Macromol. Symp. 2009, 282, 1–13 DOI: 10.1002/masy.

200950801 1

Molecular Weight and Branching Distribution of a

High Performance Metallocene Ethylene 1-Hexene
Copolymer Film-Grade Resin
M. Vadlamudi,1 G. Subramanian,1 S. Shanbhag,1 R. G. Alamo,*1 M. Varma-Nair,2
D. M. Fiscus,3 G. M. Brown,3 C. Lu,3 C. J. Ruff 3

Summary: The bivariate, or cross branching distribution of a gas-phase produced,

film-grade ethylene 1-hexene copolymer with enhanced Elmendorf tear in machine
direction, MD, and in transverse direction, TD, (> 400 g/mil) and high dart impact has
been characterized through the analysis of fractions obtained by molecular weight
and 1-hexene composition. The molecular weight fractions, obtained by a solvent-
non-solvent fractionation technique, are each mixtures of molecules with at least
two different 1-hexene compositions, one component with a constant relatively high
density (
1 mol% hexene) and a second of a lower density broadly distributed along
the molecular weight fractions. The content of the low density component increases
with increasing molecular weight of the fraction while the level of 1-hexene
decreases. The mixed compositional character of these fractions is easily inferred
by their high crystallization rates and both high melting and crystallization tem-
peratures compared to the values of model random ethylene copolymers. The set of
compositional fractions obtained by TREF display an increasing 1-hexene concen-
tration with increasing molecular weight, and except for the highest molecular
weight components (Mw > 150,000 g/mol) their melting and crystallization behavior
followed the random pattern. Higher than expected melting temperatures and a
constancy of the high melting temperature peak with increasing crystallization
temperature, suggests that the intra-chain 1-hexene distribution of the highly
branched, high molecular weight fraction deviates strongly from the random
behavior. These structural features and the bimodal character of the composition
distribution of this resin, that contains high molecular weight chains with both low
and high 1-hexene contents, are correlated with the enhanced key film properties.

Keywords: bimodal branching distribution; ethylene 1-hexene; ethylene copolymers;

gas-phase LLDPE

Introduction and in coordination catalysis has provided

the polyolefin industry with the means to
A rich variety of combinatorial catalysts engineer novel products and the possibility
and advances in organometallic chemistry to tailor molecular microstructures with
unique performance. The advent of metal-
1
locene chemistry has played a major role in
FAMU/FSU College of Engineering, Department of
laying out this path.[1,2] These catalysts
Chemical Engineering 2525 Pottsdamer St., Tallahas-
see, FL 32310, USA provide excellent control of stereoregular-
E-mail: alamo@eng.fsu.edu ity and copolymerization with polar and
2
ExxonMobil Research and Engineering Co., Rt 22 other types of comonomers that was not
East, Annandale, NJ 08801, USA
3
ExxonMobil Chemical Co., 5200 Bayway Drive,
possible with the classical Ziegler-Natta
Baytown, TX 77522, USA catalyst systems. The single site nature of

Copyright ß 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

2 Macromol. Symp. 2009, 282, 1–13

the metallocene catalyst leads to LLDPEs across the molecular weight distribution of
with narrow molecular weight and narrow this novel resin. This is accomplished by
inter-chain comonomer composition. An characterizing the branching and chain
early benefit of the metallocene chemistry length microstructure of two sets of frac-
was the production of polyethylene resins tions, one set was obtained by molecular
with bimodal molecular weight distribu- weight fractionation using a standard
tions and a preferred introduction of the solvent/non-solvent technique, and a sec-
comonomer in the longest chains for a ond set fractionating by the 1-hexene
superior process/properties balance.[3,4] content via preparative TREF. The avail-
This microstructure differs from the ability of independent fractions allows
characteristic inter-chain comonomer dis- comparative analysis of the bivariate dis-
tribution given by classical Ziegler-Natta tribution profiles obtained from each type
catalysts where the shorter chains have the of fractionation. In addition, the thermal
highest concentration of comonomer.[5] It properties and crystallization behavior of
has been speculated that the incorporation both types of fractions are discussed in
of the comonomer in the high molar mass reference to the behavior of random model
portion of the distribution increases the ethylene copolymers and single site metal-
number of tie-chains (molecules that locene-made LLDPEs that are known to
connect two or more crystallites) account- have a nearly equivalent inter-chain como-
ing for better balanced properties and nomer content and random intra-chain
enhanced impact.[6] distribution.
Although this concept was initially
engineered via blending different propor-
tions of high and low molecular weight Experimental Part
metallocene LLDPEs with high or low
comonomer contents,[7] resins with bimodal The starting metallocene catalyzed 1-hex-
comonomer composition distribution (BCD) ene LLDPE resin was recently produced in
and/or bimodal molecular weight distribu- a commercial gas-phase Unipol-type reac-
tion were subsequently synthesized using tor using standard conditions and the
tandem (staggered) series reactors. Special methodology described in reference 8.
attention was given to properties of The whole resin was fractionated by
LLDPEs with a placement of the comono- molecular mass into 10 fractions using the
mer as a function of molecular weight solvent/non-solvent fractionation techni-
reversed or orthogonal to the standard que (these fractions are termed M frac-
distribution of Z/N catalyzed LLDPEs, i.e., tions).[9] The fractionation was carried out
with an increasing comonomer content with at 130 8C using xylene/diethylene glycol
increasing molecular weight. These resins monobutyl ether (DEGME) as solvent/
are referred as having bimodal orthogonal non-solvent pair. The content of non-
comonomer composition distribution solvent was varied between 60 and 41%.
(BOCD). The process and properties of Both solvents were stabilized with 600 ppm
LLDPE resins of this type made in single of BHT (butylated hydroxy toluene). A set
gas-phase reactors are described in a US of 11 comonomer composition fractions
2005 patent.[8] A film grade ethylene was also obtained using preparative tem-
1-hexene resin (1.0 MI, 0.920 g/cm3 density) perature rising elution fractionation
produced following this method resulted in (TREF) in a CRYSTAF-TREF instrument,
enhanced Elmendorf tear in the machine Model MC2 manufactured by Polymer
and transverse directions, MD and TD Char S.A., Valencia, Spain, with ortho-
(>400 g/mil), over the present resins dichloro benzene (o-DCB) as elution
values,[4] and with high dart impact. Our solvent, stabilized with 300 ppm of BHT
interest here is to characterize the details of (T fractions).[10,11] The 0.4 g/100cc solution
the distribution of the content of 1-hexene was dissolved at 160 8C, subsequently

Copyright ß 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.ms-journal.de
Macromol. Symp. 2009, 282, 1–13 3

stabilized at 95 8C, and slowly cooled from Results and Discussion

95 8C to 20 8C at a rate of 0.5 8C /min. In a
second step TREF fractions were collected Fractionation
raising the temperature in a range from -20 All M fractions, obtained by solvent/non-
to 120 8C. Data for molecular characteriza- solvent fractionation, have narrow molec-
tion of the fractions are listed in Table 1. ular weight distribution (Mw/Mn  1.7) and
The average molecular weights of the display a systematic increase of Mn and Mw
whole polymer and both sets of fractions along the fractionation process (i.e.,
were determined by standard Gel Permea- increasing xylene content). Compared to
tion Chromatography (GPC) and the the broad GPC profile of the unfractio-
average comonomer composition was nated resin, the GPC profiles of each M
obtained using solution 1H NMR. TREF fraction are unimodal and relatively nar-
profiles of each individual M or T fraction row, as depicted in Figure 1(a).
were also collected. Crystallizations and The average content of butyl branches of
further melting were followed by DSC at M fractions (determined by NMR) changes
10 8C/min using a Perkin Elmer DSC-7 slightly in a narrow range, between 1 and
calibrated with indium and operating under 2 mol% (branches per 100 backbone
nitrogen flow. The sample mass was about carbons). However, the TREF profiles of
4 mg. The DSC was calibrated for static each M fraction are bi or tri-modal, as
temperature and thermal lag effects with shown in Figure 1(b), indicating that the
indium. Overall isothermal crystallization branching content determined by NMR
rates were associated with the inverse of the spectroscopy is an average of at least two
time corresponding to the exothermic DSC branching compositions. TREF profiles are
peak. The DSC was connected to an analyzed on the basis of compositional
intracooler to maximize heat transfer and partitioning during crystallization.[12] This
allow sub-ambient temperature control. analysis assumes that molecules of low
The crystalline morphology was analyzed comonomer content do not co-crystallize
by optical microscopy (OM), small angle with molecules having a higher comonomer
light scattering (SALS) and thin section content, consequently, the crystallites formed
transmission electron microscopy (TEM) from the former will dissolve (elute) at
after staining with RuO4. higher temperatures. The two-three peaks

Table 1.
Molecular weight and NMR branching data of the whole ethylene 1-hexene initial resin and fractions. M-F# refers
to molecular weight fractions and T-F# refers to TREF fractions.

Molecular Weight Fractions Comonomer Composition Fractions

Fraction % Mn x 103 Mw x 103 Mw / Branch Fraction Collection Mn x 103 Mw x 103 Mw / Branch
ID DEGME (g/mol) (g/mol) Mn points ID Temperature (g/mol) (g/mol) Mn points
(mol%) Range (8C) (mol%)
Parent 34 123 3.6 1.66 Parent – 34 123 3.6 1.66
resin resin
M-F1 60.0 5.8 10 1.7 1.42 T-F1 < 15 15 231 15.4 5.48
M-F2 53.0 13 18 1.4 0.89 T-F2 15 to 36 44 249 5.7 3.53
M-F3 49.0 23 35 1.5 1.13 T-F3 36 to 51 19 169 8.8 3.14
M-F4 47.0 33 48 1.5 1.34 T-F4 51 to 59 30 207 6.8 2.85
M-F5 44.3 51 86 1.7 1.57 T-F5 59 to 65 37 170 4.6 2.10
M-F6 43.0 68 118 1.7 1.73 T-F6 65 to 71 27 131 4.8 1.61
M-F7 42.4 92 156 1.7 1.78 T-F7 71 to 77 24 95 3.9 1.13
M-F8 41.9 112 187 1.7 1.81 T-F8 77 to 83 24 70 2.9 0.76
M-F9 41.3 147 234 1.6 1.81 T-F9 83 to 87 24 59 2.5 0.52
M-F10 0 226 336 1.5 1.74 T-F10 87 to 91 26 57 2.2 0.44
T-F11 >91 31 61 1.9 0.46
The percentage of non-solvent (DEGME) and temperature range for collection of molecular weight and
compositional fractions respectively are also listed.

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4 Macromol. Symp. 2009, 282, 1–13

Figure 1.
(a) GPC profiles of M Fractions. The curves shift systematically to higher values with increasing fraction number.
The profile of the unfractionated resin is shown as black thicker line. (b) TREF profiles of M Fractions.

observed in the TREF profiles of M fractionation (TREF) in order to isolate

fractions represent molecules of equivalent chain components with different branching
length with different 1-hexene composition. composition. These fractions provide direct
All M fractions contain a population of evidence of the progressive compositional
chains with a fixed low 1-hexene content nature of chains eluting in the range of
that elute at about the same temperature, temperatures marked as Te2 in Figure 1(b).

92 8C, labeled Te1 in the figure. A second The average molecular masses and NMR
population of crystals (Te2) dissolves in a compositional data are listed in Table 1.
broad (40–80 8C) and lower range of Fractionation by preparative TREF sepa-
temperatures and correspond to chains rates copolymer molecules preferentially
with a higher content of 1-hexene. The by comonomer content.[10–12] Molecules
value of Te2 increases with fraction number with the highest 1-hexene content lead to
reflecting a decreasing content of 1-hexene thin crystallites that dissolve (elute) at the
as the molecular weight of this population lowest temperatures, providing not co-
of chains increases. The intensity of Te2 crystallization occurs with chains having a
increases with Mw and levels off for lower 1-hexene content. Co-crystallization,
fractions beyond M-F8, indicating a although not totally avoided, is minimized
progressive increase in the weight fraction by increasing dilution and slowing down the
of the highly branched component with initial crystallization step prior to elution,
increasing molar mass up to Mw
190,000. for example reducing the cooling rate.
A lower intensity peak at
80 8C, also Crystallites formed from molecules with
present in all fractions, may indicate a third the lowest 1-hexene content are the last to
compositional component of intermediate dissolve and elute at the highest tempera-
branching content. tures. The expected systematic decrease of
Eleven (11) fractions were also collected branching with increasing elution tempera-
by preparative temperature rising elution ture is indeed observed in the data for T

Copyright ß 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.ms-journal.de
Macromol. Symp. 2009, 282, 1–13 5

fractions of Table 1 with 1-hexene content 95 8C in the TREF profiles. The GPC
changing from 5.48 to 0.44 mol% among the curves are relatively broad, as expected
fractions. The increase in branching paral- from the results of Figure 1b, while the
lels the increase in Mw, following the TREF profiles of Figure 2b are narrow and
characteristics of BOCD resins. It does progressively shift to higher temperatures,
not follow a systematic increase with Mn as the content of 1-hexene decreases.
because of the large polydispersity in chain Notice that the least branched fractions,
length of fractions with a fixed content of T-F10 and T-F11, are expected to have
1-hexene, as shown by the relatively high much broader molecular weights than
Mw/Mn values in the Table. Details of lower T fractions (T-F1 – T-F3), as the
chain length distribution and homogeneity molecules of T-F10 and T-F11 correspond
of 1-hexene content distribution of each T to the Te1 component of all M fractions
fraction are extracted from the GPC and (see Figure 1b). One explanation for the
TREF profiles of each TREF fraction relatively narrow GPG profiles of T-F10
shown in Figure 2(a,b). and T-F11 is that some of the molecules in
Unimodal distributions are the general the 103–104 molecular weight range elute
features of the T fractions, except for a with highly branched molecules at the
small peak in the low molecular weight side lowest elution temperatures. This would
of the GPC profiles and between 85 and explain the small peaks in the profiles of

Figure 2.
(a) GPC profiles of each T fraction. (b) TREF profiles of each T fraction

Copyright ß 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.ms-journal.de
6 Macromol. Symp. 2009, 282, 1–13

Figure 2(a) and at
93 8C in the profiles of Density Functions (PDF) or bivariate
T-F1 to T-F5 of Figure 2(b). Moreover, distributions were computed separately
repeated TREF fractionations led to very for each M and T sets of fractions. The
similar results. bivariate three-dimensional distribution
A two-dimensional plot of the average was constructed assuming independence
Mw data of each TREF fraction over the of the molecular weight distributions
TREF profile of the unfractionated (MWD) and elution temperature distribu-
LLDPE, such as Figure 3, is often used tions (ETD). From the GPC and TREF
to characterize the molecular weight – profiles of M fractions the bivariate was
comonomer content cross-distribution of obtained as:
these copolymers.[4] In a further step, Ortin
et al. in 2007 described an automated method P
i¼10
wM-Fi fM-Fi ðmÞfM-Fi ðtÞ
to represent in a 3D map the molecular fM ðm; tÞ ¼ i¼1
weight distributions of TREF eluted material P
i¼10
wM-Fi
in a range of temperatures.[13] i¼1
According to Figure 3, the character- and from the GPC and TREF profiles of T
istics of the cross - distribution of the novel fractions as:
resin appear analogous to a BOCD copo-
lymer because the comonomer content P
j¼11

increases with the average Mw data. wT -Fj fT -Fj ðmÞfT -Fj ðtÞ
j¼1
However, this is not accurate since GPC fT ðm; tÞ ¼
P
j¼11
and TREF profiles of M-F8 to M-F10 wT -Fj
fractions indicate that the initial resin j¼1

contains high molecular weight chains Where:

(
200,000 g/mol) with both, relatively low
and high 1-hexene content, as shown in fM-Fi (m) ¼ Logarithmic molecular weight
Figure 1(b). distribution of M fraction M-Fi
Having characterized individually M fT-Fj (m) ¼ Logarithmic molecular weight
and T fractions for their length (GPC) distribution of TREF fraction T-Fj
and comonomer (TREF elution tempera- fM-Fi (t) ¼ TREF profile of M fraction
tures) distributions, the joint Probability M-Fi

Figure 3.
TREF profile of whole resin and weight average molecular weight of TREF fractions (filled squares) collected at
the indicated elution temperature.

Copyright ß 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.ms-journal.de
Macromol. Symp. 2009, 282, 1–13 7

Figure 4.
Bivariate distribution and surface contour from data corresponding to M fractions.

fT-Fj (t) ¼ TREF profile of TREF fraction weight distribution than the range of the
T-Fj first component. Although there is agree-
wM-Fi ¼ Weight fraction of M fraction ment in the general features of the PDF
M-Fi distribution from both sets of fractions, the
wT-Fj ¼ Weight fraction of TREF fraction contour topological view or weight fraction
T-Fj distribution is not identical. The mismatch
reflects experimental uncertainties from
Using spline interpolation for data each type of fractionation. For example,
smoothing, PDF distributions are plotted the solvent non-solvent technique leads to
in Figure 4 (from data of M fractions), and fractions that are not unimodal in chain
in Figure 5 (from data of T fractions). Both length, and the extent to which co-crystal-
plots display graphically the same general lization may occur during TREF prepara-
unique complex bimodal 1-hexene compo- tive fractionation, and thus affect the TREF
sition distribution of the resin. The heights profiles is unknown. The uncertainties from
of the 3-D profile indicate two major both fractionation types are averaged in the
components moving in increasing direction joint PDF, f (m,t) as:
of the elution temperature axis (inversely
proportional to the comonomer content). fM ðm; tÞ þ fT ðm; tÞ
f ðm; tÞ ¼
One component corresponds to chains that 2
elute in a narrow temperature range, at with fM (m, t) and fT (m, t) given as:

95 8C (
1 mol% 1-hexene). These mole-
cules have narrow 1-hexene content and f (m, t) ¼ Joint PDF of specimens fractio-
broad molecular weight distribution. A nated by TREF, and by molecular weight
second component corresponds to mole- f M (m, t) ¼ Joint PDF of molecular weight
cules that elute in a broad temperature fractions
range, between 20 and 90 8C. The range of fT (m, t) ¼ Joint PDF of TREF fractions
comonomer content of the latter molecules
is broad, between 11 and 2 mol% 1-hexene, The combined profile is shown in
and have somewhat narrower molecular Figure 6.

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8 Macromol. Symp. 2009, 282, 1–13

Figure 5.
Bivariate distribution and surface contour from data corresponding to T fractions.

The fractional content of the high- Melting Behavior

density component, obtained from the The advantage of having molecular weight
volume above a temperature range of 80– and compositional fractions physically
85 8C, corresponds to 59–52%. Conversely, separated, with respect to other automated
medium and highly branched molecules modes of characterizing the bivariate dis-
make for 41–48% by weight of the tribution,[13,14] is that additional analyses
enhanced resin. can be carried out in the fractions for

Figure 6.
Joint bivariate distribution and surface contour from data corresponding to M and T fractions.

Copyright ß 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.ms-journal.de
Macromol. Symp. 2009, 282, 1–13 9

Figure 7.
Melting endotherms of molar mass fractions (M fractions) after cooling from the melt at 10 8C/min. The arrows
indicate the variation of the bimodal comonomer composition with increasing molecular weight.

conformity with expectations from the PDF cene copolymers is single peaked, while
distribution. For example, TREF analyses double melting is expected for fractions
of the individual M fractions indicated with a bimodal 1-hexene content. As seen
compositional heterogeneity of molecules in Figure 7 most M fractions display double
with a fixed length, possibly of a bimodal melting. The variation of the peak melting
nature. This feature is tested by analyzing temperature as a function of molecular
the melting behavior of these fractions in weight is given in Figure 8(a) where the
reference to the behavior of random continuous line represents the data of
ethylene copolymers of matched comono- hydrogenated polybutadienes (HPBDs)
mer content narrowly distributed across an with 2.2 mol% ethyl branches.[16] HPBDs
also narrow molecular weight distribution. are model materials analogs to random
Melting data for the latter are available ethylene 1-butene copolymers. They have
from previous works.[15–18] very narrow molecular weight distribution
Under relatively rapid crystallization, (
1.2), uniform inter-chain branching con-
the melting of hydrogenated polybuta- tent and a random intra-chain distribution
dienes and narrowly distributed metallo- of branches. Since both, the ethyl and the

Figure 8.
Variation of the melting peak of M fractions with molecular weight (a) and with mol% of branch points
(b). Squares and triangles denote bimodal melting (see text). The continuous lines represent the melting
behavior of model random ethylene 1-alkene copolymers (ethyl and longer branches) extracted from
references 15 – 18.

Copyright ß 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.ms-journal.de
10 Macromol. Symp. 2009, 282, 1–13

butyl branch are excluded from the crystal- plots of the observed melting temperatures
line regions, HPBDs are ideal copolymers versus the NMR averaged branching con-
to test for inter-molecular compositional tent, such as Figure 8(b), contain data that
heterogeneity or for the non random are above or below the HPBD data. Data
intra-molecular branching distribution in above the reference line correspond to
matched ethylene copolymers. melting of crystallites formed from the
The observed double melting for M high-density component of the M fractions,
fractions with Mw > 100,000 g/mol is in while those below the line correspond to
agreement with the bimodal comonomer the lower density component of the same
composition behavior inferred from the fraction.
TREF profiles, earlier referred as Te1 As shown, the melting behavior gives
and Te2 components. Note in Figure 8(a) additional evidence for the heterogeneous
the modest decrease of the highest melting compositional nature of the molecular
peak with increasing molecular weight, weight fractions. Each fraction is a mixture
paralleling the trend of the model of chains with two different l-hexene
HPBDs.[16] This reflects that all M fractions contents. This heterogeneity also affects
have one population of molecules with the DSC-measured isothermal crystalliza-
similar low 1-hexene content (lower than tion rates of M fractions which are led by
2 mol%). In contrast, the low temperature the lowest l-hexene component and are
peak increases over 20 degrees with significantly higher than those of HPBDs at
increasing molecular weight, indicating matched branching content.
molecules with higher branching content The compositional heterogeneity of M
(>2 mol%), or a lower density component. fractions leads to lamellar morphologies
The 1-hexene content of the latter that clearly differ from those of homo-
decreases with increasing molecular weight, genous matched copolymers, as found in
as it is inferred by the corresponding the representative TEM images given in
increase in melting temperature. Since Figure 9. Here the morphology of M-F9 is
the NMR determined branching content compared with a compositionally matched
(listed on Table 1) is the average value from narrow metallocene under the same slow
both compositions weighted by the relative crystallization. The bimodal lamellar size
mass of all components in each M fraction, distribution seen in M-F9 (left micrograph)

Figure 9.
TEM micrographs of M-F9 (1.81 mol% branches, Mw ¼ 234,000 g/mol) (left), and narrow metallocene ethylene
1-hexene (2.2 mol% branches, Mw ¼ 221,000 g/mol, Mw/Mn ¼ 2.1) (right). Specimens were slowly crystallized
from the melt at 1 8C/min.

Copyright ß 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.ms-journal.de
Macromol. Symp. 2009, 282, 1–13 11

contrasts with a more homogeneous lamel- crystal, such as 1-butene and longer linear
lar distribution observed at the same 1-alkenes, the variation of the melting
magnification for a narrow metallocene temperatures of ethylene copolymers with
ethylene l-hexene copolymer of similar mol increasing branching content is analyzed on
% branching. The high-density component the basis of Flory’s phase equilibrium
or lowly branched molecules of M-F9 theory.[19] According to this theory, in
develop long crystalline lamellae, with reference to the value of the pure chain,
thicknesses of
112 Å and spanning lengths the depression of the equilibrium melting
over 1.5 mm, while molecules of M-F9 with temperature of the copolymer is indepen-
higher branching content form much dent of the type of comonomer. It only
shorter lamellae with thicknesses of depends on the crystalline sequence

70 Å. In the random ethylene 1-hexene propagation probability (p). For random
copolymer, the long thick lamellae are copolymers the value of p equals the
absent because the comonomer composi- fraction of ethylene crystalline component.
tion is uniform, thus the average crystal- The melting of compositional TREF frac-
lizable ethylene sequence length is shorter tions is analyzed on this basis to infer the
than the value corresponding to the random intra-molecular distribution. This
lowly branched component in the M-F9 is clearly an advantage of preparative
fraction. Correspondingly, more uniformly TREF over automated techniques, since
arranged, shorter and thinner lamella each fraction can be independently
(
90 Å) are observed for the narrow analyzed.
copolymer. T-fractions with <
2 mol % branching
The melting temperatures of TREF follow the random pattern, their melting
fractions are shown vs. mol % of branches behavior is identical to the HPBDs melting.
in Figure 10. The continuous line is the T-fractions with a higher branching display
same as in Figure 8(b), and gives the broader or double melting and deviate from
behavior of narrow random copolymers the observed continuous line of the random
extracted from references 14 and 15. When model copolymers. This suggests an intra-
the comonomer does not participate in the chain distribution of branching that devi-
ates from the random pattern, i.e. the
chains rich in l-hexene posses a more blocky
branching distribution, also supported by
isothermal crystallization studies. Isother-
mally crystallized fractions with a low
branching content melt at progressively
increasing temperatures with increasing Tc
as expected for random copolymers. How-
ever, as shown in the inset of Figure 10,
after isothermal crystallization, the frac-
tions with the highest l-hexene content
(T–F1) have a basically constant melting,
characteristic of a blocky branching dis-
Figure 10. tribution.
Peak melting temperatures versus mol% branching of To test the possibility that higher melt-
compositional fractions (T-Fractions). Square and ing crystallites are formed from lightly
triangles represent higher and lower melting peaks. branched low molecular weight chains that
The continuous line represents the melting behavior
appeared to have been flushed from the
of model random ethylene 1-alkene copolymers
(ethyl and longer branches). The inset displays DSC TREF column together with higher molar
melting thermograms of fraction T-F1 after isothermal mass chains, a detailed solvent non-solvent
crystallization at the indicated crystallization fractionation was carried out on combined
temperatures (Tc). F-T1 to F-T2 fractions. However, very low

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12 Macromol. Symp. 2009, 282, 1–13

Figure 11.
TEM micrographs of T-F4 (2.85 mol% branches, Mw ¼ 207,000 g/mol) (left) and narrow metallocene ethylene
1-hexene (3.0 mol% branches, Mw ¼ 280,000 g/mol, Mw/Mn ¼ 2.1), (right). Specimens were slowly crystallized
from the melt at 1 8C/min.

molar mass chains could not be separated composition of an ethylene 1-hexene film-
from longer ones, the three fractions grade resin with enhanced mechanical
obtained had double melting characteristics performance over classical BOCD resins,
similar to that of the original F-T1 and F- allows comparative details of the bivariate
T2. Therefore, we conclude that long distribution obtained from each set. Both
crystalline sequences responsible for the distributions display the same overall
higher melting appear to be an integral part features. Gas-phase produced resins with
of the long molecules. To further investi- balanced mechanical properties and
gate the intra-molecular branching distri- Elmendorf MD tear > 400 g/mil, have a
bution of T fractions, a comonomer triad unique and complex bimodal distribution
distribution analysis from 13C NMR spectra of 1-hexene over the distribution of chain
is currently under study. lengths. The copolymer displays two major
The lamellar morphology of T fractions components with respect to 1-hexene con-
in the non-random range presents features tent. About 50% by mass are molecules
in agreement with a more blocky branching broadly distributed in chain length with a
distribution. A representative example is low content of 1-hexene (
1 mol%). The
given by the TEM micrographs of T-F4 second component are molecules with a
(2.85 mol%, Mw ¼ 207,000 g/mol, left broad range of 1-hexene content (1.5–
image) and a narrowly distributed 11 mol%) and somewhat narrower mole-
metallocene ethylene 1-hexene copolymer cular weight distribution than the range of
(3.0 mol%, Mw ¼ 280,000 g/mol) shown in the first component. This bimodal como-
Figure 11. A more blocky distribution of nomer composition of equal length chains is
comonomer in T-F4 is deduced from the responsible for the observed double melt-
fewer and longer radially oriented lamellae ing of M fractions. The high temperature
as compared with segmented, thinner, and melting, between 125 and 115 8C, corre-
more abundant lamellae of the random sponds to the lowly branched first compo-
narrow copolymer. nent, while the increase of the lower
melting peak from
65 to 85 8C with
molecular weight reflects a progressive
Conclusion decrease of branching content.
In addition, the melting behavior and
The analysis of two sets of fractions crystalline morphology of each fraction,
obtained by molecular weight and comonomer compared with data of model random

Copyright ß 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.ms-journal.de
Macromol. Symp. 2009, 282, 1–13 13

systems of matched composition, are useful Acknowledgements: We are indebted to Exxon-

to infer the intramolecular branching Mobil for financial support and clearance for
publication of this work.
distribution. The data of Figure 10 indicate
that the chains from the first component
(low l-hexene content) are randomly dis-
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