甲基丙烯酸2,2,2-三氟乙酯的原子转移自由基聚合  

Atom transfer radical polymerization of 2,2,2-trifluoroethylmethacrylate

作　　者：夏攀登[1] 路翠苹 张书香[3] 

机构地区：[1]山东省产品质量监督检验研究院,山东济南250100 [2]济南市槐荫区房地产开发集团总公司,山东济南250021 [3]济南大学化学与化工学院,山东济南250022

出　　处：《合成橡胶工业》2009年第6期459-462,共4页China Synthetic Rubber Industry

基　　金：国家自然科学基金资助项目(20774037)

摘　　要：以α-溴代丙酸乙酯（EPN-B）／CuCl／联二吡啶（bpy）作为引发／催化体系、环己酮为溶剂，对甲基丙烯酸2,2,2-三氟乙酯（TFEMA）进行原子转移自由基聚合（ATRP），研究了TFEMA的反应动力学，并考察了引发／催化体系、引发剂EPN-B用量、配位剂bpy用量及单体配比对聚合反应的影响。结果表明，采用EPN-B／CuCl／bpy引发／催化体系对TFEMA进行ATRP，可得到窄分子量分布的聚甲基丙烯酸2，2，2-三氟乙酯（PTFEMA），在实验范围内，聚合速率对单体浓度呈一级动力学关系，该反应过程具有活性聚合特征；随着引发剂EPN-B和配住剂bpy用量的增加，聚合速率加快，当EPN-B相对摩尔用量为0.5，1.0，2.0时，其相应的表观链增长速率常数分别为3.143×10^-4，3.478×10^-4，4.435×10^-4s^-1；增大[TFEMA]／[EPN-B]（摩尔比），聚合速率明显降低，但无论[TFEMA]／[EPN-B]高与低，聚合物的分布指数均为1.15－1.23。The atom transfer radical polymerization of 2,2,2-trifluoroethylmethacrylate （TFEMA） was conducted by using ethy1-2-bromopropionate （EPN-B）/cuprous chloride （CuCl）/bipyridine （bpy） as the initiating/catalytic system and cyclohexanone as solvent, polymerization kinetics of TFEMA was studied, and the effects of initiator/catalytic system, amount of initiator and complexant , mole ratio of monomer on polymerization rate were investigated. The results showed that the poly（2,2,2-trifluoroeth-ylmethacrylate） （PTFEMA） with narrow molecular weight distribution was obtained by using EPN-B/ CuCl/bpy as initiating/catalytic system. In the experiment range, the reation was first order in kinetics and behaved like living polymerization. The polymerization rate improved with increasing EPN-B and bpy, and the appatent chain constant was 3.143×10^-4,3.478×10^-4,4.435×10^-4s^-1 when the levels of EPN-B were 0.5, 1.0, 2.0 relative mole, respectively. The polymerization rate increased and polydispersion index （PDI） of PTFEMA decreased with increasing [TFEMA]/[EPN-B] （mole ratio） , but PDI kept at 1.15-1.23 no matter how the [TFEMA]/[EPN-B] （mole ratio）changed.

关 键 词：甲基丙烯酸2 2 2-三氟乙酯 α-溴代丙酸乙酯 氯化亚铜 联二吡啶 原子转移自由基聚 合 反应动力学 

分 类 号：TQ316.322[化学工程—高聚物工业]