluid phase in-line
blending process disclosed herein may be similar or different. The polymer blends disclosed herein may also derive
similar improvements from combinations of different materials in similar or different proportions. One non-limiting example
25 of a useful polymer blend made by the fluid phase in-line blending process disclosed herein includes a major fraction
of a highly crystalline moderate molecular weight polymer and a minor fraction of a very high molecular weight, elastomeric
polymer with low or no inherent crystallinity. Another non-limiting example of a useful polymer blend made by the fluid
phase in-line blending process disclosed herein includes a major fraction of a soft, tough, low melting polymer with a
minor fraction of a highly crystalline, high melting polymer. Still another non-limiting example of a useful polymer blend
30 made by the fluid phase in-line blending process disclosed herein includes a major fraction of a highly crystalline polymer
with a minor fraction of a low or non-crystalline polymer where the low or non-crystalline polymer is non-elastomeric.
This example also encompasses plasticized polymer blends.
[0174] The plasticized polymer blends made by the fluid phase in-line blending process disclosed herein provide for
improved properties, and hence use in a wide array of applications. One such exemplary, but non-limiting application,
35 is in medical applications requiring improved resistance to sterilizing doses of high-energy radiation. A polymer blend
useful for this particular application may include from 75 to 99 wt % moderate molecular weight propylene homopolymer
with 1 to 25 wt % of an ethylene plastomer, which acts as a plasticizing component. Alternatively, the ethylene plastomer
may be replaced by a propylene-ethylene copolymer containing from 8-16 wt % ethylene, which also acts as a plasticizing
component. The plastomer or high propylene copolymer component of the blend provides superior initial ductility as well
40 as retention of ductility and tolerance of the sterilizing radiation to the blend while the homopolymer component imparts
excellent strength, stiffness and resistance to deformation at elevated temperature to the blend. Polymer blends of
propylene homopolymer and ethylene plastomer or propylene-ethylene copolymer are generally clearer or nearly as
clear as the unblended propylene homopolymer component.
[0175] Another exemplary, but non-limiting application of where the plasticized polymer blends made by the fluid phase
45 in-line blending process disclosed herein find application is in various conversion processes. In particular, by combining
high and low molecular weight propylene polymers in either similar or different proportion, the molecular weight distribution
of the blend may be significantly broader than of either individual component. The ratio for blending the high and low
molecular weight propylene polymers depends upon the desired final melt flow rate and molecular weight distribution.
Such broader molecular weight distribution polymers are easier to extrusion blow mold, blow into film, thermoform, orient
50 into film, and stretch blow mold than narrower molecular weight distribution polymers. Optionally, one of the polymer
components can have long chain branching introduced through addition of a small quantity of alpha-omega-diene.
[0176] Still another exemplary, but non-limiting application of where the plasticized polymer blends made by the fluid
phase in-line blending process disclosed herein find application is in devices and packaging materials requiring good
impact resistance, and particularly in low temperature environments. Plasticized polymer blends useful for this particular
55 application may include from 80 to 99 wt % of a propylene impact copolymer (a blend of high crystallinity propylene
homopolymer and low crystallinity propylene-ethylene copolymer) and 1-20 wt % of plasticizer.
[0177] In applications requiring clarity, incorporating into the plasticized polymer blend a minor fraction of a highly
compatible ethylene plastomer or propylene copolymer known to have a minimal deleterious effect or even a positive

32
 EP 2 195 349 B1

effect on the clarity of blends with polypropylene may provide for such. Such plastomers comprise those with a refractive
index and viscosity similar to the polypropylene with which they are to be blended. Compatible propylene copolymers
are exemplified by propylene-ethylene copolymers containing less than 16 wt %, or less than 11 wt %, or less than 6
wt % ethylene.
5 [0178] Still yet another exemplary, but non-limiting application of where the plasticized polymer blends made by the
fluid phase in-line blending process disclosed herein find application are those where materials requiring a combination
of stiffness and impact resistance and/or a combination of heat resistance and impact resistance. A plasticized polymer
blend useful for these applications are similar in composition to the blends specified for impact resistant devices and
packages. More particularly, plasticized polymer blends useful for this particular application may include from 51 to 99
10 wt % of a stiff propylene homopolymer and/or a relatively stiff, low comonomer containing propylene copolymer and
1-49 wt % of a plasticizer. The stiffness and heat resistance may be increased by increasing the homopolymer or stiff
copolymer portion of the polymer blend. Correspondingly, the impact resistance may be improved by increasing the
plasticizer portion of the blend. The desired balance of product attributes may be accomplished by a careful balancing
of the two components.
15 [0179] Still yet another exemplary, but non-limiting application of where the plasticized polymer blends made by the
fluid phase in-line blending process disclosed herein find application are those where a device and/or package must be
sterilized by high temperature and also must be soft and able to withstand impact abuse even at low temperatures.
Plasticized polymer blends useful for this particular application may include from 75-99 wt % of one or more stiff homopol-
ymer and/or copolymer components and 1-25 wt % of one or more plasticizers. Where increasing softness of packages
20 and device is desired, one may use a greater fraction of plasticizer in the blend, including to the point that the plasticizer
is the majority component of the blend. Hence the range of polymer blends may include 10-95 wt % of the plasticizer
component.
[0180] Still yet another exemplary, but non-limiting application of where the plasticized polymer blends made by the
fluid phase in-line blending process disclosed herein find application are films which are required to melt and form a
25 seal at relatively low elevated temperature yet still maintain integrity at much higher temperature. The range of blend
compositions previously specified for soft, elevated temperature resistant devices and/or packages would apply for this
particular type of film application. Similar relationships between competing properties and the relative usages of the
relative components would also apply for this application. More particularly, a greater fraction of the stiff polymer com-
ponent may increase the seal integrity at higher temperatures, whereas a greater fraction of the plasticizer component
30 may improve seal formation at lower temperatures and seal strength at normal temperatures.
[0181] As will be appreciated by one skilled in the art of polymer engineering, variations to the aforementioned plas-
ticized polymer blends and their advantageous applications may be made without deviating from the spirit of the plasticized
polymer blends provided by fluid phase in-line blending process disclosed herein.

35 Catalyst System Overview:

[0182] The in-line process for blending polymers disclosed herein may utilize any number of catalyst systems (also
referred to as catalysts) in any of the reactors of the polymerization reactor section of the process. The in-line process
for blending polymers disclosed herein may also utilize the same or different catalysts or catalyst mixtures in the different
40 individual reactors of the reactor bank of the present invention. It should be understood that by using different catalyst
systems we mean that any part of the catalyst system can vary and any combination is allowed. For example, the
invention process may use unsupported catalyst systems in some trains while using supported catalyst systems in other
trains. In other embodiments, the catalyst systems in some reactor trains may comprise aluminoxane (for example,
MAO) activator, while comprising non-coordinating anion activators in some other trains. In another embodiments, the
45 catalyst systems in some reactor trains may comprise Ziegler-Natta catalysts, while the catalyst systems in other reactor
trains of the invention process may comprise metallocenes or nonmetallocene catalysts used for the production of
Versify™ family of polymers activated by aluminoxane or non-coordinating anion activators or any combinations thereof.
While the number of different catalyst systems deployed in the invention processes can be any number, the use of no
more than five different catalysts and more particularly, no more than three different catalysts in any given reactor is
50 advantageous for economic reasons. The deployment of no more than ten catalysts or the deployment of no more than
six catalysts in the reactor bank of the polymerization process is advantageous for economic reasons. The one or more
catalysts deployed in the reactors may be homogeneously dissolved in the fluid reaction medium or may form a heter-
ogeneous solid phase in the reactor. In one particular embodiment, the catalyst(s) is (are) homogeneously dissolved in
the fluid reaction medium. When the catalyst is present as a solid phase in the polymerization reactor, it may be supported
55 or unsupported.
[0183] The process disclosed herein may use any combination of homogeneous and heterogeneous catalyst systems
simultaneously present in one or more of the individual reactors of the polymerization reactor section, i.e., any reactor
of the polymerization section of the present invention may contain one or more homogeneous catalyst systems and one

33
 EP 2 195 349 B1

or more heterogeneous catalyst systems simultaneously. The process disclosed herein may also use any combination
of homogeneous and heterogeneous catalyst systems deployed in the polymerization reactor section. These combina-
tions comprise scenarios when some or all reactors use a single catalyst and scenarios when some or all reactors use
more than one catalyst. The one or more catalysts deployed in the process disclosed herein may be supported on
5 particles, which either can be dispersed in the fluid polymerization medium or may be contained in a stationary catalyst
bed. When the supported catalyst particles are dispersed in the fluid reaction medium, they may be left in the polymeric
product or may be separated from the product prior to its crystallization from the fluid reactor effluent in a separation
step that is downstream of the polymerization reactor section. If the catalyst particles are recovered, they may be either
discarded or may be recycled with or without regeneration.
10 [0184] The catalyst may also be supported on structured supports, such as for example, monoliths comprising straight
or tortuous channels, reactor walls, and internal tubing. When the catalysts are supported, operation may take place on
dispersed particles. When the catalyst is supported on dispersed particles, operations may take place without catalyst
recovery i.e., the catalyst is left in the polymeric product. In another embodiment, unsupported catalysts may be dissolved
in the fluid reaction medium.
15 [0185] Catalyst systems may be introduced into the reactor by any number of methods. For example, the catalyst
may be introduced with the monomer-containing feed or separately. Also, the catalyst(s) may be introduced through
one or multiple ports to the reactor. If multiple ports are used for introducing the catalyst, those ports may be placed at
essentially the same or at different positions along the length of the reactor. If multiple ports are used for introducing
the catalyst, the composition and the amount of catalyst feed through the individual ports may be the same or different.
20 Adjustment in the amounts and types of catalyst through the different ports enables the modulation of polymer properties,
such as for example, molecular weight distribution, composition, composition distribution, and crystallinity.

Catalyst Compounds and Mixtures:

25 [0186] The processes described herein may use any polymerization catalyst capable of polymerizing the monomers
disclosed herein if that catalyst is sufficiently active under the polymerization conditions disclosed herein. Thus, Group-
3-10 transition metals may form suitable polymerization catalysts. A suitable olefin polymerization catalyst will be able
to coordinate to, or otherwise associate with, an alkenyl unsaturation. Illustrative, but not limiting, olefin polymerization
catalysts include Ziegler-Natta catalyst compounds, metallocene catalyst compounds, late transition metal catalyst
30 compounds, and other non-metallocene catalyst compounds.
[0187] Distinction should made between active catalysts, also referred to as catalyst systems herein, and catalyst
precursor compounds. Catalyst systems are active catalysts comprising one or more catalyst precursor compounds,
one or more catalyst activators, and optionally, one or more supports. Catalytic activity is often expressed based on the
concentration of the catalyst precursor compounds without implying that the active catalyst is the precursor compound
35 alone. It should be understood that the catalyst precursor is inactive without being contacted or being treated with a
proper amount of activator. Similarly, the catalyst activator is inactive without combining it with a proper amount of
precursor compound. As will become clear from the following description, some activators are very efficient and can be
used stoichiometrically, while some others are used in excess, and in sometimes large excess, to achieve high catalytic
activity as expressed based on the concentration of the catalyst precursor compounds. Since some of these activators,
40 for example methylaluminoxane (MAO), increase catalytic activity as expressed based on the concentration of the
catalyst precursor compounds, they are sometimes referred to as "cocatalysts" in the technical literature of polymerization.
[0188] As disclosed herein, Ziegler-Natta catalysts are those referred to as first, second, third, fourth, and fifth gen-
eration catalysts in the PROPYLENE HANDBOOK, E.P. Moore, Jr., Ed., Hanser, New York, 1996. Metallocene catalysts
in the same reference are described as sixth generation catalysts. One exemplary non-metallocene catalyst compound
45 comprises nonmetallocene metal-centered, heteroaryl ligand catalyst compounds (where the metal is chosen from the
Group 4, 5, 6, the lanthanide series, or the actinide series of the Periodic Table of the Elements).
[0189] Just as in the case of metallocene catalysts, these nonmetallocene metal-centered, heteroaryl ligand catalyst
compounds are typically made fresh by mixing a catalyst precursor compound with one or more activators. Nonmetal-
locene metal-centered, heteroaryl ligand catalyst compounds are described in detail in PCT Patent Publications Nos.
50 WO 02/38628, WO 03/040095 (pages 21 to 51), WO 03/040201 (pages 31 to 65), WO 03/040233 (pages 23 to 52),
WO 03/040442 (pages 21 to 54), WO 2006/38628, and U.S. Patent Application Serial No. 11/714,546.
[0190] Particularly useful metallocene catalyst and non-metallocene catalyst compounds are those disclosed in par-
agraphs [0081] to [0111] of U.S. Serial No. 10/667585 and paragraphs [0173] to [0293] of U.S. Serial No. 11/177004.
[0191] The processes disclosed herein can employ mixtures of catalyst compounds to tailor the properties that are
55 desired from the polymer. Mixed catalyst systems prepared from more than one catalyst precursor compounds can be
employed in the in-line blending processes to alter or select desired physical or molecular properties. For example,
mixed catalyst systems can control the molecular weight distribution of isotactic polypropylene when used with the
invention processes or for the invention polymers. In one embodiment of the processes disclosed herein, the polymer-

34
 EP 2 195 349 B1

ization reaction(s) may be conducted with two or more catalyst precursor compounds at the same time or in series. In
particular, two different catalyst precursor compounds can be activated with the same or different activators and intro-
duced into the polymerization system at the same or different times. These systems can also, optionally, be used with
diene incorporation to facilitate long chain branching using mixed catalyst systems and high levels of vinyl terminated
5 polymers.
[0192] As disclosed herein, two or more of the above catalyst precursor compounds can be used together.

Activators and Activation Methods for Catalyst Compounds:

10 [0193] The catalyst precursor compounds described herein are combined with activators for use as active catalysts
herein.
[0194] An activator is defined as any combination of reagents that increases the rate at which a metal complex
polymerizes unsaturated monomers, such as olefins. An activator may also affect the molecular weight, degree of
branching, comonomer content, or other properties of the polymer.
15
A. Aluminoxane and Aluminum Alkyl Activators:

[0195] In one form, one or more aluminoxanes, such as methylaluminoxane, or trialkylaluminum compounds, such
as triisobutyl aluminum or tri-n-octyl aluminum are utilized as an activator in the in-line blending processes disclosed
20 herein. Alkyl aluminoxanes, sometimes called alumoxanes in the art, are generally oligomeric compounds containing --
Al(R)--O-- subunits, where R is an alkyl group. Examples of aluminoxanes include methylaluminoxane (MAO), modified
methylaluminoxane (MMAO), ethylaluminoxane and isobutylaluminoxane. Alkylaluminoxanes and modified alkylalumi-
noxanes are suitable as catalyst activators, particularly when the abstractable ligand is a halide. Mixtures of different
aluminoxanes and modified aluminoxanes may also be used. For further descriptions, see U.S. Patent Nos. 4,665,208,
25 4,952,540, 5,041,584, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,329,032,
5,248,801, 5,235,081, 5,157,137, 5,103,031 and European and PCT Patent Publication Nos. EP 0 561 476 A1, EP 0
279 586 B1, EP 0 516 476 A, EP 0 594 218 A1 and WO 94/10180.
[0196] When the activator is an aluminoxane (modified or unmodified), some embodiments select the maximum
amount of activator at a 5000-fold molar excess, or at a 1000-fold molar excess, or at a 500-fold molar excess Al/
30 Transition Metal over the catalyst compound (per metal catalytic site). The minimum activator-to-catalyst-compound is
typically a 1:1 molar ratio.

B. Ionizing Activators:

35 [0197] It is contemplated to use an ionizing or stoichiometric activator, neutral or ionic, such as tri(n-butyl)ammonium
tetrakis (pentafluorophenyl)boron, a trisperfluorophenyl borone metalloid precursor or a trisperfluoronaphtyl borone
metalloid precursor, polyhalogenated heteroborane anions (PCT patent publication no. WO 98/43983), boric acid (U.S.
Patent No. 5,942,459) or combination thereof as an activator herein. Also contemplated for use herein are neutral or
ionic activators alone or in combination with aluminoxane or modified aluminoxane activators.
40 [0198] Examples of neutral stoichiometric activators include tri-substituted boron, aluminum, gallium and indium or
mixtures thereof. The three substituent groups are each independently selected from alkyls, alkenyls, halogen, substituted
alkyls, aryls, arylhalides, alkoxy and halides. The three groups are independently selected from halogen, mono or
multicyclic (including halosubstituted) aryls, alkyls, and alkenyl compounds and mixtures thereof, advantageous are
alkenyl groups having 1 to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20
45 carbon atoms and aryl groups having 3 to 20 carbon atoms (including substituted aryls). Alternately, the three groups
are alkyls having 1 to 4 carbon groups, phenyl, napthyl or mixtures thereof. Alternately, the three groups are halogenated,
or fluorinated, aryl groups. Alternately, the neutral stoichiometric activator is trisperfluorophenyl boron or trisperfluoro-
napthyl boron.
[0199] Ionic stoichiometric activator compounds may contain an active proton, or some other cation associated with,
50 but not coordinated to, or only loosely coordinated to, the remaining ion of the ionizing compound. Such compounds
and the like are described in European patent publication Nos. EP-A-0 570 982, EP-A-0 520 732, EP-A-0 495 375, EP-
B1-0 500 944, EP-A-0 277 003 and EP-A-0 277 004, and U.S. Patent Nos. 5,153,157, 5,198,401, 5,066,741, 5,206,197,
5,241,025, 5,384,299 and 5,502,124 and U.S. patent application No. 08/285,380, filed Aug. 3, 1994, all of which are
herein fully incorporated by reference. Some of the useful activators chosen from trimethylammonium tetraphenylborate,
55 trisperfluorophenyl borane, trisperfluoronaphtyl borane, triethylammonium tetraphenylborate, tripropylammonium tetra-
phenylborate, tri(n-butyl)ammonium tetraphenylborate, tri(t-butyl)ammonium tetraphenylborate, N,N-dimethylanilinium
tetraphenylborate, N,N-diethylanilinium tetraphenylborate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetraphenylborate,
trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammonium tetrakis(pentafluorophenyl)-borate, tripropy-

35
 EP 2 195 349 B1

lammonium tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, tri(sec-butyl)

ammonium tetrakis(pentafluorophenyl) borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate, N,N-diethyl-
anilinium tetrakispentafluorophenyl) borate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis(pentafluorophenyl) borate,
trimethylammonium tetrakis-(2,3,4,6-tetrafluorophenylborate, triethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl) bo-
5 rate, tripropylammonium tetrakis-(2,3,4,6-tetrafluorophenyl) borate, tri(n-butyl)-ammonium tetrakis-(2,3,4,6-tetrafluoro-
phenyl) borate, dimethyl(t-butyl)ammonium tetrakis-(2,3,4,6-tetrafluorophenyl) borate, N,N-dimethylanilinium tet-
rakis-(2,3,4,6-tetrafluorophenyl) borate, N,N-diethylanilinium tetrakis-(2,3,4,6-tetrafluoro-phenyl) borate, N,N-dime-
thyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl) borate, di-(i-propyl)ammonium tetrakis(pentafluoroph-
enyl) borate, dicyclohexyl-ammonium tetrakis(pentafluorophenyl) borate, triphenylphosphonium tetrakis(pentafluoroph-
10 enyl) borate, tri(o-tolyl)phosphonium tetrakis(pentafluoro-phenyl) borate, tri(2,6-dimethylphenyl)phosphonium tetrakis
(pentafluorophenyl) borate, N,N-dimethyl-anilinium tetra(perfluorophenyl)borate, triphenylcarbenium tetra(perfluoroph-
enyl)-borate, and combinations thereof. Some of the useful activators are represented by the following formula:

(St+)u (NCAv-)w
15
wherein:
St+ is a cation component having the charge t+
NCAv- is a non-coordinating anion having the charge v-t is an integer from 1 to 3;
v is an integer from 1 to 3;
20 u and v are constrained by the relationship: (u) x (t) = (v) x (w); where St+) is a Bronsted acids or a reducible Lewis acids
capable of protonating or abstracting a moiety.

C. Non-Ionizing Activators:

25 [0200] Activators are typically strong Lewis-acids which may play either the role of ionizing or non-ionizing activator.
Activators previously described as ionizing activators may also be used as non-ionizing activators.
[0201] Abstraction of formal neutral ligands may be achieved with Lewis acids that display an affinity for the formal
neutral ligands. These Lewis acids are typically unsaturated or weakly coordinated. Examples of non-ionizing activators
include R10(R11)3, where R10 is a group 13 element and R11 is a hydrogen, a hydrocarbyl, a substituted hydrocarbyl,
30 or a functional group. Typically, R11 is an arene or a perfluorinated arene. Non-ionizing activators also include weakly
coordinated transition metal compounds such as low valent olefin complexes.
[0202] Non-limiting examples of non-ionizing activators include BMe3, BEt3, B(iBu)3, BPh3, B(C6F5)3, AlMe3, AlEt3,
Al(iBu)3, AlPh3, B(C6F5)3, aluminoxane, CuCl, Ni(1,5-cyclooctadiene)2.
[0203] Additional neutral Lewis-acids are known in the art and will be suitable for abstracting formal neutral ligands.
35 See in particular the review article by E. Y.-X. Chen and T. J. Marks, "Cocatalysts for Metal-Catalyzed Olefin Polymer-
ization: Activators, Activation Processes, and Structure-Activity Relationships", Chem. Rev., 100, 1391-1434 (2000).
[0204] Suitable non-ionizing activators include R10(R11)3, where R10 is a group 13 element and R11 is a hydrogen, a
hydrocarbyl, a substituted hydrocarbyl, or a functional group. Typically, R11 is an arene or a perfluorinated arene.
[0205] Other non-ionizing activators include B(R12)3, where R12 is an arene or a perfluorinated arene. Alternately,
40 non-ionizing activators include B(C6H5)3 and B(C6F5)3. Another non-ionizing activator is B(C6F5)3. Alternatively, acti-
vators include ionizing and non-ionizing activators based on perfluoroaryl borane and perfluoroaryl borates such as
PhNMe2H+ B(C6F5)4- , (C6H5)3C+ B(C6F5)4-, and B(C6F5)3.
[0206] Additional activators that may be used with the catalyst compounds disclosed herein include those described
in PCT patent publication No. WO 03/064433A1, which is incorporated by reference herein in its entirety.
45 [0207] Additional useful activators for use in the processes disclosed herein include clays that have been treated with
acids (such as H2SO4) and then combined with metal alkyls (such as triethylaluminum) as described in US Patent No.
6,531,552 and EP Patent No. 1 160 261 A1, which are incorporated by reference herein.
[0208] Activators also may be supports and include ion-exchange layered silicate having an acid site of at most -8.2
pKa, the amount of the acid site is equivalent to at least 0.05 mmol/g of 2,6-dimethylpyridine consumed for neutralization.
50 Non-limiting examples include chemically treated smectite group silicates, acid-treated smectite group silicates. Addi-
tional examples of the ion-exchange layered silicate include layered silicates having a 1:1 type structure or a 2:1 type
structure as described in "Clay Minerals (Nendo Kobutsu Gaku)" written by Haruo Shiramizu (published by Asakura
Shoten in 1995).
[0209] Examples of an ion-exchange layered silicate comprising the 1:1 layer as the main constituting layer include
55 kaolin group silicates such as dickite, nacrite, kaolinite, metahalloysite, halloysite or the like, and serpentine group
silicates such as chrysotile, lizaldite, antigorite or the like. Additional non-limiting examples of the ion-exchange layered
silicate include ion-exchange layered silicates comprising the 2:2 layer as the main constituting layer include smectite
group silicates such as montmorillonite, beidellite, nontronite, saponite, hectorite, stephensite or the like, vermiculite

36
 EP 2 195 349 B1

group silicates such as vermiculite or the like, mica group silicates such as mica, illite, sericite, glauconite or the like,
and attapulgite, sepiolite, palygorskite, bentonite, pyrophyllite, talc, chlorites and the like. The clays are contacted with
an acid, a salt, an alkali, an oxidizing agent, a reducing agent or a treating agent containing a compound intercalatable
between layers of an ion-exchange layered silicate. The intercalation means to introduce other material between layers
5 of a layered material, and the material to be introduced is called as a guest compound. Among these treatments, acid
treatment or salt treatment is particularly advantageous. The treated clay may then be contacted with an activator
compound, such as TEAL, and the catalyst compound to polymerize olefins.
[0210] In another form, the polymerization systems comprise less than 5 weight % polar species, or less than 4 weight
%, or less than 3 weight %, or less than 2 weight %, or less than 1 weight %, or less than 1000 ppm, or less than 750
10 ppm, or less than 500 ppm, or less than 250 ppm, or less than 100 ppm, or less than 50 ppm, or less than 10 ppm. Polar
species include oxygen containing compounds (except for alumoxanes) such as alcohols, oxygen, ketones, aldehydes,
acids, esters and ethers.
[0211] In yet another form, the polymerization systems comprise less than 5 weight % trimethylaluminum and/or
triethylaluminum, or less than 4 weight %, or less than 3 weight %, or less than 2 weight %, or less than 1 weight %, or
15 less than 1000 ppm, or less than 750 ppm, or less than 500 ppm, or less than 250 ppm, or less than 100 ppm, or less
than 50 ppm, or less than 10 ppm.
[0212] In still yet another form, the polymerization systems comprise methylaluminoxane and less than 5 weight %
trimethylaluminum and or triethylaluminum, or less than 4 weight %, or less than 3 weight %, or less than 2 weight %,
or less than 1 weight %, or less than 1000 ppm, or less than 750 ppm, or less than 500 ppm, or less than 250 ppm, or
20 less than 100 ppm, or less than 50 ppm, or less than 10 ppm.
[0213] The in-line blending processes disclosed herein may use finely divided, supported catalysts to prepare propyl-
ene/1-hexene copolymers with greater than 1.0 mole % 1-hexene. In addition to finely divided supports, in-line blending
processes disclosed herein may use fumed silica supports in which the support particle diameter may range from 200
angstroms to 1500 angstroms, small enough to form a colloid with reaction media.
25
Catalyst Supports:

[0214] In another form, the catalyst compositions of fluid phase in-line blending processes disclosed herein may
include a support material or carrier. For example, the one or more catalyst components and/or one or more activators
30 may be deposited on, contacted with, vaporized with, bonded to, or incorporated within, adsorbed or absorbed in, or
on, one or more supports or carriers.
[0215] The support material may be any of the conventional support materials. In one form, the supported material
may be a porous support material, for example, talcs, inorganic oxides, and inorganic chlorides, polystyrene, polystyrene
divinyl benzene polyolefins, zeolites, clays, silica, fumed silica, alumina, silica-alumina, magnesia, titania, zirconia,
35 magnesium chloride, montmorillonite phyllosilicate, porous acrylic polymers, nanocomposites, spherulites, polymeric
beads and combinations thereof. Other support materials may include resinous support materials such as polystyrene,
Functionalized or crosslinked organic supports, such as polystyrene divinyl benzene polyolefins or polymeric compounds,
zeolites, clays, or any other organic or inorganic support material and the like, or mixtures thereof.
[0216] Useful support materials are inorganic oxides that include those Group 2, 3, 4, 5, 13 or 14 metal oxides. In one
40 form, the supports include silica, which may or may not be dehydrated, fumed silica, alumina (PCT patent publication
No. WO 99/60033), silica-alumina and mixtures thereof. Other useful supports include magnesia, titania, zirconia, mag-
nesium chloride (U.S. Patent No. 5,965,477), montmorillonite (European Patent No. EP-B1 0 511 665), phyllosilicate,
zeolites, talc, clays (U.S. Patent No. 6,034,187) and the like. Also, combinations of these support materials may be
used, for example, silica-chromium, silica-alumina, silica-titania and the like. Additional support materials may include
45 those porous acrylic polymers described in European Patent No. EP 0 767 184 B1. Other support materials include
nanocomposites as described in PCT WO 99/47598, aerogels as described in WO 99/48605, spherulites as described
in U.S. Pat. No. 5,972,510 and polymeric beads as described in WO 99/50311.
[0217] The support material, for example an inorganic oxide, has a surface area in the range of from about 10 to about
700 m2/g, pore volume in the range of from about 0 to about 4.0 cc/g and average particle size in the range of from
50 about 0.02 to about 50 mm. Alternatively, the surface area of the support material is in the range of from about 50 to
about 500 m2/g, pore volume of from about 0 to about 3.5 cc/g and average particle size of from about 0.02 to about 20
mm. In another form, the surface area of the support material is in the range is from about 100 to about 400 m2/g, pore
volume from about 0 to about 3.0 cc/g and average particle size is from about 0.02 to about 10 mm.
[0218] Non-porous supports may also be used as supports in the processes described herein. For example, in a one
55 embodiment the nonporous, fumed silica supports described in U.S. Pat. No. 6,590,055 may be used.

37
 EP 2 195 349 B1

Scavengers:

[0219] Compounds that destroy impurities are referred to as scavengers by one skilled in the art of polymerization.
Impurities may harm catalysts by reducing their activity. Scavengers may be optionally fed to the reactor(s) of the in-
5 line blending process disclosed herein. Catalytic activity may be defined many different ways. For example, catalytic
activity can be expressed as turnover frequency, i.e., the number of moles of monomers converted to the product in a
unit time by one mole of catalyst precursor employed in preparing the active catalyst system. For a given reactor operating
at the same residence time, catalytic activity may also be measured in terms of catalyst productivity, customarily ex-
pressed as the weight of polymer made by a unit weight of catalyst precursor with or without the weight of the activator.
10 [0220] The scavengers for use in the processes disclosed herein may be different chemical compound(s) from the
catalyst activator. Non-limiting exemplary scavengers include diethyl zinc, and alkyl aluminum compounds, such as
trimethyl aluminum, triethyl aluminum, tri-isobutyl aluminum, and trioctyl aluminum. The scavenger may also be the
same as the catalyst activator and is generally applied in excess of what is needed to fully activate the catalyst. These
scavengers include, but are not limited to, aluminoxanes, such as methyl aluminoxane. The scavenger may also be
15 introduced to the reactor with the monomer feed or with any other feed stream. In one particular embodiment, the
scavenger is introduced with the monomer-containing feed. The scavenger may be homogeneously dissolved in the
polymerization reaction medium or may form a separate solid phase. In one particular embodiment, scavengers are
dissolved in the polymerization medium.

20 Reaction Monomers and Comonomers:

[0221] The processes disclosed herein may be used to polymerize any monomer having one or more (non-conjugated)
aliphatic double bond(s) and two or more carbon atoms. In the embodiments producing one or more plasticizers in-line,
the monomers used for making the base polymer and for making the plasticizer components of the in-line-plasticized
25 polymers, polymer blends, and polymer masterbatches are often of the same type, for example, the base polymer may
be made of propylene (an aliphatic olefin) and the plasticizer may be made of ethylene and propylene or higher alpha-
olefins. The most commonly used monomers for making the base polymer components are ethylene and propylene and
their combinations with each other or (to a smaller degree) with lower concentrations of monomers that modify the parent
polymer by, for example, introducing long-chain branching as done with alpha-omega dienes. These, combinations are
30 well known in the art of olefin polymerization. Useful monomers for producing and blending plasticizers in-line include
mixed C6-C14 linear 1-olefins, ethylene-butene, ethylene-hexene, ethylene-octene, propylene, propylene-butene, pro-
pylene-hexene mixtures, styrene and alpha-methyl styrene. Monomers for use in the in-line blending process thus
include ethylene, propylene, C4 and higher α-olefins (non-limiting examples include butene-1, hexene-1, octene-1, and
decene-1); substituted olefins (non-limiting examples include styrene, and vinylcyclohexane); non-conjugated dienes
35 (non-limiting examples include vinylcyclohexene, dicyclopentadiene); α,ω-dienes (non-limiting examples include 1,5-
hexadiene, 1,7-octadiene); cycloolefins (non-limiting examples include cyclopentene, cyclohexene); and norbornene.
[0222] The processes disclosed herein may be used to polymerize any unsaturated monomer or monomers including
C3 to C100 olefins, alternatively C3 to C60 olefins, alternatively C3 to C40 olefins, alternatively C3 to C20 olefins, and
alternately C3 to C12 olefins. The processes disclosed herein may also be used to polymerize linear, branched or cyclic
40 alpha-olefins including C3 to C100 alpha-olefins, alternatively C3 to C60 alpha-olefins, alternately C3 to C40 alpha-olefins,
alternatively C5 to C20 alpha-olefins, and alternatively C5 to C12 alpha-olefns. Suitable olefin monomers may be one or
more of propylene, butene, pentene, hexene, heptene, octene, nonene, decene, dodecene, 4-methyl-pentene-1, 3-
methyl pentene-1, 3,5,5-trimethyl-hexene-1, and 5-ethylnonene-1. C5 to C20 alpha-olefins and their mixtures are par-
ticularly useful for making plasticizer poly(alpha-olefins) also referred to as PAOs. The mixtures of ethylene and propylene
45 are particularly useful for making ethylene-propylene plasticizer copolymers such as plastomers, elastomers, and other
ethylene-propylene plasticizer copolymers.
[0223] In another embodiment of the processes disclosed herein, the polymer produced herein is a copolymer of one
or more linear or branched C3 to C30 prochiral alpha-olefins or C5 to C30 ring containing olefins or combinations thereof
capable of being polymerized by either stereospecific and non-stereospecific catalysts. Prochiral, as used herein, refers
50 to monomers that favor the formation of isotactic or syndiotactic polymer when polymerized using stereospecific catalyst
(s).
[0224] Other monomers for use with the in-line blending process disclosed herein may also include aromatic-group-
containing monomers containing up to 30 carbon atoms. Suitable aromatic-group-containing monomers comprise at
least one aromatic structure, alternately from one to three, and alternately a phenyl, indenyl, fluorenyl, or naphthyl moiety.
55 The aromatic-group-containing monomer further comprises at least one polymerizable double bond such that after
polymerization, the aromatic structure is pendant from the polymer backbone. The aromatic-group containing monomer
may further be substituted with one or more hydrocarbyl groups including but not limited to C1 to C10 alkyl groups.
Additionally two adjacent substitutions may be joined to form a ring structure. Aromatic-group-containing monomers

38
 EP 2 195 349 B1

may also contain at least one aromatic structure appended to a polymerizable olefinic moiety. Non-limiting exemplary
aromatic monomers include styrene, alpha-methylstyrene, para-alkylstyrenes, vinyltoluenes, vinylnaphthalene, allyl ben-
zene, and indene, and alternatively styrene, paramethyl styrene, 4-phenyl-1-butene and allyl benzene.
[0225] Non aromatic cyclic group containing monomers may also be used in the processes disclosed herein. These
5 monomers may include up to 30 carbon atoms. Suitable non-aromatic cyclic group containing monomers may have at
least one polymerizable olefinic group that is either pendant on the cyclic structure or is part of the cyclic structure. The
cyclic structure may also be further substituted by one or more hydrocarbyl groups, for example, but not limited to, C1
to C10 alkyl groups. Non-limiting exemplary non-aromatic cyclic group containing monomers include vinylcyclohexane,
vinylcyclohexene, vinylnorbornene, ethylidene norbornene, cyclopentadiene, cyclopentene, cyclohexene, cyclobutene,
10 and vinyladamantane.
[0226] Diolefin monomers may also be used in the processes disclosed herein. These diolefin monomers include any
hydrocarbon structure, or alternatively C4 to C30, having at least two unsaturated bonds, wherein at least two of the
unsaturated bonds are readily incorporated into a polymer by either a stereospecific or a non-stereospecific catalyst(s).
The diolefin monomers may also be selected from alpha, omega-diene monomers (i.e. di-vinyl monomers), alternatively
15 linear di-vinyl monomers containing from 4 to 30 carbon atoms. Non-limiting exemplary dienes include butadiene, pen-
tadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene, tetradec-
adiene, pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene, heneicosadi-
ene, docosadiene, tricosadiene, tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene, no-
nacosadiene, triacontadiene, particularly advantageous dienes include 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene,
20 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene, and low molecular weight
polybutadienes (Mw less than 1000 g/mol). Non-limiting exemplary cyclic dienes include cyclopentadiene, vinylnor-
bomene, norbomadiene, ethylidene norbomene, divinylbenzene, dicyclopentadiene or higher ring containing diolefins
with or without substituents at various ring positions.
[0227] Non-limiting examples of polar unsaturated monomers include 6-nitro-1-hexene, N-methylallylamine, N-allyl-
25 cyclopentylamine, N-allylhexylamine, methyl vinyl ketone, ethyl vinyl ketone, 5-hexen-2-one, 2-acetyl-5-norbomene, 7-
syn methoxymethyl-5-norbomen-2-one, acrolein, 2,2-dimethyl-4-pentenal, undecylenic aldehyde, 2,4-dimethyl-2,6-hep-
tadienal, acrylic acid, vinylacetic acid, 4-pentenoic acid, 2,2-dimethyl-4-pentenoic acid, 6-heptenoic acid, trans-2,4-
pentadienoic acid, 2,6-heptadienoic acid, nona-fluoro-1-hexene, allyl alcohol, 7-octene-1,2-diol, 2-methyl-3-buten-1-ol,
5-norbornene-2-carbonitrile, 5-norbomene-2-carboxaldehyde, 5-norbomene-2-carboxylic acid, cis-5-norbornene-endo-
30 2,3-dicarboxylic acid, 5-norbornene-2,2,-dimethanol, cis-5-norbornene-endo-2,3-dicarboxylic anhydride, 5-norbornene-
2-endo-3-endo-dimethanol, 5-norbornene-2-endo-3-exo-dimethanol, 5-norbornene-2-methanol, 5-norbornene-2-ol, 5-
norbomene-2-yl acetate, 1-[2-(5-norbornene-2-yl)ethyl]-3,5,7,9,11,13,15-heptacyclopentylpentacyclo-[9.5.1.13,9.15,15.
17,13]octasiloxane, 2-benzoyl-5- norbomene, allyl 1,1,2,2,-tetrafluoroethyl ether, acrolein dimethyl acetal, butadiene
monoxide, 1,2-epoxy-7-octene, 1,2-epoxy-9-decene, 1,2-epoxy-5-hexene, 2-methyl-2-vinyloxirane, allyl glycidyl ether,
35 2,5-dihydrofuran, 2-cyclopenten-1-one ethylene ketal, allyl disulfide, ethyl acrylate, methyl acrylate.
[0228] Polymerizations may be carried out with any suitable feed composition to yield the desired product composition
at an economical single-pass conversion. Monomer concentrations are generally lower when substantial amounts of
inert solvents/diluents are cofed with the monomers and catalyst. Although inert solvents/diluents may be used if so
desired, low solvent/diluent concentration is often advantageous due to reduced solvent and monomer recovery-recycle
40 cost. In one embodiment, olefin polymerization is carried out in the presence of less than 60 wt % of inert solvent/diluent
affording olefin concentrations in the combined feeds of the individual reators of 40 wt % or more, or even 55 wt % or
more, and advantageously 75 wt % or more.
[0229] In another embodiment, polymerizations yielding the in-line blend components are carried out in bulk monomer
phases, i.e., with combined reactor feeds comprising inert solvent/diluent at less than 40 wt %, or less than 30 wt %, or
45 less than 20 wt %, or less than 15 wt %, or less than 10 wt %, or less than 5 wt %, or even less than 1 wt %.
[0230] In a particular embodiment, ethylene-propylene copolymer blend components are made with essentially diluent-
free monomer feeds containing 1-18 wt % ethylene and 75-99 wt % propylene. In another embodiment, ethylene-
propylene copolymer blend components are produced with essentially diluent-free monomer feeds containing 5-30 wt
% of butene-1, or hexene-1 and 65-95 wt % of propylene or ethylene.
50 [0231] The processes disclosed herein may be used to produce homopolymers or copolymers. A copolymer refers
to a polymer synthesized from two, three, or more different monomer units. Polymers produced by the processes
disclosed herein include homopolymers or copolymers of any of the above monomers.
[0232] In one embodiment of the processes disclosed herein, the polymer is a homopolymer of any C3 to C12 alpha-
olefin, or a homopolymer of propylene. In another embodiment the polymer is a copolymer comprising propylene and
55 ethylene wherein the copolymer comprises less than 70 weight % ethylene, or less than 60 weight % ethylene, or less
than 40 weight % ethylene, or less than 20 weight % ethylene. In another embodiment the polymer is a copolymer
comprising propylene and one or more of any of the monomers listed above. In another embodiment, the copolymers
comprise one or more diolefin comonomers, alternatively one or more C6 to C40 non-conjugated diolefins, alternatively

39
 EP 2 195 349 B1

one or more C6 to C40 α,ω-dienes.

[0233] In another embodiment of the processes disclosed herein, the one or more polymer blend components are a
copolymer of ethylene, propylene, or other higher olefin and optionally any third monomer, typically another higher olefin,
such as C4 to C20 linear, branched or cyclic monomers. In another embodiment, the one or more polymer blend com-
5 ponents produced herein are a copolymer of ethylene and one or more of propylene, butene, pentene, hexene, heptene,
octene, nonene, decene, dodecene, 4-methyl-pentene-1, 3-methyl pentene-1, and 3,5,5-trimethyl-hexene-1. In still
another embodiment, the one or more polymer blend components produced herein are a copolymer of propylene and
one or more of ethylene, butene, pentene, hexene, heptene, octene, nonene, decene, dodecene, 4-methyl-pentene-1,
3-methyl-pentene-1, and 3,5,5-trimethylhexene-1. In still yet another embodiment, the one or more polymer blend com-
10 ponents produced herein are a copolymer of a C4 or higher olefin and one or more of ethylene, propylene, butene,
pentene, hexene, heptene, octene, nonene, decene, dodecene, 4-methyl-pentene-1, 3-methyl-pentene-1, and 3,5,5-
trimethylhexene-1.
[0234] In another embodiment of the processes disclosed herein, the copolymers described comprise at least 50 mole
% of a first monomer and up to 50 mole % of other monomers. In another embodiment, the polymer comprises: a first
15 monomer present at from 40 to 95 mole %, or 50 to 90 mole %, or 60 to 80 mole %, and a comonomer present at from
5 to 40 mole %, or 10 to 60 mole %, or 20 to 40 mole %, and a termonomer present at from 0 to 10 mole %, or from 0.5
to 5 mole %, or from 1 to 3 mole %. Such copolymer blending components can be readily produced when the comonomer
(s) is (are) present between 0.1 and 85 mole % in the combined feeds to the reactor making the copolymers.
[0235] In another embodiment of the processes disclosed herein, the first monomer comprises one or more of any
20 C3 to C8 linear branched or cyclic alpha-olefins, including propylene, butene, (and all isomers thereof), pentene (and all
isomers thereof), hexene (and all isomers thereof), heptene (and all isomers thereof), and octene (and all isomers
thereof). Advantageous monomers include propylene, 1-butene, 1-hexene, 1-octene, cyclohexene, cyclooctene, hexa-
diene, cyclohexadiene and the like.
[0236] In another embodiment of the processes disclosed herein, the comonomer comprises one or more of any C2
25 to C40 linear, branched or cyclic alpha-olefins (provided ethylene, if present, is present at 5 mole% or less), including
ethylene, propylene, butene, pentene, hexene, heptene, and octene, nonene, decene, undecene, dodecene, hexa-
decene, butadiene, hexadiene, heptadiene, pentadiene, octadiene, nonadiene, decadiene, dodecadiene, styrene, 3,5,5-
trimethylhexene-1, 3-methylpentene-1, 4-methylpentene-1, cyclopentadiene, and cyclohexene.
[0237] In another embodiment of the processes disclosed herein, the termonomer comprises one or more of any C2
30 to C40 linear, branched or cyclic alpha-olefins, (provided ethylene, if present, is present at 5 mole% or less), including
ethylene, propylene, butene, pentene, hexene, heptene, and octene, nonene, decene, un-decene, dodecene, hexa-
decene, butadiene, hexadiene, heptadiene, pentadiene, octadiene, nonadiene, decadiene, dodecadiene, styrene, 3,5,5-
trimethyl-hexene-1, 3-methylpentene-1, 4-methylpentene-1, cyclopentadiene, and cyclohexene.
[0238] In another embodiment of the processes disclosed herein, the polymers described above further comprise one
35 or more dienes at up to 10 weight %, or at 0.00001 to 1.0 weight %, or at 0.002 to 0.5 weight %, or at 0.003 to 0.2 weight
%, based upon the total weight of the composition. In some embodiments 500 ppm or less of diene is added to the
combined feed of one or more polymerization trains, alternately 400 ppm or less, alternatively 300 ppm or less. In other
embodiments at least 50 ppm of diene is added to the combined feed of one or more polymerization trains, or 100 ppm
or more, or 150 ppm or more. In yet another embodiment the concentration of diene in the combined feed to the reactor
40 is between 50 wt ppm and 10,000 wt ppm.
[0239] In another embodiment of the processes disclosed herein, the processes used to produce propylene copolymers
with other monomer units, such as ethylene, other α-olefin, α-olefinic diolefin, or non-conjugated diolefin monomers, for
example C4-C40 olefins, C4-C20 diolefins, C4-C20 cyclic olefins, C8-C20 styrenic olefins. Other unsaturated monomers
besides those specifically described above may be copolymerized using the processes disclosed herein, for example,
45 styrene, alkyl-substituted styrene, ethylidene norbornene, norbornadiene, dicyclopentadiene, vinylcyclohexane, vinyl-
cyclohexene, acrylates, and other olefinically-unsaturated monomers, including other cyclic olefins, such as cyclopen-
tene, norbornene, and alkyl-substituted norbornenes. Copolymerization can also incorporate α-olefinic macromonomers
produced in-situ or added from another source. Some embodiments limit the copolymerization of α-olefinic macromon-
omers to macromonomers with 2000 or less mer units. U.S. Patent No. 6,300,451 discloses many useful comonomers.
50 That disclosure refers to comonomers as "a second monomer."
[0240] In another embodiment of the processes disclosed herein, when propylene copolymers are desired, the following
monomers can be copolymerized with propylene: ethylene, but-1-ene, hex-1-ene, 4-methylpent-1-ene, dicyclopentadi-
ene, norbornene, C4-C2000, C4-C200, or C4-C40 linear or branched, α,ω-dienes; C4-C2000, C4-C200, or C4-C40 cyclic
olefins; and C4-C2000, C4-C200, or C4-C40 linear or branched α-olefins.
55
Other Primary Monomer:

[0241] The polymerization processes disclosed herein may polymerize butene-1 (Tc = 146.5˚C; Pc = 3.56 MPa),

40
 EP 2 195 349 B1

pentene-1 (Tc = 191.8˚C; Pc = 3.56 MPa), hexene-1 (Tc = 230.8˚C; Pc = 3.21 MPa), 3-methyl-butene-1 (Tc = 179.7˚C;
Pc = 3.53 MPa), and 4-methyl-pentene-1 using these monomers or mixtures comprising the monomers at supercritical
conditions or as a liquid. These processes may employ at least one of butene-1, pentene-1, or 3-methyl-butene-1 as
monomer. These processes may also employ reaction media that comprise butene-1, pentene-1, 3-methyl-butene-1 or
5 4-methyl-pentene-1. These processes can employ polymerization feeds that contain greater than 50 mole % of butene-
1, pentene-1, or 3-methyl-butene-1 and their concentration can vary between 0.1 and 85 mole %. Of course, these
compounds can be freely mixed with each other and with propylene as monomer, bulk reaction media, or both.

Reaction Solvents/Diluents:
10
[0242] Solvent and or diluent may be present in the polymerization system. Any hydrocarbon, fluorocarbon, or fluor-
ohydrocarbon inert solvent or their mixtures may be used at concentrations not more than 80 wt % in the feeds to any
individual polymerization reactor of the in-line blending process disclosed herein. The concentration of the inert solvent
in the reactor feed and thus in the polymerization system in certain embodiments utilizing bulk polymerization processes
15 is not more than 40 wt %, or not more than 30 wt %, or not more than 20 wt %, alternatively not more than 10 wt %,
alternatively not more than 5 wt %, and alternatively not more than 1 wt %.
[0243] Diluents for use in the in-line blending process disclosed herein may include one or more of C2-C24 alkanes,
such as ethane, propane, n-butane, i-butane, n-pentane, i-pentane, n-hexane, mixed hexanes, cyclopentane, cyclohex-
ane, etc., single-ring aromatics, such as toluene and xylenes. In some embodiments, the diluent comprises one or more
20 of ethane, propane, butane, isobutane, pentane, isopentane, and hexanes. In other embodiments, the diluent is recy-
clable.
[0244] Other diluents may also include C4 to C150 isoparaffins, or C4 to C100 isoparaffins, or C4 to C25 isoparaffins,
or C4 to C20 isoparaffins. By isoparaffin is meant that the paraffin chains possess C1 to C10 alkyl branching along at
least a portion of each paraffin chain. More particularly, the isoparaffins are saturated aliphatic hydrocarbons whose
25 molecules have at least one carbon atom bonded to at least three other carbon atoms or at least one side chain (i.e.,
a molecule having one or more tertiary or quaternary carbon atoms), and advantageously wherein the total number of
carbon atoms per molecule is in the range between 6 to 50, and between 10 and 24 in another embodiment, and from
10 to 15 in yet another embodiment. Various isomers of each carbon number will typically be present. The isoparaffins
may also include cycloparaffins with branched side chains, generally as a minor component of the isoparaffin. The
30 density of these isoparaffins may range from 0.70 to 0.83 g/cm3; the pour point is -40˚C or less, alternately -50˚C or
less, the kinematic viscosity at 25˚C is from 0.5 to 20 cSt; and number-averaged molecular weight (Mn) in the range of
100 to 300 g/mol. Some suitable isoparaffins are commercially available under the tradename ISOPAR (ExxonMobil
Chemical Company, Houston TX), and are described in, for example in US Patent Nos. 6,197,285, 3,818,105 and
3,439,088, and sold commercially as ISOPAR series of isoparaffms. Other suitable isoparaffins are also commercial
35 available under the trade names SHELLSOL, SOLTROL and SASOL. SHELLSOL is a product of the Royal Dutch/Shell
Group of Companies, for example Shellsol TM (boiling point = 215-260˚C). SOLTROL is a product of Chevron Phillips
Chemical Co. LP, for example SOLTROL 220 (boiling point = 233-280˚C). SASOL is a product of Sasol Limited (Johan-
nesburg, South Africa), for example SASOL LPA-210, SASOL-47 (boiling point = 238-274˚C).
[0245] In another embodiment of the in-line blending process disclosed herein, diluents may include C4 to C25 n-
40 paraffins, or C4 to C20 n-paraffins, or C4 to C15 n-paraffins having less than 0.1%, or less than 0.01% aromatics. Some
suitable n-paraffins are commercially available under the tradename NORPAR (ExxonMobil Chemical Company, Hou-
ston TX), and are sold commercially as NORPAR series of n-paraffins. In another embodiment, diluents may include
dearomaticized aliphatic hydrocarbon comprising a mixture of normal paraffins, isoparaffins and cycloparaffins. Typically
they are a mixture of C4 to C25 normal paraffins, isoparaffins and cycloparaffins, or C5 to C18, or C5 to C12. hey contain
45 very low levels of aromatic hydrocarbons, or less than 0.1, or less than 0.01 aromatics. Suitable dearomatized aliphatic
hydrocarbons are commercially available under the tradename EXXSOL (ExxonMobil Chemical Company, Houston
TX), and are sold commercially as EXXSOL series of dearomaticized aliphatic hydrocarbons.
[0246] In another embodiment of the in-line blending process disclosed herein, the inert diluent comprises up to 20
weight % of oligomers of C6 to C14 olefins and/or oligomers of linear olefins having 6 to 14 carbon atoms, or 8 to 12
50 carbon atoms, or 10 carbon atoms having a Kinematic viscosity at 100˚C of 2 cSt or more, or 4 cSt or more, or 6 cSt or
more, or 8 cSt or more, or 10 cSt or more.
[0247] In another embodiment of the fluid phase in-line process for blending disclosed herein, the inert diluent comprises
up to 20 weight % of oligomers of C20 to C1500 paraffins, alternately C40 to C1000 paraffins, alternately C50 to C750
paraffins, alternately C50 to C500 paraffins. In another embodiment of the fluid phase in-line process for blending disclosed
55 herein, the diluent comprises up to 20 weight % of oligomers of 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene,
1-decene, 1-undecene and 1-dodecene. Such oligomers are commercially available SpectraSyn (ExxonMobil Chemical
Company, Houston TX). Other useful oligomers include those sold under the tradenames Synfluid™ available from
ChevronPhillips Chemical Co. in Pasedena Texas, Durasyn™ available from Ineos in London England, Nexbase™

41
 EP 2 195 349 B1

available from Fortum Oil and Gas in Finland, Synton™ available from Chemtura Corporation in Middlebury CT, USA,
EMERY™ available from Chemtura in Ohio, USA.
[0248] In another embodiment of the fluid phase in-line process for blending disclosed herein, the diluent comprises
a flourinated hydrocarbon. Exemplary fluorocarbons include perfluorocarbons ("PFC" or "PFC’s") and or hydrofluoro-
5 carbons ("HFC" or "HFC’s"), collectively referred to as "fluorinated hydrocarbons" or "fluorocarbons" ("FC" or "FC’s").
Fluorocarbons are defined to be compounds consisting essentially of at least one carbon atom and at least one fluorine
atom, and optionally hydrogen atom(s). A perfluorocarbon is a compound consisting essentially of carbon atom and
fluorine atom, and includes for example linear branched or cyclic, C1 to C40 perfluoroalkanes. A hydrofluorocarbon is a
compound consisting essentially of carbon, fluorine and hydrogen. FC’s include those represented by the formula:
10 CxHyFz wherein x is an integer from 1 to 40, alternatively from 1 to 30, alternatively from 1 to 20, alternatively from 1 to
10, alternatively from 1 to 6, alternatively from 2 to 20 alternatively from 3 to 10, alternatively from 3 to 6, alternatively
from 1 to 3, wherein y is an integer greater than or equal to 0 and z is an integer and at least one, alternatively, y and
z are integers and at least one. For purposes of the in-line blending processes disclosed herein and the claims thereto,
the terms hydrofluorocarbon and fluorocarbon do not include chlorofluorocarbons.
15 [0249] In one embodiment of the fluid phase in-line process for blending disclosed herein, a mixture of fluorocarbons
are used, alternatively a mixture of a perfluorinated hydrocarbon and a hydrofluorocarbon, and alternatively a mixture
of a hydrofluorocarbons. In yet another embodiment, the hydrofluorocarbon is balanced or unbalanced in the number
of fluorine atoms in the HFC used.
[0250] With regard to the polymerization media, suitable diluents and solvents are those that are soluble in and inert
20 to the monomer and any other polymerization components at the polymerization temperatures and pressures.

Reactor configuration:

[0251] The polymer and plasticizer reaction processes of the fluid phase in-line process for blending disclosed herein
25 may be carried out in two or more reactors making the polymers and plasticizers for downstream blending. The reactors
may be fed with essentially the same or different feeds and can run at essentially the same or different reactor conditions.
The reactors may also produce essentially the same or different polymeric products.
[0252] When multiple reactors are used in the processes disclosed herein, the production of plasticized polymer blends
including two or more polymers is possible. In one embodiment, homopolymer and copolymer blends are made by using
30 at least two reactor trains in a parallel configuration. Non-limiting exemplary homopolymers include polyethylene, poly-
propylene, polybutene, polyhexene, and polyoctane. In one embodiment, the homopolymer comprises polyethylene,
polypropylene, polybutylene, polyhexene, and polystyrene. In another embodiment, the homopolymer is polyethylene
or polypropylene. The copolymers may be any two- or three-component combinations of ethylene, propylene, butene-
1, hexene-1, octene-1, styrene, norbomene, 1,5-hexadiene, and 1,7-octadiene. In one embodiment, the copolymers are
35 made from a two-component combination of ethylene, propylene, butene-1, hexene-1, styrene, norbomene, 1,5-hexa-
diene, and 1,7-octadiene. In another embodiment, the copolymer is an ethylene-propylene, propylene-butene-1, pro-
pylene-hexene-1, propylene-octene-1, ethylene-butene-1, ethylene-hexene-1, and/or ethylene-octene- 1 copolymer.
[0253] As previously described, the in-line blending polymer components are produced in a reactor bank composed
of at least two parallel reactor trains. A reactor train of the parallel reactor bank may include one or more reactors that
40 may be configured in series configuration. The number of parallel reactors trains or branches in a parallel bank may be
any number, but for practical reasons, is generally limited to less than ten, alternatively not more than six parallel reactor
trains, alternatively not more than five or not more than four reactor trains, alternatively not more than three parallel
reactor trains, and alternatively not more than two parallel reactor trains. The number of series cascade reactors con-
stituting a given reactor train or branch of a parallel configuration may be any number, but for practical reasons, is
45 generally limited to not more than ten reactors in series, alternatively not more than six reactors in series, alternatively
not more than three reactors in series, and alternatively not more than two reactors in series.
[0254] In one embodiment, the base polymer containing effluent and plasticizer-containing effluent from two or more
reactor trains configured in a parallel configuration are combined yielding a plasticized polymer blend comprising the
base polymer and plasticizer products of the individual reactors without first recovering the base polymer and plasticizer
50 products of the individual reactors in solid or liquid forms. The two or more reactor trains constituting the parallel con-
figuration generally include a single reactor, or alternatively, two or more reactors in series.
[0255] Another embodiment of the processes disclosed herein, blends the base polymer containing effluent with one
or more in-line-produced plasticizer and optionally one or more off-line-produced plasticizers in-line. The base polymer
is blended in the form of a diluted effluent stream that contains at least some of the light components of the reactor
55 effluent, such as the monomers and optional inert solvent/diluents. Such streams are advantageous for in-line blending
due to their lower viscosity and thus enhanced ability for fluid phase blending. However, unlike in the previously described
embodiment, the in-line-produced plasticizer is blended as a fully recovered plasticizer fluid, i.e, in its essentially pure
form. The full recovery of the in-line-produced plasticizer may be advantageous when the plasticizer is a liquid at ambient

42
 EP 2 195 349 B1

temperature, and/or when some of the in-line-produced plasticizer product is exported from the in-line blending process
for sales or for other uses. The base polymer and in-line-produced plasticizer components are produced in two or more
parallel reactor trains. The reactor trains constituting the parallel configuration generally include a single reactor, or
alternatively, two or more reactors in series.
5 [0256] The reactors of the polymerization system for the fluid phase in-line process for blending disclosed herein may
be stirred or unstirred. When a reactor train comprises two or more reactors, the members of the reactor train are not
necessarily constructed the same way, for example, the individual members of a reactor train may be stirred, unstirred,
or a combination thereof. The individual reactors may also be of equal or different size. The same is true for the reactors
in the entire reactor bank. The optimal reactor configuration and sizes may be determined by standard engineering
10 techniques known to those skilled in the art of chemical engineering.
[0257] Any type of reactor may be deployed in the fluid phase in-line process for blending disclosed herein. The optimal
reactor design may be determined by standard engineering techniques known to those skilled in the art of chemical
engineering. Non-limiting exemplary reactor designs include stirred tank with or without an external loop, tubular reactor,
and loop reactor. The reactors may operate adiabatically or may be cooled. The cooling may be achieved within the
15 reactor, or through the reactor jacket, or dedicated heat exchange loops may be applied.

Reaction Process Details:

[0258] The fluid phase in-line process for blending disclosed herein relates to processes to polymerize or oligomerize
20 olefins comprising contacting one or more olefins having at least two carbon atoms with a suitable catalyst compound
and an activator in a fluid reaction medium comprising one or two fluid phases in a reactor. Polymerization in a single
fluid phase may be advantageous due to improved heat transfer and reduced tendency for fouling. In one embodiment,
the fluid reaction medium is in its supercritical state. Catalyst compound and activator may be delivered as a solution
or slurry, either separately to the reactor, mixed in-line just prior to the reactor, or mixed and pumped as an activated
25 solution or slurry to the reactor. In one particular embodiment, two solutions are mixed in-line. For a given reactor train
of the parallel configuration, polymerizations may be carried out in either single reactor operation, in which monomer,
comonomers, catalyst(s)/activator(s), scavenger(s), and optional solvent(s) are added continuously to a single reactor
or in series reactor operation, in which the above components are added to two or more reactors connected in series.
The catalyst components may be added to the first reactor in the series. The catalyst component may also be added to
30 each reactor in the series reactor train. The fresh catalyst feed if added to more than one reactor in the series train may
be the same or different to each reactor and their feed rates may be the same or different.
[0259] Some embodiments of the polymerization processes of the fluid phase in-line process for blending disclosed
herein also comprehend high-pressure reactors where the reactor is substantially unreactive with the polymerization
reaction components and is able to withstand the high pressures and temperatures that occur during the polymerization
35 reaction. Withstanding these high pressures and temperatures may allow the reactor to maintain the fluid reaction
medium in its supercritical condition. Suitable reaction vessel designs include those necessary to maintain supercritical
or other high-pressure ethylene polymerization reactions. Non-limiting exemplary reactors include autoclave, pump-
around loop or autoclave, tubular, and autoclave/tubular reactors.
[0260] The polymerization processes of the fluid phase in-line process for blending disclosed herein may operate
40 efficiently in autoclave (also referred to as stirred tank) and tubular reactors. Autoclave reactors may be operated in
either a batch or continuous mode, although the continuous mode is advantageous. Tubular reactors always operate
in continuous mode. Typically, autoclave reactors have length-to-diameter ratios of 1:1 to 20:1 and are fitted with a high-
speed (up to 2000 RPM) multiblade stirrer and baffles arranged for optimal mixing. Commercial autoclave pressures
are typically greater than 5 MPa with a maximum of typically less than 260 MPa. The maximum pressure of commercial
45 autoclaves, however, may become higher with advances in mechanical and material science technologies.
[0261] When the autoclave has a low length-to-diameter ratio (such as less than four), the feed streams may be
injected at one position along the length of the reactor. Reactors with large diameters may have multiple injection ports
at nearly the same or different positions along the length of the reactor. When they are positioned at the same length
of the reactor, the injection ports are radially distributed to allow for faster intermixing of the feed components with the
50 reactor content. In the case of stirred tank reactors, the separate introduction of the catalyst and monomer(s) may be
advantageous in preventing the possible formation of hot spots in the unstirred feed zone between the mixing point and
the stirred zone of the reactor. Injections at two or more positions along the length of the reactor is also possible and
may be advantageous. In one exemplary embodiment, in reactors where the length-to-diameter ratio is from 4 to 20,
the reactor may contain up to six different injection positions along the reactor length with multiple ports at some or each
55 of the lengths.
[0262] Additionally, in the larger autoclaves, one or more lateral mixing devices may support the high-speed stirrer.
These mixing devices can also divide the autoclave into two or more zones. Mixing blades on the stirrer may differ from
zone to zone to allow for a different degree of plug flow and back mixing, largely independently, in the separate zones.

43
 EP 2 195 349 B1

Two or more autoclaves with one or more zones may connect in a series reactor cascade to increase residence time
or to tailor polymer structure in a reactor train producing a polymer blending component. As previously described, a
series reactor cascade or configuration consists of two or more reactors connected in series, in which the effluent of at
least one upstream reactor is fed to the next reactor downstream in the cascade. Besides the effluent of the upstream
5 reactor(s), the feed of any reactor in the series reactor cascade of a reactor train can be augmented with any combination
of additional monomer, catalyst, or solvent fresh or recycled feed streams. Therefore, it should be understood that the
polymer blending component leaving a reactor train of the process disclosed herein may itself be a blend of the same
polymer with increased molecular weight and/or compositional dispersion or even a blend of homo- and copolymers.
[0263] Tubular reactors may also be used in the fluid phase in-line process for blending disclosed herein and more
10 particularly tubular reactors capable of operating up to about 350 MPa. Tubular reactors are fitted with external cooling
and one or more injection points along the (tubular) reaction zone. As in autoclaves, these injection points serve as entry
points for monomers (such as propylene), one or more comonomer, catalyst, or mixtures of these. In tubular reactors,
external cooling often allows for increased monomer conversion relative to an autoclave, where the low surface-to-
volume ratio hinders any significant heat removal. Tubular reactors have a special outlet valve that can send a pressure
15 shockwave backward along the tube. The shockwave helps dislodge any polymer residue that has formed on reactor
walls during operation. Alternatively, tubular reactors may be fabricated with smooth, unpolished internal surfaces to
address wall deposits. Tubular reactors generally may operate at pressures of up to 360 MPa, may have lengths of
100-2000 meters or 100-4000 meters, and may have internal diameters of less than 12.5 cm. Typically, tubular reactors
have length-to-diameter ratios of 10:1 to 50,000:1 and include up to 10 different injection positions along its length.
20 [0264] Reactor trains that pair autoclaves with tubular reactors are also contemplated within the scope of the fluid
phase in-line process for blending disclosed herein. In this reactor system, the autoclave typically precedes the tubular
reactor or the two types of reactors form separate trains of a parallel reactor configuration. Such reactor systems may
have injection of additional catalyst and/or feed components at several points in the autoclave, and more particularly
along the tube length. In both autoclaves and tubular reactors, at injection, feeds are typically cooled to near ambient
25 temperature or below to provide maximum cooling and thus maximum polymer production within the limits of maximum
operating temperature. In autoclave operation, a preheater may operate at startup, but not after the reaction reaches
steady state if the first mixing zone has some back-mixing characteristics. In tubular reactors, the first section of double-
jacketed tubing may be heated (especially at start ups) rather than cooled and may operate continuously. A well-designed
tubular reactor is characterized by plug flow wherein plug flow refers to a flow pattern with minimal radial flow rate
30 differences. In both multizone autoclaves and tubular reactors, catalyst can not only be injected at the inlet, but also
optionally at one or more points along the reactor. The catalyst feeds injected at the inlet and other injection points can
be the same or different in terms of content, density, and concentration. Catalyst feed selection allows polymer design
tailoring within a given reactor or reactor train and/or maintaining the desired productivity profile along the reactor length.
[0265] At the reactor outlet valve, the pressure drops to begin the separation of polymer and unreacted monomer,
35 co-monomers, solvents and inerts, such as for example ethane, propane, hexane, and toluene. More particularly, at the
reactor outlet valve, the pressure drops to levels below that which critical phase separation allowing for a polymer-rich
phase and a polymer-lean phase in the downstream separation vessel. Typically, conditions remain above the polymer
product’s crystallization temperature. The autoclave or tubular reactor effluent may be depressurized on entering the
downstream high-pressure separator (HPS or also referred to as a separator, separator vessel, separation vessel,
40 separator/blender vessel, or separation/blending vessel).
[0266] As will be subsequently described in detail, the temperature in the separation vessel is maintained above the
solid-fluid phase separation temperature, but the pressure may be below the critical point. The pressure need only be
high enough such that the monomer may condense upon contacting standard cooling water. The liquid recycle stream
may then be recycled to the reactor with a liquid pumping system instead of the hyper-compressors required for poly-
45 ethylene units. The relatively low pressure in separator reduces the monomer concentration in the liquid polymer phase
which results in a lower polymerization rate. The polymerization rate may be low enough to operate the system without
adding a catalyst poison or "killer". If a catalyst killer is required (e.g., to prevent reactions in the high pressure recycle)
then provision must be made to remove any potential catalyst poisons from the recycled polymer rich monomer stream
for example, by the use of fixed bed adsorbents or by scavenging with an aluminum alkyl.
50 [0267] In an alternative embodiment, the HPS may be operated over the critical pressure of the monomer or monomer
blend but within the dense fluid-fluid two phase region, which may be advantageous if the polymer is to be produced
with a revamped high-pressure polyethylene (HPPE) plant. The recycled HPS overhead is cooled and dewaxed before
being returned to the suction of the secondary compressor, which is typical of HPPE plant operation. The polymer from
this intermediate or high-pressure vessel then passes through another pressure reduction step to a low pressure sep-
55 arator. The temperature of this vessel is maintained above the polymer melting point so that the polymer from this vessel
can be fed as a liquid directly to an extruder or static mixer. The pressure in this vessel is kept low by using a compressor
to recover the unreacted monomers, etc. to the condenser and pumping system referenced above.
[0268] In addition to autoclave reactors, tubular reactors, or a combination of these reactors, loop-type reactors may be

44
 EP 2 195 349 B1

utilized in the fluid phase in-line process for blending disclosed herein. In this reactor type, monomer enters and polymer
exits continuously at different points along the loop, while an in-line pump continuously circulates the contents (reaction
liquid). The feed/product takeoff rates control the total average residence time. A cooling jacket removes reaction heat
from the loop. Typically feed inlet temperatures are near to or below ambient temperatures to provide cooling to the
5 exothermic reaction in the reactor operating above the crystallization temperature of the polymer product. The loop reactor
may have a diameter of 41 to 61 cm and a length of 100 to 200 meters and may operate at pressures of 25 to 30 MPa.
In addition, an in-line pump may continuously circulate the polymerization system through the loop reactor.
[0269] The polymerization processes of the fluid phase in-line process for blending polymers disclosed herein may
have residence times in the reactors as short as 0.5 seconds and as long as several hours, alternatively from 1 sec to
10 120 min, alternatively from 1 second to 60 minutes, alternatively from 5 seconds to 30 minutes, alternatively from 30
seconds to 30 minutes, alternatively from 1 minute to 60 minutes, and alternatively from 1 minute to 30 minutes. More
particularly, the residence time may be selected from 10, or 30, or 45, or 50, seconds, or 1, or 5, or 10, or 15, or 20, or
25, or 30 or 60 or 120 minutes. Maximum residence times may be selected from 1, or 5, or 10, or 15, or 30, or 45, or
60, or 120 minutes.
15 [0270] The monomer-to-polymer conversion rate (also referred to as the conversion rate) is calculated by dividing the
total quantity of polymer that is collected during the reaction time by the amount of monomer added to the reaction.
Lower conversions may be advantageous to limit viscosity although increase the cost of monomer recycle. The optimum
total monomer conversion thus will depend on reactor design, product slate, process configuration, etc., and can be
determined by standard engineering techniques. Total monomer conversion during a single pass through any individual
20 reactor of the fluid phase in-line process for blending disclosed herein may be up to 90%, or below 80%, or below 60%
or 3-80% , or 5-80%, or 10-80%, or 15-80%, or 20-80%, or 25-60%, or 3-60%, or 5-60%, or 10-60%, or 15-60%, or
20-60%, or 10-50%, or 5-40%, or 10-40%, or 40-50%, or 15-40%, or 20-40%, or 30-40% or greater than 5%, or greater
than 10%. In one embodiment, when the product is isotactic polypropylene and long-chain branching (LCB) of the
polypropylene is desired (g’ ≤ 0.97 based on GPC-3D and using an isotactic polypropylene standard), single pass
25 conversions may be above 30% and alternatively single-pass conversions may be above 40%. In another embodiment,
when isotactic polypropylene essentially free of LCB is desired (0.97 < g’ < 1.05), single-pass conversions may be not
higher than 30% and alternatively single-pass-conversions may be not higher than 25%. To limit the cost of monomer
separation and recycling, single-pass conversions may be above 3%, or above 5%, or above 10%. It should be understood
that the above exemplary conversion values reflect total monomer conversion, i.e., the conversion obtained by dividing
30 the combined conversion rate of all monomers by the total monomer feed rate. When monomer blends are used, the
conversion of the more reactive monomer component(s) will always be higher than that of the less reactive monomer
(s). Therefore, the conversion of the more reactive monomer component(s) can be substantially higher than the total
conversion values given above, and can be essentially complete, approaching 100%.

35 Product Separation and Downstream Processing:

[0271] The base polymer and the optionally in-line-produced plasticizer reactor effluents of the processes disclosed
herein are depressurized to a pressure significantly below the cloud point pressure. This allows separation of a polymer-
rich phase for further purification and a monomer-rich phase for optional separation and recycle compression back to
40 the reactor(s). The base polymer and the optional plasticizer reactor effluents may be optionally heated before pressure
let down to avoid the separation of a solid polymer phase, which causes fouling of the separators and associated reduced-
pressure lines. The blending of the base polymer and optional in-line-produced plasticizer containing streams and the
separation of the plasticized polymer-rich phase and the monomer-rich phase in the processes disclosed herein is
carried out in a vessel known as a high-pressure separator (also referred to as an HPS, separator, separator vessel, or
45 separation vessel). The high-pressure separator located after the mixing point of the polymer-containing product streams
and plasticizer-containing product streams of all reactor trains of the parallel reactor bank is also referred to as, separator-
blender, separator-blender vessel, or separation-blending vessel recognizing its dual function of blending the said pol-
ymer-containing and plasticizer-containing product streams while also separating a monomer-rich phase and solvent-
rich phase from a plasticized polymer-rich phase, the latter of which comprises the plasticized polymer blend of the in-
50 line blending processes disclosed herein.
[0272] In certain embodiments, single-stream high-pressure separators employed to partially recover the monomer
(s) and optional solvent(s) from the effluent of a single reactor train before sending the polymer-enriched stream and
plasticizer-enriched stream to the downstream separator-blender. In such embodiments, the separator-blender blends
one or more base polymer-enriched stream optionally (as in options (1) and (2) of the process examples described
55 earlier) with one or more unreduced plasticizer reactor train effluent to yield a monomer-rich phase and a plasticized
polymer-rich phase, the latter of which comprises the plasticized polymer blend of the in-line blending process disclosed
herein. In another embodiment, the single-stream high-pressure separator placed upstream of the separator-blender
also functions as a buffer vessel (separator-buffer vessel) by allowing the fluid level of the polymer-enriched phase or

45
 EP 2 195 349 B1

plasticizer-enriched phase to vary in the separator-buffer vessel. Such buffering enables a more precise control of the
blend ratios by compensating for the momentary fluctuations in the production rates in the individual reactor trains of
the in-line blending process disclosed herein.
[0273] The plasticized polymer rich phase of the separator-blender may then be transferred to one or more low-
5 pressure separators (LPS also referred to as a low-pressure separation vessel) running at just above atmospheric
pressure for a simple flash of light components, reactants and oligomers thereof, for producing a low volatile-containing
polymer melt entering the finishing extruder or optional static mixer. The one or more low-pressure separators are
distinguished from the one or more high-pressure separators in generally operating at lower pressures relative to the
high-pressure separators. The one or more low-pressure separators also are located downstream of the one or more
10 high-pressure separators including the separator-blender. In some embodiments of the processes described herein,
the plasticized polyolefin-containing stream are mixed with the optional off-line-produced plasticizer and/or other polymer
additive feeds upstream of or in the low-pressure separator. As previously stated, a high-pressure separator may be
alternatively referred to herein as an HPS, separator, separator vessel, separation vessel, separator-blender vessel, or
separation-blending vessel, or separator-blender even if some blend components are introduced in the low-pressure
15 separator section of the in-line blending processes disclosed herein. The use of the term "pressure" in conjunction with
low-pressure separator and high-pressure separator is not meant to identify the absolute pressure levels at which these
separators operate at, but is merely intended to given the relative difference in pressure at which these separators
operate. Generally, separators located downstream in the in-line blending processes disclosed herein operate at lower
pressure relative to separators located upstream.
20 [0274] In one embodiment of the fluid phase in-line process for blending polymers disclosed herein, polymerization
is conducted in two or more reactors of a type described herein above under agitation and above the cloud point for the
polymerization system. Then, the polymer-monomer mixtures are transferred into a high-pressure separation-blending
vessel, where the pressure is allowed to drop below the cloud point. This advantageously results in the denser, polymer-
rich phase separating from the lighter monomer-rich phase. As may be appreciated by those skilled in the art, it may
25 optionally be necessary to increase the temperature before or in the high-pressure separation vessel to prevent the
formation of a solid polymer phase as the polymer becomes more concentrated. The monomer-rich phase is then
separated and recycled to the reactors while the polymer-rich phase is fed to a coupled devolatilizer - such as a LIST
dryer (DTB) or devolatizing extruder.
[0275] The recycle runs through a separator, where the pressure depends on the pressure-temperature relationship
30 existing within the reactor. For example, supercritical propylene polymerization can be carried out under agitation in the
single-phase region in the reactor at 40-200 MPa and 95-180˚C (see FIG. 23). The product mixture can be discharged
into a separator vessel, where the pressure is dropped to a level of 25 MPa or lower, in which case, the mixture is below
its cloud point, while the monomer has not yet flashed off (again, see FIG. 23). Under such conditions, it would be
expected from Radosz et al., Ind. Eng. Chem. Res. 1997, 36, 5520-5525 and Loos et al., Fluid Phase Equil. 158-160,
35 1999, 835-846 that the monomer-rich phase would comprise less than about 0.1 wt % of low molecular weight polymer
and have a density of approximately 0.3-0.7 g/mL (see FIG. 24). The polymer-rich phase would be expected to have a
density of approximately 0.4-0.8 g/mL.
[0276] Assuming that the pressure is dropped rapidly enough, for example, greater than or equal to about 6 MPa/sec,
the phases will separate rapidly, permitting the recycle of the monomer-rich phase as a liquid, without the issue of having
40 the monomer-rich phase return to the gas phase. As may be appreciated by those skilled in the art, this eliminates the
need for the energy-intensive compression and condensation steps.
[0277] The plasticized polymer-rich phase is sent directly to a coupled devolatilizer. Suitable devolatilizers may be
obtained, for example, from LIST USA Inc., of Charlotte, North Carolina. The devolatilization is a separation process to
separate remaining volatiles from the final plasticized polymer, eliminating the need for steam stripping. Working under
45 low vacuum, the polymer solution flashes into the devolatilizer, exits the unit and is then transferred on for further
processing, such as pelletization.
[0278] Any low or very low molecular weight polymer present in the monomer-rich phase to be recycled may optionally
be removed through "knock-out" pots, standard hardware in reactors systems, or left in the return stream depending
upon product requirements and the steady-state concentration of the low molecular weight polymer fraction in the product.
50 [0279] In solution reactor processes, present practices employed by those skilled in the art typically effect separation
by flashing monomer and solvent or accessing the high-temperature cloud point.
[0280] In another form, polymerization is conducted at conditions below the cloud point, with the polymer-monomer
mixture transported to a gravimetric separation vessel, where the pressure could be further lowered if desired to enhance
phase separation of the polymer-rich and monomer-rich phases. In either of the forms herein described, the monomer,
55 for example, propylene, is recycled while staying in a relatively high density, liquid-like (dense supercritical fluid or bulk
liquid) state. Once again, one or more knock-out pots may be employed to aid in the removal of low molecular weight
polymer from the recycle stream.
[0281] As may be appreciated, there are possible and optimal operating regimes for the polymer blend and plasticizer

46
 EP 2 195 349 B1

blend component reactors and for the gravity (lower critical solution temperature (LCST)) separator. Referring now to
FIG. 25, for reactors operating in a single liquid phase regime, a possible region for operation is just above the LCST
and vapor pressure (VP) curves. The optimal region (shown within the shaded oval) for operation occurs at temperatures
just above the lower critical end point (LCEP) and at pressures slightly above the LCST curve.
5 [0282] Referring now to FIG. 26, for reactors operating within a two-phase fluid-fluid regime, the possible region for
operation occurs basically anywhere below the LCST curve. The optimal region (again, shown within the shaded oval)
occurs just below the LCST and above the VP curve, although, as may be appreciated, many factors could have a
bearing on what actually is optimal, such as the final properties of the desired product. As recognized by those skilled
in the art, the two-phase liquid-liquid regime is the economically advantageous method if polypropylene is to be produced
10 with a revamped HPPE plant.
[0283] Referring now to FIG. 27, for the case where polymerization is conducted at conditions below the cloud point
and the polymer-monomer mixture transported to a gravimetric LCST separator, the possible region of operation is
anywhere below the LCST curve and above the VP curve. The optimal region (again, shown within the shaded oval)
occurs within that portion that is below the spinodal, but not too low in pressure, as shown. Operating in this regime
15 assures that the energy use is optimized. It is also desirable to avoid operation in the region between the LCST and
spinodal curves in order to obtain good gravity settling performance. Moreover, it is desirable that the separation is
effected at sufficiently high temperatures, so that crystallization does not occur in the polymer-rich phase. This may
require that the temperature of the mixture in the separator be higher than the temperature in the reactor(s).
[0284] Advantageously, the liquid monomer-rich recycle stream can be recycled to the reactor using a liquid pumping
20 system instead of a hyper-compressor, required for conventional polyethylene units.
[0285] In another embodiment of the invention, polymerization is as described in WO2004/026921, and with the
pressure above the cloud point pressure for the polymerization medium. The polymerization medium is continuously
transferred without heating to a pressure reducing device (which may be a letdown valve), where the pressure is reduced
below the cloud point pressure. This advantageously results in the formation of a denser, polymer-rich phase and a less
25 dense monomer-rich phase, which are then transferred to a fluid-liquid separation vessel called a High Pressure Separator
(HPS), where the monomer-rich phase and polymer-rich phase form and separate into two layers via gravity settling.
[0286] In another embodiment, it may be necessary to increase the temperature of the polymerization medium by a
heating device located upstream of the pressure reducing device (letdown valve) to prevent a solid-liquid phase transition
(crystallization) of the polymer-rich phase in the HPS, which could occur as the polymer oncentration increases, or to
30 allow operation of the HPS at a higher pressure and thereby avoid full or partial vaporization of the monomer-rich phase.
The monomer-rich phase is then recycled from the top of the HPS to the reactor while the polymer-rich phase is fed to
optional low-pressure phase separators (LPS) placed downstream of the first phase separator, and ultimately to a
coupled devolatilizer - such as a LIST dryer (DTB) or devolatizing extruder. The operating pressures of the separators
are decreasing in the separator cascade causing the polymer-rich phase in a downstream separator to become more
35 concentrated in the the polymer and depleted in the light components of the polymerization system such as monomers
and optional inert solvents diluents as compared to the corresponding phase concentrations upstream.

Phase Separation Temperature:

40 [0287] In all embodiments of the current invention, the optional heating of the polymerization medium upstream of the
pressure letdown device is minimized within the constraints imposed by the phase diagram for the polymerization
medium. For efficient phase separation, the temperature of the polymerization medium at the entrance to the pressure
reducing device (letdown valve) must be high enough to prevent a solid-liquid phase separation from taking place
upstream of, or inside, the fluid-liquid phase separation vessel (HPS). The efficient phase separation temperature must
45 also be high enough such that when the pressure is reduced across the pressure reducing device (letdown valve), that
there exists a pressure where an efficient separation of the polymerization medium into a monomer-rich phase and a
polymer-rich phase can occur at a high enough pressure to prevent full or partial vaporization of the monomer-rich
phase. The applicable operating range of temperatures and pressures that satisfy these criteria may be determined
from a T,P phase diagram of the polymerization medium of the type depicted in Fig. 29. Because heating of the polym-
50 erization medium increases investment costs (installation of heaters), and also increases operating cost (consumption
of a heating utility), the preferred embodiments of the process generally employ no heating if the polymerization system
is already operating at a temperature that exceeds the efficient phase seapration temperature criteria. Alternatively,
embodiments where the polymerization medium is at a temperature lower than that required to satisfty the efficient
phase separation criteria will employ minimal heating to raise the temperature at the inlet of the pressure reducing device
55 (letdown valve) to 0-100˚C, or 5-50˚C, or 10-30˚C above minimum required temperature for efficient phase separation.
[0288] In consideration of the efficient phase separation temperature criteria, the process of the current invention can
be carried out at the following temperatures. In one embodiment, the temperature of the polymerization system is above
the solid-fluid phase transition temperature of the polymer-containing fluid reaction medium at the reactor pressure,

47
 EP 2 195 349 B1

preferably at least 5˚C above the solid-fluid phase transition temperature of the polymer-containing fluid reaction medium
at the reactor pressure, more preferably, at least 10˚C above the solid-fluid phase transformation point of the polymer-
containing fluid reaction medium at the reactor pressure. In another embodiment, the temperature is between 50 and
350˚C, or between 60 and 250˚C, or between 70 and 200˚C, or between 80 and 180˚C, or between 90 and 160˚C, or
5 between 100 and 140˚C.

Spinodal Decomposition:

[0289] In preferred embodiments of the current invention, the pressure reducing device is designed to drop the pressure
10 rapidly enough, and to an optimal pressure, via the process of spinodal decomposition, which results in a phase mor-
phology of an interpenetrating network of the two phases (also called a co-continuous morphology), with the desirable
result that the polymer-rich and monomer-rich phases disengage easily and settle rapidly in the fluid-liquid gravity
separation vessel (HPS). Spinodal decomposition prevents the formation of a very slow disengaging and slow settling
mixture of monomer-rich and polymer-rich phases with a morophology that has droplets of monomer-rich phase dispersed
15 in a continuous polymer-rich phase, which tends to occur naturally when the polymer concentration in the fluid exceeds
a critical value, and when temperature and pressure in the phase separating vessel are in the region of the phase
diagram between the fluid-liquid phase boundary (binodal boundary) and the spinodal boundary as illustrated by the
cross-hatched area in Fig. 29. In the preferred embodiments of the current invention, the polymer concentration in the
polymerization medium is always higher than the critical concentration described above (and conceptually illustrated in
20 Fig. 28) and thus these embodiments utilize the process of spinodal decomposition to avoid gravity settling problems.
In one embodiment of the spinodal decomposition process for polymerization systems described in WO2004/026921,
the rate of pressure reduction across the pressure reducing device (letdown valve) is 1 MPa/sec or more, or 2 Mpa/sec
or more, or 4 MPa/sec or more, or 6 MPa/sec or more.

25 Phase Separation Pressure:

[0290] In all embodiments of the current invention, the pressure downstream of the pressure reducing device (letdown
valve) and inside the fluid-liquid phase separation vessel (HPS) is selected to be below the cloud point pressure to
ensure that a fluid-liquid phase separation will take place, but high enough to be above the vapor pressure of the
30 monomer-rich phase to prevent full or partial vaporization of the monomer-rich phase. In preferred embodiments, to
induce rapid phase separation and settling, the pressure in the fluid-liquid phase separation vessel (HPS) is lower than
the spinodal boundary pressure. Within this preferred pressure range, ie. below the spinodal boundary pressure and
above the vapor pressure of the monomer-rich phase, an operating pressure can be chosen that will prove to be most
economical. Higher pressures reduce the cost of pumping or compression of the monomer-rich phase for recycle, but
35 higher pressures also reduce the rate of phase disengagement and result in higher density of the monomer-rich phase,
which reduces the density difference between polymer-rich and monomer-rich phases, thereby slowing the rate of settling
in the fluid-liquid phase separation vessel (HPS), and ultimately requiring a larger HPS vessel. Thus, at some experi-
mentally determined pressure within the preferred pressure range, the lowest total cost of pumping/compression and
HPS vessel size will be achieved. In one embodiment of the invention, the pressure downstream of the pressure reducing
40 device (letdown valve) and inside the fluid-liquid phase separation vessel (HPS) is below the spinodal boundary pressure,
or at least 1 MPa lower than the spinodal boundary pressure, or at least 5 MPa lower than the spinodal boundary
pressure, or at least 10 MPa lower than the spinodal boundary pressure. In one embodiment, the pressure is no lower
than the vapor pressure of monomer-rich phase, no lower than 0.2 MPa above, no lower than 1 MPa above, or no lower
than 10 MPa above the vapor pressure of the monomer-rich phase. In another embodiment, the difference in density
45 between the polymer-rich phase and the monomer-rich phase is 0.1 g/mL, or 0.2 g/mL, or 0.4 g/mL, or 0.6 g/mL. In
another embodiment, the pressure is between 2 and 40 MPa, 5 and 30 MPa, 7 and 20 MPa, or between 10 and 18 MPa.

Polymer Recovery:

50 [0291] The polymer-rich phase may be sent directly to a coupled devolatilization system, which may be comprised of
one or more flash vessels, or low pressure separators (LPS), in series, each operating at a successively lower pressure,
and said devolatization system may include as a final step a devolatizing extruder or other devolatizing devices such
as a LIST DTB, which may be obtained from LIST USA Inc., of Charlotte, North Carolina. The low pressure separator
vessel(s) may operate adiabatically, or optionally may have internal heaters of the thin film or falling strand type. This
55 devolatilization is a separation process to separate remaining volatiles from the final polymer, without resorting to older,
inefficient processes such as steam stripping. The final devolatizing device (extruder, LIST DTB, etc.) may operate under
a strong vacuum, and may optionally use stripping agents such as water or nitrogen, to further reduce the volatiles
content of the polymer. Once devolatized, the product exits the final devolatizing step and is then transferred on for

48
 EP 2 195 349 B1

further processing, such as pelletization and packaging.

Efficient And Economical Recycle Of Monomer-Rich Phase:

5 [0292] In preferred embodiments of the invention, the monomer-rich phase is recycled to the polymerization system
with minimal processing to avoid costly investment in reycle equipment, and also to avoid consumption of costly utilties
including heating media (steam, hot oil, electricity, etc.) and cooling media (cooling water, brine, cooling air, etc.). In
embodiments where the temperature of the monomer-rich phase in the fluid-liquid separation vessel (HPS) is higher
than the polymerization system feed temperature, some cooling of the monomer-rich phase will be required. If removal
10 of water or other polar contaminants is not required to maintain an economical catalyst productivity in the polymerization
system, then cooling of the monomer-rich recycle stream to the polymerization system feed temperature may be all that
is required. One embodiment of this type involves cooling the monomer-rich recycle stream to -40 to 100˚C, or -20 to
90˚C, or 0 to 90˚C, or 20 to 90˚C, or 50 to 90˚C. Where removal of water or polar contaminants is required to maintain
an economical catalyst productivity in the polymerization system, then drying over desiccant beds may be used, and
15 the monomer-rich recycle stream must be a cooled to the lower of the polymerization feed temperature or the temperature
where the desiccant has an acceptable capacity for removing water and/or other polar impurities (eg. catalyst poisons).
In this case where desiccant drying is required, one embodiment involves cooling the monomer-rich recycle stream to
-40 to 80˚C, , or -20 to 60˚C, or 0 to 40˚C, or 20 to 40˚C. When cooling the monomer-rich recycle stream, low or very
low molecular weight polymer present in the monomer-rich stream may precipitate as solids, which may optionally be
20 removed through filters, "knock-out" pots, etc. or left in the return stream depending upon product requirements and the
steady-state concentration of the low molecular weight polymer fraction in the product.

Heat Integration:

25 [0293] In embodiments of the invention where heating of the polymerization medium and cooling of the monomer-rich
recycle stream are both required, it is often advantageous to install a heat integrating exchanger, which will be defined
as any device that exchanges heat between the monomer-rich phase leaving the fluid-liquid separator and the polym-
erization medium upstream of the pressure reducing device. This exchange of heat simultaneously heats the polymer-
ization medium and cools the monomer-rich recycle stream. In embodiments where this exchange of heat is insufficient
30 to raise the polymerization medium to its desired temperature and/or to cool the monomer-rich recycle stream to its
desired temperature, supplemental heating and cooling systems may be employed in conjunction with the heat integrating
exchanger. In such embodiments, preferred heating media for the the polymerization medium include, but are not
restricted to, steam, hot oil systems, and electric heater systems. Preferred supplemental cooling media for the monomer-
rich recycle stream include, but are not restricted to, fresh water cooling systems, salt water cooling systems, air-cooled
35 exchangers, and the like.

Application To Two-Phase Polymerization System:

[0294] In another embodiment of the invention, the polymerization system of WO2004/026921 is operated at a pressure
40 below the cloud point pressure, with the two phase (fluid-liquid) polymerization medium transported directly to a gravi-
metric separation vessel, optionally by way of a pressuring reducing device where the pressure may be further lowered
if desired to enhance phase separation of the polymer-rich and monomer-rich phases. In this embodiment, the monomer-
rich phase is recycled to the polymerization system in the same manner as described for a polymerization system
operating above the cloud point pressure. Other aspects of the current invention, including spinodal decomposition,
45 supplemental cooling of the monomer-rich recycle stream, desiccant drying of the monomer-rich recycle stream, removal
of low molecular weight polymer that precipitates from the monomer-rich recycle stream, hydrogen removal, and catalyst
killing may also be employed in this embodiment.

Hydrogen Removal From Monomer-Rich Recycle Stream:

50
[0295] Many of the catalyst systems of the polymerization system of WO2004/026921, and thus of the current invention,
produce small amounts of hydrogen as a byproduct of the polymerization reaction. Additonally, hydrogen is disclosed
as one of the possible reactor feeds for this polymerization process. For these two reasons, in all embodiments of the
polymerization process where the hydrogen is not totally consumed in the polymerization process, there will be small
55 amounts of hydrogen in the polymerization medium, and most of this hydrogen will remain in the monomer-rich phase
leaving the fluid-liquid phase separation vessel (HPS). In one embodiment, this amount of hydrogen in the monomer-
rich recycle stream is less than the amount of hydrogen added to the combined feed stream to the polymerization
process, and in this embodiment, the fresh makeup of hydrogen to the polymerization process feed can be reduced to

49
 EP 2 195 349 B1

compensate for this recycled hydrogen, and no further processing of the monomer-rich recycle stream to remove hy-
drogen is required. In another embodiment, the amount of hydrogen in the monomer-rich recycle stream is greater than
the total amount of hydrogen desired in the combined feed stream to the polymerization process, and in this embodiment,
an additional treatment step may be added to the process for recycling the monomer-rich phase. This additional treatment
5 step may comprise, but is not restricted to, single or multiple stage flash vessels, fractionation towers, or hydrogenation
beds. Treatment for removal of hydrogen may be applied to the entire monomer-rich recycle stream, or in instances
where the hydrogen removal requirements permit, to only a portion, or slip-stream of the monomer-rich recycle stream.

Catalyst killing:
10
[0296] The use of the processes disclosed herein and the relatively low pressure in the separator vessel greatly
reduces the monomer concentration in the liquid polymer-rich phase, which, in turn, results in a much lower polymerization
rate. This polymerization rate may be low enough to operate this system without adding a catalyst poison or "killer". If
no killing compounds are added then the killer removal step may be eliminated.
15 [0297] If a catalyst killer is required, then provision must be made to remove any potential catalyst poisons from the
recycled monomer-rich stream (e.g. by the use of fixed bed adsorbents or by scavenging with an aluminum alkyl). The
catalyst activity may be killed by addition of a polar species. Non-limiting exemplary catalyst killing agents include water,
alcohols (such as methanol and ethanol), sodium/calcium stearate, CO, and combinations thereof. The choice and
quantity of killing agent will depend on the requirements for clean up of the recycle propylene and comonomers as well
20 as the product properties, if the killing agent has low volatility. The catalyst killing agent may be introduced into the
polymer blend and plasticizer blend component reactor effluent stream after the pressure letdown valve, but before the
HPS. The choice and quantity of killing agent may depend on the requirements for clean up of the recycle propylene
and comonomers as well as the product properties, if the killing agent has low volatility.

25 Base polymer blending components:

[0298] The base polymer and plasticizer blending components produced by the in-line blending processes disclosed
herein may have any type of chain architecture, including, but not limited to, block, linear, radial, star, branched, hyper-
branched, dendritic, and combinations thereof. Exemplary base polymers include, high density polyethylene (HDPE),
30 low density polyethylene (LDPE), linear low density polyethylene (LLDPE), very low density polyethylene (vLDPE),
isotactic polypropylene (iPP), syndiotactic polypropylene (sPP), ethylene-propylene random copolymers typically con-
taining less than 10 wt % ethylene (RCPs), ethylene-propylene plastomers typically containing 65-85 wt % ethylene,
ethylene-propylene elastomers typically containing 10-20 wt % ethylene, impact copolymers of ethylene and propylene
(ICPs), ethylene-propylene rubbers (EPRs), ethylene-propylene-diene terpolymers (EPDs), ethylene-propylene-butene-
35 1 (EPB) terpolymers, olefin block copolymers, poly(1-butene), styrenic block copolymers, butyl, halobutyl, thermoplastic
vulcanizers, and blends thereof. Advantageously, the base polymer comprises isotactic polypropylene or ethylene-
propylene random copolymers.
[0299] Some forms produce polypropylene and copolymers of polypropylene with a unique microstructure. The proc-
esses disclosed herein can be practiced such that novel isotactic and syndiotactic compositions are made. In other
40 forms, low crystallinity polymers are made.
[0300] In other forms, the copolymer includes from 90 to 99.999 weight % of propylene units, from 0.000 to 8 weight
% of olefin units other than propylene units and from 0.001 to 2 weight % α,ω-diene units. Copolymer forms may have
weight-average molecular weights from 20,000 to 2,000,000, crystallization temperatures (without the addition of external
nucleating agents) from 115˚C to 135˚C and melt flow rates (MFRs) from 0.1 dg/min to 100 g/10 min. The accompanying
45 olefin may be any of C2-C20 α-olefins, diolefins (with one internal olefin) and their mixtures thereof. More specifically,
olefins include ethylene, butene-1, pentene-1, hexene-1, heptene-1, 4-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-
1-hexene, 5-methyl-1-hexene, 1-octene, 1-decene, 1-undecene, and 1-dodecene.
[0301] Plasticizer copolymers of propylene made under supercritical conditions include ethylene and C4-C12 comon-
omers such as butene-1, 3-methylpentene-1, hexene-1, 4-methylpentene-1, and octene-1. The in-line blending proc-
50 esses disclosed herein can prepare these copolymers without the use of solvent or in an environment with low solvent
concentration.
[0302] Propylene-based polymers produced typically comprise 0 to 60 weight % of a comonomer, or 1 to 50 weight
%, or 2 to 40 weight %, or 4 to 30 weight %, or 5 to 25 weight %, or 5 to 20 weight %, and have one or more of:

55 1. a heat of fusion, ∆Hf, of 30 J/g or more, or 50 J/g or more, or 60 or more, or 70 or more, or 80 or more, or 90 or
more, or 95 or more, or 100 or more, or 105 or more or an ∆Hf of 30 J/g or less, or 20 J/g or 0;
2. a weight-averaged molecular weight (as measured by GPC DRI) of 20,000 or more, or 30,000 to 1,000,000, or
50,000 to 500,000, or 50,000 to 400,000;

50
 EP 2 195 349 B1

3. a melt flow rate of 0.1 g/10 min or more, or 0.5 g/10 min or more, or 1.0 g/10 min or more, or between 0.1 and
10,000 g/10 min;
4. a melting peak temperature of 55˚C or more, or 75˚C or more, or 100˚C or more, or 125˚C or more, or 150˚C or
more, between 145 and 165˚C;
5 5. an Mw/Mn (as measured by GPC DRI) of about 1.5 to 20, or about 1.5 to 10, or 1.8 to 4.

[0303] In another form, the polymer blend components produced by the in-line blending processes disclosed herein
have a melt viscosity of less than 10,000 centipoises at 180˚C as measured on a Brookfield viscometer, or between
1000 to 3000 cP for some forms (such as packaging and adhesives) or between 5000 and 10,000 cP for other applications.
10
Plasticizer Blending Components:

[0304] The plasticizer blend component is any compound which improves particular properties of the in-line produced
plasticized polymer blend directed towards softness, impact strength (e.g., Gardner impact), toughness, flexibility (e.g.,
15 lower flexural modulus), and or processability (e.g., higher melt flow) and the like. In certain embodiments, the plasticizer
blend component has a lower glass transition temperature (Tg) than the base polymer, such that the Tg of the plasticized
polymer blend is lower than the Tg of the base polymer. In other embodiments, the plasticizer has a lower crystallinity
than the base polymer, such that the total crystallinity of the plasticized polymer blend is lower than the crystallinity of
the base polymer. Advantageous plasticizers are characterized in that, when blended with the base polymer to form a
20 blend, the plasticizer and the polymer form a homogeneous composition, also referred to as a homogeneous blend.
Advantageously, the plasticizer is miscible with the one or more polymers, as indicated by no change in the number of
peaks in the Dynamic Mechanical Thermal Analysis trace (DMTA), as compared to the DMTA trace of the one or more
polymers in the absence of the plasticizer.
[0305] It should be understood that any plasticizer component conducive to in-line production and in-line blending
25 may also be produced off-line and then blended in-line. However, plasticizer components that are not conducive to in-
line production, advantageously are produced off-line and then are blended in-line.

I. In-Line-Produced In-line Blended Plasticizers

30 [0306] Advantageous plasticized polymer blends are composed of a blend of one or more high molecular weight base
polymer blend components and one or more plasticizer blend components. One or more the plasticizer blend components
for the in-line blending process may be produced (formed, reacted) in-line, i.e., in a one or more reactor trains parallel
to the one or more reactor trains that polymerize the high molecular weight polymer components. The one or more
plasticizers polymerized in-line are then subsequently in-line blended with the one or more high molecular weight polymer
35 components. Non-limiting exemplary plasticizers for in-line reacting and blending with one or more high molecular weight
polymers include polyolefin oligomers and soft polyolefins.

I.A. In-Line-Produced In-line Blended Soft Polyolefin Plasticizers

40 [0307] The in-line produced plasticizer may comprise, or may consist essentially of one or more soft polyolefins acting
as plasticizers that are either produced in-line, off-line or a combination thereof (i.e. one or more soft polyolefin produced
in-line and one or more soft polyolefins produced in an off-line process, outside the process boundary of the disclosed
processes). If produced off-line, the one or more soft polyolefins are in-line blended from one or more polymer/additive
storage tanks with the plasticized polymer blend components of the in-line blending process disclosed herein. In an
45 advantageous embodiment, the one or more soft polyolefins are reacted in-line and subsequently blended in-line with
the one or more high molecular weight polyolefin components, which avoids the necessity for one or more separate
polymer/additive storage tanks dedicated for soft polyolefins.
[0308] In one embodiment, the soft polyolefin plasticizers have a density of 0.88 g/mL or less, more preferably 0.87
g/mL or less, most preferably 0.86 g/mL or less. In another embodiment, the soft polyolefin plasticizers has a weight %
50 crystallinity of 15% or less, preferably 10% or less, preferably 5% or less. In another embodiment, the soft polyolefin
plasticizers comprise at least 50 mole % ethylene and has a weight % crystallinity of 15% or less, preferably 10% or
less, preferably 5% or less. In yet another embodiment, the soft polyolefin comprises at least 50 mole % propylene and
has a weight % crystallinity of 25% or less, preferably 20% or less, preferably 15% or less. Suitable ethylene copolymers
have a weight-averaged molecular weight (Mw) of 0.5 to 10 kg/mol, a weight/number-averaged molecular weight ratio
55 (Mw/Mn) of 1.5 to 3.5, and a comonomer content of 20 to 70 mol%. Comonomers for the said ethylene copolymers are
selected from C3 to C20 linear or branched alpha-olefins and diolefins. Specific examples of ethylene copolymers include,
but are not limited to, ethylene-propylene, ethylene-butene, ethylene-hexene, and ethylene-octene copolymers. In one
embodiment, the ethylene copolymer desirably has a Tg of from -80 to -30˚C, or from -75 to -40˚C, or from -70 to -45˚C.

51
 EP 2 195 349 B1

In anther embodiment, the ethylene copolymer has an ethylene crystallinity, as determined by DSC, of less than 10%,
or less than 5%.
[0309] In one embodiment, the soft polyolefin plasticizer may comprise, or consist essentially of one or more ethylene-
rich soft polyolefin. In another embodiment, the soft polyolefin plasticizer may comprise, or may consist essentially of
5 one or more propylene-rich soft polyolefin. In another embodiment, the soft polyolefin plasticizer may comprise, or consist
essentially of one or more butene-1-rich soft polyolefin.

I.B. In-Line-Produced In-line Blended Polyolefin Oligomer Plasticizers

10 [0310] In one embodiment, the plasticizer may comprise, or may consist essentially of one or more polyolefin oligomers
that are either produced in-line, off-line or a combination thereof (i.e. one or more type of polyolefin oligomer reacted
in-line and one or more type of polyolefin oligomer reacted in an off-line process). If produced off-line, the one or more
polyolefin oligomers are in-line blended from one or more additive storage tanks with the plasticized polymer blend
components of the in-line blending process disclosed herein. In an advantageous embodiment, the one or more polyolefin
15 oligomers are reacted in-line and subsequently blended in-line with the one or more base polyolefin components, which
avoids the necessity for one or more separate additive storage tanks dedicated for the polyolefin oligomers.
[0311] In another embodiment, the polyolefin oligomers have a density of less than 0.90 g/cm3, or less than 0.89
g/cm3, or less than 0.88 g/cm3, or less than 0.87 g/cm3, or less than 0.86 g/cm3.
[0312] In another embodiment, the polyolefin oligomers have a Hf of less than 70 J/g, or less than 60 J/g, or less than
20 50 J/g, or less than 40 J/g, or less than 30 J/g, or less than 20 J/g, or less than 10 J/g, or less than 5 J/g, or the Hf can
not be reliably measured.

I.B.1. In-Line-Produced In-line Blended Ethylene-Based Polyolefin Oligomer Plasticizers

25 [0313] The polyolefin oligomer plasticizer may comprise C10 to C2000, or C15 to C1500, or C20 to C1000, or C30 to C800,
or C35 to C400, or C40 to C250 oligomers (dimers, trimers, etc.) manufactured by the catalytic polymerization of ethylene
and optionally one or more C3 to C20 alpha-olefins. Ethylene-based polyolefin oligomers comprise greater than 50 wt%
ethylene.
[0314] In one embodiment, the ethylene-based polyolefin oligomers comprise greater than 60 wt% ethylene, or greater
30 than 70 wt% ethylene, or greater than 80 wt% ethylene, or greater than 90 wt% ethylene, or 100 wt% ethylene.

I.B.2. In-Line-Produced In-line Blended Propylene-Based Polyolefin Oligomer Plasticizers

[0315] The polyolefin oligomer plasticizer may comprise C10 to C2000, or C15 to C1500, or C20 to C1000, or C30 to C800,
35 or C35 to C400, or C40 to C250 oligomers (dimers, trimers, etc.) manufactured by the catalytic polymerization of propylene
and optionally one or more C5 to C20 alpha-olefins. Propylene-based polyolefin oligomers comprise greater than 50 wt%
propylene.
[0316] In one embodiment, the propylene-based polyolefin oligomers comprise greater than 60 wt% propylene, or greater
than 70 wt% propylene, or greater than 80 wt% propylene, or greater than 90 wt% propylene, or 100 wt% propylene.
40
I.B.3. In-Line-Produced In-line Blended Butene-Based Polyolefin Oligomer Plasticizers

[0317] The polyolefin oligomer plasticizer may comprise C10 to C2000, or C15 to C1500, or C20 to C1000, or C30 to C800,
or C35 to C400, or C40 to C250 oligomers (dimers, trimers, etc.) manufactured by the catalytic polymerization of butene
45 olefins, including 1-butene, 2-butene, and isobutylene, and optionally one or more olefins selected from C5 to C20 alpha-
olefins.
[0318] In one embodiment, the polyolefin oligomer comprises a "polybutenes" liquid, which comprises oligomers of
C4 olefins (including 1-butene, 2-butene, isobutylene, and butadiene, and mixtures thereof) and up to 10 wt% other
olefins, and most often comprises primarily isobutylene and 1-butene. As used herein, the term "polybutenes" also
50 includes homopolymer oligomers of isobutylene or 1-butene, copolymer oligomers of a C4 raffinate stream, and copolymer
oligomers of C4 olefins with a minority amount of ethylene and/or propylene and/or C5 olefins. Polybutenes are described
in, for example, SYNTHETIC LUBRICANTS AND HIGH-PERFORMANCE FLUIDS, L.R. Rudnick & R.L. Shubkin, eds.,
Marcel Dekker, 1999, p. 357-392.
[0319] Preferred polybutenes include those in which isobutylene derived units comprise 40 to 100 wt% (preferably 40
55 to 99 wt%, preferably 40 to 96 wt%) of the polymer; and/or the 1-butene derived units comprise 0 to 40 wt% (preferably
2 to 40 wt%) of the copolymer; and/or the 2-butene derived units comprise 0 to 40 wt% (preferably 0 to 30 wt%, preferably
2 to 20 wt%) of the polymer.
[0320] Suitable polybutenes may have a kinematic viscosity at 100˚C of 3 to 50,000 cSt (more commonly 5 to 3000

52
 EP 2 195 349 B1

cSt), a pour point of -60 to 10˚C (more commonly -40 to 0˚C), and a number-average molecular weight of 300 to 10,000
g/mol (more commonly 500 to 2,000 g/mol).
[0321] Desirable polybutenes liquids are commercially available from a variety of sources including Innovene (In-
dopol™ grades) and Infineum (C-Series grades). When the C4 olefin is exclusively isobutylene, the material is referred
5 to as "polyisobutylene" or PIB. Commercial sources of PIB include Texas Petrochemical (TPC Enhanced PIB grades).
When the C4 olefin is exclusively 1-butene, the material is referred to as "poly-n-butene" or PNB. Properties of some
polybutenes liquids made from C4 olefin(s) are summarized in the table below.

Commercial Examples of Oligomers of C4 olefin(s)

10
Grade KV @ 100˚C, cSt VI Pour Point, ˚C Specific gravity Flash Point, ˚C
TPC 137 (PIB) 6 132 -51 0.843 120
TPC 1105 (PIB) 220 145 -6 0.893 200
TPC 1160 (PIB) 660 190 +3 0.903 230
15
Innovene Indopol H-25 52 87 -23 0.869 ∼150
Innovene Indopol H-50 108 90 -13 0.884 ∼190
Innovene Indopol H-100 218 121 -7 0.893 ∼210
Infineum C9945 11 74* -34 0.854 170
20 Infineum C9907 78 103* -15 0.878 204
Infineum C9995 230 131* -7 0.888 212
Infineum C9913 630 174* +10 0.888 240
* Estimated based on the kinematic viscosity at 100˚C and 38˚C
25

I.B.4. In-Line-Produced In-line Blended Higher-Alphaolefin-Based Polyolefin Oligomer Plasticizers

[0322] In one or more embodiments, the polyolefin oligomer plasticizer component comprises C10 to C2000, or C15 to
C1500, or C20 to C1000, or C30 to C800, or C35 to C400, or C40 to C250 oligomers (dimers, trimers, etc.) manufactured by
30
the catalytic polymerization of C5 to C20 alpha-olefins. Such polyolefin oligomers are "polyalphaolefin" or "PAO" fluids,
or simply "PAO".
[0323] PAO fluids (or simply, PAOs) are described in, for example, U.S. Patent Nos. 3,149,178; 4,827,064; 4,827,073;
5,171,908; and 5,783,531 and in SYNTHETIC LUBRICANTS AND HIGH-PERFORMANCE FUNCTIONAL FLUIDS,
Leslie R. Rudnick & Ronald L. Shubkin, ed. Marcel Dekker, Inc. 1999, p. 3-52. PAOs are high purity hydrocarbons, with
35
a fully paraffinic structure and a high degree of branching. PAO liquids can be conveniently prepared by the oligomerization
of alpha-olefins in the presence of a polymerization catalyst, including Lewis acid catalysts such as aluminimu trichloride
and polyolefin polymerization catalysts such as Ziegler-Natta catalysts, metallocene or other single-site catalysts, and
chromium catalysts.
[0324] In one or more embodiments, the PAO comprises oligomers of C5 to C18, or C6 to C14, or C8 to C12 alpha-
40
olefins. The use of linear alpha-olefins (LAOs) is advantageous and the use of C8 to C12, are particularly advantageous.
Suitable LAOs include 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-
tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, and blends thereof.
[0325] In one or more embodiments, the PAO comprises oligomers of two or more C5 to C18 LAOs, to make ’bipolymer’
or ’terpolymer’ or higher-order copolymer combinations. An advantageous embodiment involves oligomerization of a
45
mixture of LAOs selected from C6 to C18 LAOs with even carbon numbers. Another advantageous embodiment involves
oligomerization of 1-octene, 1-decene, and 1-dodecene.
[0326] In one or more embodiments, the PAO comprises oligomers of a single alpha-olefin species having a carbon
number of 5 to 24, or 6 to 18, or 8 to 12, or 10. Oligomers of a single alpha-olefin species having a carbon number of
10 are advantageous. In one or more embodiments, the NFP comprises oligomers of mixed alpha-olefins (i.e., two or
50
more alpha-olefin species), each alpha-olefin having a carbon number of 5 to 24, or 6 to 18, or 8 to 12. In one or more
embodiments, the PAO comprises oligomers of mixed alpha-olefins (i.e., involving two or more alpha-olefin species)
where the weighted average carbon number for the alpha-olefin mixture is 6 to 14, or 8 to 12, or 9 to 11. Mixed alpha-
olefins with weighted average carbon number for the alpha-olefin mixture of 8 to 12, or 9 to 11 are advantageous, and
with weighted average carbon number for the alpha-olefin mixture of 9 to 11 are particularly advantageous.
55
[0327] In one or more embodiments, the PAO comprises oligomers of one or more alpha-olefin with repeat unit
formulas of -[CHR-CH2]- where R is a C3 to C18 saturated hydrocarbon branch. In one or more embodiments, R is
constant for all oligomers. In one or more embodiments, there is a range of R substituents covering carbon numbers

53
 EP 2 195 349 B1

from 3 to 18. Advantageously, R is linear, i.e., R is (CH2)nCH3, where n is 3 to 17, or 4 to 11, and or 5 to 9. Linear R
groups with n of 4 to 11, and or 5 to 9 are advantageous, and with n of 5 to 9 are particularly advantageous. Optionally,
R can contain one methyl or ethyl branch, i.e., R is (CH2)m[CH(CH3)](CH2)zCH3 or R is (CH2)x[CH(CH2CH3)](CH2)yCH3,
where (m + z) is 1 to 15, advantageously 1 to 9, or 3 to 7, and (x + y) is 1 to 14, advantageously 1 to 8, or 2 to 6.
5 Advantageously m > z; m is 0 to 15, advantageously 2 to 15, or 3 to 12, more advantageously 4 to 9; and n is 0 to 10,
advantageously 1 to 8, or 1 to 6, more advantageously 1 to 4. Advantageously x > y; x is 0 to 14, advantageously 1 to
14, or 2 to 11, more advantageously 3 to 8; and y is 0 to 10, advantageously 1 to 8, or 1 to 6, more advantageously 1
to 4. Advantageously, the repeat units are arranged in a head-to-tail fashion with minimal head-to-head connections.
[0328] The PAO can be atactic, isotactic, or syndiotactic. In one or more embodiments, the PAO has essentially the
10 same population of meso and racemic diads, on average, making it atactic. In certain embodiments, the PAO has more
than 50%, or more than 60%, or more than 70%, or more than 80%, advantageously more than 90% meso triads (i.e.,
[mm]) as determined by 13C-NMR. In other embodiments, the PAO has more than 50%,or more than 60%, or more than
70%, or more than 80%, advantageously more than 90% racemic triads (i.e., [rr]) as determined by 13C-NMR. In other
embodiments, the ratio of meso to racemic diads, [m]/[r], as determined by 13C-NMR is between 0.9 and 1.1. In another
15 embodiment, [m]/[r] is greater than 1.0 and [m]/[r] is less than 1.0 in yet another embodiment.
[0329] The PAO plasticizer can include one or more distinct PAO components. In one or more embodiments, the
plasticizer is a blend of one or more PAOs with different compositions (e.g., when different alpha-olefin pools were used
in two or more reactor trains of the in-line blending processes disclosed in U.S. Patent Application No. 60/876,193, filed
on December 20, 2006 to make the oligomers) and/or different physical properties (e.g., kinematic viscosity, pour point,
20 and/or viscosity index).
[0330] In one or more embodiments, the PAO or blend of PAOs has a number-averaged molecular weight (Mn) of
from 400 to 15,000 g/mol, advantageously 400 to 12,000 g/mol, or 500 to 10,000 g/mol, or 600 to 8,000 g/mol, more
advantageously 800 to 6,000 g/mol, or 1,000 to 5,000 g/mol). In one or more embodiments, the PAO or blend of PAOs
has a Mn greater than 1,000 g/mol, or greater than 1,500 g/mol, advantageously greater than 2,000 g/mol, or greater
25 than 2,500 g/mol).
[0331] In one or more embodiments, the PAO or blend of PAOs has a kinematic viscosity at 100˚C (KV100˚C) of 3
cSt or more, or 4 cSt or more, or 5 cSt or more, or 6 cSt or more, or 8 cSt or more, or 10 cSt or more, or 20 cSt or more,
or 30 cSt or more, or 40 cSt or more, advantageously 100 or more, or 150 cSt or more. In one or more embodiments,
the PAO has a KV100˚C of 3 to 3,000 cSt, or 4 to 1,000 cSt, advantageously 6 to 300 cSt, or 8 to 150 cSt, or 8 to 100
30 cSt, or 8 to 40 cSt). In one or more embodiments, the PAO or blend of PAOs has a KV 100˚C of 10 to 1000 cSt,
advantageously 10 to 300 cSt, or 10 to 100 cSt. In yet another embodiment, the PAO or blend of PAOs has a KV100˚C
of 4 to 8 cSt. In yet another embodiment, the PAO or blend of PAOs has a KV100˚C of 25 to 300 cSt, advantageously
40 to 300 cSt, or 40 to 150 cSt. In one or more embodiments, the PAO or blend of PAOs has a KV 100˚C of 100 to 300 cSt.
[0332] In one or more embodiments, the PAO or blend of PAOs has a Viscosity Index (VI) of 120 or more, advanta-
35 geously 130 or more, or 140 or more, or 150 or more, or 170 or more, or 190 or more, or 200 or more, preferably 250
or more, or 300 or more. In one or more embodiments, the PAO or blend of PAOs has a VI of 120 to 350, advantageously
130 to 250.
[0333] In one or more embodiments, the PAO or blend of PAOs has a pour point of -10˚C or less, advantageously
-20˚C or less, or -25˚C or less, or -30˚C or less, or -35˚C or less, or -40˚C or less, or -50˚C or less. In one or more
40 embodiments, the PAO or blend of PAOs has a pour point of -15 to -70˚C, advantageously -25 to -60˚C.
[0334] In one or more embodiments, the PAO or blend of PAOs has a glass transition temperature (Tg) of -40˚C or
less, advantageously -50˚C or less, or -60˚C or less, or -70˚C or less, or -80˚C or less. In one or more embodiments,
the PAO or blend of PAOs has a glass transition temperature (Tg) measured by differential thermal calorimetry of -50
to -120˚C, advantageously -60 to -100˚C, or -70 to -90˚C.
45 [0335] In one or more embodiments, the PAO or blend of PAOs has a flash point of 200˚C or more, advantageously
210˚C or more, or 220˚C or more, or 230˚C or more, more advantageously between 240˚C and 290˚C.
[0336] In one or more embodiments, the PAO or blend of PAOs has a specific gravity (15.6˚C) of 0.86 or less,
advantageously 0.855 or less, or 0.85 or less, or 0.84 or less.
[0337] In one or more embodiments, the PAO or blend of PAOs has a molecular weight distribution as characterized
50 by the ratio of the weight- and number-averaged molecular weights (Mw/Mn) of 2 or more, advantageously 2.5 or more,
or 3 or more, or 4 or more, or 5 or more, or 6 or more, or 8 or more, or 10 or more. In one or more embodiments, the
PAO or blend of PAOs has a Mw/Mn of 5 or less, advantageously 4 or less, or 3 or less and a KV 100˚C of 10 cSt or
more, advantageously 20 cSt or more, or 40 cSt or more, or 60 cSt or more.
[0338] Particularly advantageous PAOs and blends of PAOs are those having a) a flash point of 200˚C or more,
55 advantageously 210˚C or more, or 220˚C or more, or 230˚C or more; and b) a pour point less than -20˚C, advantageously
less than -25˚C, or less than -30˚C, or less than -35˚C or less than -40˚C) and/or a KV100˚C of 10 cSt or more, advan-
tageously 35 cSt or more, or 40 cSt or more, or 60 cSt or more.
[0339] Further advantageous PAOs or blends of PAOs have a KV100˚C of at least 3 cSt, advantageously at least 4

54
 EP 2 195 349 B1

cSt, or at least 6 cSt, or at least 8 cSt, or at least 1.0 cSt; a VI of at least 120, advantageously at least 130, or at least
140, or at least 150; a pour point of -10˚C or less, advantageously -20˚C or less, or -30˚C or less, or -40˚C or less; and
a specific gravity (15.6˚C) of 0.86 or less advantageously 0.855 or less, or 0.85 or less, or 0.84 or less.
[0340] Advantageous blends of PAOs include blends of two or more PAOs where the ratio of the highest KV100˚C
5 to the lowest KV100˚C is at least 1.5, advantageously at least 2, or at least 3, or at least 5. In an additional embodiment,
KV100˚C of the PAOs are less than 1000 cSt, advantageously less than 300 cSt, or less than 150 cSt, or less than 100
cSt, or less than 40 cSt, or less than 25 cSt, or less than 10 cSt, or less than 8 cSt.
[0341] Advantageous blends of PAO also include: blends of two or more PAOs where at least one PAO has a KV100˚C
of 300 cSt or more and at least one PAO has a KV100˚C of less than 300 cSt, advantageously 150 cSt or less, or 100
10 cSt or less, or 40 cSt or less; blends of two or more PAOs where at least one PAO has a KV100˚C of 150 cSt or more
and at least one PAO has a KV100˚C of less than 150 cSt, advantageously 100 cSt or less, or 40 cSt or less); blends
of two or more PAOs where at least one PAO has a KV100˚C of 100 cSt or more and at least one PAO has a KV100˚C
of less than 100 cSt, advantageously 40 cSt or less, or 25 cSt or less, or 10 cSt or less; blends of two or more PAOs
where at least one PAO has a KV100˚C of 40 cSt or more and at least one PAO has a KV100˚C of less than 40 cSt,
15 advantageously 25 cSt or less, or 10 cSt or less, or 8 cSt or less; blends of two or more PAOs where at least one PAO
has a KV100˚C of 10 cSt or more and at least one PAO has a KV100˚C of less than 10 cSt, advantageously 8 cSt or
less, or 6 cSt or less, or 4 cSt or less); blends of two or more PAOs where at least one PAO has a KV100˚C of 8 cSt or
more and at least one PAO has a KV100˚C of less than 8 cSt, advantageously 6 cSt or less, or 4 cSt or less); and blends
of two or more PAOs where at least one PAO has a KV100˚C of 6 cSt or more and at least one PAO has a KV100˚C
20 of less than 6 cSt, advantageously 4 cSt or less).
[0342] Examples for PAO plasticizer components with desirable properties include commercial products, such as
SpectraSyn™ and SpectraSyn Ultra™ from ExxonMobil Chemical (USA), some of which are summarized in Table A.
Other useful PAOs include those available as Synfluid™ from ChevronPhillips Chemical (USA), as Durasyn™ from
Ineos (UK), as Nexbase™ from Neste Oil (Finland), and as Synton™ from Chemtura (USA).
25
Commercial Examples of PAOs
KV 40˚C, cSt KV 100˚C , cSt VI Pour Point , ˚C Specific gravity Flash Point, ˚C
SpectraSyn 4 19 4 126 -66 0.820 220
30 SpectraSyn Plus 17 4 126 -60 0.820 228
4
SpectraSyn 6 31 6 138 -57 0.827 246
SpectraSyn Plus 30 6 143 -54 0.827 246
6
35 SpectraSyn 8 48 8 139 -48 0.833 260
SpectraSyn 10 66 10 137 -48 0.835 266
SpectraSyn 40 396 39 147 -36 0.850 281
SpectraSyn 100 1240 100 170 -30 0.853 283
40
SpectraSyn Ultra 1,500 150 218 -33 0.850 > 265
150
SpectraSyn Ultra 3,100 300 241 -27 0.852 > 265
300
SpectraSyn Ultra 10,000 1,000 307 -18 0.855 > 265
45 1000

[0343] The disclosed novel processes for making in-line plasticized polymers can make polymer blends with many
different in-line produced and blended plasticizer components. These plasticizer components are made in one or more
parallel reactor trains of the in-line polymer blending process disclosed in U.S. Patent Application No. 60/876,193 filed
50
on December 20, 2006. Some embodiments for making in-line plasticized polymers can make polymer blends comprising
PAO plasticizer components.

II. Off-Line-Produced In-Line-Blended Plasticizers

55
[0344] The plasticizer component may comprise, or may consist essentially of one or more fluids and/or polymers
that are produced off-line, but are in-line blended from one or more polymer/additive storage tanks with the plasticized
polymer blend components of the in-line blending process disclosed herein. Suitable off-line-produced plasticizers are

55
 EP 2 195 349 B1

capable of being codissolved with the base polymer in the high-pressure separator and have a glass transition temperature
(Tg) of -20 or less and at least one of the following: a Mw of 10 kg/mol or less, or a flexural modulus of 20 MPa or less.
Non-limiting exemplary plasticizers conducive to in-line blending include paraffin oils and waxes (e.g., isoparaffins or n-
paraffins), mineral oils, vegetable or other bio-derived oils, and other synthetic or natural oils such as described in
5 SYNTHETICS, MINERAL OILS, AND BIO-BASED LUBRICANTS: CHEMISTRY AND TECHNOLOGY, L.S. Rudnick,
Ed., CRC Press, 2006. Particularly preferred plasticizers include isoparaffins, process oils, high purity hydrocarbon fluids
derived from a so-called Gas-To-Liquids processes, and Group III lubricant basestocks.

II.A. Off-Line-Produced In-Line-Blended Paraffins

10
[0345] The off-line produced plasticizer may comprise, or may consist essentially of one or more C6 to C200 paraffins.
In one embodiment, the paraffin plasticizer may comprise C6 to C100 paraffins, or C6 to C200 paraffins, or C8 to C100
paraffins. In yet another embodiment, the paraffin plasticizer may comprise C20 to C1500 paraffins, or C20 to C500 paraffins,
or C30 to C400 paraffins, or C40 to C250 paraffins.
15 [0346] In another embodiment, an paraffin plasticizer may comprise, or may consist essentially of one or more linear
or normal paraffins (n-paraffins). Advantageous paraffin plasticizers comprise at least 50 weight %, or at least 60 wt %,
or at least 70 wt %, or at least 80 wt %, or at least 90 wt %, or at least 95 wt % or essentially 100 wt % of C5 to C25 n-
paraffins, or C5 to C20 n-paraffins, or C5 to C15 n-paraffins. Advantageous n-paraffins may also comprise less than 0.1
wt %, or less than 0.01 wt % aromatics.
20 [0347] In another embodiment, an paraffin plasticizer may comprise, or may consist essentially of one or more branched
paraffins (isoparaffins). Advantageous paraffin plasticizers comprise at least 50 wt %, or at least 60 wt %, or at least 70
wt %, or at least 80 wt %, or at least 90 wt %, or at least 95 wt % or essentially 100 wt % of C6 to C150 isoparaffins. The
paraffin plasticizer may also comprise C6 to C100 isoparaffins, or C6 to C25 isoparaffins, or C8 to C20 isoparaffins.
Advantageous isoparaffins may have: a density of 0.70 to 0.83 g/mL; and/or a pour point of -40˚C or less, or -50˚C or
25 less; and/or a viscosity at 25˚C of 0.5 to 20 cSt; and/or a weight-averaged molecular weight (Mw) of 100 to 300 g/mol.
[0348] The isoparaffins may include greater than 50 wt % (by total weight of the isoparaffin) mono-methyl species,
for example, 2-methyl, 3-methyl, 4-ethyl, 5-methyl or the like, with minimum formation of branches with substituent
groups of carbon number greater than 1, (e.g. , ethyl, propyl, butyl and the like). In one embodiment, the isoparaffin
includes greater than 70 wt % mono-methyl species, based on the total weight of the isoparaffin present. Advantageously,
30 the isoparaffin has a boiling point of from 100˚C to 350˚C, or 110˚C to 320˚C. In preparing different grades of isoparaffin,
a paraffinic mixture may be fractionated into cuts having narrow boiling ranges, for example, of about 35˚C.
[0349] Suitable isoparaffins are commercially available under the tradename ISOPAR (ExxonMobil Chemical Com-
pany, Houston Tex.), and are described in, for example, U.S. Pat. No. 6,197,285 (column 5, lines 1-18), U.S. Pat. Nos.
3,818,105 and 3,439,088, and sold commercially as ISOPAR series of isoparaffins, examples of which are summarized
35 in the table below.

Commercial Examples of Isoparaffins

Distillation range Avg. Specific Saturates &
Name Pour point (˚C) KV 25˚C (cSt)
(˚C) Gravity aromatics (wt %)
40
ISOPAR E 117-136 -63 0.72 0.85 <0.01
ISOPAR G 161-176 -57 0.75 1.46 <0.01
ISOPAR H 178-188 -63 0.76 1.8 <0.01
ISOPAR K 179-196 -60 0.76 1.85 <0.01
45 ISOPAR L 188-207 -57 0.77 1.99 <0.01
ISOPAR M 223-254 -57 0.79 3.8 <0.01
ISOPAR V 272-311 -63 0.82 14.8 <0.01

50 II.B. Off-Line-Produced In-Line-Blended Mineral and Process Oils

[0350] The off-line produced plasticizer may comprise, or may consist essentially of one or more mineral oils (also
called process oils).
[0351] Characteristics of some commercially available mineral oils used as process oils are listed in the table below.
55 Such fluids typically have a viscosity index less than 110, and many have a viscosity index of 100 or less. Advantageously,
the mineral oil plasticizer has a kinematic viscosity at 40˚C of 80 cSt or more and a pour point of -15˚C.

56
 EP 2 195 349 B1

Commercial Examples of Process Oils

KV @ 40˚C cSt KV @ 100˚C VI Pour Point ˚C Specific Flash Point ˚C
cSt gravity
5 Drakeol 341 76 9 99 -12 0.872 254
Paralux 20 4 99 -17 0.849 212
1001R2
Paralux 43 6 101 -12 0.866 234
2401R2
10
Paralux 118 12 102 -21 0.875 274
6001R2
Sunpar 1203 41 6 106 -15 0.872 228
Sunpar 1503 94 11 97 -12 0.881 245
15
Sunpar 22803 475 31 95 -9 0.899 305
Plastol 1354 24 5 104 -9 0.865 210
Plastol 5374 103 11 97 -3 0.880 240
Plastol 21054 380 30 110 -15 0.885 270
Flexon 8434 30 5 91 -12 0.869 218
20 Flexon 8654 106 11 93 -3 0.879 252
Flexon 8154 457 32 101 -9 0.895 310
Shellflex 2105 19 4 95 -18 0.860 216
Shellflex 3305 70 9 95 -10 0.875 256
Shellflex 8105 501 33 95 -9 0.896 324
25
Diana PW326 31 5 104 -18 0.862 226
Diana PW906 90 11 105 -22 0.872 262
Diana PW3806 376 26 106 -19 0.877 293
(1) Available from Penreco (USA).
30 (2) Available from Chevron (USA).
(3) Available from Sunoco (USA).
(4) Available from ExxonMobil (USA).
(5) Available from Royal Dutch Shell (UK/Netherlands).
(6) Available from Idemitsu (Japan).
35

[0352] In certain embodiments, the mineral oil plasticizer has a viscosity index less than 120 (preferably 90 to 119);
and a kinematic viscosity at 40˚C of 80 cSt or more (preferably 90 cSt or more, or 100 cSt or more, or 120 cSt or more,
or 150 cSt or more, or 200 cSt or more, or 250 cSt or more, or 300 cSt or more); and a pour point of 15˚C or less
40 (preferably 18˚C or less, or 20˚C or less, or 25˚C or less, or 30˚C or less, or 35˚C or less).
[0353] In other embodiments, the mineral oil plasticizer comprises one or more Group I or II lubricant basestocks.
Group I basestocks are mineral oils that may have been refined using solvent extraction of aromatics, solvent dewaxing,
and hydrofining; they may have sulfur levels greater than 0.03 weight %, saturates levels of 60 to 80%, and a VI of about
90. Group II basestocks are mineral oils that have been mildly hydrocracked with conventional solvent extraction of
45 aromatics, solvent dewaxing, and more severe hydrofining to reduce sulfur levels to less than or equal to 0.03 weight
%, as well as removing double bonds from some of the olefinic and aromatic compounds such that saturate levels are
greater than 95-98%; they have a VI of about 80-120.

II.C. Off-Line-Produced In-Line-Blended High-Purity Hydrocarbon Fluids

50
[0354] The off-line produced plasticizer may comprise, or may consist essentially of one or more "high purity" hydro-
carbon fluids.
[0355] In one embodiment, the "high purity" hydrocarbon fluids comprise one or more paraffins having 6 to 1500
carbon atoms, or 8 to 1000 carbon atoms, or 10 to 500 carbon atoms, or 12 to about 200 carbon atoms, or 14 to 150
55 carbon atoms, or 16 to 100 carbon atoms, or 20 to 500 carbon atoms, or 30 to 400 carbon atoms, or 40 to 200 carbon
atoms, or 20 to 100 carbon atoms. The high purity hydrocarbon fluid composition may have an isoparaffin:n-paraffin
ratio of about 0.5:1 to about 9:1, or about 1:1 to about 4:1. The isoparaffins of the "high purity" hydrocarbon fluid
composition may contain greater than fifty percent mono-methyl species, e.g., 2-methyl, 3-methyl, 4-methyl, ^ 5-methyl

57
 EP 2 195 349 B1

or the like, with minimum formation of branches with substituent groups of carbon number greater than one, i.e., ethyl,
propyl, butyl or the like, based on the total weight of isoparaffins in the mixture. Advantageously, the isoparaffins of the
"high purity" hydrocarbon fluid composition contain greater than 70 percent of the mono-methyl species, based on the
total weight of the composition.
5 [0356] An advantageous high purity hydrocarbon fluid may have: a KV at 25˚C of 1 to 100,000 cSt, or 10 cSt to 2000
cSt; and/or a KV at 40˚C of 1 to 30,000 cSt, or 10 cSt to 2000 cSt; and/or a pour point below -10˚C, or below -20˚C, or
below -30˚C, or from about -20˚C to about -70˚C. In an advantageous embodiment, a high purity hydrocarbon fluid may
comprise paraffins having: a number average molecular weight of 500 to 21,000 g/mol; and/or less than 10% side chains
having 4 or more carbons, or less than 8 weight %, or less than 5 weight %, or less than 3 weight %, or less than 2
10 weight %, or less than 1 weight %, or less than 0.5 weight %, or less than 0.1 weight %, or at less than 0.1 weight %,
or at 0.001 weight %; and/or at least 1 or 2 carbon branches present at 15 weight % or more, or 20 weight % or more,
or 25 weight % or more, or 30 weight % or more, or 35 weight % or more, or 40 weight % or more, or 45 weight % or
more, or 50 weight % or more; and/or less than 2.5 weight % cyclic paraffins, or less than 2 weight %, or less than 1
weight %, or less than 0. 5 weight %, or less than 0.1 weight %, or at less than 0. 1 weight %, or at 0.001 weight %.
15 [0357] In another advantageous embodiment, a high purity hydrocarbon fluid may comprise paraffins having: a KV
of 2 cSt or more at 100˚C; and/or a viscosity index of 120 or more, or 130 or more, or 140 or more, or 150 or more, or
170 or more, or 190 or more, or 200 or more, or 250 or more, or 300 or more; and/or a mixture of paraffins of carbon
number ranging from about C8 to C20, or from about C8 to C500; and/or a molar ratio of isoparaffins to n--paraffins of
about 0. 5:1 to about 9:1; and/or greater than 50 percent of mono-methyl species, based on the total weight of the
20 isoparaffins; and/or a pour point of about -20˚F to about -70˚F, or -10 to -70˚C; and/or a kinematic viscosity at 25˚C of
about 1 cSt to about 10 cSt; and/or a kinematic viscosity at 100˚C of about 3 to about 25 cSt; and/or a carbon number
of C10 to about C16, or of about C20 to about C100; and/or greater than 70 percent mono-methyl species; and/or a boiling
temperature of about 320˚F to about 650˚F, or of about 350˚F to about 550˚F.
[0358] In an advantageous embodiment, the high-purity hydrocarbon fluid comprises a mixture of paraffins having a
25 carbon number of C10 to about C16, or of about C20 to about C100; contains greater than 70 percent mono-methyl species;
has a boiling temperature of about 350˚F to about 550˚F, and has a molar ratio of isoparaffins to n-paraffins of about 1:
1 to about 4:1. The high purity hydrocarbon fluid may also be derived from a Fischer-Tropsch process followed by a
wax isomerization process, such as those disclosed in U.S. Pat. No. 5,906,727.
[0359] In another embodiment, the off-line plasticizer is a high-purity hydrocarbon fluid of lubricating viscosity com-
30 prising a mixture of C20 to C120 paraffins, 50 wt % or more being isoparaffinic hydrocarbons and less than 50 wt % being
hydrocarbons that contain naphthenic and/or aromatic structures. Or, the mixture of paraffins comprises a wax isomerate
lubricant base stock or oil, which includes:

1. hydroisomerized natural and refined waxes, such as slack waxes, deoiled waxes, normal alpha-olefin waxes,
35 microcrystalline waxes, and waxy stocks derived from gas oils, fuels hydrocracker bottoms, hydrocarbon raffinates,
hydrocracked hydrocarbons, lubricating oils, mineral oils, polyalphaolefins, or other linear or branched hydrocarbon
compounds with carbon number of about 20 or more; and
2. hydroisomerized synthetic waxes, such as Fischer-Tropsch waxes (i.e., the high boiling point residues of Fischer-
Tropsch synthesis, including waxy hydrocarbons); or mixtures thereof.
40
[0360] Particularly advantageous are lubricant base stocks or oils derived from hydrocarbons synthesized in a Fischer-
Tropsch process as part of an overall Gas-to-Liquids (GTL) process.
[0361] In one embodiment, the mixture of paraffins useful as an off-line plasticizer has:

45 1. a naphthenic content of less than 40 wt %, or less than 30 wt %, or less than 20 wt %, or less than 15 wt %, or
less than 10 wt %, or less than 5 wt %, or less than 2 wt %, or less than 1 wt % (based on the total weight of the
hydrocarbon mixture); and/or
2. a normal paraffins content of less than 5 wt %, or less than 4 wt %, or less than 3 wt %, or less than 1 wt % (based
on the total weight of the hydrocarbon mixture); and/or
50 3. an aromatic content of 1 wt % or less, or 0.5 wt % or less; and/or
4. a saturates level of 90 wt % or higher, or 95 wt % or higher, or 98 wt % or higher, or 99 wt % or higher; and/or
5. a branched paraffin:normal paraffin ratio greater than about 10:1, or greater than 20:1, or greater than 50:1, or
greater than 100:1, or greater than 500:1, or greater than 1000:1; and/or
6. sidechains with 4 or more carbons making up less than 10% of all sidechains, or less than 5%, or less than 1%;
55 and/or
7. sidechains with 1 or 2 carbons making up at least 50% of all sidechains, or at least 60%, or at least 70%, or at
least 80%, or at least 90%, or at least 95%, or at least 98%; and/or
8. a sulfur content of 300 ppm or less, or 100 ppm or less, or 50 ppm or less, or 10 ppm or less (where ppm is on

58
 EP 2 195 349 B1

a weight basis.

[0362] In another embodiment, the mixture of paraffins useful as an off-line plasticizer has:

5 1. a number-averaged molecular weight of 300 to 1800 g/mol, or 400 to 1500 g/mol, or 500 to 1200 g/mol, or 600
to 900 g/mol; and/or
2. a kinematic viscosity at 40˚C of 10 cSt or more, or 25 cSt or more, or between about 50 and 400 cSt; and/or
3. a kinematic viscosity at 100˚C ranging from 2 to 50 cSt, or 3 to 30 cSt, or 5 to 25 cSt, or 6 to 20 cSt, more or 8
to 16 cSt; and/or
10 4. a viscosity index (VI) of 80 or greater, or 100 or greater, or 120 or greater, or 130 or greater, or 140 or greater,
or 150 or greater, or 160 or greater, or 180 or greater; and/or
5. a pour point of -5˚C or lower, or -10˚C or lower, or -15˚C or lower, or -20˚C or lower, or -25˚C or lower, or -30˚C
or lower; and/or
6. a flash point of 200˚C or more, or 220˚C or more, or 240˚C or more, or 260˚C or more; and/or
15 7. a specific gravity (15.6˚C/15.6˚C) of 0.86 or less, or 0.85 or less, or 0.84 or less.

[0363] In an advantageous embodiment, the off-line plastizier is a mixture of paraffins comprising a GTL base stock
or oil. GTL base stocks and oils are fluids of lubricating viscosity that are generally derived from waxy synthesized
hydrocarbons, that are themselves derived via one or more synthesis, combination, transformation, and/or rearrangement
20 processes from gaseous carbon-containing compounds and hydrogen-containing compounds as feedstocks. Advanta-
geously, the feedstock is "syngas" (synthesis gas, essentially CO and H2) derived from a suitable source, such as natural
gas and/or coal. GTL base stocks and oils include wax isomerates, comprising, for example, hydroisomerized synthesized
waxes, hydroisomerized Fischer-Tropsch (F-T) waxes (including waxy hydrocarbons and possible analogous oxygen-
ates), or mixtures thereof. GTL base stocks and oils may further comprise other hydroisomerized base stocks and base
25 oils. Particularly advantageous GTL base stocks or oils are those comprising mostly hydroisomerized F-T waxes and/or
other liquid hydrocarbons obtained by a F-T synthesis process. The production of lube base stocks by GTL is well known
in the art. The in-line blending processes disclosed herein may use off-line-produced GTL base stocks from any one of
the known GTL processes. Desirable GTL-derived fluids are expected to become broadly available from several com-
mercial sources, including Chevron, ConocoPhillips, ExxonMobil, Sasol, SasolChevron, Shell, Statoil, and Syntroleum.
30
II.D. Off-Line-Produced In-Line-Blended Group III Lubricant Basestocks

[0364] The off-line produced plasticizer may may comprise, or may consist essentially of one or more Group III lubricant
basestock, which also herein includes mineral oils with a VI of 120 or more (a "Group III mineral oil").
35 [0365] In one embodiment, the Group III mineral oil plasticizer has a saturates levels of 90% or more, or 92% or more,
or 94% or more, or 95% or more, or 98% or more; a sulfur content of less than 0.03%, or between 0.001 and 0.01%;
and a VI of 120 or more, or 130 or more, or 140 or more. In another embodiment, the Group III mineral oil plasticizer
has a kinematic viscosity at 100˚C of 3 to 50, or 4 to 40 cSt, or 6 to 30 cSt, or 8 to 20; and/or a Mn of 300 to 5,000 g/mol,
or 400 to 2,000 g/mol, or 500 to 1,000 g/mol. In another embodiment, the Group III mineral oil plasticizer has a pour
40 point of -10˚C or less, a flash point of 200˚C or more, and a specific gravity (15.6˚C) of 0.86 or less.
[0366] Desirable Group III basestocks are commercially available from a number of sources and include those de-
scribed in the table below.

Commercial Examples of Group III Basestocks

45
KV @ 100˚C, cSt VI Pour Point, ˚C Specific gravity Flash Point, ˚C
UCBO 4R1 4.1 127 -18 0.826 216
UCBO 7R1 7.0 135 -18 0.839 250
Nexbase 30432 4.3 124 -18 0.831 224
50 Nexbase 30502 5.1 126 -15 0.835 240
Nexbase 30602 6.0 128 -15 0.838 240
Nexbase 30802 8.0 128 -15 0.843 260
Yubase YU-43 4.2 122 -15 0.843 230
Yubase YU-63 6.5 131 -15 0.842 240
55
Yubase YU-83 7.6 128 -12 0.850 260
Ultra-S 44 4.3 123 -20 0.836 220
Ultra-S 64 5.6 128 -20 0.839 234

59
 EP 2 195 349 B1

(continued)
KV @ 100˚C, cSt VI Pour Point, ˚C Specific gravity Flash Point, ˚C
Ultra-S 84 7.2 127 -15 0.847 256
5 VHVI 45 4.6 128 -21 0.826
VHVI 85 8.0 127 -12 0.850 248
Visom 46 4.0 210
Visom 66 6.6 148 -18 0.836 250

10
1 Available from ChevronTexaco (USA).
2 Available from Neste Oil (Finland).
3 Available from SK Corp (South Korea).
4 Available from ConocoPhillips (USA) / S-Oil (South Korea).
5 Available from PetroCanada (Canada).
15
6 Available from ExxonMobil (USA).

II.E. Other Off-Line-Produced In-Line-Blended Plasticizers

[0367] The off-line produced in-line-blended plasticizers may also include any other compounds used for plasticizing
20 polymers. These include phthalate esters, such as di-isononyl phthalate (DINP), di-isoctyl phthalate (DOP), trimellitites,
citrates, etc. Examples for polymeric plasticizers can be found in J.K. Sears, J.R. Darby, THE TECHNOLOGY OF
PLASTICIZERS, Wiley, New York, 1982.

III. Advantageous Properties for Liquid Plasticizers

25
[0368] Certain embodiments will use plasticizers that are liquids at ambient temperature. The advantageous properties
for such liquid plasticizers can be defined as follows.
[0369] In an advantageous embodiment, any of the plasticizers described above has a flash point of 200˚C or more
(or 220˚C, or more, or 230˚C or more, or 250˚C or more). In a particularly advantageous embodiment any of the plasticizers
30 described above has a flash point of 200˚C or more (or 220˚C, or more, or 230˚C or more, or 250˚C or more) and a pour
point of -20˚C or less (or less than -25˚C, or less than -30˚C, or less than -35˚C, or less than -40˚C), and/or a kinematic
viscosity at 100˚C of 35 cSt or more (or 40 cSt or more, or 50 cSt or more, or 60 cSt or more).
[0370] In another advantageous embodiment, any of the plasticizers described above has flash point of 200˚C or
greater, or 220˚C or greater, or 200 to 350˚C, or 210 to 300˚C, or 215 to 290˚C, or 220 to 280˚C, or 240 to 280˚C, wherein
35 a desirable range may be any combination of any lower limit with any upper limit described herein.
[0371] In still another advantageous embodiment, any of the plasticizers described above has a pour point of -10˚C
or less, or -20˚C or less, or -30˚C or less, or -40˚C or less, or -45˚C or less, or -50˚C or less, or -10 to -80˚C, or -15 to
-75˚C. or -0 to -70˚C, or -25 to -65˚C, wherein a desirable range may be any combination of any lower limit with any
upper limit described herein.
40 [0372] In still yet another advantageous embodiment, any of the plasticizers described above has a viscosity index
(VI) of 100 or more, or 110 or more, or 120 or more, or 120 to 350, or 135 to 300, or 140 to 250, or 150 to 200, wherein
a desirable range may be any combination of any lower limit with any upper limit described herein.
[0373] In still yet another advantageous embodiment, any of the plasticizers described above has a specific gravity
of 0.86 or less, or 0.855 or less, or 0.84 or less, or 0.78 to 0.86, or 0. 80 to 0.85, or 0.82 to 0.845, wherein a desirable
45 range may be any combination of any lower limit with any upper limit described herein.
[0374] In still yet another advantageous embodiment, any of the plasticizers described above has a kinematic viscosity
at 100˚C (KV100˚C) of 4 cSt or more, or 5 cSt or more, or 6 to 5000 cSt, or 8 to 3000 cSt, or 10 to 1000 cSt, or 12 to
500 cSt, or 15 to 350 cSt, or 35 cSt or more, or 40 cSt or more, wherein a desirable range may be any combination of
any lower limit with any upper limit described herein.
50 [0375] In still yet another advantageous embodiment, any of the plasticizers described above has a number-averaged
molecular weight (Mn) of 300 g/mol or more, or 500 g/mol or more, or 300 to 21,000 g/mol, or 300 to 10,000 g/mol, or
400 to 5,000 g/mol, or 500 to 3,000 g/mol, or less than 1,000 g/mol, wherein a desirable range may be any combination
of any lower limit with any upper limit described herein.
[0376] In still yet another advantageous embodiment, any of the plasticizers described above has a specific gravity
55 of 0.86 or less (or 0.855 or less, or 0.85 or less), and one or more of the following:

a) a VI of 120 or more (or 135 or more, or 140 or more), and/or

b) a flash point of 200˚C or more (or 220˚C or more, or 240˚C or more).

60
 EP 2 195 349 B1

[0377] In still yet another advantageous embodiment, any of the plasticizers described above has a pour point of
-10˚C or less (or -15˚C or less, or -20˚C or less, or -25˚C or less), a VI of 120 or more (or 135 or more, or 140 or more),
and optionally a flash point of 200˚C or more (or 220˚C or more, or 240˚C or more).
[0378] In still yet another advantageous embodiment, any of the plasticizers described above has a pour point of
5 -20˚C or less (or -25˚C or less, or -30˚C or less, or -40˚C or less) and one or more of the following:

a) a flash point of 200˚C or more (or 220˚C or more, or 240˚C or more), and/or
b) a VI of 120 or more (or 135 or more, or 140 or more), and/or
c) a KV100˚C of 4 cSt or more (or 6 cSt or more, or 8 cSt or more, or 10 cSt or more), and/or
10 d) a specific gravity of 0.86 or less (or 0.855 or less, or 0.85 or less).

[0379] In another advantageous embodiment, any of the plasticizers described above has a KV100˚C of 4 cSt or more
(or 5 cSt or more, or 6 cSt or more, or 8 cSt or more, or 10 cSt or more), a specific gravity of 0.86 or less (or 0.855 or
less, or 0.85 cSt or less), and a flash point of 200˚C or more (or 220˚C or more, or 240˚C or more).
15 [0380] In yet another advantageous embodiment, any of the plasticizers described above has a flash point of 200˚C
or more (or 220˚C or more, or 240˚C or more), a pour point of 110˚C or less (or 15˚C or less, or 20˚C or less, or 25˚C
or less), a specific gravity of 0.86 or less (or 0.855 or less, or 0.85 or less), a KV100˚C of 4 cSt or more (or 5 cSt or
more, or 6 cSt or more, or 8 cSt or more, or 10 cSt or more), and optionally a VI of 100 or more (or 120 or more, or 135
or more).
20 [0381] In still yet another advantageous embodiment, any of the plasticizers described above has a KV100˚C of 35
cSt or more (or 40 or more) and a specific gravity of 0.86 or less (or 0.855 or less), and optionally one or more of the
following:

a) a flash point of 200˚C or more (or 220˚C or more, or 240˚C or more), and/or
25 b) a pour point of 10˚C or less (or 15˚C or less, or 20˚C or less, or 25˚C or less).

[0382] In yet another advantageous embodiment, any of the plasticizers described above has a flash point of 200˚C
or more (or 210˚C or more, or 220˚C or more), a pour point of 10˚C or less (or 20˚C or less, or 30˚C or less), and a KV
100˚C of 6 cSt or more (or 8 cSt or more, or 10 cSt or more, or 15 cSt or more).
30 [0383] In still yet another advantageous embodiment, any of the plasticizers described above has a pour point of 40˚C
or less (or 50˚C or less) and a specific gravity of 0.84 or less (or 0.83 or less).
[0384] It should be understood that sometimes even soft polyolefins need plasticizer to further soften them while the
same soft polyolefins may serve as plasticizers, particlularly with highly crystalline, hard polyolefins, such as, for example,
ethylene and propylene homopolymers. Therefore, such soft polyolefins may serve both as plasticizers and base poly-
35 mers. The description of such dual-purpose soft polyolefin (SPO) polymers is given below.

IV. Soft Polyolefin (SPO) Polymers

[0385] Preferred SPOs have a percent crystallinity of 0.1% to less than 35%. Advantageously, within this range, the
40 SPO comprises less than 30% crystallinity, or less than 25% crystallinity, or less than 20% crystallinity, or less than 15%
crystallinity, or less than 10% crystallinity. Also advantageously, the SPO comprises at least 0.5% crystallinity, or at
least 1% crystallinity, or at least 2% crystallinity, or at least 5% crystallinity.
[0386] Advantageously, SPOs have a DSC melting point of 105˚C or less, or 90˚C or less, or between 25 and 90˚C,
or between 30 and 80˚C, or between 35 and 75˚C, as measured by DSC and have a Mw/Mn ratio of less than 5, or
45 between 1.5 and 4, or between 1.5 and 3.
[0387] In one embodiment, a useful SPO comprises a first monomer consisting of at least 50 wt % ethylene or at least
50 wt % propylene, and less than 50 wt% of at least one other monomer selected from C2-C20 olefins, or C2-C6 alpha-
olefins, which is different from the first monomer. Suitable olefin comonomers may be any polymerizable olefin monomer
and are preferably a linear, branched or cyclic olefin, even more preferably an alpha-olefin. Examples of suitable olefins
50 include butene, isobutylene, pentene, isopentene, cyclopentene, hexene, isohexene, cyclohexene, heptene, isoheptene,
cycloheptene, octene, isooctene, cyclooctene, nonene, cyclononene, decene, isodecene, dodecene, isodecene, 4-
methyl-pentene-1, 3-methyl-pentene-1, 3,5,5-trimethyl hexene-1. Suitable comonomers also include dienes, trienes,
and styrenic monomers such as styrene, alpha-methyl styrene, para-alkyl styrene (such as para-methyl styrene), hex-
adiene, norbomene, vinyl norbomene, ethylidene norbomene, butadiene, isoprene, heptadiene, octadiene, and cy-
55 clopentadiene.

61
 EP 2 195 349 B1

IV.A. Propylene-Rich Soft Polyolefins

[0388] A propylene-rich soft polyolefin (prSPO) is a propylene copolymer or a propylene homopolymer with a low level
of isotactic or syndiotactic monomer orientation in the polymer chain comprising at least 50 wt % propylene and having
5 the properties of a soft polyolefin. In some embodiments, the prSPO comprises at least 60 wt % propylene, or at least
70 wt % propylene, or at least 80 wt % propylene, or at least 90 wt % propylene, or 100 wt % propylene.
[0389] In one embodiment, the prSPO has a mm triad tacticity index of 75% or more (or 80% or more, or 85% or more,
or 90% or more). In another embodiment, the prSPO has a melt flow rate (MFR) of 0.1 to 2000 dg/10 min (preferably
100 dg/10 min or less). In another embodiment, the prSPO has an intermolecular compositional distribution as determined
10 by thermal fractionation in hexane such that 85% by weight or more of the polyolefin is isolated as one or two adjacent,
soluble fractions with the balance of the polyolefin in immediately preceding or succeeding fractions; and wherein each
of these fractions has a wt% comonomer content with a difference of no greater than 20 wt% relative to the average
wt% co-monomer content of the copolymer polyolefin. In another embodiment, the prSPO has an Mw/Mn of 1.5 to 40,
preferably 1.6 to 20, preferably 1.8 to 10, even more preferably 1.8 to 2.5.
15 [0390] In one embodiment, a prSPO has a heat of fusion of less than 70 J/g and a mm triad tacticity index of 75% or
more; and/or a MFR of 0.1 to 2000 dg/min (preferably 100 dg/min or less); and/or an intermolecular compositional
distribution as determined by thermal fractionation in hexane such that 85% by weight or more of the polymer is isolated
as one or two adjacent, soluble fractions with the balance of the polymer in immediately preceding or succeeding fractions;
and wherein each of these fractions has a wt% comonomer content with a difference of no greater than 20 wt% relative
20 to the average wt% comonomer content of the copolymer; and/or an Mw/Mn of 1.5 to 4.
[0391] Advatageous prSPOs useful in this invention preferably have a Melt Flow Rate (MFR) of 0.1 to 200 g/10 min,
preferably 0.1 to 100, preferably 0.5 to 50, preferably 1 to 25, preferably 1 to 15, preferably 2 to 10 g/10 min; alternately
the MFR is from 15 to 50 g/10 min.
[0392] Advantageous prSPOs useful in the processes of this disclosure have an intermolecular composition distribution
25 of 75% or more, preferably 80% or more, preferably 85% or more, preferably 90% or more by weight of the polymer
isolated as one or two adjacent, soluble fractions with the balance of the polymer in immediately preceding or succeeding
fractions; and wherein each of these fractions has a weight % comonomer content with a difference of no greater than
20 wt% (relative), preferably 10% (relative), of the average weight % comonomer of the copolymer. The fractions are
obtained at temperature increases of approximately 8˚C between stages.
30 [0393] The intermolecular composition distribution of the prSPO may be determined by thermal fractionation in hexane
as follows: about 30 grams of the prSPO is cut into small cubes of about 1/8 inch (0.32 cm) on the side and is then
introduced into a thick walled glass bottle closed with screw cap along with 50 mg of Irganox1076, an antioxidant
commercially available from Ciba-Geigy Corporation. Then, 425 mL of hexane (a principal mixture of normal and iso-
isomers) is added to the contents of the bottle and the sealed bottle is maintained at about 23˚C for 24 hours. At the
35 end of this period, the solution is decanted and the residue is treated with additional hexane for an additional 24 hours
at 23˚C. At the end of this period, the two hexane solutions are combined and evaporated to yield a residue of the
polymer soluble at 23˚C. To the residue is added sufficient hexane to bring the volume to 425 mL and the bottle is
maintained at about 31˚C for 24 hours in a covered circulating water bath. The soluble polymer is decanted and the
additional amount of hexane is added for another 24 hours at about 31˚C prior to decanting. In this manner, fractions
40 of the prSPO soluble at 40˚C, 48˚C, 55˚C, and 62˚C are obtained at temperature increases of approximately 8˚C between
stages. The soluble polymers are dried, weighed and analyzed for composition, as wt % ethylene content. To produce
a prSPO copolymer having the desired narrow composition, it is beneficial if (1) a single sited metallocene catalyst is
used which allows only a single statistical mode of addition of the first and second monomer sequences and (2) the
copolymer is well-mixed in a continuous flow stirred tank polymerization reactor which allows only a single polymerization
45 environment for substantially all of the polymer chains of the copolymer.
[0394] In some advantageous embodiments, the prSPO may comprise a propylene-based copolymer referred to
herein as a random copolymer of propylene or as a propylene-"comonomer" plastomer (e.g., propylene-ethylene plas-
tomer). Suitable random copolymers of propylene have a heat of fusion of less than 70 J/g, and thus are low crystallinity,
and advanatgeously comprise an average propylene content on a molar basis of from about 68 mol% to about 92 mol%,
50 or from about 75 mol% to about 91 mol%, or from about 78 mol% to about 88 mol%, or from about 80 mol% to about
88 mol%. The balance of the random copolymer of propylene (i.e., the one or more comonomers) may be one or more
alpha-olefins as specified above and/or one or more diene monomers. Advantageously, the balance of the random
copolymer of propylene is ethylene.
[0395] The comonomer of the random copolymer of propylene may comprise about 8 to 32 mol % of ethylene (C2)
55 and/or a C4-C20 olefin, advantageously about 9 to about 25 mol %, or about 12 to about 22 mol %, or about 13 to 20
mol % being.
[0396] Advantageously, the random copolymer of propylene comprises about 8 to 32 mol % ethylene, more preferably
about 9 to about 25 mol % ethylene, even more preferably about 12 to about 22 mol % ethylene, with about 13 to 20

62
 EP 2 195 349 B1

mol % ethylene being still more preferred as the comonomer.

[0397] The random copolymer of propylene may have a weight-averaged molecular weight (Mw) of 5,000,000 g/mol
or less, a number-averaged molecular weight (Mn) of about 3,000,000 g/mol or less, a z-average molecular weight (Mz)
of about 5,000,000 g/mol or less, and a g’ index of 1.5 or less measured at the weight-averaged molecular weight (Mw)
5 of the polymer using isotactic polypropylene as the baseline, all of which may be determined by GPC, also known as
size exclusion chromatography, e.g., 3D SEC.
[0398] In an embodiment, the random copolymer of propylene may have a Mw of about 5,000 to about 5,000,000 g/
mole, more preferably a Mw of about 10,000 to about 1,000,000 g/mol, more preferably a Mw of about 20,000 to about
500,000, more preferably a Mw of about 50,000 to about 300,000g/mol, wherein Mw is determined as described herein.
10 [0399] In another embodiment, the random copolymer of propylene may have a Mn of about 5,000 to about 3,000,000
g/mole, more preferably a Mn of about 10,000 to about 1,000,000 g/mol, more preferably a Mn of about 30,000 to about
500,000 g/mol, more preferably a Mn of about 50,000 to about 200,000 g/mol, wherein Mn is determined as described
herein.
[0400] In a preferred embodiment, the random copolymer of propylene may have a Mz of about 10,000 to about
15 5,000,000 g/mole, more preferably a Mz of about 50,000 to about 1,000,000 g/mol, more preferably a Mz of about 80,000
to about 500,000 g/mol, more preferably a Mz of about 100,000 to about 300,000 g/mol, wherein Mz is determined as
described herein.
[0401] The molecular weight distribution index (MWD = Mw/Mn) of the random copolymer of propylene may be about
1.5 to 40.0, more preferably about 1.8 to 5 and most preferably about 1.8 to 3. Techniques for determining the molecular
20 weight (Mn and Mw) and molecular weight distribution (MWD) may be found in U.S. Pat. No. 4,540,753 (Cozewith, Ju
and Verstrate) (which is incorporated by reference herein for purposes of U.S. practices) and references cited therein
and in Macromolecules, 1988, volume 21, p 3360 (Verstrate et al.),
and references cited therein.
[0402] In a preferred embodiment, the random copolymer of propylene may have a g’ index value of about 1 to about
25 1.5, more preferably a g’ of about 1.25 to about 1.45, when measured at the Mw of the polymer using the intrinsic
viscosity of isotactic polypropylene as the baseline. For use herein, the g’ index is defined as:

30

where ηb is the intrinsic viscosity of the random copolymer of propylene and ηl is the intrinsic viscosity of a linear polymer
of the same viscosity-averaged molecular weight (Mv) of the random copolymer of propylene. ηl = KMvα, K and α were
measured values for linear polymers and should be obtained on the same instrument as the one used for the g’ index
35 measurement.
[0403] In some embodiments, the random copolymer of propylene may have a crystallization temperature (Tc) meas-
ured with differential scanning calorimetry (DSC) of about 200˚C or less, more preferably, 150˚C or less.
[0404] In other embodiments, the random copolymer of propylene may have a density of about 0.85 to about 0.95
g/ml, more preferably, about 0.87 to 0.92 g/ml, more preferably about 0.88 to about 0.91 g/ml as measured per the
40 ASTM D-1505 test method at 25˚C.
[0405] In a preferred embodiment, the random copolymer of propylene may have a melt flow rate (MFR) equal to or
greater than 0.2 g/10 min, preferably between 2-500 g/10 mi. and more preferably between 20-200 g/10 min, as measured
according to the ASTM D-1238 test method.
[0406] In a preferred embodiment, the random copolymer of propylene may have a heat of fusion (∆Hf) determined
45 according to the procedure described in ASTM E 794-85, which is less than 70 J/g, preferably greater than or equal to
about 0.5 Joules per gram (J/g), and is less than or equal to about 25 J/g. Preferably less than or equal to about 20 J/g,
preferably less than or equal to about 15 J/g. Also preferably greater than or equal to about 1 J/g, preferably greater
than or equal to about 5 J/g according to the procedure described in ASTM E 794-85.
[0407] A chiral metallocene catalyst may ensure methyl groups of the propylene residues in the random copolymer
50 of propylene have predominantly the same tacticity. Both syndiotactic and isotactic configuration of the propylene are
possible, though the isotactic polymers may be preferred. The tacticity of the propylene residues leads to an amount of
crystallinity in the polymers. The relatively low levels of crystallinity in the random copolymer of propylene may be derived
from isotactic polypropylene obtained by incorporating alpha-olefin comonomers as described above.
[0408] The random copolymer of propylene may be partially crystalline, which preferably arises from crystallizable
55 stereoregular propylene sequences. For use herein, the crystallinity of the random copolymer of propylene can also be
expressed in terms of percentage of crystallinity, based on the heat of fusion of the polymer divided by the thermal
energy for the highest order of polypropylene, which is estimated at 189 J/g (i.e., 100% crystallinity is equal to 189 J/g.)
for purposes herein.

63
 EP 2 195 349 B1

[0409] The random copolymer of propylene of the present invention preferably has a polypropylene crystallinity of
about 0.25% to about 15%, more preferably 0.5 to 25%, more preferably 1 to 20%, more preferably 2 to 15%, more
preferably from about 0.5% to about 13%, and most preferably from about 0.5% to about 11%.
[0410] In addition to this level of crystallinity, the random copolymer of propylene preferably has a single broad melting
5 transition. However, suitable random copolymer of propylene polymer may show secondary melting peaks adjacent to
the principal peak, but for purposes herein, such secondary melting peaks are considered together as a single melting
point, with the highest of these peaks being considered the melting point of the random copolymer of propylene. The
random copolymer of propylene preferably has a melting point of less than 100˚C, preferably from about 25˚C to about
75˚C, preferably about 25˚C to about 65˚C, more preferably about 30˚C to about 60˚C.
10 [0411] The procedure for Differential Scanning Calorimetry (DSC) is described as follows: About 6 to 10 mg of a sheet
of the polymer pressed at approximately 200˚C to 230˚C is removed with a punch die. This is annealed at room temperature
for 240 hours. At the end of this period, the sample is placed in a Differential Scanning Calorimeter (Perkin Elmer 7
Series Thermal Analysis System) and cooled to about -50˚C to about -70˚C. The sample is heated at 20˚C/min to attain
a final temperature of about 200˚C to about 220˚C. The thermal output, recorded as the area under the melting peak of
15 the sample which is typically peaked at about 30˚C to about 175˚C and occurs between the temperatures of about 0˚C
and about 200˚C is a measure of the heat of fusion expressed in Joules per gram of polymer. The melting point is
recorded as the temperature of the greatest heat absorption within the range of melting of the sample.
[0412] The random copolymer of propylene may have a Mooney viscosity ML (1+4)@125˚C, as determined according
to ASTM D1646, of less than 100, more preferably less than 75, even more preferably less than 60, most preferably
20 less than 30.
[0413] The random copolymer of propylene of the present invention preferably comprises a random crystallizable
copolymer having a narrow compositional distribution. The intermolecular composition distribution of random copolymer
of propylene (e.g., the narrow compositional distribution) may be determined by thermal fractionation in a solvent such
as a saturated hydrocarbon e.g., hexane or heptane. This thermal fractionation procedure is described below. Typically,
25 approximately 75% by weight and more preferably 85% by weight of the polymer is isolated as one or two adjacent,
soluble fraction with the balance of the polymer in immediately preceding or succeeding fractions. Each of these fractions
has a composition (wt% ethylene content) with a difference of no greater than 20% (relative) and more preferably 10%
(relative) of the average weight percent (wt%) ethylene content of random copolymer of propylene. Thus the random
polypropylene copolymer is said to have a narrow compositional distribution if it meets this fractionation test criteria.
30 [0414] The length and distribution of stereoregular propylene sequences in a preferred random copolymer of propylene
is consistent with substantially random statistical copolymerization. It is well known that sequence length and distribution
are related to the copolymerization reactivity ratios. By substantially random, we mean a copolymer for which the product
of the reactivity ratios is generally 2 or less. In stereoblock structures, the average length of polypropylene sequences
is greater than that of substantially random copolymers with a similar composition. Prior art polymers with stereoblock
35 structure have a distribution of polypropylene sequences consistent with these blocky structures rather than a random
substantially statistical distribution. The reactivity ratios and sequence distribution of the random copolymer of propylene
polymer may be determined by 13C NMR in such as way so as to locate the ethylene residues in relation to the neighboring
propylene residues.
[0415] As outlined herein, to produce random copolymer of propylene with the required randomness and narrow
40 composition distribution, it is desirable to use (1) a single sited catalyst and (2) a well-mixed, continuous flow stirred
tank polymerization reactor which allows only a single polymerization environment for substantially all of the polymer
chains of preferred random copolymer of propylene polymers.
[0416] A preferred random copolymer of propylene used in the present invention is described in detail as the "Second
Polymer Component (SPC)" in co-pending U.S. applications U.S. Ser. No. 60/133,966, filed May 13, 1999, and U.S.
45 Ser. No. 60/342,854, filed Jun. 29, 1999, and described in further detail as the "Propylene Olefin Copolymer" in U.S.
Ser. No. 90/346,460, filed Jul. 1, 1999, which are both fully incorporated by reference herein for purposes of U.S. practice.
[0417] In addition to one or more comonomers making up the major portion of the random copolymer of propylene
polymer (i.e., alpha-olefins) selected such as, but not limited to, ethylene, alpha-olefins having 4 to 8 carbon atoms, and
styrenes, random copolymer of propylene polymers, as described above can contain long chain branches, which can
50 optionally be generated using one or more alpha, omega-dienes. Alternatively, random copolymer of propylene may
comprise at least one diene, and more preferably at least one non-conjugated diene, which may aid in vulcanization
and other chemical modification and/or cross-linking processes. The amount of diene in random copolymer of Propylene
may preferably be no greater than about 10 wt %, more preferably no greater than about 5 wt %.
[0418] In a preferred embodiment, the diene may be selected from the group consisting of those that are used for the
55 vulcanization of ethylene propylene rubbers. Specific examples of preferred dienes include ethylidene norbomene, vinyl
norbomene, dicyclopentadiene, and 1,4-hexadiene (available from DuPont Chemicals).
[0419] In another embodiment, the prSPO of the polymer concentrate may comprise random copolymer of propylene
in the form of a blend of discrete random copolymers of propylene. Such blends can include two or more polyethylene

64
 EP 2 195 349 B1

copolymers (as described above), two or more polypropylene copolymers (as described above), or at least one of each
such polyethylene copolymer and polypropylene copolymer, so long as each of the polymers of the random copolymer
of propylene blend would individually qualify as a random copolymer of propylene. Each of the random copolymers of
propylene are described above and the number of random copolymer of propylene in a preferred embodiment may be
5 three or less, more preferably two or less.
[0420] In an embodiment of the invention, the random copolymer of propylene polymer may comprise a blend of two
random copolymer of propylene polymers differing in the olefin content. Preferably, one random copolymer of propylene
may comprise about 7 to 13 mole % olefin, while the other random copolymer of propylene may comprise about 14 to
22 mole % olefin. In an embodiment, the preferred olefin in the random copolymer of propylene is ethylene.
10 [0421] The random copolymer of propylene polymers useful in the instant invention preferably comprise a particular
triad tacticity. The term "tacticity" refers to the stereogenicity in the polymer. For example, the chirality of adjacent
monomers can be of either like or opposite configuration. The term "diad" is used herein to designate two contiguous
monomers; thus, three adjacent monomers are referred to herein as a triad. In the instance wherein the chirality of
adjacent monomers is of the same relative configuration, the diad is termed isotactic. In the instance wherein the chirality
15 of adjacent monomers is in an opposite relative configuration, the diad is termed syndiotactic. Another way to describe
the configurational relationship is to term contiguous pairs of monomers having the same chirality as meso (m) and
those of opposite configuration racemic (r).
[0422] When three adjacent monomers are of the same configuration, the stereoregularity of the triad is abbreviated
as "mm". If two adjacent monomer in a three-monomer sequence have the same chirality and that is different from the
20 relative configuration of the third unit, this triad has ’mr’ tacticity. An ’rr’ triad has the middle monomer unit having an
opposite configuration from either neighbor. The fraction of each type of triad in a polymer may be determined, and then
multiplied by 100 to indicate the percentage of that type of triad found in the polymer. The reactivity ratios and sequence
distribution of the polymer may be determined by 13C NMR, which locates the ethylene residues in relation to the
neighboring propylene residues.
25 [0423] Random copolymers of propylene have unique propylene tacticity as measured by the % meso triad. As shown
in detail in U.S. Ser. No. 09/108,772, filed Jul. 1, 1998, random copolymer of propylene polymers of this invention have
a lower % meso triad for any given ethylene content when compared to U.S. Pat. No. 5,504,172. The lower content of
% meso triads corresponds to relatively lower crystallinity that translates into better elastomeric properties such as high
tensile strength and elongation at break coupled with very good elastic recovery. Good elastomeric properties are
30 important for some of the potential applications of the present invention.
[0424] Preferred random copolymers of propylene used in embodiments of the present invention have a mm tacticity
index (m/r), also referred to herein as a propylene tacticity index and/or as mm triad tacticity index, of at least 75%. The
propylene tacticity index, expressed herein as "m/r", is determined by 13C nuclear magnetic resonance (NMR). The
propylene tacticity index m/r is calculated as defined in H.N. Cheng, Macromolecules, 17, 1950 (1984). The designation
35 "m" or "r" describes the stereochemistry of pairs of contiguous propylene groups, "m" referring to meso and "r" to racemic.
An m/r ratio of 0 to less than 1.0 generally describes a syndiotactic polymer, and an m/r ratio of 1.0 an atactic material,
and an m/r ratio of greater than 1.0 an isotactic material. An isotactic material theoretically may have a ratio approaching
infinity, and many by-product atactic polymers have sufficient isotactic content to result in ratios of greater than 50.
[0425] In a preferred embodiment, the random copolymers of propylene have isotactic stereoregular propylene crys-
40 tallinity. The term "stereoregular" as used herein means that the predominant number, i.e. greater than 80%, of the
propylene residues in the polypropylene exclusive of any other monomer such as ethylene, has the same 1,2 insertion
and the stereochemical orientation of the pendant methyl groups is the same, either meso or racemic.
[0426] Advantaged random copolymers of propylene useful in this invention have an mm triad tacticity index of three
propylene units, as measured by 13C NMR, of 75% or greater, 80% or greater, 82% or greater, 85% or greater, or 90%
45 or greater. The mm triad tacticity index of a polymer is the relative tacticity of a sequence of three adjacent propylene
units, a chain consisting of head to tail bonds, expressed as a binary combination of m and r sequences. For purposes
herein, it is expressed for random copolymers of propylene of the present invention as the ratio of the number of units
of the specified tacticity to all of the propylene triads in the copolymer. The tacticity index (mm fraction) of a propylene
copolymer can be determined from a 13C NMR spectrum of the propylene copolymer and the following formula:
50

55 where PPP(mm), PPP(mr) and PPP(rr) denote peak areas derived from the methyl groups of the second units in the
following three propylene unit chains consisting of head-to-tail bonds:

65
 EP 2 195 349 B1

10

15

20

[0427] The 13C NMR spectrum of the propylene copolymer is measured as described in U.S. Patent No. 5,504,172.
The spectrum relating to the methyl carbon region (19-23 parts per million (ppm)) can be divided into a first region
25 (21.2-21.9 ppm), a second region (20.3-21.0 ppm) and a third region (19.5-20.3 ppm). Each peak in the spectrum was
assigned with reference to an article in the journal Polymer, Volume 30 (1989), page 1350. In the first region, the methyl
group of the second unit in the three propylene unit chain represented by PPP (mm) resonates. In the second region,
the methyl group of the second unit in the three propylene unit chain represented by PPP (mr) resonates, and the methyl
group (PPE-methyl group) of a propylene unit whose adjacent units are a propylene unit and an ethylene unit resonates
30 (in the vicinity of 20.7 ppm). In the third region, the methyl group of the second unit in the three propylene unit chain
represented by PPP (rr) resonates, and the methyl group (EPE-methyl group) of a propylene unit whose adjacent units
are ethylene units resonates (in the vicinity of 19.8 ppm). The calculation of the mm triad tacticity is outlined in the
techniques shown in U.S. Patent No. 5,504,172. Subtraction of the peak areas for the error in propylene insertions (both
2,1 and 1,3) from peak areas from the total peak areas of the second region and the third region, the peak areas based
35 on the 3 propylene units-chains (PPP(mr) and PPP(rr)) consisting of head-to-tail bonds can be obtained. Thus, the peak
areas of PPP(mm), PPP(mr) and PPP(rr) can be evaluated, and hence the triad tacticity of the propylene unit chain
consisting of head-to-tail bonds can be determined. The triad tacticity can be determined from a 13C-NMR spectrum of
the polymer, as described by J. A. Ewen, "Catalytic Polymerization of Olefins", (the Ewen method); and Eds. T. Keii, K.
Soga; Kodanska Elsevier Pub.; Tokyo, 1986, P 271, and as described in detail in U.S. Patent Application US2004/054086
40 filed March 18, 2004 on page 8, in numbered paragraphs [0046] to [0054].
[0428] Propylene polymers useful as prSPOs herein are available commercially under the trade name Vistamaxx™
(ExxonMobil, Baytown TX). Suitable examples include: VM 1100, VM1120, VM2100, VM2120, VM2125, VM2210,
VM2260, VM2320, VM2330, VM2371, VM3000, VM6100, VM6200.

45 Preparation of prSPOs:

[0429] Random copolymer of propylene useful as soft polyolefins herein can be prepared either in-line or off-line by
polymerizing propylene with one or more of a C2 or C5-C20 alpha olefin, most preferably the random copolymer of
propylene comprises propylene and ethylene. The monomers are advantageously polymerized in the presence of a
50 chiral metallocene catalyst with an activator and optionally a scavenger. The comonomer or comonomers used in
combination with propylene may be linear and/or branched. Advantageous linear alpha-olefins include ethylene or C4
to C8 alpha-olefins, more advantageously ethylene, 1-butene, 1-hexene, and 1-octene, ethylene or 1-butene are par-
ticularly advantageous. Advantageous branched alpha-olefins include 4-methyl-1-pentene, 3-methyl-1-pentene, and
3,5,5-trimethyl-1-hexene.
55 [0430] In one embodiment, a continuous polymerization process may be used to produce random copolymer of
propylene in-line comprising, for example, propylene and one or more of ethylene, octene, or a diene. The polymerization
process may use a metallocene catalyst, for example, one prepared by reacting dimethyl 1,1’-bis(4-triethylsilylphenyl)
methylene-(cyclopentadienyl)(2,7-di-tertiary-butyl-9-fluorenyl)hafnium precursor with dimethylaniliniumtetrakis(pen-

66
 EP 2 195 349 B1

tafluorophenyl)borate as an activator. An organo-aluminum compound, namely, tri-n-octylaluminum, may be added as

a scavenger to the monomer feed streams prior to introduction into the polymerization process. For production of more
crystalline polymers, dimethylsilylbis(indenyl)hafnium dimethyl precursor may be used in combination with dimethyl-
aniliniumtetrakis(pentafluorophenyl) borate. Hexane or bulk monomers may be employed as solvent. In addition, toluene
5 may be added to increase the solubility of the co-catalyst. The feed is fed to the first reactor where the exothermic
polymerization reaction is conducted at a reaction temperature between about 50˚C to about 220˚C. Hydrogen gas may
also be added to the reactors as a further molecular weight regulator. If desired, polymer product is transferred to the
second reactor in series, which is also operated at a temperature between about 50˚C to 200˚C. Note that the one
reactor or two reactors in series represent a single reactor train (in this particular case a plasticizer reactor train) of the
10 disclosed proccesses. Additional monomers, solvent, metallocene catalyst, and activators can be fed to the second
and/or additional reactors.
[0431] In some embodiments, the polymer content leaving the second reactor is preferably from 8 to 22 weight percent.
A heat exchanger then heats the polymer solution to a temperature of about 220˚C. The polymer solution is then brought
to a Lower Critical Solution Temperature (LCST) liquid-liquid phase separator which causes the polymer solution to
15 separate into two liquid phases - an upper lean phase and a lower polymer-rich phase. The upper lean phase contains
about 70 wt % of the solvent and the lower polymer rich phase contains about 30 wt % polymer. The polymer solution
then enters a low pressure separator vessel which operates at a temperature of about 150˚C and a pressure of 4-10
bar-g (400 to 1000 Pa) and flashes the lower polymer rich phase to remove volatiles and to increase the polymer content
to about 76 wt%. A gear pump at the bottom of the flash vessel drives the polymer rich solution to a List devolatilizer.
20 An extruder is coupled to the end of the List devolatilizer whereby the polymer material is transferred to a gear pump
which pushes the polymer material through a screen pack. Then the polymer may be cut into pellets and fed to a water
bath. A spin dryer may be used to dry the polymer pellets, which preferably have a final solvent content of less than
about 0.5 wt %.
[0432] As stated above, advantageous random copolymers of propylene of the present invention may be prepared
25 by polymerizing propylene and at least one C2 or C4-C20 alpha olefin in the presence of a chiral metallocene catalyst
with an activator and optional scavenger, most preferably ethylene and propylene. The terms "metallocene" and "met-
allocene catalyst precursor" are terms known in the art to mean compounds possessing a Group IV, V, or VI transition
metal M, with a cyclopentadienyl (Cp) ligand or ligands which may be may be substituted, at least one non-cyclopenta-
dienyl-derived ligand X, and zero or one heteroatom-containing ligand Y, the ligands being coordinated to M and cor-
30 responding in number to the valence thereof. The metallocene catalyst precursors generally require activation with a
suitable activator (also referred to as an co-catalyst) in order to yield an active metallocene catalyst or catalyst system.
An active metallocene catalyst refers generally to an organometallic complex with a vacant coordination site that can
coordinate, insert, and polymerize olefins.
[0433] Metallocenes for making soft random copolymers of propylene herein include bridged and unbridged biscy-
35 clopentadienyl complexes where the cyclopentadienyl group are, independently, a substituted or unsubstituted cyclopen-
tadienyl group, a substituted or unsubstituted indenyl group, or a substituted or unsubstituted fluorenyl group. Metal-
locenes include those represented by the formula: TCpCpMX2, where T is a bridging group such as a dialkyl silicon
group (such as dimethylsilyl) or a hydrocarbyl group ( such as methyl, ethyl, or propyl), each Cp is, independently a
substituted or unsubstituted cyclopentadienyl group, a substituted or unsubstituted indenyl group (preferably a 2,4 or 2,
40 4, 7 substituted indenyl group), or a substituted or unsubstituted fluorenyl group, M is a group 4 metal (preferably Hf, Zr
or Ti) and each X is independently a halogen or hydrocarbyl group (such as chlorine, bromine, methyl, ethyl, propyl,
butyl, or phenyl).
[0434] Metallocenes for making soft random copolymers of propylene herein include cyclopentadienyl (Cp) complexes
which have two Cp ring systems for ligands. The Cp ligands preferably form a "bent sandwich complex" with the metal
45 and are preferably locked into a rigid configuration through a bridging group. Such preferred cyclopentadienyl complexes
may have the general formula:

(Cp1R1m)R3n(Cp2R2p)MXq

50 wherein Cp1 of ligand (Cp1R1m) and Cp2 of ligand (Cp2R2p) are preferably the same, R1 and R2 each are, independently,
a halogen or a hydrocarbyl, halocarbyl, hydrocarbyl-substituted organometalloid or halocarbyl-substituted organomet-
alloid group containing up to 20 carbon atoms;
m is preferably 1 to 5;
p is preferably 1 to 5;
55 preferably two R1 and/or R2 substituents on adjacent carbon atoms of the cyclopentadienyl ring associated there can
be joined together to form a ring containing from 4 to 20 carbon atoms;
R3 is a bridging group;
n is the number of atoms in the direct chain between the two ligands and is preferably 1 to 8, most preferably 1 to 3;

67
 EP 2 195 349 B1

M is a transition metal having a valence of from 3 to 6, preferably from group 4, 5, or 6 of the periodic table of the
elements and is preferably in its highest oxidation state,
each X is a non-cyclopentadienyl ligand and is, independently, a hydrocarbyl, oxyhydrocarbyl, halocarbyl, hydrocarbyl-
substituted organometalloid, oxyhydrocarbyl-substituted organometalloid or halocarbyl-substituted organometalloid
5 group containing up to 20 carbon atoms; and
q is equal to the valence of M minus 2.
[0435] Numerous examples of the biscyclopentadienyl metallocenes described above for the invention are disclosed
in U.S. Pat. Nos. 5,324,800; 5,198,401; 5,278,119; 5,387,568; 5,120,867; 5,017,714; 4,871,705; 4,542,199; 4,752,597;
5,132,262; 5,391,629; 5,243,; 5,278,264; 5,296,434; and 5,304,614. Illustrative, but not limiting examples of preferred
10 biscyclopentadienyl metallocenes of the type described above for the invention include the racemic isomers of:

m-(CH3)2Si(indenyl)2M(Cl)2
m-(CH3)2Si(indenyl)2M(CH3)2
m-(CH3)2Si(tetrahydroindenyl)2M(Cl)2
15 m-(CH3)2Si(tetrahydroindenyl)2M(CH3)2
m-(CH3)2Si(indenyl)2M(CH2CH3)2
m-(C6H5)2C(indenyl)2M(CH3)2;

wherein M may include Zr, Hf, and/or Ti.

20 [0436] These metallocenes may advantageously be used in combination with one or more aluminoxanes (preferably
methyl aluminoxane, or modified methyl aluminoxane) and or one or more ionic activators such as N,N-dimethylanilinium
tetraphenylborate, N,N-dimethylanilinium tetrakis(penta-fluorophenyl) borate, diphenylcarbenium tetra(perfluorophenyl)
borate, or N,N-dimethylanilinium tetrakis (heptafluoronaphthyl)borate.

25 IV.B. Ethylene-Rich Soft Polyolefins

[0437] An ethylene-rich soft polyolefin (erSPO) is an ethylene copolymer comprising at least 50 wt% ethylene and
having the properties of a soft polyolefin. In some embodiments, the erSPO comprises at least 60 wt% ethylene, or at
least 70 wt% ethylene, or at least 80 wt% ethylene, or at least 90 wt% ethylene.
30 [0438] In one embodiment, the erSPO may comprise 10 to 50 wt %, or 10 to 40 wt %, or 10 to 30 wt%, or 10 to 20
wt% of a C3-C20 comonomer. In another embodiment,erSPOs advantageously have a composition distribution breadth
index (CDBI) above 90%, even more preferably above 95%. In another embodiment, erSPOs has a density of 0.86 to
0.925 g/mL and a CDBI of over 90%, preferably between 95% and 99%. In another embodiment, erSPOs has a MI of
0.1 to 100 g/10 min, preferably 0.5 to 50 g/10 min, more preferably 0.8 to 30 g/10 min.
35 [0439] In one embodiment, the erSPOs are metallocene polyethylenes (mPE’s). The mPE homopolymers or copoly-
mers may be produced using mono- or bis-cyclopentadienyl transition metal catalysts in combination with an activator
of aluminoxane and/or a non-coordinating anion in homogeneous supercritical, solution, or slurry process. Advanta-
geously, the polymerization is performed in a homogeneous supercritical or solution process. The catalyst and activator
may be supported or unsupported and the cyclopentadienyl rings by may substituted or unsubstituted. Several com-
40 mercial products produced with such catalyst/activator combinations are commercially available from ExxonMobil Chem-
ical Company in Baytown, Texas under the tradename EXACT™. For more information on the methods and catalysts/
activators to produce such mPE homopolymers and copolymers see WO 94/26816; WO 94/03506; EPA 277 003; EPA
277 004; U.S. Pat. No. 5,153,157; U.S. Pat. No. 5,198,401; U.S. Pat. No. 5,240,894; U.S. Pat. No. 5,017,714; CA
1,268,753; U.S. Pat. No. 5,324,800; EPA 129 368; U.S. Pat. No. 5,264,405; EPA 520 732; WO 92 00333; U.S. Pat. No.
45 5,096,867; U.S. Pat. No. 5,507,475; EPA 426 637; EPA 573 403; EPA 520 732; EPA 495 375; EPA 500 944; EPA 570
982; WO 91/09882; WO 94/03506 and U.S. Pat. No. 5,055,438.
[0440] Examples of Exact Plastomers suitable for use herein as solft polyolefins include:

EXACT-Plastomers
50
EXACT- Plastomers Composition Density (g/mL) Melt-Index (g/10 min) DSC-Melting Peak (˚C),
Grade 10 ˚C/min
3024 Ethylene/butene 0.905 4.5 98
3035 Ethylene/butene 0.900 3.5 88
55 3128 Ethylene/butene 0.900 1.2 92
4006 Ethylene/butene 0.880 10 60
4011 Ethylene/butene 0.888 2.2 70

68
 EP 2 195 349 B1

(continued)
EXACT- Plastomers Composition Density (g/mL) Melt-Index (g/10 min) DSC-Melting Peak (˚C),
Grade 10 ˚C/min
5 4033 Ethylene/butene 0.880 0.8 60
4049 Ethylene/butene 0.873 4.5 55
3040 Ethylene/hexene 0.900 16.5 96
3131 Ethylene/hexene 0.900 3.5 95
3132 Ethylene/hexene 0.900 1.2 96
10
3139 Ethylene/hexene 0.900 7.5 95
4056 Ethylene/hexene 0.883 2.2 72
4151 Ethylene/hexene 0.895 2.2 89
0201 Ethylene/octene 0.902 1.1 95
15 0203 Ethylene/octene 0.902 3.0 95
0210 Ethylene/octene 0.902 10 96
0230 Ethylene/octene 0.902 30 95
5061 Ethylene/octene 0.868 0.5 53
5062 Ethylene/octene 0.860 0.5 43
20 5101 Ethylene/octene 0.902 1.1 98
5171 Ethylene/octene 0.870 1.0 55
5181 Ethylene/octene 0.882 1.1 73
5361 Ethylene/octene 0.860 3.0 36
25
5371 Ethylene/octene 0.870 5.0 64
8201 Ethylene/octene 0.882 1.1 67
8203 Ethylene/octene 0.882 3.0 73
8210 Ethylene/octene 0.882 10 67
8230 Ethylene/octene 0.882 30 77
30

[0441] Other suitable erSPOs include low-density polyethylene (LDPE), linear-low density polyethylene (LLDPE), and
very-low density polyethylene (vLDPE) type polyethylene polymers and copolymers which have the properties of a soft
polyolefin.

35
III.C. Elastomeric Soft Polyolefins

[0442] The SPO may be a cross-linkable polyolefin elastomer containing ethylene, propylene, and optionally one or
more diene. Illustrative examples include ethylene-propylene (EP) elastomers and ethylene-propylene-diene (EPDM)
elastomers.
40
[0443] A suitable EP elastomer can have an ethylene content of 40 to 80 wt % (preferably 45 to 75 wt %, preferably
50 to 70 wt %). A suitable EP elastomer can also have an ethylene content of 5 to 25 wt % (preferably 10 to 20 wt %).
A suitable EPDM elastomer can have an ethylene content of 40 to 80 wt % (preferably 45 to 75 wt %, preferably 50 to
70 wt %) and a diene content of less than 15 wt % (preferably 0.5 to 15 wt %, preferably 1 to 12 wt %, preferably 2 to
10 wt %, preferably 3 to 9 wt %). In one or more embodiments, a suitable EPDM elastomer can have an ethylene content
45
of 5 to 25 wt % (preferably 10 to 20 wt %). In other embodiments, a suitable EPDM elastomer can have a diene content
of 0.1 to 3 wt % (preferably 0.3 to 2 wt %), or 0.3 to 10 wt % (preferably 1 to 5 wt %). Suitable dienes can have at least
two unsaturated bonds, at least one of which can be incorporated into a polymer, and can be straight chained, branched,
cyclic, bridged ring, bicyclic, etc.; preferably the unsaturated bonds are nonconjugated. Preferred dienes include 5-
ethylidene-2-norbomene (ENB), 5-vinyl-2-norbornene (VNB), divinyl benzene (DVB), dicyclopentadiene (DCPD), and
50
1,4-hexadiene.
[0444] Preferred EP and EPDM elastomers can have one or more of the following properties: a density of 0.885 g/cm3
or less (preferably 0.88 g/cm3, preferably 0.87 g/cm3 or less, preferably 0.865 g/cm3 or less, preferably 0.86 g/cm3 or
less, preferably 0.855 g/cm3 or less); and/or a heat of fusion (Hf) of less than 70 J/g (preferably less than 60 J/g, preferably
less than 50 J/g, preferably less than 40 J/g, preferably less than 30 J/g, preferably less than 20 J/g, preferably less
55
than 10 J/g, preferably less than 5 J/g, preferably indiscernible); and/or an ethylene or propylene crystallinity of less than
15 wt% (preferably less than 10 wt%, preferably less than 5 wt%, preferably less than 2 wt%, preferably undetectable);
and/or a melting point (Tm) of 120˚C or less (preferably 100˚C or less, preferably 80˚C or less, preferably 70˚C or less,

69
 EP 2 195 349 B1

preferably 60˚C or less, preferably 50˚C or less, preferably 40˚C or less, preferably 35˚C or less, preferably undetectable);
and/or a glass transition temperature (Tg) of -20˚C or less (preferably -30˚C or less, preferably -40˚C or less, preferably
-50˚C or less, preferably -60˚C or less); and/or a Mw of 50 to 5,000 kg/mol (preferably 100 to 3,000 kg/mol, preferably
150 to 2,000 kg/mol, preferably 200 to 1,000 kg/mol); and/or a Mw/Mn of 1.5 to 40 (preferably 1.6 to 30, preferably 1.7
5 to 20, preferably 1.8 to 10); and/or a Mooney viscosity, ML(1+4) at 125˚C of 1 to 100 (preferably 5 to 95, preferably 10
to 90, preferably 15 to 85, preferably 20 to 80).
[0445] In one or more embodiments, the EP or EPDM elastomer can be functionalized. For example, the ethylene-
propylene elastomers can be functionalized by reacting with organic compounds with polar moieties, such as amine-,
carboxy-, and/or epoxy-moieties. Examples include maleated EP and EPDM elastomers.
10 [0446] Suitable ethylene-propylene elastomers include those available from ExxonMobil Chemical under the Vis-
talon®, and Exxelor™ tradenames.

III.D. Other Soft Polyolefins

15 [0447] Other suitable soft polyolefins include propylene homopolymer and/or propylene copolymers that have been
contacted with less than about 10 wt % of a highly crystalline branched or coupled polymeric nucleating agent under
nucleation conditions. Such polymers may be produced with an activated non metallocene, metal-centered, heteroaryl
ligand catalyst, as described in WO 03/040095 on pages 21-52. Examples include a propylene-ethylene copolymer
comprising at least about 60 weight percent of units derived from propylene and at least about 0.1 weight percent of
20 units derived from ethylene.
[0448] Particular embodiments of such polymers include a propylene-ethylene copolymer comprising at least about
60 weight percent of units derived from propylene and at least about 0.1 weight percent of units derived from ethylene,
as disclosed in WO 03/040095 A2 at page 9.
[0449] Other polymers useful as the soft polyolefin include one or more polypropylene copolymers having elastic
25 properties. Such preferred propylene copolymers having elastic properties may be prepared according the procedures
in WO 02/36651 which is incorporated by reference here. Likewise, the SPO may comprise polymers consistent with
those described in WO 03/040202, WO 03/040095, WO 03/040201, WO 03/040233, and/or WO 03/040442. Additionally,
the SPO may comprise polymers consistent with those described in EP 1 233 191, and US 6,525,157.
[0450] Other polymers useful as the soft polyolefin include homopolymer and copolymers of butene-1; isobutylene-
30 based elastomers such as butyl, halobutyl, and functionalized (e.g., by halogenation) or unfunctionalized copolymers
of isobutylene and one or more styrenic comonomer such as p-methylstyrene; styrenic block copolymers such as SBS,
SIS, SEBS, and SEPS; and thermoplastic vulcanizates. The SPO may also be a blend of one or more individual SPO
components as described above.
[0451] The above identified composition and properties described for the various in-line produced and off-line produced
35 plasticizers of the instant invention may also be combined to form numerous combinations of plasticizer types and
properties that have not be specifically set forth above, but still fall within the scope of the present disclosure.

Plasticized Polymer Blends and Polymer Additives:

40 [0452] In one embodiment, the plasticized polymer blends produced by the fluid phase in-line polymer blending process
disclosed herein include a single high molecular base polymer blend component made in one of the parallel reactor
trains and a single plasticizer blend component produced in a second parallel reactor train.
[0453] In one form, the plasticizer is an alpha-olefin oligomer fluid with a molecular weight of 20,000 g/mol or less,
15,000 g/mol or less, 10,000 g/mol or less, or 5,000 g/mol or less. In another embodiment, the alpha-olefin oligomer
45 has a molecular weight of 500 to 5,000 g/mol. At these low molecular weights, the alpha olefin oligomer fluids are miscible
to a degree with the polymer blend components disclosed herein to provide a plasticizing effect. In another embodiment,
the plasticizer is a low glass transition temperature polymeric material with a glass transition temperature of less than
0˚C, or less than -5˚C, or less than -25˚C. Partial miscibility of the low glass transition temperature polymeric material
with the high molecular polymer blend component is advantageous.
50 [0454] In another embodiment, the plasticized polymer blends produced produced by the fluid phase in-line polymer
blending process disclosed herein include a single high molecular weight base polymer blend component made in one
of the parallel reactor trains and two or more In-Line-Produced Plasticizer blend components.
[0455] In another embodiment, the plasticized polymer blends produced by the fluid phase in-line polymer blending
process disclosed herein include two or more high molecular weight base polymer components, including but not limited
55 to, thermoplastic polymer(s) and/or elastomer(s) blended with one or more In-Line-Produced Plasticizer blend compo-
nents.
[0456] In yet another embodiment, any of the preceding embodiments including one or more high molecular weight
base polymers and one or more plasticizer components produced and blended in-line may further include one or more

70
 EP 2 195 349 B1

other plasticizer components that are not produced in-line (off-line-produced plasticizer component), but blended in-line.
These plasticizers which are not produced in-line because they are not conducive to such may still be in-line blended
with the plasticized polymer components from the previous three embodiments from one or more polymer/additive
storage tanks. Plasticizers that may not be reacted in-line, but may be in-line blended, include, but are not limited to the
5 following: paraffin oils and waxes (n-paraffins, isoparaffins, paraffin blends), dearomatized aliphatic hydrocarbons, proc-
ess oils, high purity hydrocarbon fluids, lubricant basestocks, other oils, phthalates, mellitates and adipates, etc.
[0457] A "thermoplastic polymer(s)" is a polymer that can be melted by heat and then cooled with out appreciable
change in properties. Thermoplastic polymers typically include, but are not limited to, polyolefins, polyamides, polyesters,
polycarbonates, polysulfones, polyacetals, polylactones, acrylonitrile-butadiene-styrene resins, polyphenylene oxide,
10 polyphenylene sulfide, styrene-acrylonitrile resins, styrene maleic anhydride, polyimides, aromatic polyketones, or mix-
tures of two or more of the above. The disclosed procceses make and blend polyolefin base polymer components in-
line. Polyolefins include, but are not limited to, polymers comprising one or more linear, branched or cyclic C2 to C40
olefins, polymers comprising propylene copolymerized with one or more C2 or C4 to C40 olefins, C3 to C20 alpha olefins,
or C3 to C10 α-olefins. Also, polyolefins include, but are not limited to, polymers comprising ethylene including but not
15 limited to ethylene copolymerized with a C3 to C40 olefin, a C3 to C20 alpha olefin, propylene and/or butene.
[0458] "Elastomers" encompass all natural and synthetic rubbers, including those defined in ASTM D1566). Examples
of useful elastomers include, but are not limited to, ethylene propylene rubber, ethylene propylene diene monomer
rubber, styrenic block copolymer rubbers (including SI, SIS, SB, SBS, SEBS and the like, where S=styrene, I=isobutylene,
and B=butadiene), butyl rubber, halobutyl rubber, copolymers of isobutylene and para-alkylstyrene, halogenated copol-
20 ymers of isobutylene and para-alkylstyrene, natural rubber, polyisoprene, copolymers of butadiene with acrylonitrile,
polychloroprene, alkyl acrylate rubber, chlorinated isoprene rubber, acrylonitrile chlorinated isoprene rubber, polybuta-
diene rubber (both cis and trans).
[0459] In another form, the plasticized polymer blends produced herein may include one or more of isotactic polypro-
pylene, highly isotactic polypropylene, syndiotactic polypropylene, random copolymer of propylene and ethylene and/or
25 butene and/or hexene, polybutene, ethylene vinyl acetate, low density polyethylene (density 0.915 to less than 0.935
g/mL), linear low density polyethylene, ultra low density polyethylene (density 0.86 to less than 0.90 g/mL), very low
density polyethylene (density 0.90 to less than 0.915 g/mL), medium density polyethylene (density 0.935 to less than
0.945 g/mL), high density polyethylene (density 0.945 to 0.98 g/mL), ethylene vinyl acetate, ethylene methyl acrylate,
copolymers of acrylic acid, polymethylmethacrylate or any other polymers polymerizable by a high-pressure free radical
30 process, polyvinylchloride, polybutene-1, isotactic polybutene, ABS resins, ethylene-propylene rubber (EPR), vulcanized
EPR, EPDM, block copolymer, styrenic block copolymers, polyamides, polycarbonates, PET resins, crosslinked poly-
ethylene, polymers that are a hydrolysis product of EVA that equate to an ethylene vinyl alcohol copolymer, polymers
of aromatic monomers such as polystyrene, poly-1 esters, polyacetal, polyvinylidine fluoride, polyethylene glycols and/or
polyisobutylene.
35 [0460] In another form, elastomers are blended using the processes disclosed herein to form rubber-toughened com-
positions. In some forms, the rubber toughened composition is a two (or more) phase system where the elastomer is a
discontinuous phase and the polymer produced herein is a continuous phase. This blend may be combined with tackifiers
and/or other additives as described herein.
[0461] In another form, the plasticized polymer blends produced by the processes disclosed herein may include
40 elastomers or other soft polymers to form impact copolymers. In some forms, the blend is a two (or more) phase system
where the elastomer or soft polymer is a discontinuous phase and other polymer(s) is a continuous phase. The blends
produced herein may be combined with tackifiers and/or other additives as described herein.
[0462] In some forms, the plasticized polymers blends disclosed herein include metallocene polyethylenes (mPEs)
or metallocene polypropylenes (mPPs). The mPE and mPP homopolymers or copolymers are typically produced using
45 mono- or bis-cyclopentadienyl transition metal catalysts in combination with an activator of aluminoxane and/or a non-
coordinating anion in solution, slurry, high pressure or gas phase. The catalyst and activator may be supported or
unsupported and the cyclopentadienyl rings may be substituted or unsubstituted. Several commercial products produced
with such catalyst/- activator combinations are commercially available from ExxonMobil Chemical Company in Baytown,
Texas under the tradenames EXCEED™, ACHIEVE™ and EXACT™. For more information on the methods and cata-
50 lysts/activators to produce such homopolymers and copolymers see WO 94/26816; WO 94/03506; EPA 277 003; EPA
277 004; U.S. Pat. No. 5,153,157; U.S. Pat. No. 5,198,401; U.S. Pat. No. 5,240,894; U.S. Pat. No. 5,017,714; CA
1,268,753; U.S. Pat. No. 5,324,800; EPA 129 368; U.S. Pat. No. 5,264,405; EPA 520 732; WO 92 00333; U.S. Pat. No.
5,096,867; U.S. Pat. No. 5,507,475; EPA 426 637; EPA 573 403; EPA 520 732; EPA 495 375; EPA 500 944; EPA 570
982; WO 91/09882; WO 94/03506 and U.S. Pat. No. 5,055,438.
55 [0463] In some forms the plasticized polymer blends produced by the processes disclosed herein include one or more
high molecular weight base polymers at from 10 to 99.9 wt %, based upon the weight of the plasticizer and polymers in
the blend, or 20 to 99.9 wt %, or at least 30 to 99.9 wt %, or at least 40 to 99.9 wt %, or at least 50 to 99.9 wt %, or at
least 60 to 99.9 wt %, or at least 70 to 99.9 wt % with plasticizers and other polymer additives constituting the remainder

71
 EP 2 195 349 B1

of the blend. In one form, the one or more plasticizer blend components are present in the plasticized polymer blend at
lower limits of 0.1 wt %, or 0.25 wt %, or 0.5 wt %, or 0.75 wt %, or 1 wt %, or 2 wt %, or 5 wt %, or 10 wt %, 15 wt %,
or 20 wt %, or 30 wt %, or 40 wt %, or 50 wt % based on the overall weight of the plasticized polymer blend. In another
form, the one or more plasticizer blend components are present in the plasticized polymer blend at upper limits of 20
5 wt %, or 25 wt %, or 30 wt %, or 35 wt %, or 40 wt %, or 45 wt %, or 50 wt %, or 60 wt %, 70 wt %, or 80 wt %, or 90
wt % based on the overall weight of the plasticized polymer blend.
[0464] In another form, in-line plasticized polymer blends are produced from propylene-based base polymers and
plasticizers made at homogeneous polymerization conditions, particularly at bulk homogeneous polymerization condi-
tions, such as bulk homogeneous supercritical or bulk solution polymerization, and comprise the following:
10
(a) 10-20 wt % of isotactic polypropylene with 0.8-10,000 g/10 min MFR and melting peak temperatures of 80-165˚C
plus 80-90 wt % crystallizable ethylene-propylene copolymer comprising 10-16 wt % ethylene content and 0.8-100
g/10 min MFR or
(b) 15-90 wt % of isotactic polypropylene with 0.8-10,000 dg/min MFR and melting peak temperatures of 80-165˚C
15 plus 10-85 wt % propylene copolymer of isotactic polypropylene crystallinity comprising 1-20 wt % ethylene or 1-40
wt % hexene-1 or 1-30 wt butene-1 content and 0.8-100 g/10 min MFR or
(c) 10-30 wt % of isotactic polypropylene with 0.8-10,000 dg/min MFR and melting peak temperatures of 80-165˚C
plus 90-70 wt % low-crystallinity (0-30 J/g) homo- or copolymer with MFR of 0.8-500 g/10 min or

20 [0465] The in-line-plasticized polymer blends produced by the process disclosed herein may be also blended with
other polymers and additives using the in-line blending process for other polymers and additives depicted in FIG. 11, in
an extrusion process downstream of in-line polymerization/separation/blending processes disclosed herein, or blended
in an off-line compounding process.
[0466] Any of the above polymers included in the in-line polymer blends produced by the processes disclosed herein
25 may be functionalized. Functionalized means that the polymer has been contacted with an unsaturated acid or anhydride.
Forms of unsaturated acids or anhydrides include any unsaturated organic compound containing at least one double
bond and at least one carbonyl group. Representative acids include carboxylic acids, anhydrides, esters and their salts,
both metallic and non-metallic. The organic compound contains an ethylenic unsaturation conjugated with a carbonyl
group (-C=O). Non-limiting examples include maleic, fumaric, acrylic, methacrylic, itaconic, crotonic, alpha-methyl cro-
30 tonic, and cinnamic acids as well as their anhydrides, esters and salt derivatives. Maleic anhydride is one particular
form. The unsaturated acid or anhydride is present at about 0.1 wt % to about 5 wt %, or at about 0.5 wt % to about 4
wt %, or at about 1 to about 3 wt %, based upon the weight of the hydrocarbon resin and the unsaturated acid or anhydride.
[0467] Tackifiers may also be blended either in-line by the processes disclosed herein (see FIG. 11), in-line via an
extrusion process downstream of in-line polymerization/separation/blending processes disclosed herein, or in an off-
35 line compounding process. Examples of useful tackifiers include, but are not limited to, aliphatic hydrocarbon resins,
aromatic modified aliphatic hydrocarbon resins, hydrogenated polycyclopentadiene resins, polycyclopentadiene resins,
gum rosins, gum rosin esters, wood rosins, wood rosin esters, tall oil rosins, tall oil rosin esters, polyterpenes, aromatic
modified polyterpenes, terpene phenolics, aromatic modified hydrogenated polycyclopentadiene resins, hydrogenated
aliphatic resin, hydrogenated aliphatic aromatic resins, hydrogenated terpenes and modified terpenes, and hydrogenated
40 rosin esters. In some embodiments the tackifier is hydrogenated. In other embodiments the tackifier is non-polar. Non-
polar tackifiers are substantially free of monomers having polar groups. The polar groups are generally not present;
however, if present, they are not present at more that 5 wt %, or not more that 2 wt %, or no more than 0.5 wt %. In
some embodiments, the tackifier has a softening point (Ring and Ball, as measured by ASTM E-28) of 80˚C to 140˚C,
or 100˚C to 130˚C. In some embodiments the tackifier is functionalized. By functionalized is meant that the hydrocarbon
45 resin has been contacted with an unsaturated acid or anhydride. Useful unsaturated acids or anhydrides include any
unsaturated organic compound containing at least one double bond and at least one carbonyl group. Representative
acids include carboxylic acids, anhydrides, esters and their salts, both metallic and non-metallic. The organic compound
may contain an ethylenic unsaturation conjugated with a carbonyl group (-C=O). Non-limiting examples include maleic,
fumaric, acrylic, methacrylic, itaconic, crotonic, alpha-methyl crotonic, and cinnamic acids as well as their anhydrides,
50 esters and salt derivatives. Maleic anhydride is particularly useful. The unsaturated acid or anhydride may be present
in the tackifier at about 0.1 wt % to 10 wt %, or at 0.5 wt % to 7 wt %, or at 1 to 4 wt %, based upon the weight of the
hydrocarbon resin and the unsaturated acid or anhydride.
[0468] The tackifier, if present, is typically present at 1 wt % to 50 wt %, based upon the weight of the blend, or 10 wt
% to 40 wt %, or 20 wt % to 40 wt %. Generally however, tackifier is not present, or if present, is present at less than
55 10 wt %, or less than 5 wt %, or at less than 1 wt %.
[0469] In another form, the plasticized polymer blends produced by the processes disclosed herein further comprise
a crosslinking agent. The crosslinking agent may be blended either either in-line by the processes disclosed herein (see
FIG. 11), in-line via an extrusion process downstream of in-line polymerization/separation/blending processes disclosed

72
 EP 2 195 349 B1

herein, or in an off-line compounding process. Useful crosslinking agents include those having functional groups that
can react with the acid or anhydride group and include alcohols, multiols, amines, diamines and/or triamines. Non-limiting
examples of crosslinking agents useful include polyamines such as ethylenediamine, diethylenetriamine, hexamethyl-
enediamine, diethylaniinopropylamine, and/or menthanediamine.
5 [0470] In another form, the plasticized polymer blends produced by the processes disclosed herein, and/or blends
thereof, further comprise typical additives known in the art such as fillers, cavitating agents, antioxidants, surfactants,
adjuvants, other plasticizers, block, antiblock, color masterbatches, pigments, dyes, processing aids, UV stabilizers,
neutralizers, lubricants, waxes, nucleating agents and/or clarifying agents. These additives may be present in the typically
effective amounts well known in the art, such as 0.001 wt % to 10 wt %. These additive may be blended either either
10 in-line by the processes disclosed herein (see FIG. 11), in-line via an extrusion process downstream of in-line polym-
erization/separation/blending processes disclosed herein, or in an off-line compounding process.
[0471] Useful fillers, cavitating agents and/or nucleating agents include titanium dioxide, calcium carbonate, barium
sulfate, silica, silicon dioxide, carbon black, sand, glass beads, mineral aggregates, talc, clay and the like. Nucleating
agents of the non-clarifying type include, but are not limited to, sodium benzoate, Amfine NA 11, Amfine NA 21, and
15 Milliken HPN 68.
[0472] Useful antioxidants and UV stablilizers include phenolic antioxidants, such as Irganox 1010, Irganox 1076 both
available from Ciba-Geigy. Oils may include paraffinic or naphthenic oils such as Primol 352, or Primol 876 available
from ExxonMobil Chemical France, S.A. in Paris, France. The oils may include aliphatic naphthenic oils, white oils or
the like.
20 [0473] Useful processing aids, lubricants, waxes, and/or oils include low molecular weight products such as wax, oil
or low Mn polymer, (low meaning below Mn of 5000, or below 4000, or below 3000, or below 2500). Useful waxes include
polar or non-polar waxes, functionalized waxes, polypropylene waxes, polyethylene waxes, and wax modifiers.
[0474] Useful functionalized waxes include those modified with an alcohol, an acid, or a ketone. Functionalized means
that the polymer has been contacted with an unsaturated acid or anhydride. Useful unsaturated acids or anhydrides
25 include any unsaturated organic compound containing at least one double bond and at least one carbonyl group.
Representative acids include carboxylic acids, anhydrides, esters and their salts, both metallic and non-metallic. The
organic compound may contain an ethylenic unsaturation conjugated with a carbonyl group (-C=O). Non-limiting exam-
ples include maleic, fumaric, acrylic, methacrylic, itaconic, crotonic, alpha-methyl crotonic, and cinnamic acids as well
as their anhydrides, esters and salt derivatives. Maleic anhydride is particularly useful. The unsaturated acid or anhydride
30 may be present at 0.1 wt % to 10 wt %, or at 0.5 wt % to 7 wt %, or at 1 to 4 wt %, based upon the weight of the
hydrocarbon resin and the unsaturated acid or anhydride. Examples include waxes modified by methyl ketone, maleic
anhydride or maleic acid. Low Mn polymers include polymers of lower alpha olefins such as propylene, butene, pentene,
hexene and the like. A useful polymer includes polybutene having an Mn of less than 1000 g/mol. An example of such
a polymer is available under the trade name PARAPOL™ 950 from ExxonMobil Chemical Company. PARAPOL™ 950
35 is a liquid polybutene polymer having an Mn of 950 g/mol and a kinematic viscosity of 220 cSt at 100˚C, as measured
by ASTM D 445.
[0475] Useful clarifying agents include, but are not limited to, the benzalsorbitol family of clarifiers, and more particularly
dibenzalsorbitol (Millad 3905), di-p-methylbenzalsorbitol (Milliad 3940), and bis-3,4-dimethylbenzalsorbitol (Milliad
3988).
40
Applications:

[0476] The plasticized polymer blends produced by the processes disclosed herein are typically used in any known
thermoplastic or elastomer application. Non-limiting examples include uses in molded parts, films, tapes, sheets, tubing,
45 hose, sheeting, wire and cable coating, adhesives, shoe soles, bumpers, gaskets, bellows, films, fibers, elastic fibers,
nonwovens, spunbonds, sealants, surgical gowns and medical devices. The plasticized polymer blends produced by
the processes disclosed herein are particularly advantageous in applications requiring toughness, flexibility, and impact
resistance at low temperatures. Non-limiting exemplary applications include polyolefin based parts used in appliances
(i.e. refrigerators, and freezers) as wells as parts used in cold temperature environments.
50

Claims

1. An in-line blending process for plasticized polymers comprising:

55
(a) providing two or more reactor trains configured in parallel and a high-pressure separator downstream fluidly
connected to the two or more reactor trains configured in parallel, wherein one or more of the reactor trains
produces one or more base polymers and one or more of the reactor trains produces one or more plasticizers;

73
 EP 2 195 349 B1

(b) contacting in the two or more reactor trains configured in parallel 1) olefin monomers having two or more
carbon atoms 2) one or more catalyst systems, 3) optional one or more comonomers, 4) optional one or more
scavengers, and 5) optional one or more diluents or solvents,
wherein at least one of the reactor trains configured in parallel is at a temperature above the solid-fluid phase
5 transition temperature of the polymerization system and a pressure no lower than 10 MPa below the cloud point
pressure of the polymerization system and less than 1500 MPa,
wherein the polymerization system for each reactor train is in its dense fluid state and comprises the olefin
monomers, any comonomer present, any diluent or solvent present, any scavenger present, and the polymer
product,
10 wherein the catalyst system for each reactor train comprises one or more catalyst precursors, one or more
activators, and optionally, one or more catalyst supports,
wherein the one or more catalyst systems are chosen from Ziegler-Natta catalysts, metallocene catalysts,
nonmetallocene metal-centered, heteroaryl ligand catalysts, late transition metal catalysts, and combinations
thereof;
15 (c) forming an unreduced polymer or unreduced plasticizer reactor effluent including a homogeneous fluid phase
polymer-monomer mixture in one or more parallel reactor trains and a homogeneous fluid phase plasticizer-
monomer mixture in one or more parallel reactor trains;
(d) passing the reactor effluents comprising the homogeneous fluid phase polymer-monomer mixture and plas-
ticizer-monomer mixture from each parallel reactor train through the high-pressure separator for product blending
20 and product-feed separation;
(e) maintaining the temperature and pressure within the high-pressure separator above the solid-fluid phase
transition point but below the cloud point pressure and temperature to form a fluid-fluid two-phase system
comprising a plasticized polymer-rich blend phase and a monomer-rich phase; and
(f) separating the monomer-rich phase from the plasticized polymer-rich blend phase in the high pressure
25 separator to form a plasticized polymer blend and a separated monomer-rich phase.

2. The process of claim 1 wherein in (b) the polymerization systems for the two or more reactor trains configured in
parallel are at temperatures above the solid-fluid phase transition temperatures and pressures no lower than 10
MPa below the cloud point pressures and less than 1500 MPa, and comprise less than 40 wt % of optional one or
30 more diluents or solvents.

3. The process of claim 1 wherein the olefin monomers having two or more carbon atoms of (b) comprise propylene.

4. The process of claim 1 wherein the olefin monomers and optional one or more comonomers of (b) comprise one
35 or more of ethylene, propylene, butenes, hexenes, octenes, decenes, or dodecenes.

5. The process of claim 1 further comprising providing one or more storage tanks, and feeding from the one or more
storage tanks one or more polymers, one or more off-line produced plasticizers and/or one or more polymer additives
to the process after (c).
40
6. The process of claim 5 further comprising feeding the polymer-rich phase of the high-pressure separator of (a)
containing the plasticized polymer blend to one or more-low pressure separators to further separate the monomers
and other volatiles from the plasticized polymer blend to form a further-enriched plasticized polymer blend, and
feeding the further-enriched plasticized polymer blend to a coupled devolatilizer to further separate other volatiles
45 from the further-enriched plasticized polymer blend to form a plasticized polymer product blend, wherein the coupled
devolatilizer operates under vacuum enabling the further-enriched plasticized polymer blend to flash off the mono-
mers and other volatiles, and wherein the coupled devolatilizer is a devolatilizing extruder, and wherein one or more
polymers, one or more off line produced plasticizer and/or one or more polymer additives are added to the plasticized
polymer product blend at the high-pressure separator, the low-pressure separator, the devolatilizing extruder or
50 combinations thereof.

7. The process of claim 6 wherein the one or more off-line produced plasticizers are chosen from ethylene-based
polyolefin oligomers, propylene-based polyolefin oligomers, butene-based polyolefin oligomers, higher alphaolefin-
based polyolefin oligomers, paraffins, mineral oils, process oils, high purity hydrocarbon fluids, Group III lubricant
55 basestocks, esters, propylene-rich soft polyolefins, ethylene-rich soft polyolefins, elastomeric soft polyolefins, pro-
pylene homopolymers, propylene copolymers, butene-1 homopolymers, butene-1 copolymers, isobutylene-based
elastomers, thermoplastic vulcanizates and combinations thereof.

74
 EP 2 195 349 B1

8. The process of claim 1 wherein the one or more plasticizers comprise an ethylene-based polyolefin oligomer, a
propylene-based polyolefin oligomer, a butene-based polyolefin oligomer, a higher-alphaolefin-based polyolefin
oligomer, propylene-rich soft polyolefins, ethylene-rich soft polyolefins, elastomeric soft polyolefins, propylene
homopolymers, propylene copolymers, butene-1 homopolymers, butene-1 copolymers, isobutylene-based elas-
5 tomers, thermoplastic vulcanizates and combinations thereof.

9. The process of claim 8 wherein the propylene-rich soft polyolefins and ethylene-rich soft polyolefins have a Tg of
-20˚C or less and a crystallinity of 15% or less.

10 10. The process of claim 8 wherein the ethylene-based polyolefin oligomer has a Mn of 300 to 10,000 g/mol and a pour
point of -20˚C or less.

11. The process of claims 8 wherein the higher-alphaolefin-based polyolefin oligomer has a Mn of of 300 to 10,000
g/mol and a pour point of -20˚C or less.
15
12. The process of claim 1 wherein the one or more base polymers are chosen from HDPE, LDPE, LLDPE,vLDPE,
isotactic PP, syndiotactic PP, ethylene-propylene random copolymer, ethylene-propylene plastomer, ethylene-pro-
pylene elastomer, ethylene-propylene impact copolymer, ethylene-propylene rubber, ethylene-propylene-diene ter-
polymer, ethylene-propylene-butene-1 terpolymer, olefin block copolymers, poly(1-butene), styrenic block copoly-
20 mer, butyl, halobutyl, thermoplastic vulcanizates and combinations thereof.

13. A in-line blending process for plasticized polymers comprising:

(a) providing two or more reactor trains configured in parallel and two or more high-pressure separators fluidly
25 connected to the two or more reactor trains configured in parallel, wherein one or more of the reactor trains
produces one or more base polymers and one or more of the reactor trains produces one or more plasticizers;
(b) contacting in the two or more reactor trains configured in parallel 1) olefin monomers having two or more
carbon atoms 2) one or more catalyst systems, 3) optional one or more comonomers, 4) optional one or more
scavengers, and 5) optional one or more diluents or solvents,
30 wherein at least one of the reactor trains configured in parallel is at a temperature above the solid-fluid phase-
transition temperature of the polymerization system and a pressure no lower than 10 MPa below the cloud point
pressure of the polymerization system and less than 1500 MPa,
wherein the polymerization system for each reactor train is in its dense fluid state and comprises the olefin
monomers, any comonomer present, any diluent or solvent present, any scavenger present, and the polymer
35 product,
wherein the catalyst system for each reactor train comprises one or more catalyst precursors, one or more
activators, and optionally, one or more catalyst supports,
wherein the one or more catalyst systems are chosen from Ziegler-Natta catalysts, metallocene catalysts,
nonmetallocene metal-centered, heteroaryl ligand catalysts, late transition metal catalysts, and combinations
40 thereof;
(c) forming an unreduced polymer or unreduced plasticizer reactor effluent including a homogenous fluid phase
polymer-monomer mixture or plasticizer-monomer mixture in each parallel reactor train;
(d) passing the reactor effluents from one or more of the parallel reactor trains through one or more high-
pressure separators, maintaining the temperature and pressure within the one or more high-pressure separators
45 above the solid-fluid phase transition point but below the cloud point pressure and temperature to form one or
more fluid-fluid two-phase systems with each two-phase system comprising a polymer-enriched phase or plas-
ticizer-enriched phase and a monomer-rich phase, and separating the monomer-rich phase from the polymer-
enriched phase or plasticizer-enriched phase in each of the one or more high-pressure separators to form one
or more separated monomer-rich phases, one or more polymer-enriched phases or one or more plasticizer-
50 enriched phases;
(e) passing the one or more polymer-enriched phases and one or more plasticizer-enriched phases from the
one or more high-pressure separators of (d), any unreduced polymer reactor effluents from the one or more
parallel reactor trains through another high-pressure separator for product blending and product-feed separation;
(f) maintaining the temperature and pressure within the another high pressure separator of (e) above the solid-
55 fluid phase transition point but below the cloud point pressure and temperature to form a fluid-fluid two-phase
system comprising a plasticized polymer-rich blend phase and a monomer-rich phase; and
(g) separating the monomer-rich phase from the plasticized polymer-rich blend phase in the high pressure
separator to form a plasticized polymer blend and a separated monomer-rich phase.

75
 EP 2 195 349 B1

14. An in-line blending process for plasticized polymers comprising:

(a) providing two or more reactor trains configured in parallel, a high-pressure separator downstream fluidly
connected to the two or more reactor trains configured in parallel, and one or more storage tanks, wherein the
5 two or more reactor trains produce one or more base polymers and the one or more storage tanks store one
or more off-line produced plasticizers;
(b) contacting in the two or more reactor trains configured in parallel 1) olefin monomers having two or more
carbon atoms 2) one or more catalyst systems, 3) optional one or more comonomers, 4) optional one or more
scavengers, and 5) optional one or more diluents or solvents,
10 wherein at least one of the reactor trains configured in parallel is at a temperature above the solid-fluid phase
transition temperature of the polymerization system and a pressure no lower than 10 MPa below the cloud point
pressure of the polymerization system and less than 1500 MPa,
wherein the polymerization system for each reactor train is in its dense fluid state and comprises the olefin
monomers, any comonomer present, any diluent or solvent present, any scavenger present, and the polymer
15 product,
wherein the catalyst system for each reactor train comprises one or more catalyst precursors, one or more
activators, and optionally, one or more catalyst supports,
wherein the one or more catalyst systems are chosen from Ziegler-Natta catalysts, metallocene catalysts,
nonmetallocene metal-centered, heteroaryl ligand catalysts, late transition metal catalysts, and combinations
20 thereof
(c) forming an unreduced polymer reactor effluent including a homogeneous fluid phase polymer-monomer
mixture in each parallel reactor train;
(d) passing the polymer reactor effluent comprising the homogeneous fluid phase polymer-monomer mixture
from each parallel reactor train through the high-pressure separator for product blending and product-feed
25 separation;
(e) maintaining the temperature and pressure within the high-pressure separator above the solid-fluid phase
transition point but below the cloud point pressure and temperature to form a fluid-fluid two-phase system
comprising a polymer-rich blend phase and a monomer-rich phase;
(f) separating the monomer-rich phase from the polymer-rich blend phase in the high pressure separator to
30 form a polymer blend and a separated monomer-rich phase; and
(g) feeding the one or more off-line produced plasticizers from the one or more storage tanks to the process
after (c) to form a plasticized polymer blend.

15. A in-line blending process for plasticized polymers comprising:

35
(a) providing two or more reactor trains configured in parallel and two or more high-pressure separators fluidly
connected to the two or more reactor trains configured in parallel, and one or more storage tanks, wherein two
or more of the reactor trains produce one or more base polymers and the one or more storage tanks store one
or more off-line-produced plasticizers;
40 (b) contacting in the two or more reactor trains configured in parallel 1) olefin monomers having two or more
carbon atoms 2) one or more catalyst systems, 3) optional one or more comonomers, 4) optional one or more
scavengers, and 5) optional one or more diluents or solvents,
wherein at least one of the reactor trains configured in parallel is at a temperature above the solid-fluid phase-
transition temperature of the polymerization system and a pressure no lower than 10 MPa below the cloud point
45 pressure of the polymerization system and less than 1500 MPa,
wherein the polymerization system for each reactor train is in its dense fluid state and comprises the olefin
monomers, any comonomer present, any diluent or solvent present, any scavenger present, and the polymer
product,
wherein the catalyst system for each reactor train comprises one or more catalyst precursors, one or more
50 activators, and optionally, one or more catalyst supports,
wherein the one or more catalyst systems are chosen from Ziegler-Natta catalysts, metallocene catalysts,
nonmetallocene metal-centered, heteroaryl ligand catalysts, late transition metal catalysts, and combinations
thereof;
(c) forming an unreduced polymer reactor effluent including a homogenous fluid phase polymer-monomer
55 mixture in each parallel reactor train;
(d) passing the reactor effluents from one or more of the parallel reactor trains through one or more high-
pressure separators, maintaining the temperature and pressure within the one or more high-pressure separators
above the solid-fluid phase transition point but below the cloud point pressure and temperature to form one or

76
 EP 2 195 349 B1

more fluid-fluid two-phase systems with each two-phase system comprising a polymer-enriched phase and a
monomer-rich phase, and separating the monomer-rich phase from the polymer-enriched phase in each of the
one or more high-pressure separators to form one or more separated monomer-rich phases and one or more
polymer-enriched phases;
5 (e) passing the one or more polymer-enriched phases from the one or more high-pressure separators of (d),
any unreduced polymer reactor effluents from one or more parallel reactor trains through another high-pressure
separator for product blending and product-feed separation;
(f) maintaining the temperature and pressure within the another high pressure separator of (e) above the solid-
fluid phase transition point but below the cloud point pressure and temperature to form a fluid-fluid two-phase
10 system comprising a polymer-rich blend phase and a monomer-rich phase;
(g) separating the monomer-rich phase from the polymer-rich blend phase in the high pressure separator to
form a polymer blend and a separated monomer-rich phase; and
(h) feeding the one or more off-line produced plasticizers from the one or more storage tanks to the process
after (c) to form a plasticized polymer blend.
15

Patentansprüche

1. In-Rohr-Mischverfahren (In-Line-Blending) für weichgemachte Polymere, bei dem

20
(a) zwei oder mehr parallel konfigurierte Reaktorzüge und ein stromabwärts in Fluidkommunikation mit den
zwei oder mehreren parallel konfigurierten Reaktorzügen angeordneter Hochdruckseparator bereitgestellt wer-
den, wobei einer oder mehrere der Reaktorzüge ein oder mehrere Basispolymere produzieren und einer oder
mehrere der Reaktorzüge ein oder mehrere Weichmacher produzieren,
25 (b) in den zwei oder mehreren parallel konfigurierten Reaktorzügen 1) Olefinmonomere mit zwei oder mehr
Kohlenstoffatomen, 2) ein oder mehrere Katalysatorsysteme, 3) gegebenenfalls ein oder mehrere Comonomere,
4) gegebenenfalls ein oder mehrere Abfangmittel und 5) gegebenenfalls ein oder mehrere Verdünnungsmittel
oder Lösemittel kontaktiert werden,
wobei sich mindestens einer der parallel konfigurierten Reaktorzüge bei einer Temperatur oberhalb der Tem-
30 peratur für den Fest-Flüssig-Phasenübergang des Polymerisationssystems und einem Druck befindet, der nicht
niedriger ist als 10 MPa unterhalb des Trübungspunktdrucks des Polymerisationssystems und weniger als 1500
MPa beträgt,
wobei das Polymerisationssystem für jeden Reaktorzug in seinem dichten Fluidzustand ist und die Olefinmo-
nomere und jegliche vorhandende Comonomere,
35 jegliches vorhandenes Verdünnungsmittel oder Lösemittel, jegliches vorhandenes Abfangmittel und das Poly-
merprodukt umfasst,
wobei das Katalysatorsystem für jeden Reaktorzug einen oder mehrere Katalysatorvorläufer, einen oder meh-
rere Aktivatoren und gegebenenfalls einen oder mehrere Katalysatorträger umfasst,
wobei das eine oder die mehreren Katalysatorsysteme ausgewählt sind aus Ziegler-Natta-Katalysatoren, Me-
40 tallocenkatalysatoren, Metall-zentrierten Nichtmetallocenkatalysatoren, Katalysatoren mit Heteroarylliganden,
Katalysatoren der späten Übergangsmetalle und Kombinationen davon ausgewählt ist bzw. sind,
(c) ein nicht reduzierter Polymer- oder nicht reduzierter Weichmacherreaktorausfluss gebildet wird, der in einem
oder mehreren parallelen Reaktorzügen eine homogene Fluidphase einer Mischung aus Polymer und Monomer
und in einem oder mehreren parallelen Reaktorzügen eine homogene Fluidphase einer Mischung aus Weich-
45 macher und Monomer einschließt,
(d) die Reaktorausflüsse, die die homogene Fluidphase der Mischung aus Polymer und Monomer und der
Mischung aus Weichmacher und Monomer aus jedem der parallelen Reaktorzüge umfassen, zum Mischen des
Produkts und zur Trennung von Produkt und Einsatzmaterial durch den Hochdruckseparator geleitet werden,
(e) die Temperatur und der Druck innerhalb des Hochdruckseparators oberhalb des Fest-Flüssig-Phasenüber-
50 gangspunkts gehalten werden, jedoch unterhalb des Trübungspunktdrucks und der Trübungspunkttemperatur,
so dass sich ein Flüssig-Flüssig-Zweiphasensystem bildet, das eine an weichgemachtem Polymer reiche Misch-
phase und eine an Monomer reiche Phase umfasst, und
(f) die an Monomer reiche Phase aus der an weichgemachtem Polymer reichen Mischphase in dem Hochdruck-
separator abgetrennt wird, um ein weichgemachtes Polymergemisch und eine getrennte, an Monomer reiche
55 Phase zu bilden.

2. Verfahren nach Anspruch 1, wobei in (b) die Polymerisationssysteme für die zwei oder die mehreren parallel kon-
figurierten Reaktorzüge bei Temperaturen oberhalb der Temperaturen für den Fest-Flüssig-Phasenübergang und

77
 EP 2 195 349 B1

bei Drücken, die nicht niedriger als 10 MPa unterhalb der Trübungspunktdrücke liegen und weniger als 1500 MPa
betragen, gehalten werden, und die weniger als 40 Gew.-% von gegebenenfalls einem oder mehreren Verdün-
nungsmitteln oder Lösemitteln umfassen.

5 3. Verfahren nach Anspruch 1, wobei die Olefinmonomere mit zwei oder mehreren Kohlenstoffatomen aus (b) Propylen
umfassen.

4. Verfahren nach Anspruch 1, wobei die Olefinmonomere und das gegebenenfalls eine oder die gegebenenfalls
mehreren Comonomere aus (b) eines oder mehrere von Ethylen, Propylen, Butenen, Hexenen, Octenen, Decenen
10 oder Dodecenen umfassen.

5. Verfahren nach Anspruch 1, bei dem ferner einer oder mehrere Lagertanks bereitgestellt werden und aus dem
einen oder den mehreren Lagertanks ein oder mehrere Polymere, ein oder mehrere off-line produzierte Weichmacher
und/oder ein oder mehrere Polymeradditive nach (c) in das Verfahren eingebracht werden.
15
6. Verfahren nach Anspruch 5, bei dem ferner die an Polymer reiche Phase aus dem Hochdruckseparator aus (a),
die das weichgemachte Polymergemisch enthält, in einen oder mehrere bei niedrigem Druck betriebene Separatoren
eingebracht wird, um die Monomere und andere flüchtige Materialien weiter aus dem weichgemachten Polymer-
gemisch abzutrennen, so dass ein an weichgemachtem Polymer weiter angereichertes Gemisch gebildet wird, und
20 das an weichgemachtem Polymer weiter angereicherte Gemisch in eine gekoppelte Entspannungszone eingebracht
wird, so dass andere flüchtige Materialien weiter aus dem an weichgemachtem Polymer weiter angereicherten
Gemisch entfernt werden, sodass ein weichgemachtes Polymerproduktgemisch gebildet wird, wobei die gekoppelte
Entspannungszone unter Vakuum betrieben wird, was es ermöglicht, dass die Monomere und andere flüchtige
Materialien aus dem an weichgemachtem Polymer weiter angereicherten Gemisch abgetrieben werden, und wobei
25 die Entspannungszone ein Entspannungszonenextruder ist, und wobei ein oder mehrere Polymere, ein oder mehrere
off-line produzierte Weichmacher und ein oder mehrere Polymeradditive dem weichgemachtem Polymerprodukt-
gemisch im Hochdruckseparator, im bei niedrigem Druck betriebenen Separator, im Entspannungszonenextruder
oder Kombinationen davon zugesetzt werden.

30 7. Verfahren nach Anspruch 6, wobei der eine oder die mehreren off-line produzierten Weichmacher ausgewählt sind
aus Polyolefinoligomeren auf Ethylenbasis, Polyolefinoligomeren auf Propylenbasis, Polyolefinoligomeren auf Bu-
tenbasis, Polyolefinoligomeren auf Basis von höheren α-Olefinen, Paraffinen, Mineralölen, Prozessölen, Kohlen-
wasserstoffflüssigkeiten hoher Reinheit, Schmierstoffbasismaterialien aus Gruppe III, Estern, weichen Polyolefinen,
die reich an Propylen sind, weichen Polyolefinen, die reich an Ethylen sind, elastomeren weichen Polyolefinen,
35 Propylenhomopolymeren, Propylencopolymeren, Buten-1-Homopolymeren, Buten-1-Copolymeren, Elastomeren
auf Basis von Isobutylen, thermoplastischen Vulkanisaten und Kombinationen davon.

8. Verfahren nach Anspruch 1, wobei der eine oder die mehreren Weichmacher Polyolefinoligomer auf Ethylenbasis,
Polyolefinoligomer auf Propylenbasis, Polyolefinoligomer auf Butenbasis, Polyolefinoligomer auf Basis von höheren
40 α-Olefinen, weiche Polyolefine, die an Propylen reich sind, Polyolefine, die an Ethylen reich sind, elastomere weiche
Polyolefine, Propylenhomopolymere, Propylencopolymere, Buten-1-Homopolymere, Buten-1-Copolymere, Elasto-
mere auf Basis von Isobutylen, thermoplastische Vulkanisate und Kombinationen davon umfassen.

9. Verfahren nach Anspruch 8, wobei die an Propylen reichen weichen Polyolefine und die an Ethylen reichen weichen
45 Polyolefine eine Tg von -20˚C oder weniger und eine Kristallinität von 15 % oder weniger aufweisen.

10. Verfahren nach Anspruch 8, wobei das Polyolefinoligomer auf Ethylenbasis eine Mn von 300 bis 10.000 g/mol und
einen Stockpunkt von -20˚C oder weniger aufweist.

50 11. Verfahren nach Anspruch 8, wobei das Polyolefinoligomer auf Basis höherer α-Olefine eine Mn von 300 bis 10.000
g/mol und einen Stockpunkt von -20˚C oder weniger aufweist.

12. Verfahren nach Anspruch 1, wobei das eine oder die mehreren Basispolymere ausgewählt sind aus HDPE, LDPE,
LLDPE, vLDPE, isotaktischem PP, syndiotaktischem PP, statistischem Copolymer von Ethylen und Propylen, Ethy-
55 len-Propylen-Plastomer, Ethylen-Propylen-Elastomer, schlagzähem Polymer aus Ethylen und Propylen, Ethylen-
Propylen-Kautschuk, Ethylen-Propylen-Dien-Terpolymer, Ethylen-Propylen-Buten-1-Terpolymer, Olefinblockcopo-
lymeren, Poly(1-buten), Styrolblockcopolymeren, Butyl-, Halogenbutylthermoplastischen Vulkanisaten und Kombi-
nationen davon.

78
 EP 2 195 349 B1

13. In-Rohr-Mischverfahren (In-Line-Blending) für weichgemachte Polymere, bei dem

(a) zwei oder mehr parallel konfigurierte Reaktorzüge und zwei oder mehr Hochdruckseparatoren bereitgestellt
werden, die in Fluidkommunikation mit den zwei oder mehreren parallel konfigurierten Reaktorzügen angeordnet
5 sind, wobei einer oder mehrere der Reaktorzüge ein oder mehrere Basispolymere produzieren und einer oder
mehrere der Reaktorzüge ein oder mehrere Weichmacher produzieren,
(b) in den zwei oder mehreren parallel konfigurierten Reaktorzügen 1) Olefinmonomere mit zwei oder mehr
Kohlenstoffatomen, 2) ein oder mehrere Katalysatorsysteme, 3) gegebenenfalls ein oder mehrere Comonomere,
4) gegebenenfalls ein oder mehrere Abfangmittel und 5) gegebenenfalls ein oder mehrere Verdünnungsmittel
10 oder Lösemittel kontaktiert werden,
wobei sich mindestens einer der parallel konfigurierten Reaktorzüge bei einer Temperatur oberhalb der Tem-
peratur für den Fest-Flüssig-Phasenübergang des Polymerisationssystems und einem Druck befindet, der nicht
niedriger ist als 10 MPa unterhalb des Trübungspunktsdrucks des Polymerisationssystems und weniger als
1500 MPa beträgt,
15 wobei das Polymerisationssystem für jeden Reaktorzug in seinem dichten Fluidzustand ist und die Olefinmo-
nomere und jegliche vorhandende Comonomere, jegliches vorhandenes Verdünnungsmittel oder Lösemittel,
jegliches vorhandenes Abfangmittel und das Polymerprodukt umfasst,
wobei das Katalysatorsystem für jeden Reaktorzug einen oder mehrere Katalysatorvorläufer, einen oder meh-
rere Aktivatoren und gegebenenfalls einen oder mehrere Katalysatorträger umfasst,
20 wobei das eine oder die mehreren Katalysatorsysteme ausgewählt sind aus Ziegler-Natta-Katalysatoren, Me-
tallocenkatalysatoren, Metall-zentrierten Nichtmetallocenkatalysatoren, Katalysatoren mit Heteroarylliganden,
Katalysatoren der späten Übergangsmetalle und Kombinationen davon ausgewählt ist bzw. sind,
c) ein nicht reduzierter Polymer- oder nicht reduzierter Weichmacherreaktorausfluss gebildet wird, der in jedem
parallelen Reaktorzug eine homogene Fluidphase einer Mischung aus Polymer und Monomer oder aus Weich-
25 macher und Monomer einschließt,
d) die Reaktorausflüsse aus einem oder mehreren der parallelen Reaktorzüge durch einen oder mehrere Hoch-
druckseparatoren geleitet werden, wobei die Temperatur der Druck innerhalb des einen oder der mehreren
Hochdruckseparatoren oberhalb des Fest-Flüssig-Phasenübergangspunkts gehalten werden, jedoch unterhalb
des Trübungspunktdrucks und der Trübungspunkttemperatur, so dass sich eine oder mehrere Flüssig-Flüssig-
30 Zweiphasensysteme bilden, wobei jedes Zweiphasensystem eine an Polymer angereicherte Phase oder eine
an Weichmacher angereicherte Phase und eine an Monomer reiche Phase umfasst, und die an Monomer reiche
Phase von der an Polymer angereicherten Phase oder der an Weichmacher angereicherten Phase in jedem
von dem einen oder mehreren Hochdruckseparatoren abgetrennt wird, so dass sich eine oder mehrere getrennte
an Monomer reiche Phasen, eine oder mehrere getrennte an Polymer angereicherte Phasen oder eine oder
35 mehrere an Weichmacher angereicherte Phasen bilden,
e) die eine oder die mehreren an Polymer angereicherten Phasen und die eine oder die mehreren an Weich-
macher angereicherten Phasen aus dem einen oder den mehreren Hochdruckseparatoren von (d), jegliche
unreduzierten Polymerreaktor Ausflüsse aus dem einen oder den mehreren parallelen Reaktorzügen zum
Mischen des Produkts und zur Trennung von Produkt und Einsatzmaterial durch einen anderen Hochdruckse-
40 parator geleitet werden,
f) die Temperatur und der Druck innerhalb des anderen Hochdruckseparators von (e) oberhalb des Fest-Flüssig-
Phasenübergangspunkts gehalten werden, jedoch unterhalb des Trübungspunktdrucks und der Trübungs-
punkttemperatur, so dass sich ein Flüssig-Flüssig-Zweiphasensystem bildet, das eine an weichgemachtem
Polymer reiche Mischphase und eine an Monomer reiche Phase umfasst, und
45 (g) die an Monomer reiche Phase aus der an weichgemachtem Polymer reichen Mischphase in dem Hoch-
druckseparator abgetrennt wird, um ein weichgemachtes Polymergemisch und eine getrennte, an Monomer
reiche Phase zu bilden.

14. In-Rohr-Mischverfahren (In-Line-Blending) für weichgemachte Polymere, bei dem

50
(a) zwei oder mehr parallel konfigurierte Reaktorzüge und ein stromabwärts in Fluidkommunikation mit den
zwei oder mehreren parallel konfigurierten Reaktorzügen angeordneter Hochdruckseparator bereitgestellt wer-
den, wobei zwei oder mehrere der Reaktorzüge ein oder mehrere Basispolymere produzieren und der eine
oder die mehreren Lagertanks ein oder mehrere off-line produzierte Weichmacher lagern,
55 (b) in den zwei oder mehreren parallel konfigurierten Reaktorzügen 1) Olefinmonomere mit zwei oder mehr
Kohlenstoffatomen, 2) ein oder mehrere Katalysatorsysteme, 3) gegebenenfalls ein oder mehrere Comonomere,
4) gegebenenfalls ein oder mehrere Abfangmittel und 5) gegebenenfalls ein oder mehrere Verdünnungsmittel
oder Lösemittel kontaktiert werden,

79
 EP 2 195 349 B1

wobei sich mindestens einer der parallel konfigurierten Reaktorzüge bei einer Temperatur oberhalb der Tem-
peratur für den Fest-Flüssig-Phasenübergang des Polymerisationssystems und einem Druck befindet, der nicht
niedriger ist als 10 MPa unterhalb des Trübungspunktsdrucks des Polymerisationssystems und weniger als
1500 MPa beträgt,
5 wobei das Polymerisationssystem für jeden Reaktorzug in seinem dichten Fluidzustand ist und die Olefinmo-
nomere und jegliche vorhandende Comonomere,
jegliches vorhandenes Verdünnungsmittel oder Lösemittel, jegliches vorhandenes Abfangmittel und das Poly-
merprodukt umfasst,
wobei das Katalysatorsystem für jeden Reaktorzug einen oder mehrere Katalysatorvorläufer, einen oder meh-
10 rere Aktivatoren und gegebenenfalls einen oder mehrere Katalysatorträger umfasst,
wobei das eine oder die mehreren Katalysatorsysteme ausgewählt sind aus Ziegler-Natta-Katalysatoren, Me-
tallocenkatalysatoren, Metall-zentrierten Nichtmetallocenkatalysatoren, Katalysatoren mit Heteroarylliganden,
Katalysatoren der späten Übergangsmetalle und Kombinationen davon ausgewählt ist bzw. sind,
c) ein nicht reduzierter Polymerreaktorausfluss gebildet wird, der in jedem parallelen Reaktorzug eine homogene
15 Fluidphase einer Mischung aus Polymer und Monomer einschließt,
d) der Reaktorausfluss, der die homogene Fluidphase der Mischung aus Polymer und Monomer aus jedem der
parallelen Reaktorzüge umfasst, zum Mischen des Produkts und zur Trennung von Produkt und Einsatzmaterial
durch den Hochdruckseparator geleitet wird,
e) die Temperatur und der Druck innerhalb des Hochdruckseparators oberhalb des Fest-Flüssig-Phasenüber-
20 gangspunkts gehalten werden, jedoch unterhalb des Trübungspunktdrucks und der Trübungspunkttemperatur,
so dass sich ein Flüssig-Flüssig-Zweiphasensystem bildet, das eine an Polymer reiche Mischphase und eine
an Monomer reiche Phase umfasst, und
f) die an Monomer reiche Phase aus der an Polymer reichen Mischphase in dem Hochdruckseparator abgetrennt
wird, um ein Polymergemisch und eine getrennte, an Monomer reiche Phase zu bilden, und
25 g) der eine oder die mehreren off-line produzierten Weichmacher aus dem einen oder mehreren Lagertanks
nach (c) in das Verfahren eingebracht werden, so dass sich ein weichgemachtes Polymergemisch bildet.

15. In-Rohr-Mischverfahren (In-Line-Blending) für weichgemachte Polymere, bei dem

30 (a) zwei oder mehr parallel konfigurierte Reaktorzüge und zwei oder mehrere Hochdruckseparatoren bereitge-
stellt werden, die in Fluidkommunikation mit den zwei oder mehreren parallel konfigurierten Reaktorzügen
angeordnet sind, wobei zwei oder mehrere der Reaktorzüge ein oder mehrere Basispolymere produzieren und
der eine oder die mehreren Lagertanks ein oder mehrere off-line produzierte Weichmacher lagern,
(b) in den zwei oder mehreren parallel konfigurierten Reaktorzügen 1) Olefinmonomere mit zwei oder mehr
35 Kohlenstoffatomen, 2) ein oder mehrere Katalysatorsysteme, 3) gegebenenfalls ein oder mehrere Comonomere,
4) gegebenenfalls ein oder mehrere Abfangmittel und 5) gegebenenfalls ein oder mehrere Verdünnungsmittel
oder Lösemittel kontaktiert werden,
wobei sich mindestens einer der parallel konfigurierten Reaktorzüge bei einer Temperatur oberhalb der Tem-
peratur für den Fest-Flüssig-Phasenübergang des Polymerisationssystems und einem Druck befindet, der nicht
40 niedriger ist als 10 MPa unterhalb des Trübungspunktsdrucks des Polymerisationssystems und weniger als
1500 MPa beträgt,
wobei das Polymerisationssystem für jeden Reaktorzug in seinem dichten Fluidzustand ist und die Olefinmo-
nomere und jegliche vorhandende Comonomere,
jegliches vorhandenes Verdünnungsmittel oder Lösemittel, jegliches vorhandenes Abfangmittel und das Poly-
45 merprodukt umfasst,
wobei das Katalysatorsystem für jeden Reaktorzug einen oder mehrere Katalysatorvorläufer, einen oder meh-
rere Aktivatoren und gegebenenfalls einen oder mehrere Katalysatorträger umfasst,
wobei das eine oder die mehreren Katalysatorsysteme ausgewählt sind aus Ziegler-Natta-Katalysatoren, Me-
tallocenkatalysatoren, Metall-zentrierten Nichtmetallocenkatalysatoren, Katalysatoren mit Heteroarylliganden,
50 Katalysatoren der späten Übergangsmetalle und Kombinationen davon ausgewählt ist bzw. sind,
c) ein nicht reduzierter Polymerreaktorausfluss gebildet wird, der in jedem parallelen Reaktorzug eine homogene
Fluidphase einer Mischung aus Polymer und Monomer einschließt,
d) die Reaktorausflüsse aus einem oder mehreren der parallelen Reaktorzüge durch einen oder mehrere Hoch-
druckseparatoren geleitet werden, wobei die Temperatur der Druck innerhalb des einen oder der mehreren
55 Hochdruckseparatoren oberhalb des Fest-Flüssig-Phasenübergangspunkts gehalten werden, jedoch unterhalb
des Trübungspunktsdrucks und der Trübungspunkttemperatur, so dass sich eine oder mehrere Flüssig-Flüssig-
Zweiphasensysteme bilden, wobei jedes Zweiphasensystem eine an Polymer angereicherte Phase und eine
an Monomer reiche Phase umfasst, und die an Monomer reiche Phase von der an Polymer angereicherten

80
 EP 2 195 349 B1

Phase in jedem von dem einen oder mehreren Hochdruckseparatoren abgetrennt wird, so dass sich eine oder
mehrere getrennte an Monomer reiche Phasen, eine oder mehrere getrennte an Polymer angereicherte Phasen
bilden,
e) die eine oder die mehreren an Polymer angereicherten Phasen aus dem einen oder den mehreren Hoch-
5 druckseparatoren von (d), jegliche unreduzierten Polymerreaktorausflüsse aus dem einen oder den mehreren
parallelen Reaktorzügen zum Mischen des Produkts und zur Trennung von Produkt und Einsatzmaterial durch
einen anderen Hochdruckseparator geleitet werden,
f) die Temperatur und der Druck innerhalb des anderen Hochdruckseparators von (e) oberhalb des Fest-Flüssig-
Phasenübergangspunkts gehalten werden, jedoch unterhalb des Trübungspunktdrucks und der Trübungs-
10 punkttemperatur, so dass sich ein Flüssig-Flüssig-Zweiphasensystem bildet, das eine an Polymer reiche Misch-
phase und eine an Monomer reiche Phase umfasst, und
g) die an Monomer reiche Phase aus der an Polymer reichen Mischphase in dem Hochdruckseparator abgetrennt
wird, um ein Polymergemisch und eine getrennte, an Monomer reiche Phase zu bilden,
h) der eine oder die mehreren off-line produzierten Weichmacher aus dem einen oder mehreren Lagertanks
15 nach (c) in das Verfahren eingebracht werden, so dass sich ein weichgemachtes Polymergemisch bildet.

Revendications

20 1. Procédé de mélange en ligne pour polymères plastifiés comprenant les étapes consistant à :

(a) se procurer deux ou plus de deux trains de réacteurs configurés en parallèle et un séparateur haute pression
en aval en communication fluide avec les deux ou plus de deux trains de réacteurs configurés en parallèle,
dans lequel un ou plusieurs des trains de réacteurs produit un ou plusieurs polymères de base et un ou plusieurs
25 des trains de réacteurs produit un ou plusieurs plastifiants ;
(b) mettre en contact dans les deux ou plus de deux trains de réacteurs configurés en parallèle 1) des monomères
oléfiniques comportant deux ou plus de deux atomes de carbone 2) un ou plusieurs systèmes de catalyseur,
3) un ou plusieurs comonomères éventuels, 4) un ou plusieurs agents d’épuration éventuels, et 5) un ou plusieurs
diluants ou solvants éventuels,
30 dans lequel au moins un des trains de réacteurs configurés en parallèle est à une température supérieure à la
température de transition de phase solide-fluide du système de polymérisation et à une pression non inférieure
à 10 MPa au-dessous de la pression du point de trouble du système de polymérisation et inférieure à 1500 MPa,
dans lequel le système de polymérisation pour chaque train de réacteurs est dans son état fluide dense et
comprend les monomères oléfiniques, les éventuels comonomères présents, les éventuels diluants ou solvants
35 présents, les éventuels agents d’épuration présents, et le produit polymère,
dans lequel le système de catalyseur pour chaque train de réacteurs comprend un ou plusieurs précurseurs
de catalyseur, un ou plusieurs activateurs, et éventuellement un ou plusieurs supports de catalyseur,
dans lequel le ou les systèmes de catalyseur sont choisis parmi les catalyseurs de Ziegler-Natta, les catalyseurs
à base de métallocène, les catalyseurs à ligand hétéroaryle centré sur le métal non-métallocène, les catalyseurs
40 à base de métal de transition tardif, et leurs combinaisons ;
(c) former un effluent de réacteur constitué d’un polymère non réduit ou d’un plastifiant non réduit contenant
un mélange polymère-monomère en phase fluide homogène dans un ou plusieurs trains de réacteurs en
parallèle et un mélange plastifiant-monomère en phase fluide homogène dans un ou plusieurs trains de réacteurs
en parallèle ;
45 (d) faire passer les effluents de réacteur comprenant le mélange polymère-monomère et le mélange plastifiant-
monomère en phase fluide homogène provenant de chaque train de réacteurs en parallèle à travers le séparateur
haute pression pour effectuer le mélange du produit et séparer le produit de la charge ;
(e) maintenir la température et la pression à l’intérieur du séparateur haute pression au-dessus du point de
transition de phase solide-fluide mais au-dessous de la pression et de la température du point de trouble pour
50 former un système à deux phases fluide-fluide comprenant une phase de mélange riche en polymère plastifié
et une phase riche en monomère ; et
(f) séparer la phase riche en monomère de la phase de mélange riche en polymère plastifié dans le séparateur
haute pression pour former un mélange de polymère plastifié et une phase riche en monomère séparée.

55 2. Procédé selon la revendication 1 dans lequel, en (b), les systèmes de polymérisation pour les deux ou plus de deux
trains de réacteurs configurés en parallèle sont à des températures supérieures aux températures de transition de
phase solide-fluide et à des pressions non inférieures à 10 MPa au-dessous des pressions du point de trouble et
inférieures à 1500 MPa, et comprennent moins de 40 % en poids d’un ou plusieurs diluants ou solvants éventuels.

81
 EP 2 195 349 B1

3. Procédé selon la revendication 1 dans lequel les monomères oléfiniques comportant deux ou plus de deux atomes
de carbone de (b) comprennent du propylène.

4. Procédé selon la revendication 1 dans lequel les monomères oléfiniques et un ou plusieurs comonomères éventuels
5 de (b) comprennent un ou plusieurs des composés éthylène, propylène, butènes, hexènes, octènes, décènes ou
dodécènes.

5. Procédé selon la revendication 1 comprenant en outre le fait de se procurer un ou plusieurs réservoirs de stockage,
et de charger depuis le ou les réservoirs de stockage un ou plusieurs polymères, un ou plusieurs plastifiants produits
10 hors circuit et/ou un ou plusieurs additifs de polymères dans le procédé après (c).

6. Procédé selon la revendication 5 comprenant en outre le fait de charger la phase riche en polymère du séparateur
haute pression de (a) contenant le mélange de polymère plastifié dans un ou plusieurs séparateurs basse pression
pour mieux séparer les monomères et les autres matières volatiles du mélange de polymère plastifié pour former
15 un mélange de polymère plastifié encore enrichi, et le fait de charger le mélange de polymère plastifié encore enrichi
dans un dégazeur couplé pour mieux séparer les autres matières volatiles du mélange de polymère plastifié encore
enrichi pour former un mélange de produit polymère plastifié, dans lequel le dégazeur couplé fonctionne sous vide
ce qui permet au mélange de polymère plastifié encore enrichi de volatiliser les monomères et les autres matières
volatiles, et dans lequel le dégazeur couplé est une extrudeuse à dégazage, et dans lequel un ou plusieurs polymères,
20 un ou plusieurs plastifiants produits hors circuit et/ou un ou plusieurs additifs de polymères sont ajoutés au mélange
de produit polymère plastifié au niveau du séparateur haute pression, du séparateur basse pression, de l’extrudeuse
à dégazage ou de leurs combinaisons.

7. Procédé selon la revendication 6 dans lequel le ou les plastifiants produits hors circuit sont choisis parmi les oligo-
25 mères de polyoléfine à base d’éthylène, les oligomères de polyoléfine à base de propylène, les oligomères de
polyoléfine à base de butène, les oligomères de polyoléfine à base d’alpha-oléfine supérieure, les paraffines, les
huiles minérales, les huiles de procédé, les fluides hydrocarbonés de grande pureté, les matières de base lubrifiantes
du groupe III, les esters, les polyoléfines molles riches en propylène, les polyoléfines molles riches en éthylène, les
polyoléfines molles élastomères, les homopolymères de propylène, les copolymères de propylène, les homopoly-
30 mères de butène-1, les copolymères de butène-1, les élastomères à base d’isobutylène, les vulcanisats thermo-
plastiques et leurs combinaisons.

8. Procédé selon la revendication 1 dans lequel le ou les plastifiants comprennent un oligomère de polyoléfine à base
d’éthylène, un oligomère de polyoléfine à base de propylène, un oligomère de polyoléfine à base de butène, un
35 oligomère de polyoléfine à base d’alpha-oléfine supérieure, des polyoléfines molles riches en propylène, des poly-
oléfines molles riches en éthylène, des polyoléfines molles élastomères, des homopolymères de propylène, des
copolymères de propylène, des homopolymères de butène-1, des copolymères de butène-1, des élastomères à
base d’isobutylène, des vulcanisats thermoplastiques, et leurs combinaisons.

40 9. Procédé selon la revendication 8 dans lequel les polyoléfines molles riches en propylène et les polyoléfines molles
riches en éthylène possèdent une Tg de

- 20˚C ou moins et une cristallinité de 15% ou moins.

45 10. Procédé selon la revendication 8 dans lequel l’oligomère de polyoléfine à base d’éthylène possède une Mn de 300
à 10 000 g/mol et un point d’écoulement de -20˚C ou moins.

11. Procédé selon la revendication 8 dans lequel l’oligomère de polyoléfine à base d’alpha-oléfine supérieure possède
une Mn de 300 à 10 000 g/mol et un point d’écoulement de -20˚C ou moins.
50
12. Procédé selon la revendication 1 dans lequel le ou les polymères de base sont choisis parmi les suivantes : HDPE,
LDPE, LLDPE, vLDPE, PP isotactique, PP syndio-tactique, copolymère statistique éthylène-propylène, plastomère
éthylène-propylène, élastomère éthylène-propylène, copolymère choc éthylène-propylène, caoutchouc éthylène-
propylène, terpolymère éthylène-propylène-diène, terpolymère éthylène-propylène-butène-1, copolymères séquen-
55 cés oléfiniques, poly(1-butène), copolymère séquencé styrénique, butyl, halobutyl, vulcanisats thermoplastiques,
et leurs combinaisons.

13. Procédé de mélange en ligne pour polymères plastifiés comprenant les étapes consistant à :

82
 EP 2 195 349 B1

(a) se procurer deux ou plus de deux trains de réacteurs configurés en parallèle et deux ou plus de deux
séparateurs haute pression en communication fluide avec les deux ou plus de deux trains de réacteurs configurés
en parallèle, dans lequel un ou plusieurs des trains de réacteurs produit un ou plusieurs polymères de base et
un ou plusieurs des trains de réacteurs produit un ou plusieurs plastifiants ;
5 (b) mettre en contact dans les deux ou plus de deux trains de réacteurs configurés en parallèle 1) des monomères
oléfiniques comportant deux ou plus de deux atomes de carbone, 2) un ou plusieurs systèmes de catalyseur,
3) un ou plusieurs comonomères éventuels, 4) un ou plusieurs agents d’épuration éventuels, et 5) un ou plusieurs
diluants ou solvants éventuels,
dans lequel au moins un des trains de réacteurs configurés en parallèle est à une température supérieure à la
10 température de transition de phase solide-fluide du système de polymérisation et à une pression non inférieure
à 10 MPa au-dessous de la pression du point de trouble du système de polymérisation et inférieure à 1500 MPa,
dans lequel le système de polymérisation pour chaque train de réacteurs est dans son état fluide dense et
comprend les monomères oléfiniques, les éventuels comonomères présents, les éventuels diluants ou solvants
présents, les éventuels agents d’épuration présents et le produit polymère,
15 dans lequel le système de catalyseur pour chaque train de réacteurs comprend un ou plusieurs précurseurs
de catalyseur, un ou plusieurs activateurs et éventuellement un ou plusieurs supports de catalyseur,
dans lequel le ou les systèmes de catalyseur sont choisis parmi les catalyseurs de Ziegler-Natta, les catalyseurs
à base de métallocène, les catalyseurs à ligand hétéroaryle centré sur le métal non-métallocène, les catalyseurs
à base de métal de transition tardif, et leurs combinaisons ;
20 (c) former un effluent de réacteur constitué d’un polymère non réduit ou d’un plastifiant non réduit contenant
un mélange polymère-monomère ou un mélange plastifiant-monomère en phase fluide homogène dans chaque
train de réacteurs en parallèle ;
(d) faire passer les effluents de réacteur depuis un ou plusieurs des trains de réacteurs en parallèle à travers
un ou plusieurs séparateurs haute pression, maintenir la température et la pression à l’intérieur du ou des
25 séparateurs haute pression au-dessus du point de transition de phase solide-fluide mais au-dessous de la
pression et de la température du point de trouble pour former un ou plusieurs systèmes à deux phases fluide-
fluide, chaque système à deux phases comprenant une phase enrichie en polymère ou une phase enrichie en
plastifiant et une phase riche en monomère, et séparer la phase riche en monomère de la phase enrichie en
polymère ou de la phase enrichie en plastifiant dans chacun du ou des séparateurs haute pression pour former
30 une ou plusieurs phases riches en monomère séparées, une ou plusieurs phases enrichies en polymère ou
une ou plusieurs phases enrichies en plastifiant ;
(e) faire passer la ou les phases enrichies en polymère et une ou plusieurs phases enrichies en plastifiant
depuis le ou les séparateurs haute pression de (d), les éventuels effluents de réacteur de polymère non réduit
depuis le ou les trains de réacteurs en parallèle à travers un autre séparateur haute pression pour effectuer le
35 mélange du produit et séparer le produit de la charge ;
(f) maintenir la température et la pression à l’intérieur de l’autre séparateur haute pression de (e) au-dessus
du point de transition de phase solide-fluide mais au-dessous de la pression et de la température du point de
trouble pour former un système à deux phases fluide-fluide comprenant une phase de mélange riche en polymère
plastifié et une phase riche en monomère ; et
40 (g) séparer la phase riche en monomère de la phase de mélange riche en polymère plastifié dans le séparateur
haute pression pour former un mélange de polymère plastifié et une phase riche en monomère séparée.

14. Procédé de mélange en ligne pour polymères plastifiés comprenant les étapes consistant à :

45 (a) se procurer deux ou plus de deux trains de réacteurs configurés en parallèle, un séparateur haute pression
en aval en communication fluide avec les deux ou plus de deux trains de réacteurs configurés en parallèle, et
un ou plusieurs réservoirs de stockage, dans lequel les deux ou plus de deux trains de réacteurs produisent
un ou plusieurs polymères de base et le ou les réservoirs de stockage stockent un ou plusieurs plastifiants
produits hors circuit ;
50 (b) mettre en contact dans les deux ou plus de deux trains de réacteurs configurés en parallèle 1) des monomères
oléfiniques comportant deux ou plus de deux atomes de carbone, 2) un ou plusieurs systèmes de catalyseur,
3) un ou plusieurs comonomères éventuels, 4) un ou plusieurs agents d’épuration éventuels, et 5) un ou plusieurs
diluants ou solvants éventuels,
dans lequel au moins un des trains de réacteurs configurés en parallèle est à une température supérieure à la
55 température de transition de phase solide-fluide du système de polymérisation et à une pression non inférieure
à 10 MPa au-dessous de la pression du point de trouble du système de polymérisation et inférieure à 1500 MPa,
dans lequel le système de polymérisation pour chaque train de réacteurs est dans son état fluide dense et
comprend les monomères oléfiniques, les éventuels comonomères présents, les éventuels diluants ou solvants

83
 EP 2 195 349 B1

présents, les éventuels agents d’épuration présents et le produit polymère,

dans lequel le système de catalyseur pour chaque train de réacteurs comprend un ou plusieurs précurseurs
de catalyseur, un ou plusieurs activateurs, et éventuellement un ou plusieurs supports de catalyseur,
dans lequel le ou les systèmes de catalyseur sont choisis parmi les catalyseurs de Ziegler-Natta, les catalyseurs
5 à base de métallocène, les catalyseurs à ligand hétéroaryle centré sur le métal non-métallocène, les catalyseurs
à base de métal de transition tardif, et leurs combinaisons ;
(c) former un effluent de réacteur polymère non réduit contenant un mélange polymère-monomère en phase
fluide homogène dans chaque train de réacteurs en parallèle ;
(d) faire passer l’effluent de réacteur polymère comprenant le mélange polymère-monomère en phase fluide
10 homogène depuis chaque train de réacteurs en parallèle à travers le séparateur haute pression pour effectuer
le mélange du produit et séparer le produit de la charge ;
(e) maintenir la température et la pression à l’intérieur du séparateur haute pression au-dessus du point de
transition de phase solide-fluide mais au-dessous de la pression et de la température du point de trouble pour
former un système à deux phases fluide-fluide comprenant une phase de mélange riche en polymère et une
15 phase riche en monomère ;
(f) séparer la phase riche en monomère de la phase de mélange riche en polymère dans le séparateur haute
pression pour former un mélange de polymère et une phase riche en monomère séparée ; et
(g) charger le ou les plastifiants produits hors circuit depuis le ou les réservoirs de stockage dans le procédé
après (c) pour former un mélange de polymère plastifié.
20
15. Procédé de mélange en ligne pour polymères plastifiés comprenant les étapes consistant à :

(a) se procurer deux ou plus de deux trains de réacteurs configurés en parallèle et deux ou plus de deux
séparateurs haute pression en communication fluide avec les deux ou plus de deux trains de réacteurs configurés
25 en parallèle, et un ou plusieurs réservoirs de stockage, dans lequel deux ou plus de deux des trains de réacteurs
produisent un ou plusieurs polymères de base et le ou les réservoirs de stockage stockent un ou plusieurs
plastifiants produits hors circuit ;
(b) mettre en contact dans les deux ou plus de deux trains de réacteurs configurés en parallèle 1) des monomères
oléfiniques comportant deux ou plus de deux atomes de carbone, 2) un ou plusieurs systèmes de catalyseur,
30 3) un ou plusieurs comonomères éventuels, 4) un ou plusieurs agents d’épuration éventuels, et 5) un ou plusieurs
diluants ou solvants éventuels,
dans lequel au moins un des trains de réacteurs configurés en parallèle est à une température supérieure à la
température de transition de phase solide-fluide du système de polymérisation et à une pression non inférieure
à 10 MPa au-dessous de la pression du point de trouble du système de polymérisation et inférieure à 1500 MPa,
35 dans lequel le système de polymérisation pour chaque train de réacteurs est dans son état fluide dense et
comprend les monomères oléfiniques, les éventuels comonomères présents, les éventuels diluants ou solvants
présents, les éventuels agents d’épuration présents et le produit polymère,
dans lequel le système de catalyseur pour chaque train de réacteurs comprend un ou plusieurs précurseurs
de catalyseur, un ou plusieurs activateurs et éventuellement un ou plusieurs supports de catalyseur,
40 dans lequel le ou les systèmes de catalyseur sont choisis parmi les catalyseurs de Ziegler-Natta, les catalyseurs
à base de métallocène, les catalyseurs à ligand hétéroaryle centré sur le métal non-métallocène, les catalyseurs
à base de métal de transition tardif, et leurs combinaisons ;
(c) former un effluent de réacteur polymère non réduit contenant un mélange polymère-monomère en phase
fluide homogène dans chaque train de réacteurs en parallèle ;
45 (d) faire passer les effluents de réacteur depuis un ou plusieurs des trains de réacteurs en parallèle à travers
un ou plusieurs séparateurs haute pression, maintenir la température et la pression à l’intérieur du ou des
séparateurs haute pression au-dessus du point de transition de phase solide-fluide mais au-dessous de la
pression et de la température du point de trouble pour former un ou plusieurs systèmes à deux phases fluide-
fluide, chaque système à deux phases comprenant une phase enrichie en polymère et une phase riche en
50 monomère, et séparer la phase riche en monomère de la phase enrichie en polymère dans chacun du ou des
séparateurs haute pression pour former une ou plusieurs phases riches en monomère séparées et une ou
plusieurs phases enrichies en polymère ;
(e) faire passer la ou les phases enrichies en polymères depuis le ou les séparateurs haute pression de (d),
les éventuels effluents de réacteur de polymère non réduit provenant d’un ou plusieurs trains de réacteurs en
55 parallèle à travers un autre séparateur haute pression pour effectuer le mélange du produit et séparer le produit
de la charge ;
(f) maintenir la température et la pression à l’intérieur de l’autre séparateur haute pression de (e) au-dessus
du point de transition de phase solide-fluide mais au-dessous de la pression et de la température du point de

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trouble pour former un système à deux phases fluide-fluide comprenant une phase de mélange riche en polymère
et une phase riche en monomère ;
(g) séparer la phase riche en monomère de la phase de mélange riche en polymère dans le séparateur haute
pression pour former un mélange de polymère et une phase riche en monomère séparée ; et
5 (h) charger le ou les plastifiants produits hors circuit depuis le ou les réservoirs de stockage dans le procédé
après (c) pour former un mélange de polymère plastifié.

10

15

20

25

30

35

40

45

50

55

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REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European
patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be
excluded and the EPO disclaims all liability in this regard.

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