碱性离子液体催化金属调节的甲基丙烯酸甲酯的电子转移活化原子转移自由基聚合

doi:10.3724/SP.J.1095.2014.30372

摘要/Abstract

摘要： 通过电子转移活化原子转移自由基聚合（AGET ATRP），以2-溴代异丁酸乙酯（EBiB）为引发剂、维生素C（VC）为还原剂。以碱性离子液体1-丁基-3-甲基咪唑氢氧化盐([Bmim][OH])分别和FeCl3·6H2O、CuCl2及RuCl3形成的配合物为催化剂催化甲基丙烯酸甲酯（MMA）的本体和溶液聚合。催化量的[Bmim][OH]即可提高聚合速率，并且得到相对分子质量分布可控的PMMA（Mw/Mn为1.20～1.40）。研究了[Bmim][OH]的加入量对聚合速率和相对分子质量分布的影响，3种催化体系催化性质通过循环伏安曲线表征。扩链反应证明了碱性离子液体催化甲基丙烯酸甲酯的聚合为“活性”/可控自由基聚合。碱性离子液体良好的溶解性使其成为活性自由基聚合的良好催化剂。

关键词: 电子转移活化, 原子转移自由基聚合, 碱性离子液体-金属盐, 循环伏安曲线, 催化剂, 聚甲基丙烯酸甲酯, 扩链反应

Abstract: Basic ionic liquids(BILs), including 1-butyl-3-methyl imidazolium hydroxide([Bmim][OH]), coordinated with iron chloride, copper chloride, and ruthenium trichloride, were used as both the ligand and catalyst in activators generated by electron transfer for atom transfer radical polymerization(AGET ATRP) of methyl methacrylate(MMA) in bulk and solution, using ethyl 2-bromoisobutyrate(EBiB) as the initiator, vitamin C(VC) as the reducing agent. Catalytic amount of BILs can enhance the polymerization rate, and produce PMMA with controllable relative molecular mass and narrow relative molecular mass distribution(Mw/Mn=1.20~1.50). The influence of the addition of BILs on the polymerization rate and relative molecular mass distributions were investigated. The catalytic properties of the three catalytic systems were studied by cyclic voltammetry(CV) characterization. The nature of controlled/“living” free radical polymerization in the presence of BILs was confirmed by chain-extension experiments. The ready solubility of BILs enables them to be applied as a new type of catalyst in AGET ATRP.

Key words: activators generated by electron transfer, atom transfer radical polymerization, basic ionic liquid-metal salts, cyclic voltammetry, catalyst,polymethylmethacrylate, chain extension

中图分类号:

O622.1

陈敏, 邓之俊, 张丽本, 李小刚. 碱性离子液体催化金属调节的甲基丙烯酸甲酯的电子转移活化原子转移自由基聚合[J]. 应用化学, DOI: 10.3724/SP.J.1095.2014.30372.

CHEN Min, DENG Zhijun*, ZHANG Liben, LI Xiaogang . Metal-mediated Activators Generated by Electron Transfer for Atom Transfer Radical Polymerization of Methyl Methacrylate with Basic Ionic Liquids as the Catalyst[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2014.30372.

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