- Email: [email protected]
MAO Catalyst
Progress in Olefin Polymerization Catalysts and Polyolefin Polyolefin Materials T. Shiono, K. Nomura and M. Terano (Editors) © 2006 Elsevier B.V. All rights reserved.
193 193
31 Copolymerteation of Styrene Derivatives and Cycloolefin with Ni Compound/MAO Catalyst Naoya Nishimura, Katsuya Maeyama, Akinori Toyota* Graduate School of Engineering, Tokyo University of Agriculture and Technology, 224-16 Naka-eho, Koganei-shi, Tokyo 184-8588, Japan, email: [email protected],ac,jp
Abstract Copolymerization of styrene derivatives, such as 4-tert-hutylstymne (4TBS), 4-methylstyrene (4MS), 4-methoxystyrene (4MOS), 4-bromostyrene (4BS), and 5-ethylidene-2-norbomene (ENB) was conducted with nickel (Ni) compound/methylaluminoxane (MAO) catalysts. Polymerization behaviors and properties of the resulting copolymers were investigated. Nickel bis(acetylacetonate) (1) / MAO showed the highest activity. Ts values of the obtained copolymers reached to ca. 300 °C. 1. INTRODUCTION Recently, papers related to copolymerization of cycloolefin and olefms have been reported[l,2], Cycloolefin copolymers have been attractive because they have the excellent properties such as high glass transition temperature, high optical transparency, low birefringence, and low moisture absorption. Copolymerization of cycloolefin with styrene has also been investigated because it is easy to obtain copolymers with higher glass transition temperature than the copolymers derived from cycloolefin/olefin. However few reports have been known on copolymerization of cycloolefin with styrene derivatives[3,4]. In this paper, we would like to report the studies on the effects of the catalyst structure and those of polymerization conditions on the activities and copolymerizability in the copolymerization with Ni compound/MAO catalysts.
194
JV. Nishimura et al.
2. EXPERIMENTAL All procedures were conducted with using Schlenk techniques under nitrogen atmosphere. Styrene derivative and ENB were placed in a 50-ml flask, and then a nickel compound (2.5 X 10"6 mol) and MAO (2.5 X 10"3 mol) were sequentially charged into the flask. The reactions were carried out at room temperature for 24 h. After completion of the reaction, excess methanol was added. The resulting polymers were purified by reprecipitation with a system of CHCls/methanol and the polymer precipitates were dried in vacuum.
CH 3
CH 3
Ni(acac)2 1
Ni stearats
bis(3,5-di-terf-butylsalicylidene}1,2-cyclohexadiamino nickel 2 3 Figure 1 Ni compounds used for copolymerization
3. RESULTS AND DISCUSSION Results of 4TBS-ENB copolymerization are shown in Table 1. 4TBSENB copolymers were obtained with all nickel compound/MAO catalysts. M(acac)2 (1) /MAO catalyst showed the highest activity among the three types of nickel compounds. ENB contents increased with increasing ENB in feed. ENB contents in copolymers were in the range from 1 4 - 5 5 mol %. This is probably due to bulkiness of 4TBS. Number average molecular weight was low, and polydispersiry was narrow. The Tg values of copolymers increased with increasing ENB content in the copolymer and reached to ca. 300 °C. Relation of between Te and ENB content in the copolymer is shown in Figure 2.
31. Copolymerization ofStyrene Derivatives and Cycloolefin with Ni compdJMAO 195 Table 1 Copolymerization of 4TBS and ENB with Ni compound/MAO catalyst* ENB in feed
Activity
ENB content0
b
entry
catalyst
1
1
10
2.38
33.8
3.9
2.8
189
2
1
30
1.94
39.0
3.6
1.6
200
3
1
50
3.54
47.6
4.1
1.8
218
4
1
70
1.47
53.4
3.8
1.8
227
5
2
10
1.00
24.8
4.7
1.4
169
6
2
30
0.870
34.6
4.4
1.6
220
7
2
50
1.09
47.1
4.4
1.5
234
8
2
70
0J36
52.4
4.2
1.6
296
9
3
10
0.976
14.6
3.3
1.3
164
10
3
30
2.39
29.8
4.3
1.7
176
11
3
50
2.61
35.5
4.5
1.8
196
12
3
70
1.86
55.8
4.1
1.8
244
(xlO3)
TO
"Polymerization conditions: total volume = 25 mL, solvent = toluene, Ni = 2.5 ^mol, Al /Ni= 1000, temperature = r.t., time = 24 h. hactivity = kg (p^) mol ^'l h"1, "determined by 'H-NMR, number average molecular weight and molecular weight distribution were determined by GPC using polystyrene standards, 'determined by DSC. 350 350 300 300 --
•
250 250
Tg [oC]
Copolymerization of 4MS and ENB with three types of Ni/MAQ catalysts afforded copolymers. Copolymerization of 4BS and 4MOS with ENB was investigated with using Ni (1)/MAO catalyst. Correlations between Tg and ENB content are shown in Figures 3 and 4. On the other hand, 4MOS homopolymer was obtained in copolymerization of 4MOS and ENB. This polymerization probably proceeds via cationie polymerization predominantly.
8°'
D
200 150 150 100 -_ 100
O
Ni(acac)2
1 l Ni stearate • Ni (salen)
50 50 0
10 10
20 20
30 30
40 40
50 50
ENB content ENB content [mol%] [mol%]
Figure 2 Fg vs. ENB content for poly (4TBS-co-ENB)
60
196
N. Nishimura et al. 350 350
350
300 300
300 -
.
2000 20
o
100 - °CP 100
o n
10 10
20 20
30 30
•
f-M 200 -
A
00
„ 250 O
•
150 150
50 50
o
Tg [oC]
Tg [oC]
2500 25
050 150
Ni(acac)22 Ni stearate Ni (salen)
40 40
50 50
ENB content [mol %] %] Figure 3 Tg vs. ENB content for poly (4MS-CO-ENB)
< 60 60
100 inn
00
•
10 10
4BS-ENB
20 20 30 30 40 40 50 ENB content [mol %] %]
60
Figure 4 Tg vs. ENB content for poly (4BS-CO-ENB) obtained with Ni(acac)2 /MAO catalyst
4BS-ENB copolymers were obtained with Ni(acac)2/MAO catalyst. The Tg values of copolymers ranged from 120 to 220 °C. These copolymers have possibilities to be modified at bromo group and to be converted to functional polymers. 4. CONCLUSIONS Copolymerization of styrene derivatives and ENB was studied with using three types of nickel compounds-MAO catalysts. The catalysts showed low activity for the copolymerization, but copolymers having high Tg values in range of 90 to 300 °C were obtained. References [1] T. Hasan, T. Ikeda, and T. Shiono, Macromolecules 38 (2005) 1071-1074. [2] J. Forsyth, J. M. Perena, R. Benavente, E. Perez, 1 Tritto, L. Bogginoni, and H. H. Brintzinger, Macromol. Chem. Phys. 202 (2001) 614-620. [3] H. Suzuki, S. Matsumura, Y. Satoh, K. Sogoh, and H. Yasuda, React. Fund Polym, 58(2004)77-91. [4] C. Zhao, M.R. Ribeiro, M. F. Portela, S. Pereira, and T, Nunes, Eur, Patym. J. 37(2001)45-54.
193 193
31 Copolymerteation of Styrene Derivatives and Cycloolefin with Ni Compound/MAO Catalyst Naoya Nishimura, Katsuya Maeyama, Akinori Toyota* Graduate School of Engineering, Tokyo University of Agriculture and Technology, 224-16 Naka-eho, Koganei-shi, Tokyo 184-8588, Japan, email: [email protected],ac,jp
Abstract Copolymerization of styrene derivatives, such as 4-tert-hutylstymne (4TBS), 4-methylstyrene (4MS), 4-methoxystyrene (4MOS), 4-bromostyrene (4BS), and 5-ethylidene-2-norbomene (ENB) was conducted with nickel (Ni) compound/methylaluminoxane (MAO) catalysts. Polymerization behaviors and properties of the resulting copolymers were investigated. Nickel bis(acetylacetonate) (1) / MAO showed the highest activity. Ts values of the obtained copolymers reached to ca. 300 °C. 1. INTRODUCTION Recently, papers related to copolymerization of cycloolefin and olefms have been reported[l,2], Cycloolefin copolymers have been attractive because they have the excellent properties such as high glass transition temperature, high optical transparency, low birefringence, and low moisture absorption. Copolymerization of cycloolefin with styrene has also been investigated because it is easy to obtain copolymers with higher glass transition temperature than the copolymers derived from cycloolefin/olefin. However few reports have been known on copolymerization of cycloolefin with styrene derivatives[3,4]. In this paper, we would like to report the studies on the effects of the catalyst structure and those of polymerization conditions on the activities and copolymerizability in the copolymerization with Ni compound/MAO catalysts.
194
JV. Nishimura et al.
2. EXPERIMENTAL All procedures were conducted with using Schlenk techniques under nitrogen atmosphere. Styrene derivative and ENB were placed in a 50-ml flask, and then a nickel compound (2.5 X 10"6 mol) and MAO (2.5 X 10"3 mol) were sequentially charged into the flask. The reactions were carried out at room temperature for 24 h. After completion of the reaction, excess methanol was added. The resulting polymers were purified by reprecipitation with a system of CHCls/methanol and the polymer precipitates were dried in vacuum.
CH 3
CH 3
Ni(acac)2 1
Ni stearats
bis(3,5-di-terf-butylsalicylidene}1,2-cyclohexadiamino nickel 2 3 Figure 1 Ni compounds used for copolymerization
3. RESULTS AND DISCUSSION Results of 4TBS-ENB copolymerization are shown in Table 1. 4TBSENB copolymers were obtained with all nickel compound/MAO catalysts. M(acac)2 (1) /MAO catalyst showed the highest activity among the three types of nickel compounds. ENB contents increased with increasing ENB in feed. ENB contents in copolymers were in the range from 1 4 - 5 5 mol %. This is probably due to bulkiness of 4TBS. Number average molecular weight was low, and polydispersiry was narrow. The Tg values of copolymers increased with increasing ENB content in the copolymer and reached to ca. 300 °C. Relation of between Te and ENB content in the copolymer is shown in Figure 2.
31. Copolymerization ofStyrene Derivatives and Cycloolefin with Ni compdJMAO 195 Table 1 Copolymerization of 4TBS and ENB with Ni compound/MAO catalyst* ENB in feed
Activity
ENB content0
b
entry
catalyst
1
1
10
2.38
33.8
3.9
2.8
189
2
1
30
1.94
39.0
3.6
1.6
200
3
1
50
3.54
47.6
4.1
1.8
218
4
1
70
1.47
53.4
3.8
1.8
227
5
2
10
1.00
24.8
4.7
1.4
169
6
2
30
0.870
34.6
4.4
1.6
220
7
2
50
1.09
47.1
4.4
1.5
234
8
2
70
0J36
52.4
4.2
1.6
296
9
3
10
0.976
14.6
3.3
1.3
164
10
3
30
2.39
29.8
4.3
1.7
176
11
3
50
2.61
35.5
4.5
1.8
196
12
3
70
1.86
55.8
4.1
1.8
244
(xlO3)
TO
"Polymerization conditions: total volume = 25 mL, solvent = toluene, Ni = 2.5 ^mol, Al /Ni= 1000, temperature = r.t., time = 24 h. hactivity = kg (p^) mol ^'l h"1, "determined by 'H-NMR, number average molecular weight and molecular weight distribution were determined by GPC using polystyrene standards, 'determined by DSC. 350 350 300 300 --
•
250 250
Tg [oC]
Copolymerization of 4MS and ENB with three types of Ni/MAQ catalysts afforded copolymers. Copolymerization of 4BS and 4MOS with ENB was investigated with using Ni (1)/MAO catalyst. Correlations between Tg and ENB content are shown in Figures 3 and 4. On the other hand, 4MOS homopolymer was obtained in copolymerization of 4MOS and ENB. This polymerization probably proceeds via cationie polymerization predominantly.
8°'
D
200 150 150 100 -_ 100
O
Ni(acac)2
1 l Ni stearate • Ni (salen)
50 50 0
10 10
20 20
30 30
40 40
50 50
ENB content ENB content [mol%] [mol%]
Figure 2 Fg vs. ENB content for poly (4TBS-co-ENB)
60
196
N. Nishimura et al. 350 350
350
300 300
300 -
.
2000 20
o
100 - °CP 100
o n
10 10
20 20
30 30
•
f-M 200 -
A
00
„ 250 O
•
150 150
50 50
o
Tg [oC]
Tg [oC]
2500 25
050 150
Ni(acac)22 Ni stearate Ni (salen)
40 40
50 50
ENB content [mol %] %] Figure 3 Tg vs. ENB content for poly (4MS-CO-ENB)
< 60 60
100 inn
00
•
10 10
4BS-ENB
20 20 30 30 40 40 50 ENB content [mol %] %]
60
Figure 4 Tg vs. ENB content for poly (4BS-CO-ENB) obtained with Ni(acac)2 /MAO catalyst
4BS-ENB copolymers were obtained with Ni(acac)2/MAO catalyst. The Tg values of copolymers ranged from 120 to 220 °C. These copolymers have possibilities to be modified at bromo group and to be converted to functional polymers. 4. CONCLUSIONS Copolymerization of styrene derivatives and ENB was studied with using three types of nickel compounds-MAO catalysts. The catalysts showed low activity for the copolymerization, but copolymers having high Tg values in range of 90 to 300 °C were obtained. References [1] T. Hasan, T. Ikeda, and T. Shiono, Macromolecules 38 (2005) 1071-1074. [2] J. Forsyth, J. M. Perena, R. Benavente, E. Perez, 1 Tritto, L. Bogginoni, and H. H. Brintzinger, Macromol. Chem. Phys. 202 (2001) 614-620. [3] H. Suzuki, S. Matsumura, Y. Satoh, K. Sogoh, and H. Yasuda, React. Fund Polym, 58(2004)77-91. [4] C. Zhao, M.R. Ribeiro, M. F. Portela, S. Pereira, and T, Nunes, Eur, Patym. J. 37(2001)45-54.