Synthesis of syndiotactic-rich polystyrene with neodymium-based catalyst

ZHU Han; WANG Hejin; CAI Chunyang; WU Yixian

doi:10.11949/j.issn.0438-1157.20150665

您当前的位置：

首页 >

文章列表页 >

Synthesis of syndiotactic-rich polystyrene with neodymium-based catalyst

更新时间：2025-12-10

- Synthesis of syndiotactic-rich polystyrene with neodymium-based catalyst
- CIESC Journal Issue 8, Pages: 3084-3090(2015)
- 作者机构：
  
  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
- 作者简介：
- 基金信息：
- DOI：10.11949/j.issn.0438-1157.20150665
  CLC： Q325.2
- Online First：05 August 2015，
  
  Published：05 August 2015
- 稿件说明：
移动端阅览
ZHU Han, WANG Hejin, CAI Chunyang, et al. Synthesis of syndiotactic-rich polystyrene with neodymium-based catalyst[J]. CIESC Journal, 2015, (8): 3084-3090.
DOI：

ZHU Han, WANG Hejin, CAI Chunyang, et al. Synthesis of syndiotactic-rich polystyrene with neodymium-based catalyst[J]. CIESC Journal, 2015, (8): 3084-3090. DOI： 10.11949/j.issn.0438-1157.20150665.

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(Mn)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(Mn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℃。

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 (Mn

2.8×105—6.8×105 g·mol-1) and high melting point (Tm

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 (Mn

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 ℃.

关键词

Keywords

references

Views

286

下载量

CSCD

Alert me when the article has been cited

提交

Tools

Publicity Resources

Alumina structure and surface property regulation for catalyzing methanol dehydration to dimethyl ether

Research progress on catalytic dehydrogenation of dodecahydro-N-ethylcarbazole as liquid organic hydrogen carrier

Advances in nickel catalyzed controlled/living radical polymerization reactions

Advances on continuous synthesis of topological polymers in microreactors

Connection between kinetics and particle formation process of vinyl chloride SET-DT suspension polymerizations

Related Author

LUO Li

CHEN Wenyao

ZHANG Jing

QIAN Gang

ZHOU Xinggui

DUAN Xuezhi

FAN Yiwei

LIU Wei

Related Institution

State Key Laboratory of Chemical Engineering, School of Chemical Engineering, East China University of Science and Technology

State Key Laboratory of Chemical Engineering, Department of Chemical Engineering, Tsinghua University

Ningbo Innovation Center, Zhejiang University

College of Chemical &Biological Engineering, Zhejiang University

School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, Shanghai Jiao Tong University

⁰