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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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577
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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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.
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2.
3.
4.
5.
6.
7.
8.
9.
10.
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