烯烃可控/活性正离子聚合新方法与新工艺及其应用

吴一弦; 周琦; 杜杰; 王楠

doi:10.11777/j.issn1000-3304.2017.17045

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烯烃可控/活性正离子聚合新方法与新工艺及其应用

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- 烯烃可控/活性正离子聚合新方法与新工艺及其应用
- Controlled/Living Cationic Polymerization of Olefins:System, Process and Application
- 高分子学报 2017年第7期页码：1047-1057
- 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：
  
  [ "吴一弦, 女, 1967年2月出生.1986年、1989年和1998年分别于北京化工大学获得学士学位、硕士学位和博士学位.1989~1997年北京化工大学讲师, 1997~2001年北京化工大学副教授, 2001年至今, 北京化工大学教授, 2009年被聘为教育部\"长江学者\"特聘教授, 兼任《科学通报》编委, 入选\"国家百千万人才工程\", 并被授予\"有突出贡献中青年专家\"荣誉称号.共同主编著书1部, 发表论文120余篇, 著书1部, 申请/授权发明专利110余件(其中, 国外发明专利25件), 获国家技术发明二等奖1项及省部级科技奖励8项, 获中国青年科技奖、中国青年女科学家奖、中国化学会高分子科学邀请报告荣誉奖及北京市\"三八\"红旗奖章.主要从事引发/催化体系构筑、可控正离子聚合与大分子工程、可控配位聚合与大分子工程、基于C4/C5资源的高分子材料设计合成研究, 并将可控正离子聚合方法、可控配位聚合方法及工程化研究成果实现两项万吨级产业化应用" ]
- 基金信息：
  
  国家自然科学基金(51521062);国家自然科学基金(20934001);国家自然科学基金(51221002)
- DOI：10.11777/j.issn1000-3304.2017.17045
  中图分类号：
- 纸质出版日期：2017-7，
  
  收稿日期：2017-3-9，
  
  修回日期：2017-4-3，
扫描看全文
吴一弦, 周琦, 杜杰, 王楠. 烯烃可控/活性正离子聚合新方法与新工艺及其应用[J]. 高分子学报, 2017,(7):1047-1057.

Yi-xian Wu, Qi Zhou, Jie Du, Nan Wang. Controlled/Living Cationic Polymerization of Olefins:System, Process and Application[J]. Acta Polymerica Sinica, 2017,(7):1047-1057.
吴一弦, 周琦, 杜杰, 王楠. 烯烃可控/活性正离子聚合新方法与新工艺及其应用[J]. 高分子学报, 2017,(7):1047-1057. DOI： 10.11777/j.issn1000-3304.2017.17045.

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