TEPZZ 4Z6 98B_T

(19)

(11) EP 2 406 298 B1

(12) EUROPEAN PATENT SPECIFICATION

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

of the grant of the patent: C08F 297/08 (2006.01) C08F 210/06 (2006.01)
19.10.2016 Bulletin 2016/42 C08F 210/02 (2006.01) C08L 53/00 (2006.01)
C08L 23/14 (2006.01)
(21) Application number: 10751204.8
(86) International application number:
(22) Date of filing: 04.03.2010 PCT/US2010/026205

(87) International publication number:

WO 2010/104739 (16.09.2010 Gazette 2010/37)

(54) SUPERTRANSPARENT HIGH IMPACT STRENGTH RANDOM BLOCK COPOLYMER

HOCHTRANSPARENTES STATISTISCHES BLOCKCOPOLYMER MIT HOHER
SCHLAGFESTIGKEIT
COPOLYMÈRE SÉQUENCÉ ALÉATOIRE, SUPERTRANSPARENT, À RÉSISTANCE ÉLEVÉE AUX
CHOCS

(84) Designated Contracting States: • SCHOENE, Werner

AT BE BG CH CY CZ DE DK EE ES FI FR GB GR 69198 Schriesheim (DE)
HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL • SIEBERT, Hartmut
PT RO SE SI SK SM TR A-4072 Alkoven Strassham (AT)
• WINTER, Andreas
(30) Priority: 11.03.2009 US 381382 67271 Neuleiningen (DE)
• DIMESKA, Anita
(43) Date of publication of application: 67098 Bad Dürkheim (DE)
18.01.2012 Bulletin 2012/03 • GALIATSATOS, Vassilios
Lebanon
(73) Proprietor: Lummus Novolen Technology GmbH OH 45036 (US)
68165 Mannheim (DE)
(74) Representative: Osha Liang
(72) Inventors: 2, rue de la Paix
• PEZZUTTI, Jose 75002 Paris (FR)
Mendoza 5500 (AR)
• BENITO, Alberto (56) References cited:
Mendoza 5505 (AR) EP-A1- 2 072 545 WO-A1-03/046021
• CASSANO, Guillermo WO-A1-2008/059969 JP-A- 2005 132 979
Mendoza 5501 (AR) JP-A- 2005 314 621 JP-A- 2006 188 563
• ROTH, Leandro JP-A- 2008 144 163 JP-A- 2008 156 562
Mendoza 5501 (AR) US-A- 5 045 589 US-B2- 7 390 575
EP 2 406 298 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 2 406 298 B1

Description

BACKGROUND

5 1. Field of the Invention

[0001] The present invention relates to transparent high impact random block copolymer compositions for use in
molded and extruded articles.

10 2. Background of the Art

[0002] A variety of transparent thermoplastic compositions have been developed, some of which have been disclosed
in the patent literature and/or introduced to the marketplace. Each of those compositions has a particular level of trans-
parency, often characterized in terms of "haze," which is determined in accordance with recognized test procedures.
15 Shortcomings of those compositions include unsatisfactorily high haze values (low transparency), poor processability
and poor mechanical properties, including undue hardness, low flexibility, etc. For example, previously proposed ther-
moplastic elastomer compositions with transparency and flexibility such as compounds based on styrene-ethylene-
butadiene-styrene impact copolymers, thermoplastic vulcanized blends (TPV) or thermoplastic olefin (TPO) blends show
transparency and softness levels that are still unsatisfactory in some applications.
20 [0003] EP 1,428,853 discloses a polypropylene polymer composition including a random propylene-alpha-olefin co-
polymer, the alpha-olefin being ethylene and one or more C4 - C10 alpha-olefins. The polymer includes a matrix phase
containing 2-12 mole % ethylene and a rubber phase containing 25-65 mole % ethylene.
[0004] EP 1,354,901 discloses a heterophasic polypropylene composition with a MFR greater than 100g/10 min.
[0005] WO 03/106,553 discloses high impact polypropylene copolymers with matrix and rubber present in separate
25 phases.
[0006] WO 03/046,021 discloses a polypropylene polymer composition having a MFR of from 3 to 30 g/10 min. The
polymer includes 50-90 % of one or more propylene copolymers having a xylene insoluble fraction of not less than 85%
and 10-50% of a propylene copolymer containing 8%-40% ethylene and optionally 1-10 w-% of a C4-C8 alpha-olefin.
[0007] Other random block copolymer compositions are disclosed in EP 1,206,499, EP 373,660, EP 814,127, EP
30 860,457 and EP 1,162,213.
[0008] WO2008/059,969 A1 and EP 2,072,545 A1 describe a propylene polymer comprising a component (A) which
becomes insoluble in p-xylene at 25°C and a component (B) which can dissolve in p-xylene at 25°C, wherein (i) the
weight average molecular weight (Mw) as measure by GPC is 100,000 to 1,000,000, (ii) the content of a component
insoluble in hot p-xylene is 0.3 wt% or less, and (iii) the degree of strain-hardening as determined by the elongational
35 viscosity measurement is 2.0 or greater.
[0009] JP 2005 132,979 A describes a propylene-ethylene random block copolymer obtained by carrying out successive
polymerization by using a metallocene-based catalyst. The block copolymer of JP 2005 132,979 A is composed of (A)
a crystalline copolymer component in which an elution curve in elution and fractionation method by rise of temperature
exhibits a peak T(A) on high-temperature side between 65°C and 88°C and (B) a low-crystalline or amorphous copolymer
40 component in which the elution curve exhibits or does not exhibit a peak T(B) on lower temperature side at <=40°C. In
the block copolymer. the integrated amount of the component eluting when the temperature is raised to a temperature
T(C) which is an intermediate point of both peaks is 30-70 wt% and the integrated amount of the component eluting at
>=T(C) is 70-30 wt.% and a temperature T(D) at which 99 wt.% of total copolymer is eluted is <=90°C and tanδ has a
single peak at <=0°C in a temperature loss tangent curve obtained by measurement of solid viscoelasticity.
45 [0010] JP 2006 188,563 A describes a polypropylene-based resin composition contains 99-70 wt% of a propylene-
ethylene random block copolymer as a component (A) and 1-30 wt% of a process oil component as a component (B)
and has a modulus of flexure of <=250 MPa, wherein the component (A) comprises the propylene-ethylene random
block copolymer obtained from sequential polymerization by using a metallocene-based catalyst, so that a crystalline
propylene-ethylene random copolymer component having an ethylene content of 1-7 wt% is polymerized in an amount
50 of 30-70 wt% in a first process and sequentially a low-crystalline or amorphous propylene-ethylene random copolymer
component having an ethylene content higher than the ethylene content obtained in the first process by 6-15 wt% is
polymerized in an amount of 70-30 wt% in a second process, and satisfies condition (i) as follows: (i) a tanδ curve
obtained by solid viscoelasticity measurement of the component (A) has a single peak at a temperature of <=0°C.
[0011] Others have attempted to make transparent compositions, but many of such compositions are problematic,
55 particularly when attempting to make molded compositions that possess a desirable combination of properties, such as
softness, flexibility and strength, while also having good processability. For example, others have been confronted with
shortcomings in the area of processability, particularly for molded or extruded compositions, where the tendency of a
material to crystallize quickly has enormous advantages. Many materials that have good mechanical properties lack

2
 EP 2 406 298 B1

good crystallization properties. When a composition is used for molding, it is desirable that it has a tendency to flow well
and thus quickly and easily and completely fill all areas of the mold. While there is a general tendency for higher MFR
materials to correspond to good flowability, a higher MFR is frequently also accompanied by an unfortunate decrease
in mechanical properties; thus a higher MFR is not necessarily desirable for that reason. Furthermore, many compositions
5 experience a trade-off in properties, e.g., where good mechanical properties may be offset by poor flexibility, e.g., undue
stiffness or hardness. Accordingly, there is a need for a material that has a combination of desirable properties.
[0012] Typically, in the past one had to choose between low haze or good impact properties. The prior art does not
provide a material with both low haze and good impact properties at the same time.

10 SUMMARY

[0013] A super transparent high impact strength random block copolymer is provided herein which comprises a com-
bination of

15 (a) 65 - 97 wt. , preferably 75 - 97 wt.% of a crystalline propylene/ethylene copolymer A containing from about 0.5
wt.% to about 6 wt.% derived from ethylene and from about 94 wt.% to about 99.5 wt.% derived from propylene,
having a melting point of 120 - 159°C; and
(b) 3 - 35 wt.%, preferably 3 - 25 wt.%, of a propylene/ethylene copolymer B containing from about 8 wt.% to about
40 wt.% derived from ethylene and from about 60 wt.% to about 92 wt.% derived from propylene,
20
where the random block copolymer is produced in at least a two stage reactor cascade, where copolymer A is produced
in a first polymerization reactor and copolymer B is produced in a second polymerization reactor.
[0014] The random block copolymer is characterized by an outstanding combination of high impact strength and low
haze.
25
DETAILED DESCRIPTION

[0015] Other than in the working examples or where otherwise indicated, all numbers expressing amounts of materials,
reaction conditions, time durations, quantified properties of materials, and so forth, stated in the specification are to be
30 understood as being modified in all instances by the term "about."
[0016] It will also be understood that any numerical range recited herein is intended to include all sub-ranges within
that range.
[0017] It will be further understood that any compound, material or substance which is expressly or implicitly disclosed
in the specification and/or recited in a claim as belonging to a group of structurally, compositionally and/or functionally
35 related compounds, materials or substances includes individual representatives of the group and all combinations thereof.
[0018] The present invention provides low haze (super transparent) random block copolymers for applications such
as injection molding, sheet, film, thermoforming, blow molding and injection stretch blow molding (ISBM) by carefully
tailoring of molecular parameters.
[0019] Such parameters may include:
40
1) the proper melt flow rate difference ( delta MFR) between the products produced in the first (copolymer A) and
second polymerization reactor (copolymer B),
2) the proper ethylene content of copolymer A, produced in the first reactor,
3) the proper ethylene content of copolymer B, produced in the second reactor,
45 4) the balance of the ethylene contents of copolymers A and B,
5) the balance of long spacing within the crystalline structure of the random block copolymer,
6) the xylene soluble (XS) content of the random block copolymer, and
7) optionally adding a clarifier in the right amount to the random block copolymer.

50 [0020] Careful control and balancing of one or more of these parameters results in the growth of crystalline regions
of a certain size and type, resulting in a random block copolymer that has an unexpectedly low haze, which is desirable
yet previously thought to be impossible for impact copolymers.
[0021] Although not wishing to be limited to any theory, the low haze is believed to be the result of properly formed
crystalline domains of smaller size and type than those found in typical impact copolymers. This behavior is believed to
55 be attributable to co-crystallization of rubber polymer chains within the matrix polymer chains. Low haze may also be
attributed to the optimization of refractive index between the two phases. Smaller, more open spherulites with irregular
borders in combination with very small rubber particles (having a diameter of less than about 0.5 microns) are believed
to provide a mechanism for obtaining the combination of low haze and good impact properties in the random block

3
 EP 2 406 298 B1

copolymer of the invention. Also, low molecular weight (LMW) compatible rubber tends to migrate to the matrix domain
thereby thickening the amorphous lamella (La) and thinning the crystalline lamella (Lc).
[0022] In more detail, in one embodiment of the invention a random block copolymer is provided herein which comprises
a combination of :
5
(a) 65 - 97 wt.% of a crystalline propylene/ethylene copolymer A containing from about 0.5 wt.% to about 6 wt.%
derived from ethylene and from about 94 wt.% to about 99.5 wt.% derived from propylene, having a melting point
(measured by means of DSC in accordance with the standard ISO 3146) of 120 - 159°C; and
(b) 3 - 35 wt.% of a propylene/ethylene copolymer B containing from about 8 wt.% to about 40 wt.% derived from
10 ethylene and from about 60 wt.% to about 92 wt.% derived from propylene, where the random block copolymer has
the following properties:

(i) the propylene/ethylene copolymer B is dispersed in the crystalline propylene/ethylene copolymer A; in a first
embodiment of the invention, the two copolymers A and B are phase separated and in a second embodiment
15 of the invention, the copolymers A and B form a continuous phase random block copolymer without phase
separation,
(ii) in the case, the two copolymers A and B form a random block copolymer showing phase separation, the
particle size of the dispersed polymer B is <1.5 mm, preferably <1.0mm, particularly preferably <0.5 mm,
(iii) the haze, measured in accordance with the standard ASTM D 1003 is for random block copolymers of the
20 present invention <12%, preferably <10%, and particularly preferably <7%.
(iv) the Xylene soluble fraction (XS) at 23 °C, measured in accordance with ISO Standard 16152 (Plastics-
Determination of Xylene soluble matter in Polypropylene) is 11% to about 25 %, preferably 12% to about 22%,
particularly 15% to about 20 % ,
(v) the MFR measured in accordance with the ISO standard 1133 at 230°C with a load of 2.16 kg is 0.1 to about
25 150 dg/min, preferably 0.5 to about 100 dg/min, particularly preferably 1 to about 80 dg/min,
(vi) the ratio of powder-MFR random block copolymer to the powder-MFR copolymer A are in accordance with
the equation

30

wherein K = 1.0 to about 1.5, preferably 1.0 to about 1.3, particularly preferably 1.0 to about 1.25,
(vii) the crystalline/amorphous ratio Lc/La, determined by small angle X-ray scattering (SAXS), ranges from
about 1.00 to about 2.25, preferably 1.25 to about 2.00, particularly preferably 1.40 to about 1.70,
35 (viii) the material optionally contains nucleating and/or clarifying agents ranging from about 50 ppm to about
5,000 ppm, preferably from about 100 to about 4,500 ppm, and more preferably from about 120 to about 4,000
ppm.

[0023] Preferably, in another embodiment the random block copolymer of the present invention comprises a combi-
40 nation of:

(a) 75 - 95 wt.% of a crystalline propylene/ethylene copolymer A containing from about 1.0 wt.% to about 5 wt.%,
preferably 1.5 to about 4.5 wt.%, derived from ethylene and from about 95 wt.% to about 99 wt.%, preferably 95.5
to about 98.5 wt.%, derived from propylene, having a melting point of 135 - 150°C, preferably of 139 - 146°C; and
45 (b) 5 - 25 wt.% of a propylene/ethylene copolymer B containing from about 10 wt.% to about 30 wt.%, preferably
12 to about 25 wt.%, derived from ethylene and from about 70 wt.% to about 90 wt.%, preferably 75 to about 88
wt.%, derived from propylene,

where the random block copolymer has the above mentioned properties (i) - (viii).
50 [0024] Particularly preferably, in yet another embodiment the random block copolymer of the present invention com-
prises a combination of :

(a) 80 - 92 wt.% of a crystalline propylene/ethylene copolymer A containing from about 1.5 wt.% to about 4.5 wt.%,
preferably 2.0 to about 4.0 wt.%, derived from ethylene and from about 95.5 wt.% to about 98.5 wt.%, preferably
55 96 to about 98 wt.%, derived from propylene, having a melting point of 135 - 150°C, preferably of 139 - 146°C; and
(b) 8 - 20 wt.% of a propylene/ethylene copolymer B containing from about 10 wt.% to about 30 wt.%, preferably
12 to about 25 wt.%, derived from ethylene and from about 70 wt.% to about 90 wt.%, preferably 75 wt.% to about

4
 EP 2 406 298 B1

88 wt.%, derived from propylene,

where the random block copolymer has the above mentioned properties (i) - (viii).
[0025] Most preferably, in yet another embodiment the random block copolymer of the present invention comprises
5 a combination of

(a) 88 - 92 wt.% of a crystalline propylene/ethylene copolymer A containing from about 2.0 to about 4.0 wt.%, derived
from ethylene and from about 96 to about 98 wt.%, derived from propylene, having a melting point of 139 - 146°C; and
(b) 8 - 12 wt.% of a propylene/ethylene copolymer B containing from about 12 to about 17 wt.%, derived from
10 ethylene and from about 83 to about 88 wt.%, derived from propylene,

where the random block copolymer has the above mentioned properties (i) - (viii).
[0026] The polymers of the invention can be produced using any coordinating catalyst, like single-site catalysts or
Ziegler-Natta catalysts, the Ziegler-Natta catalyst being preferred.
15 [0027] The method of the present invention includes preparing a random block copolymer by sequential polymerization.
Ethylene and propylene are copolymerized in a first reaction zone to provide a propylene-ethylene copolymer component
A of the impact copolymer of the invention. Component A is then sent to a second reaction zone where ethylene and
propylene are copolymerized to provide the component B which is incorporated into the polymer. The ethylene content
of component A can range from about 0.5 wt.% to about 6 wt.% and the propylene content can range from 94 wt.% to
20 about 99.5 wt.%. Component B of the impact copolymer contains from about 8 wt % to about 40 wt.% of ethylene and
60 wt.% to about 92 wt.% of propylene.
[0028] Random block copolymers of the present invention can be produced in slurry polymerization processes con-
ducted in inert hydrocarbon solvents, bulk polymerization processes conducted in liquefied propylene, in gas phase
polymerization processes or in processes, where the above mentioned processes are combined. As an example, in a
25 first step copolymer A can be produced in a bulk process and copolymer B can be produced in a gas phase process.
Gas phase processes with a fluidized or stirred bed are preferable, especially a two reactor system wherein the copolymer
A is made in the first reactor and the copolymer B in the second reactor. Such a process provides for in situ blending of
the two copolymer components A and B to form a block copolymer, which is necessary, as compared to a physical
blending of the copolymer components A and B which does not produce an impact copolymer of the present invention.
30 [0029] The catalysts for use in such systems include Ziegler-Natta catalysts and single site catalysts.
[0030] Ziegler-Natta catalysts, including titanium-based catalysts, are described in U.S. Pat. Nos. 4,376,062, 4,379,758
and 5,066,737. Ziegler-Natta catalysts typically are magnesium/titanium/electron donor complexes, optionally supported
on a suitable support like silica, used in conjunction with an organoaluminum cocatalyst and an external selectivity control
agent such as an aromatic carboxylic acid ester or an alkoxy silane compound.
35 [0031] Single site catalysts, e.g., metallocene catalysts, comprise organometallic coordination complexes of one or
more ligands in association with a metal atom and are described, for example, in U.S. Pat. No. 7,169,864.
[0032] In accordance with the process, discrete portions of the catalyst components are continuously fed to the reactor
in catalytically effective amounts together with the monomers propylene and ethylene while the polymer product is
continuously removed during the continuing process. Polymerization technologies useful for this purpose are described
40 e.g., in Polypropylene Handbook, 2nd edition, p. 361 ff. (Hanser Publishers, Munich 2005).
[0033] The polymerization is generally carried out at temperatures of from 20 to 150 °C and at pressures of from 1 to
100 bar, with average residence times of from 0.5 to 5 hours, preferably at temperatures of from 60 to 90 °C and at
pressures of from 10 to 50 bar, with average residence times of from 0.5 to 3 hours. The polymerization can be carried
out batchwise or, preferably, continuously.
45 [0034] For example, in the first reactor a mixture of propylene and ethylene is introduced together with hydrogen,
catalyst, organoaluminum cocatalyst and external selectivity control agent. The amount of hydrogen to the combined
monomers propylene and ethylene is in the range of about 10 to about 200 g hydrogen / metric ton (mt) monomers,
preferably about 20 to about 100 g hydrogen / mt monomers, most preferably about 30 to about 60 g hydrogen / mt
monomers if a Ziegler-Natta catalyst is used or in the range of about 0.05 to about 20 g hydrogen / mt monomer and is
50 preferably about 0.1 to about 10 g hydrogen / mt monomer if a metallocene catalyst is used.
[0035] A mixture of copolymer A with active catalyst embedded in the polymer matrix is produced in the first reactor.
This mixture from the first reactor is transferred to the second reactor to which no additional solid catalyst need be added.
Additional cocatalyst and/or external selectivity control agent optionally may be added to the second reactor. In the
second reactor, propylene and ethylene are maintained at a gas phase composition in a range of mole ratio of about
55 0.10 to about 0.50 moles of ethylene per mole of propylene, and preferably about 0.12 to about 0.30 moles of ethylene
per mole propylene. In order to regulate the molecular weight of the copolymer B, hydrogen (H2) is introduced in the
second reactor in an amount of 100-500 g/mt of propylene, preferably 200-400 g/mt of propylene and most preferably
250-350 g/mt of propylene. Such a process creates the random block copolymer of the present invention containing the

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 EP 2 406 298 B1

copolymer A and the copolymer B.

[0036] The random block copolymer of the invention preferably contains a clarifying agent in an amount ranging from
about 50 ppm to about 5,000 ppm, preferably from about 100 to about 4,500 ppm, and more preferably from about 120
to about 4,000 ppm.
5 [0037] Of such clarifying agents, dibenzylidene sorbitol type clarifying agents are preferred, including, but not limited
to, dibenzylidene sorbitol clarifiers having alkyl, alkoxy or halogen substituents on either or both aromatic rings, whereby
the alkyl substituents can be C1 to C20, and may be branched, linear or cycloalkyl, and combinations of such sorbitol
derivatives. Some specific examples of same are bis(3,5-dimethyl benzylidene) sorbitol, bis(p-ethyl benzylidene) sorbitol,
bis(p-methyl benzylidene) sorbitol and combinations thereof. Such clarifying agents are commercially available as MIL-
10 LAD 3940 and 3988 from Milliken Chemical Co. of Spartanburg, S.C.; NC-4 from Mitsui Toatsu Chemicals, Inc. of Tokyo,
Japan; Uniplex CX 45-56 from Unitex Chemical Corp., Greensboro, N.C.; and Geniset MD from New Japan Chemical
Co.,Tokyo ,Japan.
[0038] Other possible clarifying agents are Millad NX 8000 (Milliken Co); Irgaclear XT 386 (Ciba Specialty Chemicals
Inc., Basel, Switzerland); Ricaclear PC 1 ( Rika International , Manchester, UK); ADK-STAB NA-21 and ADK-STAB NA-
15 71 (Asahi Denka, Tokyo, Japan).
[0039] The compositions of the invention may also contain additives such as thermal stabilizers, antioxidants, lubricants,
acid scavengers, synergists, anti-static agents, nucleating additives and additives which stabilize against radiation, such
as ultraviolet (UV) stabilizers and those that provide resistance to gamma irradiation.
[0040] Antioxidants include the sub-classes of primary and secondary antioxidants; examples of primary antioxidants
20 include the phenolic-type additives typified by IRGANOX 1010, IRGANOX 3114 (Ciba) or ETHANOX 330 (Albemarle).
Their main function is to provide long-term thermal stability such as is usually needed in fabricated articles.
[0041] The class of secondary antioxidants includes additives that contain phosphorus in either organophosphite or
organophosphonite configurations. Examples of such phosphites include IRGAFOS 168 or IRGAFOS 12 (Ciba), UL-
TRANOX 626, ULTRANOX 627A, ULTRANOX 641 (Chemtura), DOVERPHOS S-9228 (Dover Chemical Co.).
25 [0042] Organophosphonite secondary antioxidants are typified by IRGAFOS P-EPQ (Ciba). Other secondary antioxi-
dants are exemplified by lower molecular weight phenolic-types such as BHT or IRGANOX 1076, or high molecular
weight hydroxyl amines such as IRGASTAB FS 042 (Ciba). Secondary antioxidants function mainly by providing stability
in melt flow and color during the melt processing of the plastic material. Another class of secondary antioxidants comprises
the benzofuranone (lactone) derivatives as represented by IRGANOX HP-136 (Ciba).
30 [0043] Lubricants or mold release agents are typified by fatty acid amides, examples of which include oleamide,
erucamide or ethylene bis-(stearamide).
[0044] Acid scavengers may be categorized as salts of fatty acids, e.g. stearic acid or lactic acid salts and related
derivatives, hydrotalcite-like compounds, and certain metal oxides. Examples of each type in order include calcium
stearate, zinc stearate, calcium lactate, DHT-4A (Kyowa Chemical Co. Tokyo, Japan) , and zinc or magnesium oxides.
35 Synergists enhance the performance of primary antioxidants. Examples include the thioesters of fatty acids typified by
Di-stearyl-thio-dipropionate (DSTDP), Di-lauryl-thio-dipropionate (DLTDP) and Di-myristyl-thio-dipropionate (DMTDP).
[0045] Anti-static agents enhance static charge decay on molded parts. Key examples include glyceryl monostearate
and glyceryl distearate, as well as mixtures thereof.
[0046] Nucleating additives are typically benzoic acid salts such as sodium, lithium or aluminum benzoate, minerals
40 such as micronized talc, and organophosphorous salts such as ADK-STAB NA-11 or ADK-STAB NA-25 (Asahi Denka).
[0047] Ultraviolet stabilization is provided by light absorbers such as TINUVIN 327 (Ciba) or by hindered amine type
stabilizers such as CYASORB 3346 (Cytec Industries Inc.), TINUVIN 622, TINUVIN 770 DF or CHIMASSORB 944 (Ciba).
[0048] Resistance against gamma irradiation is provided by combinations of additives such as phosphorous-containing
secondary antioxidants and hindered amines. Additionally, Milliken’s RS 200 additive is of benefit, as are other mobilizing
45 additives such as mineral oil (cited in U.S. Pat. Nos. 4,110,185 and 4,274,932).
[0049] Preferred antioxidants include 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxy-benzyl) benzene (A); octa-
decyl 3-(3’,5’-di-tert-butyl-4’-hydroxyphenyl) propionate (B); tetrakis[methylene (3,5-di-tert-butyl-4-hydroxyhydrocinna-
mate)]methane (C); tris[3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate (D); 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid
triester with 1,3,5-tris(2-hydroxyethyl)-s-triazine-2,4,6(1H,3H,5H)-trione (E); 1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-
50 dimethylbenzyl) 1,3,5-triazine-2,4,6-(1H,3H,5H)-trione (F); bis-[3,3-bis(4-hydroxy-3-tert-butyl-phenyl)-butanoic acid]
-glycolester (G); 2,2’-methylene-bis-(4-methyl-6-tertiary-butylphenol)-terephthalate (H); and 2,2 bis[4-(2-(3,5-di-tert-
butyl-4-hydroxyhydrocinnamoyloxy)) ethoxy-phenyl]propane (I); calcium bis [monoethyl(3,5-di-tert-butyl-4-hydroxyben-
zyl)phosphonate](J); 1,2-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazine (K); and 2,2-oxamido bis[ethyl 3-(3,5-
di-tert-butyl-4-hydroxyphenyl)propionate] (L).
55 [0050] Additional additives may be used separately or blended with the above listed antioxidants. This applies to all
the above additive types and further includes fillers like talc, calcium carbonate, barium sulfate, clays, silicates, pigments,
such as titanium dioxide, zinc oxide, lead chromate, cadmium sulfides, cadmium selenide, zinc sulfide, basic carbonate
of white lead; flame retardants such as antimony oxide; ultra-violet stabilizers, slip agents, anti-impact agents, and other

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 EP 2 406 298 B1

additives which enhance the properties and processability of the random block copolymer to which they are added.
[0051] While the above listing seeks to provide key examples of the different additive types, it is not to be viewed as
limited by the examples in scope. It is also recognized that certain of the above additives are multi-functional, e.g., an
acid acceptor such as calcium stearate may also provide mold release performance, as may also be the case with
5 glycerol monostearate. Further, combinations of any or all types of additives given, or of additives within a given class,
are considered to be within the scope of the present invention.
[0052] The random block copolymer of the present invention may be subjected to a chemical degradation treatment
(visbreaking or clipping) according to processes well known in the art, in order to improve the flowability and to obtain
the required MFR values (measured according to ISO standard 1133). The chemical degradation of the copolymer is
10 carried out in the presence of a free radical initiator , such as organic peroxide. Examples of free radical initiators that
can be used for this purpose are e.g. Di-t-butyl-peroxide , (2,5-Dimethyl-2,5-ditert-butylperoxy)-hexane or 3,6,9-Triethyl-
3,6,9-trimethyl-1,4,7-triperoxononane.
[0053] The random block copolymers of the present invention may be used in any standard molded products in which
similar polyolefin resins and conventional polypropylene impact copolymers are used. However, the added advantage
15 of good stiffness and high toughness in combination with outstanding clarity expands this range of utility over standard
impact copolymers, such that the random block copolymers of the present invention can be used in food and non-food
containers, drinking cups, water bottles, caps & closures, medical devices and toys where the need for clarity otherwise
restricts use to either random propylene-ethylene copolymers of inherently lower toughness or to other polymers such
as polycarbonate, which while tough, are several times more expensive. The need for toughness at freezer temperatures,
20 combined with stiffness and clarity, is met by the materials of this invention at lower cost.
[0054] According to the present invention, random block copolymers with low hot hexane solubles content, determined
in accordance with FDA 177.1520, can be produced, enabling them to be used for cooking applications. In addition,
according to the present invention, random block copolymers can be produced which can be sterilized for medical
application by steam autoclaving or gamma irradiation. In addition, such grades can be used for microwave heating and
25 cooking.

METHODS

[0055] The following test methods were used in the Examples given below.
30 [0056] XS ( Xylene Soluble Fraction) was determined at 23 °C according to ISO 16152.
[0057] Xylene solubles are defined as the percent by weight remaining in solution after the polymer sample is dissolved
in hot Xylene and subsequent cooling down of the solution to 23 °C. The difference between Xylene solubles after the
second stage of polymerization and the first stage of polymerization largely correlates to the rubber content of the random
block copolymers of the present invention.
35 [0058] MFR (Melt Flow Rate) was determined in accordance with ISO 1133 at 230 °C with a load of 2.16 kg. According
to this measurement, the MFR refers to the weight of the polymer extruded through a standard cylindrical die at a standard
temperature of 230°C in a laboratory apparatus carrying a standard piston and load of 2.16 kg. The MFR is a measure
of the melt viscosity of a polymer and hence of its molar mass.
[0059] Haze was determined in accordance with ASTM D 1003 using test specimens with a dimension of 6 x 6 cm
40 and a thickness of 1 mm. These plates have been injection molded at a mold temperature of 210°C and a tool surface
temperature of 40°C. The tool has to be carefully polished to guarantee a glossy and scratch free surface of the test
plates produced. After a storage time of 48 hours at room temperature to ensure the maximum possible crystallization
of the polymer, the measurement was made at 23°C using a Gretag Macbeth Color-Eye 7000A spectrophotometer. The
test specimens are measured in the center of the plate. Haze is measured as a percentage of transmitted light that is
45 scattered more than 2.5 degrees from the direction of the incident beam. The reported haze value is the average result
of the individual haze values measured on three different plates. The lower the haze % numbers, the higher is the
transparency of the test specimen. Materials with haze values greater than 30% are considered to be diffusing.
[0060] The glass transition temperature (Tg) was determined by means of torsional Dynamic Mechanical Analysis
(DMA) on compression molded rectangular bars in accordance with ASTM D 4065 - 06. Temperature and frequency
50 dependent tests were made using a Rheometrics Dynamic Analyzer RDA II. Pellet samples for each material were
melted and moulded in form of a sheet of uniform thickness (1 mm) in a laboratory hot press at 200 °C and 20 MPa for
7 min, followed by cooling (inside the press) for 11 min; the cooling water temperature was 15 °C.
[0061] The test specimens were cut from the compression molded sheets in the following dimensions: length 30 mm,
width 10mm, and thickness 1 mm. They were then kept at 23°C and 50 % r.h. for a minimum length of time of 88 h (ISO
55 291) before carrying out the measurements.
[0062] The samples were subjected to a sinusoidal strain of 0.3% (to ensure viscolelastic behavior) at a constant
frequency of 1 rad/s. The temperature dependence of the dynamic mechanical loss tangent, tan *, was measured from
-150 °C up to 80 °C at an average heating rate of 3 °C/min under a nitrogen atmosphere. Finally the glass transition

7
 EP 2 406 298 B1

temperature of each sample was defined as the peak of the tan * curve as a function of temperature (tan * is defined as
the ratio of the loss modulus E" to the storage modulus E’).
[0063] The melting point (Tm) was determined by DSC in accordance with ISO standard 3146 using a 5 mg polymer
sample and applying a first heating step at a heating rate of 20°C/min up to 230°C and a hold at 230°C for 10 min,
5 followed by a crystallization step with a cooling rate of 20°C/min from 200°C to -20°C with a hold at -20°C of 10 min,
followed by a second heating step at a heating rate of 20°C/min to 230°C. The reported melting point is the temperature,
where the enthalpy of the second heating cycle displays the maximum. Instruments from Perkin Elmer (DSC 7) and TA
Instruments (Q 1000 DSC) have been used after calibration with Indium under the above mentioned measurement
conditions.
10 [0064] The hexane soluble content (HS) was determined in accordance with FDA 177.1520 by using 2 g of a respective
film of 2 mil thickness made of the polymer. The film was extracted at 50°C for 2 hours. After the extraction, the hexane
extract was separated into a flask and the content of extracted polymer was gravimetrically determined after removal of
the hexane under reduced pressure.
[0065] The ethylene content of the copolymers was determined by FT-IR (Fourier Transform Infra red Spectroscopy).
15 The test method is suitable for the quantitative determination of the ethylene content in propylene-ethylene copolymers.
The method employs calibrations based on sets of reference samples covering a suitable range of ethylene levels. The
ethylene content of these reference samples was determined by 13C NMR.
[0066] A small amount of resin is placed in a spacer frame, sandwiched between polyester film, and molded into a
film of 200 +/- 10 microns thickness at 210°C and 200 bar for 10 min, then cooled down to <40°C under pressure.
20 [0067] The test samples are then exposed to the probe of the FT-IR spectrometer and the spectra are recorded in the
relevant wave number range (absorption bands of the ethylene in the impact copolymers: 720 - 730 cm-1)
[0068] Spectra are transformed into the format suitable to be analysed by the chemometry software package. The
chemometrical analysis of the FT-IR data results in the ethylene content of the sample in percent.
[0069] The impact strength was measured by notched or un-notched Charpy test on injection moulded specimens
25 according to ISO 179-1 (Plastics - Determination of Charpy impact properties Part 1: Instrumented impact test)
[0070] Small Angle X-Ray Scattering (SAXS) was performed on injection-molded plaques to determine long spacing
(Lp) crystalline spacing (Lc) and amorphous spacing (La) quantities in the tested copolymers. The spacing was obtained
by profile fitting the peak in the SAXS data with a pseudo-Voigt function (Jade version 7, Materials Data Inc., Livermore,
CA) in which the skew was refined. The background was determined by two straight lines determined by the high and
30 low angle linear scattering limits. The data were collected on a line source system (Rigaku Ultima 3). The system was
configured with a multilayer mirror, 0.03 micron first slit and second 1mm slit set to reduce the parasitic scatter from the
mirror and the beam defining slits. The diffracted beam side of the system consisted of a vacuum pathway, scatter slit
of 0.2 mm and detector slit of 0.01 mm. Data were collected at 6 seconds/step with 0.005 degrees per step.
[0071] The tests indicated above were performed on Example 1, Comparative Examples A, B, and C , and the com-
35 mercially available clarified random copolymers indicated herein.

EXAMPLES

[0072] Various features of the invention are illustrated by Example 1 below. The Comparative Examples and commercial
40 products tested do not represent the invention but are presented for comparison purposes.
[0073] All products mentioned in Table 1 were produced by a stirred gas phase process in a reactor cascade consisting
of two 25 m 3 gas phase reactors with helical stirrers.
[0074] Example 1 as well as the comparative examples A , B and C are random block copolymers, consisting of a
crystalline propylene/ethylene copolymer A , produced in the first stirred gas phase reactor and a propylene/ethylene
45 copolymer B, produced in the second stirred gas phase reactor of the cascade.
[0075] In the first reactor, a mixture of propylene and ethylene was introduced together with hydrogen, ZN-catalyst,
organoaluminum cocatalyst and an external donor (Silane).
[0076] Temperature, pressure and the feed ratios for ethylene and hydrogen with respect to the propylene feed are
given in Table 1. After an average residence time of 60 min , a mixture of copolymer A with active catalyst embedded
50 in the polymer matrix was transferred to the second reactor without adding additional catalyst. In the second reactor,
the polymerization of the copolymer B was taking place at reduced pressure and temperature (see table 1), again at a
residence time of 60 min.
[0077] The products were stabilized / additivated by blending the polymer powder from the second reactor (powder
MFR’s between 1.7 and 2.5 as indicated in Table 1) with a combination of Irgafos 168 (secondary anti-oxidant), Irganox
55 1010 (primary anti-oxidant), Calcium stearate (acid scavenger), Glycerol monostearate (GMS) (anti-static agent) and
Millad 3988 (clarifier).
[0078] They were subsequentially visbroken by 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane to MFR’s between 12 and
15 ( see Table 1) and pelletized on a Werner & Pfleiderer corotating double screw extruder.

8
 EP 2 406 298 B1

TABLE 1
(Example 1, comparative examples A, B and C and commercial comparative examples 3240 NC and 3348 SC)

5
Polymerization
Parameters
Example Comp. Ex. Comp. Ex. Comp. Ex.
1st Reactor 1 A B C 3240NC 3348SC
10
Pressure Barg 24 24 24 24 24 24
Temperature °C 75 75 75 75 75 75
Kg
15 C2 Feed Ratio C2/tnC3 38 28 28 26 28 38
q
H2 Feed Ratio H2/tnC3 44 40 40 32 38 46
Powder C2 content wt-% 3 2.2 2.2 1.8 2.2 3
20 Powder MFR q/10 min 1.4 1.95 1.95 1.3 1.8 1.5
XS % 8.5 6.5 6.5 6.0 6.5 8.5

2nd Reactor
25
Pressure Barg 12.5 12.5 12.5 12.5 - -
Temperature °C 69 69 69 69 - -
Kg
30
C2 Feed Ratio C2/tnC3 50 50 50 80 - -
C3 Feed Ton C3/h 0.3 0.3 0 0 - -
q
H2 Feed Ratio H2/tnC3 295 160 160 530 - -
35 Powder MFR g/10 min 1.7 1.8 1.8 2.5 - -
K (MFR2ndR/MFR1stR) q/10 min 1.21 0.92 0.92 1.92 - -

Final Product
40
Final MFR pellets g/10 min 12 15 15 15 12 25
Final XS % 17.2 15.5 16.2 20.6 - -
Ratio 1st/2nd Reactor wt:wt 91:9 91:9 90:10 85:15 - -
Final Product
45
Properties
Haze % 5.8 15 20 15 11 11
Tg °C -9 -6 -6 -6/-50 -5 -5
Tm °C 142 147 146 151 150 145
50
Hexane solubles (%) 4.2 4.2 3.8 - 2.2 3.2
IS Charpy notched @ 23
EC (KJ/m2) 29 11 11 40 6 6.3
IS Charpy notched @ 0
55
EC (KJ/m2) 5 6 6 8 2 3.5
IS Charpy notched @
-20 EC (KJ/m2) 1 1 1 1 1 1
IS Charpy @ 23 EC (KJ/m2) NB NB NB NB 200 NB

9
 EP 2 406 298 B1

(continued)

Final Product
Properties
5 IS Charpy @ 0 EC (KJ/m2) NB NB NB NB 100 180
IS Charpy @ -20 EC (KJ/m2) NB NB NB NB 17 50
Flexural Modulus MPa 590 700 710 770 1050 740
NB: without break
10
EXAMPLE 1

[0079] Example 1 was produced in a two step process. In the first stage, a propylene/ethylene random copolymer with
3 wt-% ethylene content was polymerized in gas phase. In the second stage, a low molecular weight propylene/ethylene
15 rubber, rich in propylene was polymerized.
[0080] In order to obtain a low molecular weight rubber, a proper amount of hydrogen was added to the second reactor.
As a result of this, a K-value (the ratio of the second reactor powder MFR to the first reactor powder MFR) of 1.21 was
achieved.
[0081] In order to have a rubber phase rich in propylene, an additional amount of propylene was injected in the second
20 stage of polymerization.
[0082] The ratio between the propylene/ethylene random copolymer and the propylene/ethylene rubber in the final
product was 91:9 (parts by weight).
[0083] The polymer powder obtained in the polymerization was admixed with a standard additive mixture in the extrusion
step. The polymer was compounded in a twin screw extruder at 250°C. The polymer composition obtained contained
25 0.1% by weight of Irgafos 168 (from Ciba SC), 0.05% by weight of Irganox 1010 (from Ciba SC), 0.11% by weight of
Calcium Stearate (from Baerlocher), 0.06% by weight of Atmer 122 (from Ciba SC) and 0.2% by weight of Millad 3988
(from Milliken Chemical).
[0084] For visbreaking from the powder melt flow rate of 1.7 g/10 min to the final pellet melt flow rate of about 12
g/10min, 2,5-dimethyl-2,5-di (tert-butylperoxy)hexane was used.
30 [0085] Other operative conditions and general properties of the produced polymer are indicated in Table 1 above.

COMPARATIVE EXAMPLES

Comparative Example A
35
[0086] Comparative Example A was produced in a two step process. In the first stage, a propylene/ethylene random
copolymer with 2.2 wt-% ethylene was polymerized in gas phase. A composition of propylene/ethylene rubber similar
to Example 1 was polymerized in the second stage. In this comparative example, a lower amount of hydrogen was
injected, in order to obtain a higher molecular weight of the rubber phase. As a consequence, a K value (the ratio of the
40 second reactor powder MFR to the first reactor powder MFR) lower than 1 was achieved.
[0087] The ratio between the propylene/ethylene random copolymer and the propylene/ethylene rubber was 91:9
(parts by weight).
[0088] The polymer powder obtained in the polymerization was admixed with a standard additive mixture in the extrusion
step. The polymer was compounded in a twin screw extruder at 250°C. The polymer composition obtained contained
45 0.1% by weight of Irgafos 168 (from Ciba SC), 0.05% by weight of Irganox 1010 (from Ciba SC), 0.11% by weight of
calcium stearate (from Baerlocher), 0.06% by weight of Atmer 122 (from Ciba SC) and 0.2% by weight of Millad 3988
(from Milliken Chemical).
[0089] For visbreaking from the powder melt flow rate of 1.8 g/10 min to the final melt flow rate of 15 g/10 min, 2,5-
dimethyl-2,5-di(tert-butylperoxy)hexane was used.
50 [0090] In Comparative Example A, as a result of a lower amount of ethylene in the first stage composition (random
copolymer) and a higher molecular weight in the second stage polymerization (rubber phase), the resulting haze was
higher compared to the one achieved in Example 1.
[0091] Other operative conditions of the produced polymer are indicated in Table 1.

55 Comparative Example B

[0092] Comparative Example B was produced in a two step process. In the first stage, a propylene/ethylene random

10
 EP 2 406 298 B1

copolymer with 2.2 w-% ethylene was polymerized in gas phase. In this comparative example, the same amount of
hydrogen was injected as in Comparative Example A, in order to obtain a similar molecular weight of the rubber phase
(higher than in Example 1). As a consequence, a K-value lower than 1 was achieved.
[0093] Comparative Example B was produced without the injection of propylene in the second reactor, in order to
5 achieve a different composition in the rubber phase.
[0094] The ratio between the propylene/ethylene random copolymer and the propylene/ethylene rubber was 90:10
(parts by weight).
[0095] The polymer powder obtained in the polymerization was admixed with a standard additive mixture in the extrusion
step. The polymer was compounded in a twin screw extruder at 250°C. The polymer composition obtained contained
10 0.1% by weight of Irgafos 168 (from Ciba SC), 0.05% by weight of Irganox 1010 (from Ciba SC), 0.11% by weight of
calcium stearate (from Baerlocher), 0.06% by weight of Atmer 122 (from Ciba SC) and 0.2% by weight of Millad 3988
(from Milliken Chemical).
[0096] For visbreaking from the powder melt flow rate of 1.8 g/10 min to the final melt flow rate of 15 g/10min, 2,5-
dimethyl-2,5-di(ter-butylperoxy)hexane was used.
15 [0097] In Comparative Example B, as a result of a lower amount of ethylene in the first stage composition (random
copolymer), a higher molecular weight in the second stage polymerization (rubber phase), and a more incompatible
rubber phase due to its chemical composition, the resulting haze was higher compared to the one achieved in Comparative
Example A.
[0098] Other operative conditions of the produced polymer are indicated above in Table 1.
20
Comparative Example C

[0099] Comparative Example C was produced in a two step process stirred gas phase process. In the first stage, a
propylene/ethylene random copolymer with an ethylene content of 1.8 wt-% was polymerized in gas phase. Comparative
25 Example C was produced without the injection of propylene, but with a higher amount of hydrogen in the second reactor.
As a consequence, a K-value (the ratio of the second reactor powder MFR to the first reactor powder MFR) of 1.92 was
achieved, which was higher than in Example 1.
[0100] The ratio between the propylene/ethylene random copolymer and the propylene/ethylene rubber was 85:15
(parts by weight).
30 [0101] The polymer powder obtained in the polymerization was admixed with a standard additive mixture in the extrusion
step. The polymer was compounded in a twin screw extruder at 250°C. The polymer composition obtained contained
0.1% by weight of Irgafos 168 (from Ciba SC), 0.05% by weight of Irganox 1010 (from Ciba SC), 0.11% by weight of
calcium stearate (from Baerlocher), 0.06% by weight of Atmer 122 (from Ciba SC) and 0.2% by weight of Millad 3988
(from Milliken Chemical).
35 [0102] For visbreaking from the powder melt flow rate of 2.5 g/10 min to the final melt flow rate of 15 g/10min, 2,5-
dimethyl-2,5-di(tert-butylperoxy)hexane was used.
[0103] In spite of having a positive ΔMFRR2 -R1 (very low molecular weight of the rubber phase), the resulting haze of
the product of Comparative Example C was higher than that achieved in Example 1 as a result of a lower amount of
ethylene in the random copolymer of the first stage, and a more incompatible rubber phase in the second stage of the
40 polymerization.
[0104] Other operative conditions of the produced polymer are indicated in Table 1.

COMMERCIAL COMPARATIVE EXAMPLES

45 [0105] 3240NC and 3348SC are designations of random copolymers commercially available from Novolen Technology.
[0106] 3240NC and 3348SC were both produced in a single gas phase reactor. 3240NC is a propylene/ethylene
random copolymer with 2.2 wt-% ethylene. 3348 SC is a propylene/ethylene random copolymer with 3 wt-% ethylene.
[0107] The polymer powder obtained in the polymerization was admixed with a standard additive mixture in the extrusion
step. The polymers were compounded in a twin screw extruder at 250°C. The polymer composition of 3240 NC contained
50 0.1% by weight of Irgafos 168 (from Ciba SC), 0.05% by weight of Irganox 1010 (from Ciba SC), 0.11% by weight of
calcium stearate (from Baerlocher), 0.06% by weight of Atmer 122 (from Ciba SC) and 0.2% by weight of Millad 3988
(from Milliken Chemical) as clarifying agent. 3348 SC contains additionally 0.2% Atmer 122 as antielectrostatic agent.
[0108] For visbreaking from the powder melt flow rate to the final melt flow rate of about 12 g/10min for 3240NC and
25 g/10min for 3348SC, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane was used.
55 [0109] Examples presented in Table 1 clearly show that only by carefully tailoring molecular parameters, such as
matrix ethylene content, rubber composition and rubber molecular weight, a very low haze value can be obtained by
adding a rubber phase to a random copolymer matrix.
[0110] Careful control and balancing of those parameters results in the growth of crystalline regions of a certain size

11
 EP 2 406 298 B1

and type, resulting in an random block copolymer that has an unexpectedly low haze, which is desirable yet previously
thought to be impossible for impact copolymers.
[0111] Table 2 shows this fact, where contrary to conventional expectations, increasing rubber content, as shown by
increasing XS values, can result in lower haze values.
5 [0112] Starting from a random copolymer with a haze value of about 11 %, the incorporation of a properly designed
rubber phase leads to an increasing improvement in transparency while the amount of such rubber phase, measured
by the Xs content, is increased. In this way and following the polymerization parameters already presented in Example
1 (Table 1) it was possible to achieve a final haze about half the starting value. There are no significant changes in
product melting point since the random copolymer matrix has the same ethylene content.
10
TABLE 2
Haze reduction by rubber incorporation to a Random copolymer matrix
XS (%) Haze (%) Tm (°C)
15 Start Random 8.5 11.0 143
12.6 10.0 143
12.8 9.2 143
14.4 8.3 142
20
15.3 6.0 142
16.9 5.8 142
Example 1 17.2 5.8 142
25

[0113] Although not wishing to be limited to any theory, the low haze is believed to be the result of properly formed
crystalline domains of smaller size and type than those found in typical random copolymers. This behavior is believed
to be attributable to co-crystallization of rubber chains within the matrix chains. Smaller, more open spherulites with
irregular borders in combination with very small rubber particles (<0.4mm) are believed to provide a mechanism for
30
obtaining the unique balance of low haze and good impact properties in the random block copolymer of the invention.
Also, low molecular weight (LMW) compatible rubber tends to migrate to the matrix domain thereby thickening the
amorphous lamella (La) and thinning the crystalline lamella (Lc). This effect is presented in Table 3.

TABLE 3
35
Haze (%) Crystalline to Amorphous Spacing Ratio (Lc/La) Long Spacing Lp (Δ)
Example 1 5.8 1.5 129
3240NC 11 2.3 139
40

[0114] The random block copolymer of the invention (Example 1) has smaller long spacing (Lp) and lower crystalline
to amorphous spacing ratio (Lc/La), which correlates to a decrease in haze. These results suggest that the structure of
copolymer A and the presence of copolymer B of the present invention tend to reduce the size of crystallites by disrupting
their structure through co-crystallization.
45
[0115] While the above description contains many specifics, these specifics should not be construed as limitations of
the invention, but merely as exemplifications of preferred embodiments thereof.

Claims
50

1. A random block copolymer comprising:

a) 65 wt.% to 97 wt.% of a crystalline propylene/ethylene copolymer A containing from 0.5 wt.% to 6 wt.% of
units derived from ethylene and from 94 wt.% to 99.5 wt.% of units derived from propylene, having a melting
55
point of 120°C to 159°C; and copolymerized therewith, and
b) 3 wt.% to 35 wt.% of a propylene/ethylene copolymer B containing from 8 wt.% to 40 wt.% of units derived
from ethylene and from 60 wt.% to 92 wt.% of units derived from propylene, wherein the ratio of the powder

12
 EP 2 406 298 B1

MFRrandom block copolymer to the powder MFRcopolymer A is in accordance with equation

wherein K = 1.0 to 1.5, and

wherein a crystalline to amorphous spacing ratio Lc/La of said random block copolymer ranges from 1.00
to 2.25.

10 2. The random block copolymer of claim 1, wherein K = 1.0 to 1.3.

3. The random block copolymer of claim 1, wherein K = 1.0 to 1.25.

4. The random block copolymer of claim 1, comprising:

15

a) 75 wt.% to 95 wt.% of a crystalline propylene/ethylene copolymer A containing from 1 wt.% to 5 wt.% of units
derived from ethylene and from 95 wt.% to 99 wt.% of units derived from propylene, and copolymerized therewith,
b) 5 wt.% to 25 wt.% of a propylene/ethylene copolymer B containing from 10 wt.% to 30 wt.% of units derived
from ethylene and from 70 wt.% to 90 wt.% of units derived from propylene.
20

5. The random block copolymer of claim 1, comprising:

a) 80 wt.% to 92 wt.% of a crystalline propylene/ethylene copolymer A containing from 1.5 wt.% to 4.5 wt.% of
units derived from ethylene and from 95.5 wt.% to 98.5 wt.% of units derived from propylene, and copolymerized
25 therewith,
b) 8 wt.% to 20 wt.% of a propylene/ethylene copolymer B containing from 10 wt.% to 30 wt.% of units derived
from ethylene and from 70 wt.% to 90 wt.% of units derived from propylene.

6. The random block copolymer of claim 1, comprising:

30

a) 88 wt.% to 92 wt.% of a crystalline propylene/ethylene copolymer A containing from 2 wt.% to 4 wt.% of units
derived from ethylene and from 96 wt.% to 98 wt.% of units derived from propylene, and copolymerized therewith,
b) 8 wt.% to 12 wt.% of a propylene/ethylene copolymer B containing from 12 wt.% to 17 wt.% of units derived
from ethylene and from 83 wt.% to 88 wt.% of units derived from propylene.
35

7. The random block copolymer of claim 1, wherein the crystalline to amorphous spacing ratio Lc/La of said random
block copolymer ranges from 1.25 to 2.00.

8. The random block copolymer of claim 1, wherein the crystalline to amorphous spacing ratio Lc/La of said random
40 block copolymer ranges from 1.40 to 1.70.

9. The random block copolymer of claim 1, further comprising 50 ppm to 5,000 ppm of a clarifying agent.

10. The random block copolymer of claim 9, wherein the clarifying agent is selected from the group consisting of
45 dibenzylidene sorbitol derivatives having alkyl, alkoxy or halogen substituents on either or both aromatic rings,
whereby the alkyl substituents can be C 1 to C20, and may be branched, linear or cycloalkyl and combinations of
said sorbitol derivatives.

11. The random block copolymer of claim 9, having a haze value at 23°C of from 5 % to 10 % as measured by ASTM
50 D 1003, and an impact strength at 23°C of from 10 kJ/m2 to 50 kJ/m 2 as measured by the Charpy notched impact
strength test in accordance with ISO 179-2.

12. A method of making a random block copolymer, comprising:

55 a) introducing into a first reaction zone a polymerization catalyst and a first feed containing from 0.5 parts by
weight to 6 parts by weight of ethylene and from 94 parts by weight to 99.5 parts by weight of propylene;
b) copolymerizing the ethylene and propylene under first polymerization reaction conditions to provide a copol-

13
 EP 2 406 298 B1

ymer A with active catalyst embedded therein, having a melting point of 120°C to 159°C;
c) introducing the copolymer A into a second reaction zone;
d) introducing to the second reaction zone a second feed containing from 8 parts by weight to 40 parts by weight
of ethylene and from 60 parts by weight to 92 parts by weight of propylene; and
5 e) copolymerizing the ethylene and propylene of the second feed to provide a copolymer B, wherein the copol-
ymer B is copolymerized with the copolymer A under second polymerization reaction conditions and in such
proportion as to provide a random block copolymer containing from 65 wt.% to 97 wt.% blocks of copolymer A
and 3 wt.% to 35 wt.% blocks of copolymer B, wherein the ratio of the powder MFRrandom block copolymer to the
powder MFRcopolymer A is in accordance with equation
10

wherein K = 1.0 to 1.5, and

15 wherein a crystalline to amorphous spacing ratio Lc/La of said random block copolymer ranges from 1.00
to 2.25.

13. The method of claim 12, wherein:

20 the random block copolymer contains from 75 wt.% to 95 wt.% blocks of copolymer A and 5 wt.% to 25 wt.%
blocks of copolymer B.

14. The method of claim 12 or 13, wherein:

25 the first feed contains from 1 parts by weight to 5 parts by weight of ethylene and from 95 parts by weight to 99
parts by weight of propylene,
the second feed contains from 10 parts by weight to 30 parts by weight of ethylene and from 70 parts by weight
to 90 parts by weight of propylene, and
the random block copolymer contains from 75 wt.% to 95 wt.% blocks of copolymer A and 5 wt.% to 25 wt.%
30 blocks of copolymer B.

15. The method of claim 12 or 13, wherein:

the first feed contains from 1.5 parts by weight to 4.5 parts by weight of ethylene and from 95.5 parts by weight
35 to 98.5 parts by weight of propylene,
the second feed contains from 10 parts by weight to 30 parts by weight of ethylene and from 70 parts by weight
to 90 parts by weight of propylene, and
the random block copolymer contains from 80 wt.% to 92 wt.% blocks of copolymer A and 8 wt.% to 20 wt.%
blocks of copolymer B.
40

16. The method of claim 12 or 13, wherein

the first feed contains from 2 parts by weight to 4 parts by weight of ethylene and from 96 parts by weight to 98 parts
by weight of propylene,
the second feed contains from 12 parts by weight to 17 parts by weight of ethylene and from 83 parts by weight to
45 88 parts by weight of propylene, and
the random block copolymer contains from 88 wt.% to 92 wt.% blocks of copolymer A and 8 wt.% to 12 wt.% blocks
of copolymer B.

17. The method of claim 12 or 13, wherein the catalyst is a Ziegler-Natta catalyst or metallocene catalyst.
50

18. The method of claim 12 or 13, wherein both the first polymerization reaction and the second polymerization reaction
are carried out in a stirred bed gas phase process.

19. The method of claim 12 or 13, wherein the first polymerization reaction is a bulk polymerization process conducted
55 in liquefied propylene.

20. The method of claim 19, wherein the second polymerization reaction is a gas phase process and the second reaction

14
 EP 2 406 298 B1

zone includes a fluidized bed or stirred bed.

21. The method of claim 12 or 13, wherein the first and/or second polymerization reaction conditions include a temper-
ature of from 20 to 150°C, a pressure of from 1 to 100 bar, and an average residence time of from 0.5 to 5 hours.
5
22. The method of claim 12 or 13, wherein the first and/or second polymerization reaction conditions include a temper-
atures of from 60 to 90°C, a pressure of from 10 to 50 bar, and an average residence time of from 0.5 to 3 hours.

23. The method of claim 14, further comprising the introduction of hydrogen into the first and/or second polymerization
10 reaction zone.

24. The method of claim 12 or 13, wherein the polymerization catalyst comprises a Ziegler-Natta catalyst.

15 Patentansprüche

1. Statistisches Block-Copolymer, umfassend:

a) 65 Gew.-% bis 97 Gew.-% eines kristallinen Propylen-/Ethylen-Copolymers A enthaltend von 0,5 Gew.-%
20 bis 6 Gew.-% von Ethylen abgeleitete Einheiten und von 94 Gew.-% bis 99,5 Gew.-% von Propylen abgeleitete
Einheiten, mit einem Schmelzpunkt von 120 °C bis 159 °C, und damit copolymerisiert, und
b) 3 Gew.-% bis 35 Gew.-% eines Propylen-/Ethylen-Copolymers B enthaltend von 8 Gew.-% bis 40 Gew.-%
von Ethylen abgeleitete Einheiten und von 60 Gew.-% bis 92 Gew.-% von Propylen abgeleitete Einheiten, wobei
das Verhältnis aus Pulver MFRstatistisches Block-Copolymer zu Pulver MFRcopolymer A der Gleichung
25

wobei K= 1,0 bis 1,5 ist, und

30 wobei ein Abstandsverhältnis von kristallin zu amorph Lc/La des statistischen Block-Copolymers im Bereich
von 1,00 bis 2,25 liegt.

2. Statistisches Block-Copolymer nach Anspruch 1, wobei K = 1,0 bis 1,3 ist.

35 3. Statistisches Block-Copolymer nach Anspruch 1, wobei K = 1,0 bis 1,25 ist.

4. Statistisches Block-Copolymer nach Anspruch 1, umfassend:

a) 75 Gew.-% bis 95 Gew.-% eines kristallinen Propylen-/Ethylen-Copolymers A enthaltend von 1 Gew.-% bis
40 5 Gew.-% von Ethylen abgeleitete Einheiten und von 95 Gew.-% bis 99 Gew.-% von Propylen abgeleitete
Einheiten, und damit copolymerisiert,
b) 5 Gew.-% bis 25 Gew.-% eines Propylen-/Ethylen-Copolymers B enthaltend von 10 Gew.-% bis 30 Gew.-%
von Ethylen abgeleitete Einheiten und von 70 Gew.-% bis 90 Gew.-% von Propylen abgeleitete Einheiten.

45 5. Statistisches Block-Copolymer nach Anspruch 1, umfassend:

a) 80 Gew.-% bis 92 Gew.-% eines kristallinen Propylen-/Ethylen-Copolymers A enthaltend von 1,5 Gew.-%
bis 4,5 Gew.-% von Ethylen abgeleitete Einheiten und von 95,5 Gew.-% bis 98,5 Gew.-% von Propylen abge-
leitete Einheiten, und damit copolymerisiert,
50 b) 8 Gew.-% bis 20 Gew.-% eines Propylen-/Ethylen-Copolymers B enthaltend von 10 Gew.-% bis 30 Gew.-%
von Ethylen abgeleitete Einheiten und von 70 Gew.-% bis 90 Gew.-% von Propylen abgeleitete Einheiten.

6. Statistisches Block-Copolymer nach Anspruch 1, umfassend:

55 a) 88 Gew.-% bis 92 Gew.-% eines kristallinen Propylen-/Ethylen-Copolymers A enthaltend von 2 Gew.-% bis
4 Gew.-% von Ethylen abgeleitete Einheiten und von 96 Gew.-% bis 98 Gew.-% von Propylen abgeleitete
Einheiten, und damit copolymerisiert,

15
 EP 2 406 298 B1

b) 8 Gew.-% bis 12 Gew.-% eines Propylen-/Ethylen-Copolymers B enthaltend von 12 Gew.-% bis 17 Gew.-%
von Ethylen abgeleitete Einheiten und von 83 Gew.-% bis 88 Gew.-% von Propylen abgeleitete Einheiten.

7. Statistisches Block-Copolymer nach Anspruch 1, wobei das Abstandsverhältnis von kristallin zu amorph Lc/La des
5 statistischen Block-Copolymers im Bereich von 1,25 bis 2,00 liegt.

8. Statistisches Block-Copolymer nach Anspruch 1, wobei das Abstandsverhältnis von kristallin zu amorph Lc/La des
statistischen Block-Copolymers im Bereich von 1,40 bis 1,70 liegt.

10 9. Statistisches Block-Copolymer nach Anspruch 1, darüber hinaus umfassend 50 ppm bis 5000 ppm eines Klärungs-
mittels.

10. Statistisches Block-Copolymer nach Anspruch 9, wobei das Klärungsmittel aus der Gruppe bestehend aus Diben-
zylidensorbitol-Derivaten mit Alkyl-, Alkoxy- oder Halogensubstituenten an einem oder beiden aromatischen Ringen
15 ausgewählt ist, wobei die Alkylsubstituenten C1 bis C20 sein können und verzweigt, linear oder Cycloalkyl- und
Kombinationen der genannten Sorbitolderivate sein können.

11. Statistisches Block-Copolymer nach Anspruch 9, mit einem Haze-Wert bei 23 °C von 5 % bis 10 % bei Messung
gemäß ASTM D 1003, und einer Schlagzähigkeit bei 23 °C von 10 kJ/m 2 bis 50 kJ/m2 bei Messung mit dem Charpy
20 Kerbschlagzähigkeitstest gemäß ISO 179-2.

12. Verfahren zur Herstellung eines statistischen Block-Copolymers, umfassend:

a) Einführen eines Polymerisationskatalysators und eines ersten Einsatzproduktes enthaltend von 0,5 Gewichts-
25 teilen bis 6 Gewichtsteilen Ethylen und von 94 Gewichtsteilen bis 99,5 Gewichtsteilen Propylen in eine erste
Reaktionszone,
b) Copolymerisieren des Ethylens und Propylens unter ersten Polymerisations-Reaktionsbedingungen zur Be-
reitstellung eines Copolymers A mit einem darin eingebetteten aktiven Katalysator, mit einem Schmelzpunkt
von 120 °C bis 159 °C,
30 c) Einführen des Copolymers A in eine zweite Reaktionszone,
d) Einführen eines zweiten Einsatzprodukts enthaltend von acht Gewichtsteilen bis 40 Gewichtsteilen Ethylen
und von 60 Gewichtsteilen bis 92 Gewichtsteilen Propylen, und
e) Copolymerisieren des Ethylens und Propylens des zweiten Einsatzprodukts zur Bereitstellung eines Copo-
lymers B, wobei das Copolymer B mit dem Copolymer A unter zweiten Polymerisations-Reaktionsbedingungen
35 und in solchen Anteilen copolymerisiert wird, dass ein statistisches Block-Copolymer enthaltend von 65 Gew.-
% bis 97 Gew.-% Blöcke des Copolymers A und von 3 Gew.-% bis 35 Gew.-% Blöcke des Copolymers B
bereitgestellt wird, wobei das Verhältnis aus Pulver MFRstatistisches Block-Copolymer zu Pulver MFR copolymer A der
Gleichung

40

wobei K = 1,0 bis 1,5 ist, und

wobei ein Abstandsverhältnis von kristallin zu amorph Lc/La des statistischen Block-Copolymers im Bereich
45 von 1,00 bis 2,25 liegt.

13. Verfahren nach Anspruch 12, wobei:

das statistische Block-Copolymer von 75 Gew.-% bis 95 Gew.-% Blöcke des Copolymers A und 5 Gew.-% bis
50 25 Gew.-% Blöcke des Copolymers B enthält.

14. Verfahren nach Anspruch 12 oder 13, wobei:

das erste Einsatzprodukt von 1 Gewichtsteil bis 5 Gewichtsteile Ethylen und von 95 Gewichtsteile bis 99 Ge-
55 wichtsteile Propylen enthält,
das zweite Einsatzprodukt von 10 Gewichtsteile bis 30 Gewichtsteile Ethylen und von 70 Gewichtsteile bis 90
Gewichtsteile Propylen enthält, und

16
 EP 2 406 298 B1

das statistische Block-Copolymer von 75 Gew.-% bis 95 Gew.-% Blöcke des Copolymers A und 5 Gew.-% bis
25 Gew.-% Blöcke des Copolymers B enthält.

15. Verfahren nach Anspruch 12 oder 13, wobei

5 das erste Einsatzprodukt von 1,5 Gewichtsteil bis 4,5 Gewichtsteilen Ethylen und von 95,5 Gewichtsteilen bis 98,5
Gewichtsteilen Propylen enthält,
das zweite Einsatzprodukt von 10 Gewichtsteilen bis 30 Gewichtsteilen Ethylen und von 70 Gewichtsteilen bis 90
Gewichtsteilen Propylen enthält, und
das statistische Block-Copolymer von 80 Gew.-% bis 92 Gew.-% Blöcke des Copolymers A und 8 Gew.-% bis 20
10 Gew.-% Blöcke des Copolymers B enthält.

16. Verfahren nach Anspruch 12 oder 13, wobei

das erste Einsatzprodukt von 2 Gewichtsteilen bis 4 Gewichtsteilen Ethylen und von 96 Gewichtsteilen bis 98
Gewichtsteilen Propylen enthält,
15 das zweite Einsatzprodukt von 12 Gewichtsteilen bis 17 Gewichtsteilen Ethylen und von 83 Gewichtsteilen bis 88
Gewichtsteilen Propylen enthält, und
das statistische Block-Copolymer von 88 Gew.-% bis 92 Gew.-% Blöcke des Copolymers A und 8 Gew.-% bis 12
Gew.-% Blöcke des Copolymers B enthält.

20 17. Verfahren nach Anspruch 12 oder 13, wobei es sich bei dem Katalysator um einen Ziegler-Natta-Katalysator oder
Metallocen-Katalysator handelt.

18. Verfahren nach Anspruch 12 oder 13, wobei sowohl die erste Polymerisationsreaktion als auch die zweite Polyme-
risationsreaktion in einem Rührbett-Gasphasenprozess durchgeführt werden.
25
19. Verfahren nach Anspruch 12 oder 13, wobei es sich bei der ersten Polymerisationsreaktion um einen Bulk-Poly-
merisationsprozess handelt, der in verflüssigtem Propylen durchgeführt wird.

20. Verfahren nach Anspruch 19, wobei es sich bei der zweiten Polymerisationsreaktion um einen Gasphasenprozess
30 handelt und die zweite Reaktionszone eine Wirbelschicht oder ein Rührbett beinhaltet.

21. Verfahren nach Anspruch 12 oder 13, wobei die ersten und/oder zweiten Polymerisations-Reaktionsbedingungen
eine Temperatur von 20 bis 150 °C, einen Druck von 1 bis 100 bar und eine durchschnittliche Verweilzeit von 0,5
bis 5 Stunden vorsehen.
35
22. Verfahren nach Anspruch 12 oder 13, wobei die ersten und/oder zweiten Polymerisations-Reaktionsbedingungen
eine Temperatur von 60 bis 90 °C, einen Druck von 10 bis 50 bar und eine durchschnittliche Verweilzeit von 0,5 bis
3 Stunden vorsehen.

40 23. Verfahren nach Anspruch 14, darüber hinaus umfassend das Einführen von Wasserstoff in die erste und/oder zweite
Polymerisationsreaktionszone.

24. Verfahren nach Anspruch 12 oder 13, wobei es sich bei dem Polymerisationskatalysator um einen Ziegler-Natta-
Katalysator handelt.
45

Revendications

1. Copolymère séquencé aléatoire comprenant :

50
a) de 65 % en poids à 97 % en poids d’un copolymère de propylène/éthylène cristallin A contenant de 0,5 %
en poids à 6 % en poids d’unités dérivées de l’éthylène et de 94 % en poids à 99,5 % en poids d’unités dérivées
du propylène, ayant un point de fusion de 120 °C à 159 °C ; et copolymérisés ensemble ; et
b) de 3 % en poids à 35 % en poids d’un copolymère de propylène/éthylène B contenant de 8 % en poids à 40
55 % en poids d’unités dérivées de l’éthylène et de 60 % en poids à 92 % en poids d’unités dérivées du propylène,
dans lequel le rapport de MFRcopolymère séquence aléatoire de poudre au MFRpolymere A de poudre est conforme à
l’équation

17
 EP 2 406 298 B1

où K= 1,0 à 1,5, et
5 dans lequel un rapport d’espacement cristallin à amorphe Lc/La dudit copolymère séquencé aléatoire est
compris dans la plage allant de 1,00 à 2,25.

2. Copolymère séquencé aléatoire selon la revendication 1, dans lequel K = 1,0 à 1,3.

10 3. Copolymère séquencé aléatoire selon la revendication 1, dans lequel K = 1,0 à 1,25.

4. Copolymère séquencé aléatoire selon la revendication 1, comprenant :

a) de 75 % en poids à 95 % en poids d’un copolymère de propylène/éthylène cristallin A contenant de 1 % en

15 poids à 5 % en poids d’unités dérivées de l’éthylène et de 95 % en poids à 99 % en poids d’unités dérivées du
propylène, et copolymérisés ensemble,
b) de 5 % en poids à 25 % en poids d’un copolymère de propylène/éthylène B contenant de 10 % en poids à
30 % en poids d’unités dérivées de l’éthylène et de 70 % en poids à 90 % en poids d’unités dérivées du propylène.

20 5. Copolymère séquencé aléatoire selon la revendication 1, comprenant :

a) de 80 % en poids à 92 % en poids d’un copolymère de propylène/éthylène cristallin A contenant de 1,5 %

en poids à 4,5 % en poids d’unités dérivées de l’éthylène et de 95,5 % en poids à 98,5 % en poids d’unités
dérivées du propylène, et copolymérisés ensemble,
25 b) de 8 % en poids à 20 % en poids d’un copolymère de propylène/éthylène B contenant de 10 % en poids à
30 % en poids d’unités dérivées de l’éthylène et de 70 % en poids à 90 % en poids d’unités dérivées du propylène.

6. Copolymère séquencé aléatoire selon la revendication 1, comprenant :

30 a) de 88 % en poids à 92 % en poids d’un copolymère de propylène/éthylène cristallin A contenant de 2 % en

poids à 4 % en poids d’unités dérivées de l’éthylène et de 96 % en poids à 98 % en poids d’unités dérivées du
propylène, et copolymérisés ensemble,
b) de 8 % en poids à 12 % en poids d’un copolymère de propylène/éthylène B contenant de 12 % en poids à
17 % en poids d’unités dérivées de l’éthylène et de 83 % en poids à 88 % en poids d’unités dérivées du propylène.
35

7. Copolymère séquencé aléatoire selon la revendication 1, dans lequel le rapport d’espacement cristallin à amorphe
Lc/La dudit copolymère séquencé aléatoire est compris dans la plage allant de 1,25 à 2,00.

8. Copolymère séquencé aléatoire selon la revendication 1, dans lequel le rapport d’espacement cristallin à amorphe
40 Lc/La dudit copolymère séquencé aléatoire est compris dans la plage allant de 1,40 à 1,70.

9. Copolymère séquencé aléatoire selon la revendication 1, comprenant en outre de 50 ppm à 5000 ppm d’un agent
clarifiant.

45 10. Copolymère séquencé aléatoire selon la revendication 9, dans lequel l’agent clarifiant est sélectionné dans le groupe
constitué par les dérivés de dibenzyldène sorbitol ayant des substituants alkyle, alcoxy ou halogéno sur un ou les
deux cycles aromatiques, les substituants alkyle pouvant être en C1 à C20 et pouvant être ramifiés, linéaires ou
cycloalkyle et des combinaisons desdits dérivés de sorbitol.

50 11. Copolymère séquencé aléatoire selon la revendication 9, ayant une valeur de trouble à 23 °C de 5 % à 10 % mesurée
par la norme ASTM D 1003, et une résistance au choc à 23 °C de 10 kJ/m2 à 50 kJ/m2 mesurée par le test de
résistance au choc Charpy avec entaille selon la norme ISO 179-2.

12. Procédé de préparation d’un copolymère séquencé aléatoire comprenant :

55

a) l’introduction, dans une première zone de réaction, d’un catalyseur de polymérisation et d’une première
alimentation contenant de 0,5 partie en poids à 6 parties en poids d’éthylène et de 94 parties en poids à 99,5

18
 EP 2 406 298 B1

parties en poids de propylène ;

b) la copolymérisation de l’éthylène et du propylène dans des premières conditions de réaction de polymérisation
pour fournir un copolymère A avec un catalyseur actif incorporé dans celui-ci, ayant un point de fusion de 120
°C à 159 °C ;
5 c) l’introduction du copolymère A dans une seconde zone de réaction ;
d) l’introduction, dans la seconde zone de réaction, d’une seconde alimentation contenant de 8 parties en poids
à 40 parties en poids d’éthylène et de 60 parties en poids à 92 parties en poids de propylène ; et
e) la copolymérisation de l’éthylène et du propylène de la seconde alimentation pour fournir un copolymère B,
le copolymère B étant copolymérisé avec le copolymère A dans de secondes conditions de réaction de poly-
10 mérisation et en une proportion permettant de fournir un copolymère séquencé aléatoire contenant de 65 %
en poids à 97 % en poids de séquences de copolymère A et de 3 % en poids à 35 % en poids de séquences
de copolymère B, le rapport de MFR copolymère séquencé aléatoire de poudre au MFRpolymère A de poudre étant
conforme à l’équation

15

où K = 1,0 à 1,5, et
dans lequel un rapport d’espacement cristallin à amorphe Lc/La dudit copolymère séquencé aléatoire est
20 compris dans la plage allant de 1,00 à 2,25.

13. Procédé selon la revendication 12, dans lequel :

le copolymère séquencé aléatoire contient de 75 % en poids à 95 % en poids de séquences de copolymère A

25 et de 5 % en poids à 25 % en poids de séquences de copolymère B.

14. Procédé selon la revendication 12 ou 13, dans lequel :

la première alimentation contient de 1 partie en poids à 5 parties en poids d’éthylène et de 95 parties en poids
30 à 99 parties en poids de propylène,
la seconde alimentation contient de 10 parties en poids à 30 parties en poids d’éthylène et de 70 parties en
poids à 90 parties en poids de propylène, et
le copolymère séquencé aléatoire contient de 75 % en poids à 95 % en poids de séquences de copolymère A
et de 5 % en poids à 25 % en poids de séquences de copolymère B.
35

15. Procédé selon la revendication 12 ou 13, dans lequel :

la première alimentation contient de 1,5 partie en poids à 4,5 parties en poids d’éthylène et de 95,5 parties en
poids à 98,5 parties en poids de propylène,
40 la seconde alimentation contient de 10 parties en poids à 30 parties en poids d’éthylène et de 70 parties en
poids à 90 parties en poids de propylène, et
le copolymère séquencé aléatoire contient de 80 % en poids à 92 % en poids de séquences de copolymère A
et de 8 % en poids à 20 % en poids de séquences de copolymère B.

45 16. Procédé selon la revendication 12 ou 13, dans lequel :

la première alimentation contient de 2 parties en poids à 4 parties en poids d’éthylène et de 96 parties en poids
à 98 parties en poids de propylène,
la seconde alimentation contient de 12 parties en poids à 17 parties en poids d’éthylène et de 83 parties en
50 poids à 88 parties en poids de propylène, et
le copolymère séquencé aléatoire contient de 88 % en poids à 92 % en poids de séquences de copolymère A
et de 8 % en poids à 12 % en poids de séquences de copolymère B.

17. Procédé selon la revendication 12 ou 13, dans lequel le catalyseur est un catalyseur de Ziegler-Natta ou un catalyseur
55 métallocène.

18. Procédé selon la revendication 12 ou 13, dans lequel la première réaction de polymérisation et la seconde réaction

19
 EP 2 406 298 B1

de polymérisation sont toutes deux réalisées dans un procédé en phase gazeuse sur lit agité.

19. Procédé selon la revendication 12 ou 13, dans lequel la première réaction de polymérisation est un procédé de
polymérisation en masse réalisé dans du propylène liquéfié.
5
20. Procédé selon la revendication 19, dans lequel la seconde réaction de polymérisation est un procédé en phase
gazeuse et la seconde zone de réaction comprend un lit fluidisé ou un lit agité.

21. Procédé selon la revendication 12 ou 13, dans lequel les premières et/ou les secondes conditions de réaction de
10 polymérisation comprennent une température de 20 à 150 °C, une pression de 1 à 100 bars, et un temps de séjour
moyen de 0,5 à 5 heures.

22. Procédé selon la revendication 12 ou 13, dans lequel les premières et/ou les secondes conditions de réaction de
polymérisation comprennent une température de 60 à 90 °C, une pression de 10 à 50 bars, et un temps de séjour
15 moyen de 0,5 à 3 heures.

23. Procédé selon la revendication 14, comprenant en outre l’introduction d’hydrogène dans la première et/ou la seconde
zone de réaction de polymérisation.

20 24. Procédé selon la revendication 12 ou 13, dans lequel le catalyseur de polymérisation comprend un catalyseur de
Ziegler-Natta.

25

30

35

40

45

50

55

20
 EP 2 406 298 B1

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.

Patent documents cited in the description

• EP 1428853 A [0003] • EP 2072545 A1 [0008]

• EP 1354901 A [0004] • JP 2005132979 A [0009]
• WO 03106553 A [0005] • JP 2006188563 A [0010]
• WO 03046021 A [0006] • US 4376062 A [0030]
• EP 1206499 A [0007] • US 4379758 A [0030]
• EP 373660 A [0007] • US 5066737 A [0030]
• EP 814127 A [0007] • US 7169864 B [0031]
• EP 860457 A [0007] • US 4110185 A [0048]
• EP 1162213 A [0007] • US 4274932 A [0048]
• WO 2008059969 A1 [0008]

Non-patent literature cited in the description

• Polypropylene Handbook. Hanser Publishers, 2005,

361 ff [0032]

21