席夫碱铝双核配合物的合成及其对ε-己内酯的催化作用  

Synthesis and Structure of Dimeric Schiff Base Aluminum Complex and Its Catalysis on Ring-opening Polymerization of ε-Caprolactone

作　　者：李良钊[1] 尚晓敏[2] 杜鸿志[1] 崔冬梅[1] 陈学思[1] 景遐斌[1] 

机构地区：[1]中国科学院长春应用化学研究所高分子物理与化学国家重点实验室 [2]长春工业大学高分子材料教研室

出　　处：《应用化学》2007年第8期878-882,共5页Chinese Journal of Applied Chemistry

基　　金：国家自然科学面上基金资助项目(20571072);吉林省科技厅应用基础资助项目(20050555)

摘　　要：采用中性双席夫碱配体与异丙氧基铝反应制备了席夫碱铝配合物。经NMR和X射线晶体结构衍射分析证明,该配合物是双核结构。席夫碱配体上的氧和氮原子同时与铝原子配位形成独立单元。2个铝单元由甲氧基基团桥联形成双金属结构。其中铝原子与甲氧基氧原子构成一个平行四边形,它也包含该配合物分子的对称中心。该配合物可以催化ε-己内酯开环聚合。动力学研究表明,单体的转化率和聚合产物的数均分子量均随反应时间的延长而线性增加,并与理论计算值接近,而分子量分布没有明显变化,反应呈活性聚合的特征。NMR分析证明,寡聚物的端基为甲氧基和羟基,因此聚合反应为配位插入机理。A Schiff-base ligated aluminum propoxide） s with a neutral Schiff-base com dimmer. Aluminum ion is coordinated with complex was synthesized by the treatment of aluminum tris （isopound. NMR and X-ray analyses nitrogen and oxygen atoms from the reveal that the compound is a ligand to form a unit. The two units are bridged by methoxy groups to generate a bimetallic structure. The aluminum ion and methoxy oxygen form a rhombus core that contains the symmetry center of the molecule. The complex shows efficient activity towards the ring-opening polymerization of ε-caprolactone to give a biodegradable polylactone. Dynamic analysis shows that both the conversion of monomer and molecular mass of the resultant polymer increase linearly with reaction time, and the molecular mass fits well with the theoretical value, while the molecular mass distribution keeps unchanged, indicating a living polymerization fashion. The end groups of the oligomeric product were characterized by NMR spectroscopic analysis. One is methoxy derived from initiator Al-OCH3 while the other is hydroxyl from terminator methanol, suggesting a coordination insertion mechanism.

关 键 词：席夫碱 铝金属配合物 Ε-己内酯 聚合 催化作用 

分 类 号：O633[理学—高分子化学]