新型同双核钛茂金属催化MMA本体聚合  

Bulk polymerization of methyl methacrylate by novel dinuclear titanocene catalyst systems.

作　　者：郎五可[1] 孙俊全[1] 林峰[1] 张海英[1] 余肖臻[1] 

机构地区：[1]浙江大学联合化学反应工程研究所,浙江杭州310027

出　　处：《浙江大学学报（理学版）》2007年第1期50-55,共6页Journal of Zhejiang University（Science Edition）

基　　金：国家自然科学基金资助项目(批准号20374043);中国石油化工股份有限公司资助项目(X503027);国家自然科学重大基金资助项目(批准号20396009)

摘　　要：合成了两个新的同双核钛茂金属催化剂:[(C5H5)TiCl2]2[C5H4CH2CH2OCH2CH2C5H4](A)和[(C5H5)TiCl2]2[C5H4CH2C6H4C6H4CH2C5H4](B),以元素分析和1H-NMR对配合物进行了表征.在Al(i-Bu)3的助催化下,A,B两个催化剂均可有效催化MMA本体聚合.详细考察了聚合时间、温度、nAl/nCat和nMMA/nCat对反应的影响.这两个催化体系的聚合转化率均可以达到85%左右.A/Al(i-Bu)3催化体系在聚合条件nMMA/nCat=2000,nAl/nCat=20,T=60℃,t=15 h下,所得PMMA的Mn可以达到34×104,相对分子质量分布1.68,间同质量分数68%;B/Al(i-Bu)3催化体系在聚合条件nMMA/nCat=1500,nAl/nCat=10,T=60℃,t=15 h下,所得PMMA的Mn可以达到8×104,相对分子质量分布8.04,间同质量分数76%.Two new dinuclear titanocene complexes（C5 H5 ） TiCl2 ]2 [C5H4CH2CH2OCH2CH2C5 H4 ] （A） and [（C5 H5 ）TiCl2]2[C5 H4 CH2 C5 H4 C5 H4 CH2 C5 H4 ] （B） were synthesized and well characterized by element analysis and 1 H-NMR spectrometry. In combination with Al（i-Bu）3, both A and B were active to initiate methyl methacrylate （MMA） polymerization. The influence of reaction parameters such as A1/Cat molar ratio, MMA/Cat molar ratio, time and temperature on polymerization was examined in detail. The polymerization conversion by both A/Al（i-Bu）3 and B/Al（i-Bu） reached as high as around 85%. The Mn and MWD of PMMA obtained by A/AI（i-Bu）3 and B/Al（i-Bu）3 were 34 ×^ 10^4/8 × 10^4 and 1.68/8.04, respectively, under their respective polymerization condition （A/ Al（i-Bu）3 system, nMMA/nCat=2000, nAl/nCat=20, T=60℃, t=15 h B/Al（i Bu）3 system, nMMA/nCat= 1500, nAl/nCat 10, T 60℃, t=15 h）. From IR analysis, the syndiotactic contents of PMMA obtained by A and B were about 68% and 76%, respectively.

关 键 词：双核茂金属 本体聚合 甲基丙烯酸甲酯 金属有机催化剂 

分 类 号：O643.3[理学—物理化学] TQ211[理学—化学]