Kinetics and Mechanism of TiCl<sub>4</sub> Coinitiating Cationic Polymerization of Vinyl Monomer

Ying-xin QIU; Yi-xian WU; Cheng-long ZHANG; han ZHU; Guan-ying WU

doi:10.14028/j.cnki.1003-3726.2006.10.003

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Kinetics and Mechanism of TiCl₄ Coinitiating Cationic Polymerization of Vinyl Monomer

更新时间：2022-09-18

- Kinetics and Mechanism of TiCl₄ Coinitiating Cationic Polymerization of Vinyl Monomer
- Polymer Bulletin Vol. 19, Issue 10, Pages: 16-22,81(2006)
- 作者机构：
  
  北京化工大学　教育部“可控化学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.1003-3726.2006.10.003
  CLC：
- Published：2006-10，
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Ying-xin QIU, Yi-xian WU, Cheng-long ZHANG, han ZHU, Guan-ying WU. Kinetics and Mechanism of TiCl₄ Coinitiating Cationic Polymerization of Vinyl Monomer. [J]. Polymer Bulletin 19(10):16-22,81(2006)
DOI：

Ying-xin QIU, Yi-xian WU, Cheng-long ZHANG, han ZHU, Guan-ying WU. Kinetics and Mechanism of TiCl₄ Coinitiating Cationic Polymerization of Vinyl Monomer. [J]. Polymer Bulletin 19(10):16-22,81(2006) DOI： 10.14028/j.cnki.1003-3726.2006.10.003.

摘要

TiCl

共引发异丁烯（IB）或苯乙烯（St）进行正离子聚合

聚合反应速率与共引发剂TiCl

之间可呈一级和二级动力学关系

这与TiCl

浓度（［TiCl

］）、单体浓度、亲核试剂的亲核性等多方面因素有关。单分子TiCl

与休眠分子链末端进行离子化反应并产生活性中心碳正离子和反离子TiCl

－

TiCl

－

与另一个TiCl

分子进一步反应则形成双分子反离子Ti

－

导致TiCl

表现为二级动力学关系的机理。

Abstract

The kinetics and mechanism of TiCl

coinitiating cationic polymerization of isobutylene (IB) or styrene (St) were discussed in this paper.The reaction order with respect to TiCl

could be either first-order or second-order due to the affection of the concentration of TiCl

or monomer

the donicity of electron donors

etc.And it has been suggested that the second-order dependency on TiCl

was attributed to the dimeric gegenions which formed via monomeric TiCl

ionizing a dormant tert-alkyl chloride chain end to create an activated chain with a monomeric gegenion TiCl

and then the monomeric gegenion reacted with another molecule of TiCl

to form the dimeric gegenion Ti

关键词

正离子聚合机理动力学异丁烯苯乙烯

Keywords

Cationic polymerizationMechanismKineticsStyreneIsobutylene

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Kinetics and Mechanism of TiCl4 Coinitiating Cationic Polymerization of Vinyl Monomer

DOI：10.14028/j.cnki.1003-3726.2006.10.003

摘要

Abstract

关键词

Keywords

references

Kinetics and Mechanism of TiCl₄ Coinitiating Cationic Polymerization of Vinyl Monomer