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Synthesis of Poly(ethylene-co-p-methylstyrene) Copolymers by Metallocene


Catalysts with Constrained Ligand Geometry
T. C. CHUNG, H. L. LU
Department of Materials Science and Engineering, Pennsylvania State University, University Park, Pennsylvania 16802

Received 8 August 1996; accepted 27 September 1996

Keywords: polyethylene copolymer; functional polyolefin; p-methylstyrene; metallocene catalyst

For many decades, there has been constant research


interest 1 in the copolymerization of ethylene and styrene. Usually, the traditional ZieglerNatta catalysts
only produce the copolymer with very inhomogeneous
composition, 2 even a blend of polyethylene and polystyrene homopolymers.3 The multiple active species in the
ZieglerNatta catalyst, with different stereospecificity
and oxidation states, were attributed to the inhomogeneity in the copolymerization reactions. The development of metallocene catalysts, 4 with a well-defined single catalytic site, provides an excellent opportunity for
the polymer chemist to study and control olefin polymerization reactions. However, due to very different
reactivity ratios 5 between the two monomers, most of
metallocene catalysts only show very limited success in
the preparation of poly(ethylene-co-styrene) copolymers. Styrene always shows significantly lower reactivity than ethylene. The important breakthrough came
with the development of the metallocene catalysts with
constrained ligand geometry, which provide the spatially opened catalytic site for monomer insertion, including some relatively large monomers. Several excellent examples are LLDPE copolymers 6 with well-defined composition and molecular weight distribution,
Dows long chain branching polyethylene 7 and poly(ethylene-co-styrene) copolymer 8 with pseudo-random
microstructure.
Thus far, there has been no report on the copolymer-

Contract grant sponsor: Polymer Program of the National


Science Foundation
J Polym Sci A: Polym Chem 35: 575579, 1997
q 1997 John Wiley & Sons, Inc. CCC 0887-624X/97/030575-05

CHCH 1 CHCH

CH
Metallocene
Catalyst

(CHCH)x(CHCH)y

(I)

Functionalization
Reaction

CH
(CHCH)x(CHCH)y

CH
(II)

F: functional group, such as Cl, Br, OH, COOH, NH, Li, etc.

Equation 1
ization of ethylene and p-methylstyrene. Our major research interest of incorporating p-methylstyrene into
polyolefins 9 is due to its versatility to access a broad
range of functional groups. The benzylic protons are
ready for many chemical reactions, such as halogenation, 10 metallation, 11 and oxidation, 12 which can introduce functional groups at the benzylic position under
mild reaction conditions as shown in eq. 1.
In the ethylene copolymerization reaction, it is logical to predict that p-methylstyrene may show signifi575

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Table I. A Summary of Copolymerization Reactions between Ethylene (M1) and Styrene Derivatives (M2) by
Using [C5Me4(SiMe2NtBu)]TiCl2 (I) and Et(Ind)2ZrCl2 (II) Catalysts
Reaction Conditionsa

Copolymer Product
Commonomersc

Run
No.

Temperature
(7C)

Catalyst
(mmol)

1
2
3
4
5
6
7
8
9
10
11
12
13
14

30
30
30
30
30
30
30
30
30
30
53
53
53
53

(I) 10
(I) 10
(I) 10
(I) 10
(I) 10
(II) 5
(II) 5
(II) 5
(II) 5
(II) 5
(II) 17
(II) 17
(II) 17
(II) 17

Solvent
(100 mL)

M1 (psi)

toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
hexane
hexane
hexane
hexane

45
45
45
45
45
45
45
45
45
45
43.5
43.5
43.5
43.5

M2 (mmol)

Yield
(g)

M2
Concentration
(mol %)

M2
Conversion
(%)

Tm
(7C)

none
p-MS (46.6)
o-MS (46.6)
m-MS (46.6)
Styrene (46.6)
none
p-MS (68.2)
o-MS (68.2)
m-MS (68.2)
Styrene (68.2)
p-MS (33.9)
o-MS (33.9)
m-MS (33.9)
Styrene (33.9)

4.27
13.0
12.9
5.43
13.6
3.22
4.39
4.22
3.78
3.39
24.7
23.0
19.0
17.5

0
10.9
4.52
2.36
5.35
0
7.04
3.67
1.96
0.91
3.30
2.54
2.35
1.87

0
84.3
38.7
9.53
48.6
0
13.1
6.82
3.64
1.75
81.5
63.5
43.2
31.7

133.7
76.0
98.3
119.1
98.7
136.8
120.0
123.6
126.5
128.8
114.3
118.6
118.1
127.4

Reaction time 1 h.
Al/Ti 1500, Al/Zr 1500
c
M1, ethylene; p-MS, p-methylstyrene; o-MS, o-methylstyrene; m-MS, m-methylstyrene.
b

cantly better incorporation than styrene by using metallocene catalysts with constrained ligand geometry. It
is well-accepted that the cationic coordination mechanism13 is responsible for the metallocene polymerization reaction. The electron-donating p-methyl group
provides a favorable electronic effect to increase the
monomer reactivity. In fact, some experimental results 14 have shown the significantly higher reactivity
of p-methylstyrene relative to styrene in homopolymerization reactions using syndiotactic specific metallocene
catalyst. In addition, it has also been reported that pmethylstyrene and isobutylene have similar reactivity
ratios under cationic polymerization conditions. An entire compositional range of poly(isobutylene-co- pmethylstyrene) copolymers 15 have been prepared.
Both catalysts, [C5Me4 (SiMe2N tBu)]TiCl2 and
Et(Ind)2ZrCl2 , were prepared by the published procedures.8,16 Methylaluminoxane (MAO) (ethyl) was purchased and used as received. In a typical ethylene copolymerization condition, the comonomer (i.e., p-methylstyrene, o-methylstyrene, m-methylstyrene, or styrene)
was mixed with solvent (toluene or hexane) and methylaluminoxane (MAO) (30 wt % in toluene) needed in
a Parr 450 mL stainless autoclave equipped with a mechanical stirrer. The sealed reactor was then saturated
with 45 psi ethylene gas at 30 or 537C before adding
the catalyst solution, [C5Me4 (SiMe2N tBu)]TiCl2 or
Et(Ind)2ZrCl2 in toluene, to initiate the polymerization.
Additional ethylene was fed continuously into the reactor by maintaining a constant pressure about 45 psi
during the whole course of the polymerization. After 60

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min, the reaction was terminated by adding 100 mL of


dilute HCl solution in MeOH. The polymer was isolated
by filtering and washed completely with MeOH and
dried under vacuum at 507C for 8 h. Table I summarizes
the experimental results, which includes three sets of
comparative experiments (runs 25, 710, and 1114)
and two control ethylene homopolymerization (runs 1
and 6). Each set of experiments was carried out under
the same reaction condition except using different comonomers, i.e., p-methylstyrene, o-methylstyrene, mmethylstyrene, and styrene, respectively.
The compositions of copolymers were determined by
1
H-NMR spectra, and the thermal properties (melting
point and crystallinity) were obtained by DSC measurements. Overall, all comonomers show no retardation to
the catalyst activity. In fact, the significantly higher
catalyst activities were observed in all copolymerization reactions (runs 25 and 710), compared with
two ethylene homopolymerization reactions (runs 1 and
6). In the copolymerization reactions, both catalysts
exhibited similar catalyst activities, about 69 1 10 5
and 914 1 10 5 g polymer/mol Zr h at 30 and 537C,
respectively, for all styrene derivatives. Its interesting
to note that in runs 1114 the use of hexane (poor
solvent for MAO) did not reduce the catalyst activity,
which may due to the presence of aromatic comonomers. By comparing M2 concentration in each copolymer
among three sets (runs 25, 710, and 1114), [C5Me4(SiMe2N tBu)]TiCl2 shows the significantly better copolymerization efficiencies than Et(Ind)2ZrCl2 . The
higher degree of constrained ligand geometry with

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The poly(ethylene-co- p-methylstyrene) with 10.9


mol % of p-methylstyrene shows a low melting point
(767C) and very small crystallinity (5.4%), which implies the relatively random distribution of p-methylstyrene along the polyethylene backbone. The detailed sequence distribution can be quantitatively determined
by 13C-NMR measurements. Figure 1 compares the 13CNMR spectra of poly(ethylene-co- p-methylstyrene)
and poly(ethylene-co-styrene), containing about 10
mol % of comonomers (i.e., p-methylstyrene and styrene).
In the aromatic region (120150 ppm), all the chemical shifts are in good agreement with those aromatic
carbons in p-methylstyrene and styrene units, respectively. The sequence distribution was revealed by the
chemical shifts corresponding to the carbons located
along the polymer backbone. It is logical to expect that
the methyl group substitution at the para-position will
have very little effect on the chemical shifts of methylene and methine carbons in the polymer backbone. In
other words, the comparison of aliphatic chemical shifts
is a direct comparison of their sequence distributions

Figure 1. 13C-NMR spectra of (a) poly(ethylene-cop-methylstyrene) with 10.9 mol % p-methylstyrene


and (b) poly(ethylene-co-styrene) with 9.5 mol % styrene.

larger spatial opening at the catalytic site may attribute to the favorable copolymerization condition.
Within each set (runs 25, 710, and 1114) of
comparative experiments, p-methylstyrene consistently shows better incorporation than the rest of comonomers, i.e., o-methylstyrene, m-methylstyrene and
styrene. Both catalysts with constrained mono- and dicyclopentadienyl ligands are very effective to incorporate p-methylstyrene into the polyethylene backbone.
In runs 2 and 11, more than 80% of p-methylstyrene
was converted to copolymer within 1 hour under constant (45 psi) ethylene pressure. On the other hand,
only less than half of styrene (runs 5 and 14) was incorporated into ethylene copolymers under the same reaction conditions. The significantly lower styrene incorporation may be due to the lack of electronic donation
from p-methyl substitution which is very favorable in
the cationic polymerization mechanism. Some steric
hindrance of the methyl group to the propagating site
may affect the incorporation of o-methylstyrene. Both
less favorable electronic and steric effects may contribute significantly to the low incorporation of m-methylstyrene.

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Figure 2. Expanded aliphatic region of the 13C-NMR


spectra of (a) poly(ethylene-co- p-methylstyrene) with
10.9 mol % p-methylstyrene and (b) poly(ethylene-costyrene) with 9.5 mol % styrene.

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Table II. A Comparison of Calculated and Observed Chemical Shifts for Methylene and Methine Carbons in
Poly(ethylene-co-p-methylstyrene) P(E-co-p-MS) and Poly(ethylene-co-styrene) P(E-co-S)
Carbon
Typea

Sequence

Sbb
Sbd
Sdd
Sgd
Sab
Sag
Sad
Saa
Tbb
Tdd
Tgd

SES
SEE
EEE
EEE
SSEd
SES
SEE
SSEe
SSS
ESE
SSEd

Calculated
(ppm)

Observed P(E-co-p-MS)
(ppm)

25.91
28.01
30.13
30.56
34.75
37.10
37.10
4345f
41.60
47.60
47.98

27.74
29.80

37.04

45.77

Observedc P(E-co-S)
(ppm)
25.22
27.36
29.26
29.42
34.13/34.60
36.48
36.65

45.64
46.08

a
S, methylene carbon; T, methine carbon; a, b, g, d: distance from methylene or methine carbon to the adjacent aromatic
substituted methine carbon. (d includes the distance beyond four carbons away)
b
E, ethylene; S, styrene or p-methylstyrene.
c
Only showing the major peaks.
d
SS, tail-to-tail coupling.
e
SS, head-to-tail coupling.
f
Chemical shift range corresponding to methylene carbons of polystyrene with head to tail coupling.

between poly(ethylene-co- p-methylstyrene) and poly(ethylene-co-styrene).


Figure 2 is the expanded 13C-NMR spectra in the
aliphatic region of poly(ethylene-co- p-methylstyrene)
and poly(ethylene-co-styrene). In general, fewer chemical shifts shown in the poly(ethylene-co- p-methylstyrene) sample imply more homogeneous copolymer microstructure. For detailed analysis, the experimental
results were compared with the literature reference 2,17
and the theoretical chemical shifts which were calculated based on the improved Grant and Paul empirical
method.18 Table II shows the summary of the calculated
and observed chemical shifts for methylene and methine carbons in the polymer backbone.
Due to the treatment of the phenyl side group, which
was not substantiated from the alkane group in the
Grant and Paul empirical method, the calculated results only provide the guidance in the chemical shift
assignments. In general, every chemical shift in Figure
2 (a) can be easily assigned. In addition to the two
chemical shifts (21.01 and 29.80 ppm), corresponding
to the methyl carbon from p-methylstyrene and methylene carbons from ethylene, respectively, there are three
well-resolved peaks (27.74, 37.04, and 45.77 ppm) corresponding to methylene and methine carbons from pmethylstyrene units which are separated by multiple
ethylene units along the polymer chain. On the other
hand, the spectrum in Figure 2 (b) shows much more
complicated methylene and methine carbon species in
poly(ethylene-co-styrene) sample with several relatively broad bands. Many consecutive and adjacent styrene units (SSE and SES) clearly exist in the polymer
chain. There is no detectable SSS sequence in the copol-

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ymer. Similar results were also concluded by other


groups.8,17
Overall, the experimental results clearly show a new
poly(ethylene-co- p-methylstyrene) copolymer which
can be conveniently prepared by a metallocene catalyst,
such as [C5Me4 (SiMe2N tBu)]TiCl2 and Et(Ind)2ZrCl2 ,
with constrained ligand geometry. The combination of
spatially opened catalytic site and cationic coordination
mechanism provides a very favorable condition for pmethylstyrene in an ethylene copolymerization reaction. The comparison of comonomer incorporation and
the homogeneity of the resulting copolymer show that
p-methylstyrene performs distinctively better than styrene, o-methylstyrene, and m-methylstyrene. A broad
composition range of poly(ethylene-co- p-methylstyrene) copolymers have been prepared, which are very
useful intermediates in the preparation of functional
polyolefins. The functionalization results will be discussed in the near future.
The authors would like to thank the Polymer Program
of the National Science Foundation for financial support.

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