微反应器中羰基锰催化三臂星型聚合物的制备

Preparation of three-arm star polymer catalyzed by Mn_2(CO)_(10) in microreactor

构建了微尺度下光诱导阳离子聚合反应平台,开发了羰基锰高效催化制备三臂星型聚乙烯基乙醚(PEVE)的新方法。利用GPC,^(1)H NMR等方法考察了微反应器的聚合效果,探究了微尺度下阳离子聚合规律,同时拓展了单体的种类。实验结果表明,在微尺度下利用光诱导阳离子聚合,反应条件温和,聚合过程可控,所得PEVE分子量调节范围宽、分子量分布(MWD)窄,解决了传统工艺中存在的反应条件苛刻、能耗高、产品质量可控性差等问题。在微尺度反应平台上,还利用羰基锰催化体系成功合成了MWD窄的聚甲基丙烯酸甲酯,以及分子量为14 000~35 000、MWD为1.37~1.48的三臂星型聚甲基丙烯酸甲酯-嵌段-聚甲基丙烯酸十二烷基酯。

Micro-scale photo-induced cationic polymerization catalyzed by manganese carbonyl was developed for the preparation of three-arm star polyethyl vinyl ether(PEVE).GPC and ^(1)H NMR were used to investigate the polymerization efficiency of microreactor,exoplore the rules of micro-scale cationic polymerization,and expand the monomer types.The experimental results show that micro-scale photo-induced cationic polymerization has the advantages of mild reaction conditions and controllable polymerization process,and the obtained PEVE has wide range of molecular weight and narrow molecular weight distribution(MWD).Hence,the problems of harsh reaction conditions,high energy consumption and poor product quality controllability in the traditional synthesis process are solved.Furthermore,poly(methyl methacrylate) with narrow MWD and three-arm star poly(methyl methacrylate)-b-poly(dodecyl 2-methylacrylate) with molecular weight of 14 000-35 000 and MWD of 1.37-1.48 were obtained by manganese carbonyl-based catalytic system on the micro-scale polymerization platform.