光诱导铜调控丙烯酸甲酯活性自由基聚合  

Photo-Induced Copper-Mediated Living Radical Polymerisation of Methyl Acrylate

作　　者：颜秀花[1] 许伟[1] 石文艳[1] 丁建飞[1] 陈立根[1] 邵荣[1] Xiuhua Yan;Wei Xu;Wenyan Shi;Jianfei Ding;Ligen Chen;Rong Shao(School of Chemistry and Chemical Engineering,Yancheng Institute of Technology,Yancheng 224051,China)

机构地区：[1]盐城工学院化学与化工学院,江苏盐城224051

出　　处：《高分子材料科学与工程》2023年第6期8-14,共7页Polymer Materials Science & Engineering

基　　金：江苏省产学研合作项目(BY2021464)

摘　　要：用2-溴代异丁酰溴对C_(36)二醇端基进行改性得到大分子引发剂。该引发剂在0℃,以溴化铜(CuBr_(2))与三[(2-二甲氨基)乙基]胺(Me_(6)-Tren)为催化体系,通过紫外光诱导活性自由基聚合法实现了丙烯酸甲酯的聚合。通过调控CuBr_(2)与Me_(6)-Tren的量及其比例,研究其对聚合反应的影响,优化了反应条件,进而对聚合机理进行探讨。红外光谱、核磁共振、凝胶渗透色谱分析表明,合成得到的大分子引发剂的结构与理论设计相符,具有大分子端基活性点。优化后的条件,即n(MA):n(C_(36)-D-Br_(2)):n(CuBr_(2)):n(Me_(6)-Tren)=100:1:0.05:0.3下,单体转化率高达99%,聚合物的分子量分布指数为1.14;根据实验结果及相关理论,推测反应中游离的Me_(6)-Tren没有还原功能,它是光诱导聚合反应中启动和激活休眠链的必备条件。The C_(36) diol terminal group was modified with 2-bromine to synthesize a macromolecular initiator.The polymerization of methyl acrylate,in the presence of the synthesized macroinitiator,using CuBr_(2) and Me_(6)-Tren as catalytic precursor,was realized upon photo-induced living radical polymerization.The effect of CuBr_(2) and Me_(6)-Tren on polymerization reaction was investigated by regulating the amount and ratio of CuBr_(2) to Me_(6)-Tren,and the mechanism of polymerization was then investigated.FT-IR,NMR spectra and gel osmotic chromatography show that the resultant macromolecular initiator structure is consistent with the theoretical design structure,and confirms the macromolecular terminal group active point.Under the optimized condition of n(MA):n(C_(36)-D-Br_(2)):n(CuBr_(2)):n(Me_(6)-Tren)=100:1:0.05:0.3,the near-quantitative monomer conversion(99%)is obtained,and the resulting polymer has a dispersion of 1.14.According to the experimental results and related theories,it is speculated that the free Me_(6)-Tren does not function as a reducing agent,and it is necessary for initiating and activating dormant chains during light-induced polymerization reaction.

关 键 词：CuBr_(2)/Me_(6)-Tren 活性自由基聚合 大分子引发剂 丙烯酸甲酯 

分 类 号：O631.5[理学—高分子化学]