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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
邱迎昕(1971-),女,吉林市人,北京化工大学高分子化学与物理专业博士研究生,研究方向为异丁烯可控阳离子聚合及其大分子设计;
*E-mail:yxwu@263∙net.
纸质出版日期:2006-10,
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邱迎昕, 吴一弦, 张成龙, 朱寒, 武冠英. TiCl4 共引发乙烯基单体正离子聚合反应动力学及其机理[J]. 高分子通报, 2006,19(10):16-22,81.
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, 2006,19(10):16-22,81.
邱迎昕, 吴一弦, 张成龙, 朱寒, 武冠英. TiCl4 共引发乙烯基单体正离子聚合反应动力学及其机理[J]. 高分子通报, 2006,19(10):16-22,81. DOI: 10.14028/j.cnki.1003-3726.2006.10.003.
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, 2006,19(10):16-22,81. DOI: 10.14028/j.cnki.1003-3726.2006.10.003.
TiCl
4
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
5
-
与另一个TiCl
分子进一步反应则形成双分子反离子Ti
2
Cl
9
导致TiCl
表现为二级动力学关系的机理。
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
.
正离子聚合机理动力学异丁烯苯乙烯
Cationic polymerizationMechanismKineticsStyreneIsobutylene
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