化学学报 ›› 2011, Vol. 69 ›› Issue (05): 591-595. 上一篇    下一篇

研究简报

叶立德活性聚合制备基于聚亚甲基的大分子单体

赵亮1,2,陈健壮2,史丽萍2,陈蔚红2,李光玉2王玉东*,1,马志*,2   

  1. (1郑州大学材料科学与工程学院 郑州 450052)
    (2中国科学院上海有机化学研究所 上海 200032)
  • 收稿日期:2010-09-20 修回日期:2010-11-01 出版日期:2011-03-14 发布日期:2010-11-12
  • 通讯作者: 马志 E-mail:mazhi728@sioc.ac.cn

Synthesis of Polymethylene-based Macromonomer by Living Polymerization of Ylides

Zhao Liang1,2 Chen Jianzhuang2 Shi Liping2 Chen Weihong2 Li Guangyu2 Wang, Yudong*,a Ma, Zhi*,b   

  1. (1 School of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450052)
    (2 Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032)
  • Received:2010-09-20 Revised:2010-11-01 Online:2011-03-14 Published:2010-11-12

利用叶立德活性聚合方法制备了两种基于聚亚甲基的大分子单体. 其中一种是以叶立德活性聚合制备的主链链端含有羟基的聚亚甲基(PM-OH)为原料, 通过链端羟基的基团转换, 得到链端含有甲基丙烯酸酯基的大分子单体. 另一种则是以硼烷-四氢呋喃(BH3-THF)和二乙烯基苯反应得到的三烷基硼中间体为催化剂和引发剂, 然后进行叶立德活性聚合, 再经过二水合氧化三甲胺(TAO)的氧化, 最终得到基于聚亚甲基的一端含有羟基另一端含有苯乙烯基的大分子单体. 通过高温核磁氢谱、傅立叶红外光谱和高温凝胶色谱法表征了这两种大分子单体的链结构和分子量及其分布.

关键词: 叶立德活性聚合, 聚烯烃功能化, 大分子单体

Two kinds of polymethylene-based macromonomers were prepared by living polymerization of ylides. One macromonomer PM-methacrylate was obtained by the transformations of hydroxyl group at the chain end of polymethylene obtained by living polymerization of ylides. The other macromonomer PM-styryl was synthesized via living polymerization of ylides which initiated by organoborane which was prepared by hydroboration of divinylbenzene, and after the oxidation by trimethylamine-N-oxide dehydrate (TAO), α-p-vinylphenyl-ω-hydroxypolymethylene were obtained. The chain structure, molecular weight and its distribution of the two macromonomers were investigated by high temperature 1H NMR spectra, FT-IR and high temperature GPC.

Key words: living polymerization of ylides, functionalization of polyolefin, macromonomer