高等学校化学学报

高等学校化学学报 ›› 2000, Vol. 21 ›› Issue (12): 1932.

• 论文 • 上一篇    下一篇

〆-氯代乙苯/TiCl4/Ti(OiPr)4引发β-蒎烯活性阳离子聚合

卢江, 梁晖, 张荣福   

  1. 中山大学化学与化学工程学院, 广州 510275
  • 收稿日期:1999-09-30 出版日期:2000-12-24 发布日期:2000-12-24
  • 通讯作者: 卢　江(1962年出生),男,博士,副教授,主要从事可控阳离子聚合研究.
  • 基金资助:

    国家自然科学基金(批准号:29874040);国家教育部优秀年轻教师基金资助

Living Cationic Polymerization of β-Pinene with1-Phenylethyl Chloride/TiCl4/Ti(OiPr)4

LU Jiang, LIANG Hui, ZHANG Rong-Fu   

  1. School of Chemistry and Chemical Engineering, Zhongshan University, Guangzhou 510275, China
  • Received:1999-09-30 Online:2000-12-24 Published:2000-12-24

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摘要： -40℃条件下,在CH2Cl2溶剂中以α-氯代乙苯为引发剂,TiCl4和Ti(OiPr)4混合物为Lewis酸活化剂,进行β-蒎烯阳离子聚合.单独使用强的Lewis酸TiCl4时,聚合反应在瞬间完成,聚合产物的分子量分布较宽.添加本身无催化活性的弱Lewis酸Ti(OiPr)4后,聚合反应减缓且聚合产物的分子量分布变窄.当Ti(OiPr)4/TiCl4摩尔比为1/3时,产物的分子量随单体转化率线性增加,且分子量分布较窄,显示出活性聚合特性.这种活性聚合特性由单体添加实验进一步得到证实

关键词: 活性阳离子聚合, &beta, -蒎烯, &alpha, -氯代乙苯, Ti(OiPr)4/TiCl4

Abstract: The cationic polymerization of β-pinene was carried out with1phenylethyl chloride as an initiator and the mixture of TiCl4and tetraisopropoxytitanium[Ti(OiPr)4] as a Lewis acid activator in CH2Cl2at -40 ℃. The polymerization with strong Lewis acid TiCl4alone completed instantaneously and gave the polymers with broad molecular weight distributions.The addition of weak Lewis acid Ti(OiPr)4, which alone had no catalytic activity for β pinene, retarded the polymerization by TiCl4and led to polymers with narrower molecular weight distributions.When [Ti(OiPr)4]0/[TiCl4]0=1/3, the number-average molecular weight of the polymers increased in direct proportion to monomer conversion, and the molecular weight distribution of the polymers was narrow.The living nature of the polymerization was further demonstrated by monomer-addition experiments.1H NMRanalysis of the polymers obtained at [Ti(OiPr)4]0/[TiCl4]0=1/3 showed that1-phenylethyl chloride served as an initiator and generated poly( β-pinene) chains with the CH3CH(C6H5) head group and a tert-Cl tail group

Key words: Living cationic polymerization, β-Pinene, 1-Phenylethyl chloride, TiCl4/Ti(OiPr)4

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