吡啶基三唑配合物催化下甲基丙烯酸甲酯的原子转移自由基聚合研究  

Atom Transfer Radical Polymerization(ATRP)of Methyl Methacrylate (MMA) Catalyzed By Pyridyl-Triazoles Ligand

作　　者：马潇[1] 路建美[1] 张汗青[1] 陶永新[1] 

机构地区：[1]江苏工业学院材料系,江苏常州213016

出　　处：《高校化学工程学报》2007年第6期948-953,共6页Journal of Chemical Engineering of Chinese Universities

基　　金：国家自然科学基金(20571054)

摘　　要：以配体3,5-二-(4-吡啶基)-1,2,4-三唑与CuX形成催化剂,分别以α-溴代异丁酸乙酯和氯化苄为引发剂,环己酮为溶剂,进行了甲基丙烯酸甲酯(MMA)的原子转移自由基聚合(ATRP),同时考察了配比、溶剂量以及温度对聚合速率、聚合物分子量及分子量分布的影响。80℃下的聚合反应速度高于70℃;以环己酮为溶剂,单体与溶剂之比为1:1.5时可得到较低分子量分布的聚合物。实验结果表明以吡啶基三唑为配合物催化甲基丙烯酸甲酯的聚合过程中,转化率和分子量随时间的增加而增大,聚合反应符合一级动力学规律,所得聚合物分子量分布较窄(1.21～1.46),结合端基分析和扩链反应结果,证明该聚合反应符合"活性"/可控自由基聚合。Atom transfer radical polymerization of methyl methacrylate （MMA） was studied with cyclohexanone as solvent, CuX/3,5-di-（4-pyridyl）-1,2,4-triazoles as catalyst, ethyl 2-bromoisobutyrate （EBiB） and benzyl chloride as initiators, respectively. The effects of the ratio of [ligand]/[initiator], the amount of solvent used and the reaction temperature on the conversion, molecular weight and polydispersity index （PDI） of the polymers obtained were investigated. It was found that the polymerization rate at 80℃ is higher than that at 70℃, and lower polydispersity index can be obtained when the ratio of monomer to solvent is 2/3 and cyclohexanone is used as solvent. The experiments show that, during the polymerization of MMA, the product molecular weight increases with the increase of monomer conversion, and the polydispersity index remains in low value （1.21-1.46）. The experimental results show that the polymerization reaction follows the rule of first-order kinetic with respect to the monomer, and the results of the studies on terminated group analysis and chain-extension reaction show that the polymerization reaction studied accords with the controlled/＂living＂ radical polymerization.

关 键 词：3  5-二-(4-吡啶基)-1  2  4-三唑 原子转移自由壁聚合(ATRP) 可控性 甲基丙烯酸甲酯(MMA) 配体 

分 类 号：O632.52[理学—高分子化学] O631.5[理学—化学]