Mechanistic Roles of Nucleophiles in the Carbocationic Polymerization of Isobutylene

Han ZHU; Yi-xian WU; Xu XU; Guan-ying WU

doi:10.14028/j.cnki.1003-3726.2004.03.001

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Mechanistic Roles of Nucleophiles in the Carbocationic Polymerization of Isobutylene

更新时间：2022-09-18

- Mechanistic Roles of Nucleophiles in the Carbocationic Polymerization of Isobutylene
- Polymer Bulletin Vol. 17, Issue 3, Pages: 1-7,13(2004)
- 作者机构：
  
  北京化工大学教育部“可控聚合反应科学与技术基础”重点实验室，北京　100029
- 作者简介：
- 基金信息：
- DOI：10.14028/j.cnki.1003-3726.2004.03.001
  CLC：
- Published：2004-06，
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Han ZHU, Yi-xian WU, Xu XU, Guan-ying WU. Mechanistic Roles of Nucleophiles in the Carbocationic Polymerization of Isobutylene. [J]. Polymer Bulletin 17(3):1-7,13(2004)
DOI：

Han ZHU, Yi-xian WU, Xu XU, Guan-ying WU. Mechanistic Roles of Nucleophiles in the Carbocationic Polymerization of Isobutylene. [J]. Polymer Bulletin 17(3):1-7,13(2004) DOI： 10.14028/j.cnki.1003-3726.2004.03.001.

摘要

亲核性调节剂在异丁烯活性阳离子聚合中发挥着极其重要的作用，其作用机理主要包括：（1）碳阳离子稳定化作用，即亲核性试剂或它们与Lewis 酸生成的络合物与增长链的末端结合，来降低活性中心阳离子的“阳离子性”，抑制副反应，使聚合反应呈现活性聚合特征；（2）质子捕获作用，即亲核性试剂捕获质子，抑制质子的不可控引发和链转移反应；（3）增长链表观稳定作用，即亲核试剂降低了增长速率与引发速率之比，提高引发效率，降低增长速率，降低分子量分布；（4）抑制自由离子增长作用，即亲核试剂与质子源和Lewis 酸反应，生成同阴离子，产生同离子效应，抑制自由离子活性中心的引发增长作用。

Abstract

The mechanistic roles of nucleophiles in living carbocationic polymerization of isobutylene were reviewed.There are4mechanisms: A.The "carbocation stabilization" -nucleophiles and/or their complexes with Lewis acid interact with the growing chain end to reduce its "cationicity" and the reduction in cationicity to decrease the polymerization rate

suppress chain transfer and termination reactions; B.The "proton-scavenging" - the removal of protic impurities by externally added nucleophiles and the elimination of "induced" chain transfer; C.The "apparent stabilization of the growing chain ends" - the reduction in the instantaneous carbocation concentration; D.The "suppression of free ions" - the common ions in situ production via the scavenging of protic impurities.

关键词

碳阳离子聚合亲核试剂活性聚合异丁烯

Keywords

Cationic polymerizationNucleophilesLiving polymerizationIsobutylene

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