同双核钛茂金属催化甲基丙烯酸甲酯本体和溶液聚合  

Bulk and Solution Polymerization of Methyl Methacrylate by Novel Dinuclear Titallocene Catalyst

作　　者：李洪峰[1] 胡晓萍[1] 严小丽[1] 孙俊全[1] 

机构地区：[1]浙江大学材料与化学工程学院化工系,浙江杭州310027

出　　处：《化学反应工程与工艺》2007年第4期365-369,共5页Chemical Reaction Engineering and Technology

基　　金：国家自然科学基金(20374043;20396009)

摘　　要：合成了一种新的同双核钛茂金属催化剂[（CH3C5H4）TiCl2]2[C5H4CH2CH2OCH2CH2C5H4]（A），用元素分析和1^H-NMR进行了表征。在助催化剂的作用下，该催化剂体系可有效催化甲基丙烯酸甲酯（MMA）本体和溶液聚合。考察了助催化剂、反应温度和时间对聚合的影响。结果表明，Al（i-Bu）3催化性能优于Al（Et）3和甲基铝氧烷（MAO）。以Al（i-Bu）3为助催化剂，本体聚合在MMA和A的摩尔比为1500，Al（i-Bu）3和A的摩尔比为20，60℃，反应时间20h条件下，单体转化率达98．6％，PMMA的粘均分子量为7．87×10^5；溶液聚合在MMA和A的摩尔比为1500，Al（i-Bu）3和A的摩尔比为20，80℃，反应时间15h条件下，单体转化率77．3％，PMMA的粘均分子量3．24×10^5。聚合所得PMMA分子量分布为5．0～7．0。A new dinuclear titanocene complex [（CH3C5H4）TiCl2-]2[C5H4CH2CH2OCH2CH2C5H4] （A） was synthesized and characterized by elementary analysis and 1^H-NMR spectrometry. In combination with the cocatalyst of Al（Et）3, methylaluminoxane （MAO） and Al（i-Bu）3, A was active to initiate methyl methacrylate （MMA） bulk and solution polymerization. The influences of cocatalyst, reaction time and temperature on polymerization were studied in detail. The result showed that Al（i-Bu）3 was the best cocatalyst. In combination with cocatalyst of Al（i-Bu）3, under the polymerization conditions of molar ratio of MMA to A 1 500, molar ratio of Al（i-Bu）3 to A 20, 60 ℃, reaction time 20 h, the conversion of MMA and the viscosity average molecular weight of PMMA of bulk polymerization were 98.6% and 7.87 × 10^5 repectively; under the polymerization conditions of molar ratio of MMA to A 1500, molar ratio of Al（i-Bu）3 to A 20, 80 ℃, reaction time 15 h, the conversion of MMA and the viscosity average molecular weight of PMMA of solution polymerization were 77.3 % and 3.24× 10^5 respectively. The molecular weight distribution （MWD） of PMMA was 5.0 -7.0.

关 键 词：双核茂金属催化剂 甲基丙烯酸甲酯 本体聚合 溶液聚合 

分 类 号：O627.43[理学—有机化学]