稀土催化苯乙烯配位聚合制备富含间规聚苯乙烯

doi:10.11949/j.issn.0438-1157.20150665

化工学报 ›› 2015, Vol. 66 ›› Issue (8): 3084-3090.DOI: 10.11949/j.issn.0438-1157.20150665

• 催化、动力学与反应器 • 上一篇下一篇

稀土催化苯乙烯配位聚合制备富含间规聚苯乙烯

朱寒, 王和金, 蔡春杨, 吴一弦

北京化工大学化工资源有效利用国家重点实验室, 碳纤维及功能高分子教育部重点实验室, 北京 100029

收稿日期:2015-05-21 修回日期:2015-05-31 出版日期:2015-08-05 发布日期:2015-08-05
通讯作者: 吴一弦
基金资助:
国家重点基础研究发展计划项目(2011CB606004);国家自然科学基金项目(51221002,51273011)。

Synthesis of syndiotactic-rich polystyrene with neodymium-based catalyst

ZHU Han, WANG Hejin, CAI Chunyang, WU Yixian

State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China

Received:2015-05-21 Revised:2015-05-31 Online:2015-08-05 Published:2015-08-05
Supported by:
supported by the National Basic Research Program of China(2011CB606004)and the National Natural Science Foundation of China (51221002,51273011).

摘要/Abstract

摘要：

由稀土羧酸盐(RE)、烷基铝(AL)与含氯活化剂(CL)组成的催化体系用于苯乙烯(St)定向聚合,研究了催化剂配比及反应条件对苯乙烯聚合反应动力学和产物结构的影响,采用凝胶渗透色谱仪(GPC)、核磁共振波谱仪(¹³C NMR)、偏光显微镜(POM)及差示扫描量热仪(DSC)等分析测试手段表征聚苯乙烯(PS)的分子量及其分布、立构规整度、结晶性及热性能。实验结果表明:含氯活化剂为氯代羧酸酯(CE)时,聚合速率对单体浓度均呈现一级动力学关系, 表观增长活化能为34.4 kJ·mol^-1,可得到数均分子量(M_n)为2.8×10⁵～6.8×10⁵g·mol^-1、熔点为160～260℃的可结晶聚苯乙烯。对于CE与卤代烃(RX)复合的催化体系,可明显提高催化活性,当聚合温度为50、60、70℃时,表观增长速率常数可分别提高3.9倍、5.6倍及9.2倍,分子量降低(M_n为0.5×10⁴～5.0×10⁵g·mol^-1),并可得到间规度[rrrr]约为60%的可结晶聚苯乙烯,熔点为170～240℃。

关键词: 催化剂, 聚苯乙烯, 聚合, 间规度, 动力学

Abstract:

Stereospecific polymerization of styrene (St) was carried out with a rare earth catalyst system which consisting of rare earth carboxylate (RE), alkyl aluminium (AL) and chlorinating agent (CL). The influences of catalyst systems on polymerization of styrene, kinetics and microstructure of the resulting polystyrene (PS) were investigated. The resulting molecular weight and its distribution, syndiotacticity, crystalline morphology and heat capacity of polystyrene were characterized by GPC, ¹³C NMR, POM and DSC. The results show that styrene polymerization rate was first-order with respect to monomer concentration with RE/AL/chlorinated carboxylic ester (CE) catalyst system, and the apparent propagation activation energy was determined to be 34.4 kJ·mol^-1. The multiblock atactic/syndiotactic PS products with high molecular weight (M_n, 2.8×10⁵—6.8×10⁵g·mol^-1) and high melting point (T_m, 160—260℃) could be obtained using RE/AL/CE. The catalytic activity could be further improved using the mixture of CE with chlorinated hydrocarbon (RX) as chlorinating agent. The apparent propagation rate constants were 3.9, 5.6 and 9.2 times larger than those of RE/AL/CE at 50, 60 and 70℃ respectively. The molecular weight of PS decreased to relatively low molecular weight (M_n, 0.5×10⁴—5.0×10⁵g·mol^-1). The syndiotacticity of PS products was around 60% and their melting points ranged from 170℃ to 240 ℃.

Key words: catalyst, polystyrene, polymerization, syndiotacticity, kinetics

中图分类号:

TQ325.2

朱寒, 王和金, 蔡春杨, 吴一弦. 稀土催化苯乙烯配位聚合制备富含间规聚苯乙烯[J]. 化工学报, 2015, 66(8): 3084-3090.

ZHU Han, WANG Hejin, CAI Chunyang, WU Yixian. Synthesis of syndiotactic-rich polystyrene with neodymium-based catalyst[J]. CIESC Journal, 2015, 66(8): 3084-3090.

参考文献 15

[1]	Du Qiangguo (杜强国). Handbook of Plastic Industry—Polystyrene (塑料工业手册——聚苯乙烯系树脂) [M]. Beijing: Chemical Industry Press, 2004: 85-86.
[2]	Tomotsu N, Ishihara N, Newman T H, Malanga M T. Syndiospecific polymerization of styrene [J]. J. Mol. Catal. A-Chem., 1998, 128: 167-190.
[3]	Handa Y Paul, Zhang Zhiyi, Wong Betty. Effect of compressed CO2 on phase transitions and polymorphism in syndiotactic polystyrene [J]. Macromolecules, 1997, 30 (26): 8499-8504.
[4]	Yang Mujie (杨慕杰), Zheng Hao (郑豪), Zhao Jian (赵健), Shen Zhiquan (沈之荃). Homopolymerization and copolymerization of styrene and divinylbenzene by rare-earth coordination catalysts [J]. Acta Polym. Sin. (高分子学报), 1990, 4: 441-446.
[5]	Yang Mujie, Cha Congxiang, Shen Zhiquan. Polymerization of styrene by rare earth coordination catalysts [J]. Polym. J., 1990, 22 (10): 919-923.
[6]	Zhao Jian, Yang Mujie, Zheng Yi, Shen Zhiquan. Polymer-supported rare-earth catalysts for polymerization of styrene [J]. Macromol. Chem., 1991, 192: 309-315.
[7]	Jiang Liming, Shen Zhiquan, Yang Yuhui, Zhang Yifeng. Synthesis of ultra-high molecular weight polystyrene with rare earth-magnesium alkyl catalyst system: several features of bulk polymerization [J]. Polym. Int., 2001, 50: 63-66.
[8]	Nie Jian (聂建), Zhang Yifeng (张一烽), Jiang Liming (江黎明), Shen Zhiquan (沈之荃). The synthesis of ultra-high molecular weight polystyrene and polymerization kinetics [J]. Acta Polym. Sin. (高分子学报), 2002, (2): 203-207.
[9]	Liu Li (刘丽), Zheng Yulian (郑玉莲), Gong Zhi (龚志), Jing Xiabin (景遐斌). Isospecific polymerization of styrene with rare earth catalyst [J]. Chinese J. Appl. Chem. (应用化学), 1997, 14 (5): 115-116.
[10]	Liu Li, Gong Zhi, Zheng Yulian, Jing Xiabin. Isospecific polymerization of styrene with rare earth catalyst [J]. J. Polym. Sci.: Part A: Polym. Chem., 1998, 36: 1773-1778.
[11]	Wang Jing, Wu Yixian, Xu Xu, Zhu Han, Wu Guanying. An activated neodymium-based catalyst for styrene polymerization [J]. Polym. Int., 2005, 54: 1320-1325.
[12]	Zhao Jiangwei (赵姜维), Wu Yixian (吴一弦), Wang Jing (王静), Zhu Han (朱寒), Wu Guanying (武冠英), Yang Wantai (杨万泰). Synthesis of high molecular weight polystyrene with a rare earth catalyst [J]. Acta Polym. Sin. (高分子学报), 2007, (3): 240-245.
[13]	Uryu T, et al. Synthesis of polystyrenes with different stereoregularities by anionic polymerization [J]. J. Polym. Sci.: Polym. Chem. Ed., 1976, 14 (12): 3035-3044.
[14]	Zhu Han, Wu Yixian, Zhao Jiangwei, Guo Qinglei, Huang Qigu, Wu Guanying. Styrene-butadiene block copolymer with high cis-1,4 microstructure [J]. J. Appl. Polym. Sci., 2007, 106: 103-109.
[15]	Zhu Han (朱寒), Bai Zhixin (白志欣), Zhao Jiangwei (赵姜维), Ling Ping (零萍), Wu Yixian (吴一弦). Synthesis of polyisoprene with high cis-1,4-content and narrow molecular weight distribution and polymerization kinetics [J]. Acta Polym. Sin. (高分子学报), 2012, (5): 571-579.

稀土催化苯乙烯配位聚合制备富含间规聚苯乙烯

Synthesis of syndiotactic-rich polystyrene with neodymium-based catalyst

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