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Poly(ethylene-co-p-methylstyrene) Copolymers
Prepared by Metallocene Catalysts with
Constrained Ligand Geometry
T. C. CHUNG, H. L. LU
Department of Materials Science and Engineering, The Pennsylvania State University,
University Park, Pennsylvania 16802
prepared by metallocene catalysts, such as Et(Ind)2ZrCl2 and [C5Me4 (SiMe2N tBu)]TiCl2 , with constrained ligand geometry. The copolymerization reaction was examined
by comonomer reactivity (reactivity ratio and comonomer conversion versus time),
copolymer microstructure (DSC and 13C-NMR analyses) and the comparisons between
p-methylstyrene and other styrene-derivatives (styrene, o-methylstyrene and m-methylstyrene). The combined experimental results clearly show that p-methylstyrene
performs distinctively better than styrene and its derivatives, due to the cationic coordination mechanism and spatially opened catalytic site in metallocene catalysts with
constrained ligand geometry. A broad composition range of random poly(ethylene-cop-methylstyrene) copolymers were prepared with narrow molecular weight and composition distributions. With the increase of p-methylstyrene concentration, poly(ethylene-co- p-methylstyrene) copolymer shows systematical decrease of melting point and
crystallinity and increase of glass transition temperature. At above 10 mol % of pmethylstyrene, the crystallinity of copolymer almost completely disappears. q 1998 John
Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 10171029, 1998
INTRODUCTION
For many decades since the commercialization of
PE and PP, the functionalization of polyolefins 1 has
been a long scientific interest and technological important research subject to improve their adhesion
to and compatibility with other materials. Unfortunately, the chemistry to prepare functional polyolefins is very limited both in the direct and postpolymerization processes, namely due to the catalyst poison 2 and the inert nature 3 of polyolefins.
Recently, several new research approaches, including the use of late transition metals 4 and protecting
groups, 5 may provide some solutions.
Correspondence to: T. C. Chung
Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 36, 10171029 (1998)
q 1998 John Wiley & Sons, Inc.
CCC 0887-624X/98/061017-13
Our functionalization chemistry has been focusing on the reactive polyolefin approach, especially the polyolefin containing borane groups.6
The borane groups can be effectively incorporated
into polyolefin by both direct 7 and post 8 polymerization processes. In turn, borane groups in polymer can be easily interconverted to various functional groups, such as {OH and halides, under
mild reaction conditions. Recently, the borane
group has been transformed to a stable radical
initiator 9 which can then carry out living radical
graft-from polymerization of monomer containing
functional group. In other words, the reactive borane group serves as the intermediate for the
transformation reaction from transition metal to
living radical polymerizations. Such a process
produces graft 10 and block 11 copolymer struc1017
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x CHCH 1 y CHCH
Metallocene
Catalyst
CH
(CHCH)x(CHCH)y
CH
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(1)
Scheme 1.
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Figure 1. GPC curves of (a) polyethylene and three poly(ethylene-co- p-methylstyrene) copolymers, containing (b) 1.08, (c) 9.82 and (d) 18.98 mol % of p-MS comonomers, prepared by [C5Me4 (SiMe2N tBu)]TiCl2 catalyst, and the molecular weights and
molecular weight distributions (insert).
rene) copolymers. In addition, p-MS was compared with styrene and other methylstyrene derivatives (i.e. o-methylstyrene and m-methylstyrene).
Synthesis of Poly(ethylene-co-p-methylstyrene)
In a typical copolymerization, the reaction was
started by the addition of the metallocene catalyst
mixture to a solution of the two monomers in solvent under an inert gas atmosphere. The appearance of the reacting polymer solution was very
dependent on the quantity of p-MS used. In the
high p-MS cases, a homogeneous solution was observed through the whole copolymerization reaction. In the low p-MS cases, a slurry solution with
white precipitates was observed right in the beginning of the reaction. The precipitation is obviously due to the crystallinity of copolymer which
has long ethylene sequences. The copolymer was
isolated by filtering and washed completely with
MeOH and dried under vacuum at 507C for 8 h.
The copolymer was firstly analyzed by GPC and
1
H-NMR measurements. Figure 1 shows the typical GPC curves of the homo- and copolymers prepared by [C5Me4 (SiMe2N tBu)]TiCl2 catalyst. The
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uniform molecular weight distribution in all samples, with MV w /MV n 23, implies the single-site
polymerization mechanism. In fact, the GPC
curves show a slight reduction of molecular
weight distribution in the copolymers, from MV w /
MV n 2.86 in PE to 1.68 in poly(ethylene-co- pmethylstyrene) containing 18.98 mol % of p-MS.
The similar narrow molecular distribution results
were also observed in the copolymers prepared by
Et(Ind)2ZrCl2 catalyst. The better diffusibility of
monomers in the copolymer structures (due to
lower crystallinity) may help to provide the ideal
polymerization condition. It is very interesting to
note that the average molecular weight of copolymers maintain very high throughout the entire
composition range, which may be attributed to the
relatively high reactivity of p-MS.
Figure 2 shows the 1H-NMR spectra of two
poly(ethylene-co-p-methylstyrene) copolymers,
containing 2.11 and 18.98 mol % of p-MS, respectively. In addition to the major chemical shift at
1.35 ppm, corresponding to CH2 , there are three
minor chemical shifts around 2.35, 2.5 and 7.0
7.3 ppm, corresponding to CH3 , CH and aromatic
protons in p-MS units. The integrated intensity
ratio between the chemical shift at 1.35 ppm and
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Figure 2. 1H-NMR spectra of poly(ethylene-co- p-methylstyrene) copolymers, containing (a) 2.11 and (b) 18.96 mol % of p-MS comonomers.
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II/17
II/17
II/17
II/17
II/17
p-357
p-392
p-360
p-362
p-375
45
45
45
45
45
45
10
45
45
45
45
45
45
45
45
45
45
45
45
Ethylene
(psi)c
0
0.447
0.912
0.447
0.912
1.82
1.82
0.085
0.456
0.678
1.36
2.03
0.085
0.508
0.678
1.36
2.03
0.678
0.678
p-MS
(mol/L)
Toluene
Hexane
Hexane
Toluene
Toluene
Toluene
Hexane
Toluene
Toluene
Toluene
Toluene
Toluene
Hexane
Hexane
Hexane
Hexane
Hexane
Hexane
Toluene
Solvent
30
30
30
30
30
30
30
50
50
50
50
50
50
50
50
50
50
50
50
Temperature
(7C)
4.4
12.0
15.5
13.0
17.4
24.2
15.9
5.70
8.63
15.1
19.5
19.4
6.5
19.8
21.9
18.9
20.8
24.2
8.44
Yield
(g)
440.0
1200.0
1550.0
1300.0
1740.0
2420.0
1590.0
335.3
507.6
888.2
1147.1
1141.2
382.4
1164.7
1288.2
1111.8
1223.5
1423.5
496.5
Catalyst
Efficiency
(kg P/mol Mrh)
13.5
22.6
10.9
21.6
32.8
40.0
1.30
3.85
4.76
6.36
8.49
1.83
3.94
5.16
7.20
8.94
2.20
1.84
p-ms in
Copolymer
(mol %)
90.3
81.3
83.8
86.9
75.8
54.6
29.9
23.2
32.8
27.0
22.8
47.2
48.7
51.1
29.0
25.4
26.2
7.72
Conversion
of p-MS
(%)
III/10
III/10
III/10
III/10
III/10
III/10
III/10
II/17
II/17
II/17
II/17
II/17
p-356
p-372
p-358
p-361
p-371
p-270
p-377
p-378
p-267
p-379
p-380
p-383
I/17
I/17
Catalysta
(mmol)
p-363
p-365
Run
Number
Table I.
POLY(ETHYLENE-CO-p-METHYLSTYRENE)
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lent spatial freedom for p-MS to access to the propagating chain end.
In general, the catalyst activity systematically
increases with the increase of p-MS content,
which was also observed in the 1,4-hexadiene copolymerization reactions 8 and could be a physical
phenomenon relative to the improvement of
monomer diffusion in the lower crystalline copolymer structures. In [C5Me4 (SiMe2N tBu)]TiCl2
case, the catalyst activity attains a value of more
than 2.4 1 10 6 g of copolymer/mol of Ti 1 h in
run P-380, which is about 6 times the value for
the homopolymerization of ethylene in run P-270
under similar reaction conditions. It is very interesting to note that a very small solvent (hexane
and toluene) effect to the catalyst (III) activity
was observed in the comparative runs (P-377/P267) and (P-378/P-379), despite the significant
difference in the beginning of reaction conditions
(heterogeneous in hexane and homogeneous in
toluene). However, the solvent effect is very significant in both catalyst (I) and (II) systems. All
comparative reaction pairs (P-363/P-365, P-356/
P-357, P-358/P-360, P-361/P-362 and P-371/P375), carried out under similar reaction conditions, consistently show higher p-MS incorporation in hexane solution. The explanation of solvent effect is not clear.
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Reactivity Ratios
The best way to investigate a copolymerization is
to measure the reactivity ratio of the comonomers.
To obtain meaningful results, a series of experiments were carried out by varying monomer feed
ratio and comparing the resulting copolymer composition at low monomer conversion ( 10%). The
reactivity ratios between ethylene ( r1 k11 /k12 )
and p-MS (r2 k22 /k21 ) are estimated by the
KelenTudos method. The calculation 28 is based
on the equation 2.
h r1j 0 r2 / a(1 0 j )
h G/ a / F and j F/ a / F
where x [ethylene]/[comonomer] in feed and y
d[ethylene]/d[comonomer] mol ratio in polymer, G x(y 0 1)/y, F x 2 /y, a (Fm 1 FM ) 1/2 ,
and Fm and FM are the lowest and highest values
of F. Figure 4 shows a typical plot h versus j and
the least squares best fit line. In general, a good
fit of the experimental results in the straight line
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Figure 3. Plots of (a) comonomer conversion versus reaction time and (b) comonomer
concentration in copolymer versus comonomer ratio, during the copolymerization reactions of ethylene with p-methylstyrene and with styrene using [C5Me4 (SiMe2N tBu)]TiCl2 catalyst.
Table II. The Comparison of Copolymerization Reactions Between Ethylene (M1) and p-Methylstyrene or
Styrene (M2) Using [(C5Me4)SiMe2N(t-Bu)]TiCl2/MAO Catalysta
Run
Number
Reaction
Temperature
(7C)
Reaction
Time
(min.)
Ethylene [M1]
(mol/L)
[M2]b Comonomer
(mol/L)
Yield
(g)
M2 Concentration
(mol %)
p-451
p-463
p-442
p-443
20
20
20
20
60
60
60
60
0.294
0.294
0.294
0.294
p-MS/0.890
p-MS/1.186
St./0.894
St./1.192
0.726
0.667
0.425
0.454
13.1
16.6
8.2
10.6
p-418
p-416
p-412
p-411
40
40
40
40
15
15
15
15
0.22
0.22
0.22
0.22
p-MS/0.22
p-MS/0.88
St./0.22
St./0.88
2.557
3.130
1.463
2.438
5.40
18.96
2.39
12.38
p-448
p-444
p-446
p-433
p-434
p-436
60
60
60
60
60
60
15
15
15
15
15
15
0.178
0.178
0.178
0.178
0.178
0.178
p-MS/0.093
p-MS/0.178
p-MS/0.534
St./0.096
St./0.183
St./0.548
3.22
3.36
3.10
2.44
3.15
3.75
2.34
4.77
12.24
0.95
2.06
8.56
a
b
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Table III. The Comparison of Copolymerization Reactionsa Between Ethylene [M1] and Methylstyrene
Derivatives [M2] Using [(C5Me4)SiMe2N(t-Bu)]TiCl2/MAO Catalyst
Run
Number
M2b
(mmol)
Yield
(g)
M2 Concentration
(mol %)
M2 Conversion
(%)
Tm
(7C)
xc
(%)
p-277
p-267
p-275
p-274
none
p-MS (46.6)
o-MS (46.6)
m-MS (46.6)
4.27
13.0
12.9
5.43
0
11.0
4.52
2.36
84.3
38.7
9.53
133.7
76.0
98.3
119.1
51.5
5.40
12.1
23.4
a
b
Catalyst: 10 umol, reaction temp.: 307C, reaction time: 60 min. ethylene (M1) pressure: 45 psi.
p-MS: p-methylstyrene; o-MS: o-methylstyrene; m-MS: m-methylstyrene.
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Catalyst
Reaction
Temperature
(7C)
r1
r2
r 1 1 r2
[(C5Me4)SiMe2N(t-Bu)]TiCl2
[(C5Me4)SiMe2N(t-Bu)]TiCl2
Et(Ind)2ZrCl2
Et(Ind)2ZrCl2
Et(Ind)2ZrCl2
20
60
20
40
60
19.6
21.4
89.0
72.0
64.1
0.039
0.082
0
0
0
0.77
1.76
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Figure 6. DSC curves of (a) poly(ethylene-co- pmethylstyrene) copolymers with (a) 18.98, (b) 32.8 and
(c) 40 mol % of p-MS comonomer.
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Figure 8. 13C-NMR spectra of poly(ethylene-co-p-methylstyrene) with 10.9 mol % pMS and the expanded aliphatic region (insert).
EXPERIMENTAL
Instrumentation and Materials
All room and high temperature 1H-NMR and 13CNMR were recorded on a Bruker WP-200 or a
Bruker AM-300 spectrometer with the DISNMR
software. The molecular weight was determined
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CONCLUSION
A new class of random poly(ethylene-co- p-methylstyrene) copolymers, with narrow molecular
weight and composition distributions, have been
developed by metallocene catalysts with constrain
ligand geometry. The experimental results clearly
show that p-methylstyrene performs distinctively
better than styrene, o-methylstyrene and mmethylstyrene, in the ethylene copolymerization
reaction. The combination of spatially opened catalytic site and cationic coordination mechanism
in [C5Me4 (SiMe2N tBu)]TiCl2 catalyst provides a
very favorable reaction condition for p-methylstyrene to be randomly incorporated in the poly(ethylene-co-p-methylstyrene) structure. In turn, the
copolymers are very useful intermediates in the
preparation of functional polyolefins which will be
discussed in the near future.
Authors would like to thank the Polymer Program of
the National Science Foundation and Dow Chem. Co.
for financial support.
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