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	合成橡胶工业 CHINA SYNTHETIC RUBBER INDUSTRY 2009 Vol.32 No.6 P.459-462

甲基丙烯酸2,2,2-三氟乙酯的原子转移自由基聚合

夏攀登　路翠苹　张书香　

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和配位剂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~(-4)s~(-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.
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：TQ316.32~+2 　文献标识码：A
文章编号：1000-1255(2009)06-0459-04

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

Xia Pandeng（Shandong Supervision and Inspection Institute for Product Quality , Jinan 250100, China）　 Lu Cuiping（Jinan Huaiyin District Real Estate Development Corporation, Jinan 250021, China）　 Zhang Shuxiang（College of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022, China）　

Abstract：The atom transfer radical polymerization of 2,2,2-trifluoroethylmethacrylate (TFEMA) was conducted by using ethyl-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-trifluoroethylmethacrylate) (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~(-4) s~(-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.
Keywords：2,2,2-trifluoroethylmethacrylate; ethyl-2-bromopropionate; cuprous chloride; bipyridine; atom transfer radical polymerization; reaction kinetics

基金项目：国家自然科学基金资助项目(20774037).
作者简介：夏攀登(1980-),男,硕士研究生.已发表论文9篇.
作者单位：夏攀登（山东省产品质量监督检验研究院,山东,济南,250100）　
　　　　　路翠苹（济南市槐荫区房地产开发集团总公司,山东,济南,250021）　
　　　　　张书香（济南大学,化学与化工学院,山东,济南,250022）　

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收稿日期：2008年9月13日

修稿日期：2009年7月13日

出版日期：2009年11月15日