月桂烯的活性阴离子聚合及其“巯基-双键”点击反应  

Living anionic polymerization and thiol-ene click reaction of myrcene

作　　者：黄帅[1] 韩丽[1] 马红卫[1] 李杨[1] Huang Shuai;Han Li;Ma Hongwei;Li Yang(State Key Laboratory of Fine Chemicals,Department of Polymer Science and Engineering,School of Chemical Engineering,Dalian University of Technology,Dalian 116024,China)

机构地区：[1]大连理工大学精细化工国家重点实验室,辽宁省大连市116024

出　　处：《合成树脂及塑料》2020年第4期1-8,共8页China Synthetic Resin and Plastics

基　　金：国家自然科学基金(21805025,21674017);国家重点研发计划(2017YFB0307101);中央大学基础研究基金(DUT19RC(4)001)。

摘　　要：采用阴离子聚合方法,以仲丁基锂为引发剂,成功合成了均聚月桂烯(PM)、苯乙烯(St)-月桂烯(Mc)两嵌段共聚物,以及St-Mc-St三嵌段共聚物,对Mc的活性阴离子聚合特性进行了研究,并对所合成聚合物的相对分子质量和分子组成进行了表征。结果表明:合成的聚合物具有相对分子质量可控且分布窄的特点,极性调节剂N,N,N,N-四甲基乙二胺能够显著改变Mc双键的活性,实现其活性阴离子聚合的选择性控制;2,2-二甲氧基-2-苯基苯乙酮和二苯甲酮(BP)作为光引发剂均可以实现PM与3-巯基丙酸甲酯的“巯基-双键”点击反应。其中,以BP为光引发剂,双键、巯基、BP摩尔比为1.00∶10.00∶1.00,反应48 h,点击效率为99%。采用阴离子聚合方法,为PM后功能化的研究以及高性能功能化材料的合成提供了高效的方法。Homopolymyrcene(PM),styrene-myrcene(Mc)diblock copolymer and styrene-myrcenestyrene triblock copolymer were synthesized via anionic polymerization with sec-BuLi as the initiator.The activity of Mc in anionic polymerization was observed.The molecular weight and structure of the polymers were characterized as well.The results show that the polymers synthesized have controllable molecular weight and narrow molecular weight distribution.It is confirmed that the polarity modifier N,N,N,Ntetramethylethylenediamine can significantly change the activity of the double bonds of Mc and selectively control the anionic polymerization.2,2-dimethoxy-2-phenylacetophenone and benzophenone(BP)can be used as the photoinitiator to catalyze the thiol-ene click reaction of PM and methyl 3-mercaptopropionate.Among which,the click efficiency reaches 99%under the condition of the molar ratio of double bonds/thiol/BP of 1.00∶10.00∶1.00 for 48 hours.The application of anionic polymerization provides an efficient method for the study of postfunctionalization of PM and the synthesis of high-performance functional materials.

关 键 词：均聚月桂烯 阴离子聚合 “巯基-双键”点击反应 

分 类 号：TQ050.425[化学工程]