高等学校化学学报 ›› 2015, Vol. 36 ›› Issue (4): 794.doi: 10.7503/cjcu20140849

• 高分子化学 • 上一篇    下一篇

甲氧基桥联的铝-锂杂金属配合物的合成、 表征及在催化ε-己内酯开环聚合中的应用

王磊(), 杨丽, 高承永   

  1. 西北师范大学化学与化工学院, 甘肃省高分子材料重点实验室, 兰州 730070
  • 收稿日期:2014-09-18 出版日期:2015-04-10 发布日期:2015-03-18
  • 作者简介:联系人简介: 王 磊, 男, 博士, 讲师, 主要从事催化与可控聚合研究. E-mail: wanglei030@hotmail.com
  • 基金资助:
    甘肃省科技计划(批准号: 145RJZA188)、 青年教师提升计划(批准号: 145RJZA188)和甘肃省高等学校基本科研业务费资助

Synthesis, Characterization of Methoxyl-bridged Aluminium-lithium Heterobimetallic Complex and Catalysis for the Ring-opening Polymerization of ε-Caprolactone

WANG Lei*(), YANG Li, GAO Chengyong   

  1. Key Laboratory of Eco-Environment-Related Polymer Materials, Ministry of Education of China,Key Laboratory of Gansu Polymer Materials, College of Chemistry and Chemical Engineering,Northwest Normal University, Lanzhou 730070, China
  • Received:2014-09-18 Online:2015-04-10 Published:2015-03-18
  • Contact: WANG Lei E-mail:wanglei030@hotmail.com
  • Supported by:
    † Supported by the Gansu Provincial Natural Science Foundation of China(No.145RJZA188), the Young Teacher Research Foundation of Northwest Normal University, China(No.NWNU-LKQN-13-3) and the Fundamental Research Funds for Gansu Universities, China

摘要:

以四氢呋喃为溶剂, 将2,6-二(3,5-二叔丁基-2-羟苯甲基)-4-叔丁基苯酚(H3-L)与正丁基锂和三甲基铝以摩尔比1:1:1进行络合反应, 合成了甲基铝锂杂金属配合物[(L)Al(CH3)Li], 利用空气中的氧气氧化甲基铝锂杂金属配合物, 得到甲氧基桥联的铝-锂杂金属配合物[(L)Al(μ2-OMe)Li(THF)3]2(1), 并表征了其结构. 将配合物1应用于ε-己内酯的开环聚合, 考察其催化性能. 结果表明, 在敞开体系下, 配合物1催化ε-己内酯开环聚合仍然能够得到较高的单体转化率和较窄的聚酯分子量分布.

关键词: 甲氧基, 铝-锂杂金属配合物, 催化剂, ε-己内酯, 开环聚合, 聚己内酯

Abstract:

The methoxyl-bridged aluminium-lithium heterobimetallic complex [(L)Al(μ2-OMe)Li(THF)3]2(1) was synthesized and structurally characterized. Reaction of 2,6-bis(3,5-bis-t-butyl-2-hydroxybenzyl)-4-t-butyl phenol(H3-L) with n-BuLi and Al(CH3)3 in a molar of ratio 1:1:1 in THF provides methyl-aluminium-lithium phenoxide [(L)Al(CH3)Li]. Oxidation of the phenoxide by O2 in air gives target product 1 in quantitative yield. Catalysis by complex 1 for ring-opening of ε-caprolactone(ε-CL) was studied. Experimental results indicate that complex 1 could catalyze ε-CL with high conversion and narrow polydispersity even in an air atmosphere.

Key words: Methoxyl, Heterobimetallic complex, Catalysis, ε-Caprolactone, Ring-opening polymerization, Polycaprolactone

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