稀土催化苯乙烯配位聚合制备富含间规聚苯乙烯

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2.8×10⁵～6.8×10⁵ g·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0.5×10⁴～5.0×10⁵ g·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℃。

Synthesis of syndiotactic-rich polystyrene with neodymium-based catalyst

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, 2.8×10⁵-6.8×10⁵ g·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, 0.5×10⁴-5.0×10⁵ g·mol^-1). The syndiotacticity of PS products was around 60% and their melting points ranged from 170℃ to 240 ℃.