催化引发原子转移自由基聚合活化能的研究  

STUDY ON THE ACTIVATION ENERGY OF ATOM TRANSFER RADICAL POLYMERIZATION CATALYZED BY COMPLEX

作　　者：张敏[1] 朱丽荣[1] 郭蔚晖[1] 黄家贤[1] 

机构地区：[1]南开大学化学系,天津300071

出　　处：《南开大学学报（自然科学版）》2004年第4期25-30,共6页Acta Scientiarum Naturalium Universitatis Nankaiensis

基　　金：南开大学人事处科研启动基金资助项目

摘　　要：选择引发剂为氯代苯乙烷或溴代丙酸乙酯、过渡金属化合物为氯化亚铜或溴化亚铜、配体为设计合成的二哌啶乙烷或双正丙基亚砜乙烷的催化引发体系,研究不同温度下开放体系中苯乙烯和甲基丙烯酸甲酯单体的催化引发原子转移自由基聚合过程.结果表明,在一定的转化率范围内,就单体浓度而言聚合反应为一级反应,聚合过程中的活性自由基中心浓度很低,约为10-7～10-8mol/L.此外,还根据不同温度下的聚合反应速率常数推算出苯乙烯和甲基丙酸甲酯两种单体的原子转移自由基聚合反应的表观活化能.The atom transfer radical polymerization with complex-catalyzed initiated reaction was instigated at different temperatures, which contains 1-chloro-1-phenylethane or ethyl 2-bromopropanionate as initiator, cuprous chloride or bromide as transition metal support, 1, 2-diperpdinoethane or 1,2-bisd(n-propyl) sulfoethane as ligand in the open system. The polymerization was carried out with mechanical stirrer under nitrogen. The experimental results showed that the plot of ln([M]_0/[M]) vs time is linear. The concentration of living radical was controlled at 10^-7 ～10^-8 mol·L^-1 which is far below common value. Based on the data of the polymerization velocity constants, the apparent activation energy of ATRP was derived.$$$$

关 键 词：原子转移自由基聚合 活化能 二哌淀乙烷 催化 

分 类 号：O631.5[理学—高分子化学]