Controlled/Living Cationic Polymerization of Olefins:System, Process and Application

Yi-xian Wu; Qi Zhou; Jie Du; Nan Wang

doi:10.11777/j.issn1000-3304.2017.17045

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Controlled/Living Cationic Polymerization of Olefins:System, Process and Application

Feature Articles | 更新时间：2021-01-26

- Controlled/Living Cationic Polymerization of Olefins:System, Process and Application
- Acta Polymerica Sinica Issue 7, Pages: 1047-1057(2017)
- 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北京 100029
- 作者简介：
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2017.17045
  CLC：
- Published：2017-7，
  
  Received：9 March 2017，
  
  Revised：3 April 2017，
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Yi-xian Wu, Qi Zhou, Jie Du, Nan Wang. Controlled/Living Cationic Polymerization of Olefins:System, Process and Application. [J]. Acta Polymerica Sinica (7):1047-1057(2017)
DOI：

Yi-xian Wu, Qi Zhou, Jie Du, Nan Wang. Controlled/Living Cationic Polymerization of Olefins:System, Process and Application. [J]. Acta Polymerica Sinica (7):1047-1057(2017) DOI： 10.11777/j.issn1000-3304.2017.17045.

摘要

正离子聚合是高分子科学中重要的聚合方法之一，也是制备聚异丁烯或丁基橡胶等关键材料不可或缺的聚合方法.本文总结了异丁烯、苯乙烯及其衍生物等单体可控/活性正离子聚合的新引发体系、聚合反应特征的调节与转化、水相介质中正离子聚合新方法与新工艺、微观分子混合与正离子聚合新工艺及其用于设计合成异丁烯基聚合物.这些方法与技术是发展高效节能与绿色减排先进聚合物生产技术的重要途径，部分研究成果已在产业化中得到应用与验证.发展可控/活性正离子聚合新体系、新方法与新工艺，为实现绿色低碳高分子化工过程及相关产品工程（新结构、新功能、高性能与高品质）提供了新思路与新技术.

Abstract

Cationic polymerization is one of the most important polymerization methods in polymer science. Polyisobutylene (PIB) and butyl rubber (ⅡR) with excellent properties in gas barrier

chemical and thermal stability

and resistance to oxidation are useful materials for automotive manufacture and medical equipment. These polymers can be merely produced by cationic polymerization of isobutylene or its copolymerization with a small amount of isoprene under strictly anhydrous conditions. The living cationic polymerizations of olefins

such as isobutylene

styrene and its derivatives

have been achieved to synthesize the corresponding polymes with theoretical molecular weight and chlorine terminal groups by using BCl

or TiCl

as coinitiator since 1980's. This feature article is aimed to summarize the novel initiating systems for the controlled/living cationic polymerizations

transformation of polymerization character

cationic polymerization in aqueous medium with high efficiency

cationic polymerization in rotating packed bed reactor and their applications. A simple but effective FeCl

-based initiating system with low toxicity has been developed to achieve living cationic polymerization of isobutylene in the presence of isopropanol at -80℃ at much lower coinitiator concentration. It has been recognized that the living cationic polymerization could be converted to the chain-transfer dominated process

in which the rate of

-proton elimination from-CH

groups in the growing chain ends and the chain transfer reaction to monomer were dependent on the concentrations of the complex of Lewis acid with nucleophiles or free nucleophile molecules and polymerization temperature. Based on this observation

a series of initiating systems have been developed for direct synthesis of highly reactive polyisobutylenes with more than 90 mol% of

exo

-olefin terminal groups. On the other hand

the cationic stereospecific polymerization of styrene and

-methylstyrene has been achieved by mediating the tightness of the growing ion pair

conformation of the last two units of the propagating polymer segment and the approaching direction of the incoming monomer

leading to formation of high molecular weight polymers with predominant isotacticity of more than 80% for meso dyad (

). The long-chain branched isotactic-rich polystyrene was

in situ

synthesized

via

cationic stereospecific polymerization of styrene by introducing a small amount of isoprene as a comonomer and branching sites as well. The environmental problems demand clean reaction processes and do use environmental friendly reaction media

in which water is no doubt the most valuable green medium. We presented the first example of highly effective cationic polymerization of IB using classic Lewis acid-based initiating systems in aqueous medium. The new continuous process of cationic polymerization in aqueous medium has been further scaled up for preparing high molecular weight PIB or butyl rubber. The cationic polymerization in the high-gravity environment generated by a rotating packed bed reactor has been successfully conducted for the first time to produce high molecular weight butyl rubber. The controlled/living cationic polymerization provides a cost-effective method to synthesize polymers with designed architecture and will be beneficial for the resulting polymer product engineering

including new chemical structure and topology

new functionality

high performance and high quality.

关键词

正离子聚合可控/活性聚合聚异丁烯丁基橡胶

Keywords

Cationic polymerizationControlled/Living polymerizationPolyisobutyleneButyl rubber

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Related Institution

Department of Material Science and Engineering, Beijing Institute of Petrochemical Thechnology Beijing

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北京化工大学化工资源有效利用国家重点实验室

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

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