茂金属催化苯乙烯间规聚合过程研究
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摘要
间规聚苯乙烯(sPS)是一种新型热塑性塑料，由于其优良的性能，使之成为近年来研究的热点。
本文采用CpTiX3／MAO／TIBA均相茂金属催化体系，针对苯乙烯间规溶液聚合、sPS悬浮液体系流变行为以及间规聚苯乙烯种子半连续聚合工艺开发做了系统的研究，得到以下结果：
在氯苯、甲苯、庚烷、异辛烷、十氢萘及混合溶剂中进行苯乙烯间规溶液聚合，证明一定范围内提高聚合温度、提高搅拌转速、降低溶剂极性、采用无定形聚苯乙烯的不良溶剂可以促进聚合的进行，提高苯乙烯单体转化率。同时，提高搅拌转速、降低聚合温度与溶剂极性可以提高聚合产物的分子量。
同时研究了在不同聚合条件下原生态sPS结晶动力学规律。并且发现溶液聚合中改变溶剂的性质，对sPS原生晶晶型不产生影响，始终是δ晶型。对溶液聚合sPS原生态粒子粒径与粒径分布的研究表明，提高聚合温度、强化搅拌作用，采用异辛烷、十氢萘作为聚合介质可以有效改善sPS粒子的颗粒形态。
研究了sPS的悬浮液体系的流变性质，发现在氯苯体系中固含量低时，体系为牛顿流体性质；提高悬浮液浓度，体系的非牛顿性加强，呈现剪切稀化特点。同时，在高浓度悬浮液中，温度升高可以降低体系的剪切应力和表观粘度。由无定形聚苯乙烯不良溶剂(如庚烷、异辛烷等)配制的悬浮液，固含量小于15％时，体系呈现牛顿流体性质。
在500ml立式聚合釜中成功实现了sPS种子半连续聚合，表明此工艺是可行的，能够有效防止本体聚合过程中复杂的相态更迭以及凝胶、聚合釜淤塞现象的发生，达到降低聚合功率消耗的目标。
Syndiotactic polystyrene (sPS) is a new type of thermoplastics. Recently it becomes focus of research for its excellent properties.
In the thesis, a homogenous metallocene catalyst system, Cp*TiX3/MAO/TIBA was used to prepare the syndiotactic polymer. The kinetics of the solution polymerization process, the particle morphology of the produced sPS, and the rheology of the sPS suspension were studied. A seeded semi-continuous polymerization process was investigated also.
The styrene syndiotactic solution polymerization were carried out respective in the presence of chlorobenzene, tolune, heptane, isooctane, naphthane and mixed solvent. The results demonstrate that elevating the polymerization temperature and agitation speed, reducing polarity of solvent or using non-solvent for amorphous polystyrene are beneficial to polymerization and raise monomer conversion. And the molecular weight of produced polymer is increased with decrease in temperature and solvent polarity, and with an increase in agitation rate.
The investigation on crystallization kinetics of nascent sPS shows that the crystal of nascent sPS from solution polymerization is in 6 type and does not change with variety of solvent. The data of particle size and particle size distributions of the produced polymer during the polymerization indicates that elevating polymerization temperature and agitation speed, and using isooctane or naphthane to be solvent will improve the morphology of nascent particles.
By investigating the rheology of sPS suspension, we found that the sPS-chlorobenzene suspension has Newtonian fluid properties when the polymer content is lower than -10%. But suspension will be shear-thinned and turn into the Non-Newtonian fluid with an increase in the sPS content. When the solid content is relative high, temperature rising will decrease shear stress and apparent viscosity. However, when the suspension is prepared by a non-solvent for amorphous polystyrene, such as heptane and isooctane, and the sPS content is lower than 15%,
the fluid is Newtonian.
The seeded semi-continuous bulk syndiotactic polymerization of styrene is achieved in a 500mL reactor. During the polymerization process, the complicated phase change, the gelation and the reactor fouling can be avoided efficiently.
本文采用CpTiX3／MAO／TIBA均相茂金属催化体系，针对苯乙烯间规溶液聚合、sPS悬浮液体系流变行为以及间规聚苯乙烯种子半连续聚合工艺开发做了系统的研究，得到以下结果：
在氯苯、甲苯、庚烷、异辛烷、十氢萘及混合溶剂中进行苯乙烯间规溶液聚合，证明一定范围内提高聚合温度、提高搅拌转速、降低溶剂极性、采用无定形聚苯乙烯的不良溶剂可以促进聚合的进行，提高苯乙烯单体转化率。同时，提高搅拌转速、降低聚合温度与溶剂极性可以提高聚合产物的分子量。
同时研究了在不同聚合条件下原生态sPS结晶动力学规律。并且发现溶液聚合中改变溶剂的性质，对sPS原生晶晶型不产生影响，始终是δ晶型。对溶液聚合sPS原生态粒子粒径与粒径分布的研究表明，提高聚合温度、强化搅拌作用，采用异辛烷、十氢萘作为聚合介质可以有效改善sPS粒子的颗粒形态。
研究了sPS的悬浮液体系的流变性质，发现在氯苯体系中固含量低时，体系为牛顿流体性质；提高悬浮液浓度，体系的非牛顿性加强，呈现剪切稀化特点。同时，在高浓度悬浮液中，温度升高可以降低体系的剪切应力和表观粘度。由无定形聚苯乙烯不良溶剂(如庚烷、异辛烷等)配制的悬浮液，固含量小于15％时，体系呈现牛顿流体性质。
在500ml立式聚合釜中成功实现了sPS种子半连续聚合，表明此工艺是可行的，能够有效防止本体聚合过程中复杂的相态更迭以及凝胶、聚合釜淤塞现象的发生，达到降低聚合功率消耗的目标。
Syndiotactic polystyrene (sPS) is a new type of thermoplastics. Recently it becomes focus of research for its excellent properties.
In the thesis, a homogenous metallocene catalyst system, Cp*TiX3/MAO/TIBA was used to prepare the syndiotactic polymer. The kinetics of the solution polymerization process, the particle morphology of the produced sPS, and the rheology of the sPS suspension were studied. A seeded semi-continuous polymerization process was investigated also.
The styrene syndiotactic solution polymerization were carried out respective in the presence of chlorobenzene, tolune, heptane, isooctane, naphthane and mixed solvent. The results demonstrate that elevating the polymerization temperature and agitation speed, reducing polarity of solvent or using non-solvent for amorphous polystyrene are beneficial to polymerization and raise monomer conversion. And the molecular weight of produced polymer is increased with decrease in temperature and solvent polarity, and with an increase in agitation rate.
The investigation on crystallization kinetics of nascent sPS shows that the crystal of nascent sPS from solution polymerization is in 6 type and does not change with variety of solvent. The data of particle size and particle size distributions of the produced polymer during the polymerization indicates that elevating polymerization temperature and agitation speed, and using isooctane or naphthane to be solvent will improve the morphology of nascent particles.
By investigating the rheology of sPS suspension, we found that the sPS-chlorobenzene suspension has Newtonian fluid properties when the polymer content is lower than -10%. But suspension will be shear-thinned and turn into the Non-Newtonian fluid with an increase in the sPS content. When the solid content is relative high, temperature rising will decrease shear stress and apparent viscosity. However, when the suspension is prepared by a non-solvent for amorphous polystyrene, such as heptane and isooctane, and the sPS content is lower than 15%,
the fluid is Newtonian.
The seeded semi-continuous bulk syndiotactic polymerization of styrene is achieved in a 500mL reactor. During the polymerization process, the complicated phase change, the gelation and the reactor fouling can be avoided efficiently.
引文
1. N.Ishihara, T. Seimiya, et al;Macromolecules; 1986,19,2464
2．中道昌宏；合成树脂(日本)；1995，41(8)，22
3．三谷撤男；1996，42(5)，101
4．中道昌宏，佐藤信行；1996，47(2)，31
5. Plastics Technology, 1993, 39(2), 26
6. Plastics Technology, 1997, 43(6), 52
7. R. PO′ and N.Cardi; Progress In Polymer Science; 1996,21(1),47
8. A.Prasad and L.Mandelkern, Macromolecules, 1990, 23, 5401
9. C.Daniel, C.Dammer et al. Polymer, 1994,35,4243
10. US Patent 5032650, 1991
11. US Patent 5037907, 1991
12. US Patent 4950724, 1990
13. M.Gepr(?)dgs, G. Mckee and J R.W(?)nsch, Polym. Preprn., 1999,40,1,389
14. Kealy T. J. and Pauson R J.; Nature (London), 1951, 168,1039
15. Sinn H. and Kaminsky W ;Adv. Organomet. Chem., 1980, 18,99
16．阎卫东、陈金晖等；石油化工，1999，10,716
17．范荣；浙江大学博士论文，2001
18. Kaminsky W, Lenk et al. ; Macromolecules, 1997,30 (25) ,7647
19. Kaminsky W, Lenk S. ;Macromol Symp, 1997,118,45
20．祝方明，贾虹；石油化工，1999，28(6)，413，
21．伍青；合成树脂及塑料，2000，17(1)，48
22．方玉堂，祝方明等；高分子学报，2000，1，74
23．祝方明，林尚安等，高分子学报，1997，4，462
24．祝方明，王群芳等，中山大学学报(自然版)，1999，38(2)，46
25. Zambelli A, Pellecchia C, et al.; Makromol Chem, 1991,192, 223
26. Zambelli A et al.; Makromol. Chem., Makromol. Symp., 1991,297, 48
27．肖士镜；合成树脂及塑料，1999，16(2)，7
28．徐君庭，欧阳建莹 等；高等学校化学学报，1999，20(2)，327
29．王家喜，杨利营 等：茂金属催化聚合及聚合反应工程研讨会；1998，杭州
30. K. Soga, et al.; Makromol. Chem., Rapid Commun., 1993, 14(8), 511,
31. J. H. Yim, K. J. Dhu. et al.; Eur. Polym J., 1996, 39(12), 1381,
32．欧阳建莹；浙江大学硕士论文，1998．1
33. D. H. Lee, K. B. Yoon, et al., Macromol. Symp., 1995,185, 97,
34. A. Gassi, A.Zambelli Organometallics, 1996, 15,480
35. T.H. Newman et. Al. J. M. S.—Pure Appl. Chem., 1997 ,A34(10), 1921,
36. G. Xu; Macromolecules, 1998, 31,586,
37. U. Bueschges and JCW Chien J Polym. Sci., Part A, 1989, 27,1529
38. Zambelli A. and Anmendola P, Prog. Polym Sci., 1991, 16, 203
39. JCW. Chien and Salaika Z., J. Polym. Sci., Polym. Chem. Ed. , 1991, 29, 1253
40. Longo P. Grassi A. Proto A. and Ammendola P., Macromolecules, 1988, 21, 24
41. Ishihara N., Seimiya T., Macromolecules, 1988, 19, 2464
42. Zambelli A., Longo P.et al., Macromolecules, 1987,20, 2035
43. Resxoni B. Piemontesi F. et al., J. Am. Chem. Soc., 1992, 114, 1025
44. T. M. Liu, W.E.Bake et al., J. Appl. Polym. Sci., 1996,62, 1807
45. Soga K,Nakatani H., Macromolecules, 1990,23 (4),957
46. Soga K,Nakatani H., Macromolecules, 1990,23(5), 1558
47. Imayoshi M, Arai T et al.,Jpn. Pat. 63-268709, 1988
48. Imayoshi M, Maeda K et al, ,Jpn. Pat. 02238008, 1990
49. Yamamoto K, Ishikawa K et al. Eur. Pat. Appl. EP 390000, 1990
50. J. C. W. Chien ,Z. Salajka, J. Polym Sci., Polym. Chem. Ed., 1991, 29, 1243
51．祝方明，贾虹等；中山大学学报(自然科学版)，2001，40(2)，62
52．潘祖仁；《高分子化学》；化学工业出版社，北京，1997
53. MT. Malanga and T.H.Newman,U.S.Pat.4950724,1990
54．黄鹤，李建宗等；中国胶粘剂；1996，6(2)，46
55．张洪涛；高分子材料；1996，3(1)，26
56. EP328975, Idemitsu Petrochemical Co. Ltd., 1989
57. EP379128, Idemitsu Petrochemical Co. Ltd., 1990
58．JP08283312，旭化成工业株式会社，1996
59. CN1045977, The Dow Chemical Company, 1990
60. JP03020308, Idemitsu Petrochemical Co. Ltd., 1991
61. EP535582, Idemitsu Petrochemical Co. Ltd., 1992
62．JP08208713，旭化成工业株式会社，1996
63. C.De. Rosa ,M.Rapacciuolo, et al; Polymer 1992,.33(7), 1423
64. O.Greis, Y. Xu, et al.; Polymer, 1989,30, 590
65. C.De Rosa; Macromolecules, 1996, 29, 8460
66. R.Napolitano and B.Pirozzi; Macromolecules, 1993,26,7225
67. Y. Chatani,Y Shimane et al;Polymer, 1993,34,1620
68. F. De Candia, A. R. Russio,et al., Polym. Comm. 32, 306, 191
69. F. Auriemma, V. Petraccone, G Guerra. Macromolecules, 1993,26, 3772,
70．刘伟；浙江大学博士学位论文，1999
71．方志刚；浙江大学硕士学位论文，2000
72．邹盛欧；现代化工，1996，11，48
73．N.V.Gvozdi, D. J. Meier. Polym. Commun., 1991, 32(16), 493,
74．焦宁宁；甘肃化工，1998，2，6
75．浦鸿汀，沈志刚等；中国塑料，2000，12，1
76．J.A.迪安，《兰氏化学手册》，科学出版社，第一版，1991
77．卢焕章等，《石油化工基础数据手册》，化学工业出版社，第一版，1982
78．马沛生等，《石油化工基础数据手册续编》，化学工业出版社，第一版，1993
79．杨始堃，钟俊文；高分子学报，1993，2，195
80．黄炎明，匡志祥；合成纤维工业，1986，9(1)，9
81．吕美娟，马蓉；合成纤维工业，1988，11(1)，30
82．K.Tsutsui, Y.Tsujita, et al.; Polymer,1998,39(21), 5177,
83．窦红静，朱诚身等：高分子通报，2000，9，56
84．F. Deberdt,H.Berghams, Polymer, 1993,34(10), 2192
85. Cheng D. C-H; Chemistry and Industry, 1980, 17, 403
86．阎卫东，刘立新等；应用化学，2001，18(2)
87. G.Guerra, V.M.Vitagliano; Macromolecules, 1990,23,1539
2．中道昌宏；合成树脂(日本)；1995，41(8)，22
3．三谷撤男；1996，42(5)，101
4．中道昌宏，佐藤信行；1996，47(2)，31
5. Plastics Technology, 1993, 39(2), 26
6. Plastics Technology, 1997, 43(6), 52
7. R. PO′ and N.Cardi; Progress In Polymer Science; 1996,21(1),47
8. A.Prasad and L.Mandelkern, Macromolecules, 1990, 23, 5401
9. C.Daniel, C.Dammer et al. Polymer, 1994,35,4243
10. US Patent 5032650, 1991
11. US Patent 5037907, 1991
12. US Patent 4950724, 1990
13. M.Gepr(?)dgs, G. Mckee and J R.W(?)nsch, Polym. Preprn., 1999,40,1,389
14. Kealy T. J. and Pauson R J.; Nature (London), 1951, 168,1039
15. Sinn H. and Kaminsky W ;Adv. Organomet. Chem., 1980, 18,99
16．阎卫东、陈金晖等；石油化工，1999，10,716
17．范荣；浙江大学博士论文，2001
18. Kaminsky W, Lenk et al. ; Macromolecules, 1997,30 (25) ,7647
19. Kaminsky W, Lenk S. ;Macromol Symp, 1997,118,45
20．祝方明，贾虹；石油化工，1999，28(6)，413，
21．伍青；合成树脂及塑料，2000，17(1)，48
22．方玉堂，祝方明等；高分子学报，2000，1，74
23．祝方明，林尚安等，高分子学报，1997，4，462
24．祝方明，王群芳等，中山大学学报(自然版)，1999，38(2)，46
25. Zambelli A, Pellecchia C, et al.; Makromol Chem, 1991,192, 223
26. Zambelli A et al.; Makromol. Chem., Makromol. Symp., 1991,297, 48
27．肖士镜；合成树脂及塑料，1999，16(2)，7
28．徐君庭，欧阳建莹 等；高等学校化学学报，1999，20(2)，327
29．王家喜，杨利营 等：茂金属催化聚合及聚合反应工程研讨会；1998，杭州
30. K. Soga, et al.; Makromol. Chem., Rapid Commun., 1993, 14(8), 511,
31. J. H. Yim, K. J. Dhu. et al.; Eur. Polym J., 1996, 39(12), 1381,
32．欧阳建莹；浙江大学硕士论文，1998．1
33. D. H. Lee, K. B. Yoon, et al., Macromol. Symp., 1995,185, 97,
34. A. Gassi, A.Zambelli Organometallics, 1996, 15,480
35. T.H. Newman et. Al. J. M. S.—Pure Appl. Chem., 1997 ,A34(10), 1921,
36. G. Xu; Macromolecules, 1998, 31,586,
37. U. Bueschges and JCW Chien J Polym. Sci., Part A, 1989, 27,1529
38. Zambelli A. and Anmendola P, Prog. Polym Sci., 1991, 16, 203
39. JCW. Chien and Salaika Z., J. Polym. Sci., Polym. Chem. Ed. , 1991, 29, 1253
40. Longo P. Grassi A. Proto A. and Ammendola P., Macromolecules, 1988, 21, 24
41. Ishihara N., Seimiya T., Macromolecules, 1988, 19, 2464
42. Zambelli A., Longo P.et al., Macromolecules, 1987,20, 2035
43. Resxoni B. Piemontesi F. et al., J. Am. Chem. Soc., 1992, 114, 1025
44. T. M. Liu, W.E.Bake et al., J. Appl. Polym. Sci., 1996,62, 1807
45. Soga K,Nakatani H., Macromolecules, 1990,23 (4),957
46. Soga K,Nakatani H., Macromolecules, 1990,23(5), 1558
47. Imayoshi M, Arai T et al.,Jpn. Pat. 63-268709, 1988
48. Imayoshi M, Maeda K et al, ,Jpn. Pat. 02238008, 1990
49. Yamamoto K, Ishikawa K et al. Eur. Pat. Appl. EP 390000, 1990
50. J. C. W. Chien ,Z. Salajka, J. Polym Sci., Polym. Chem. Ed., 1991, 29, 1243
51．祝方明，贾虹等；中山大学学报(自然科学版)，2001，40(2)，62
52．潘祖仁；《高分子化学》；化学工业出版社，北京，1997
53. MT. Malanga and T.H.Newman,U.S.Pat.4950724,1990
54．黄鹤，李建宗等；中国胶粘剂；1996，6(2)，46
55．张洪涛；高分子材料；1996，3(1)，26
56. EP328975, Idemitsu Petrochemical Co. Ltd., 1989
57. EP379128, Idemitsu Petrochemical Co. Ltd., 1990
58．JP08283312，旭化成工业株式会社，1996
59. CN1045977, The Dow Chemical Company, 1990
60. JP03020308, Idemitsu Petrochemical Co. Ltd., 1991
61. EP535582, Idemitsu Petrochemical Co. Ltd., 1992
62．JP08208713，旭化成工业株式会社，1996
63. C.De. Rosa ,M.Rapacciuolo, et al; Polymer 1992,.33(7), 1423
64. O.Greis, Y. Xu, et al.; Polymer, 1989,30, 590
65. C.De Rosa; Macromolecules, 1996, 29, 8460
66. R.Napolitano and B.Pirozzi; Macromolecules, 1993,26,7225
67. Y. Chatani,Y Shimane et al;Polymer, 1993,34,1620
68. F. De Candia, A. R. Russio,et al., Polym. Comm. 32, 306, 191
69. F. Auriemma, V. Petraccone, G Guerra. Macromolecules, 1993,26, 3772,
70．刘伟；浙江大学博士学位论文，1999
71．方志刚；浙江大学硕士学位论文，2000
72．邹盛欧；现代化工，1996，11，48
73．N.V.Gvozdi, D. J. Meier. Polym. Commun., 1991, 32(16), 493,
74．焦宁宁；甘肃化工，1998，2，6
75．浦鸿汀，沈志刚等；中国塑料，2000，12，1
76．J.A.迪安，《兰氏化学手册》，科学出版社，第一版，1991
77．卢焕章等，《石油化工基础数据手册》，化学工业出版社，第一版，1982
78．马沛生等，《石油化工基础数据手册续编》，化学工业出版社，第一版，1993
79．杨始堃，钟俊文；高分子学报，1993，2，195
80．黄炎明，匡志祥；合成纤维工业，1986，9(1)，9
81．吕美娟，马蓉；合成纤维工业，1988，11(1)，30
82．K.Tsutsui, Y.Tsujita, et al.; Polymer,1998,39(21), 5177,
83．窦红静，朱诚身等：高分子通报，2000，9，56
84．F. Deberdt,H.Berghams, Polymer, 1993,34(10), 2192
85. Cheng D. C-H; Chemistry and Industry, 1980, 17, 403
86．阎卫东，刘立新等；应用化学，2001，18(2)
87. G.Guerra, V.M.Vitagliano; Macromolecules, 1990,23,1539