基于Mizoroki-Heck偶联反应的取代聚乙炔分子工程

In this project, we will develop a facile route to the synthesis of substituted polyacetylene via polycondensation based on Mizoroki-Heck coupling reaction. We will use (substituted)vinyl halides as AB-type monomer for Mizoroki-Heck coupling. This results in the formation of linear substituted polyacetylene bearing different pendent groups. Using bifunctional vinyl halides and multifunctional vinyl halides as monomers, respectively, hyperbranched polyacetylene and cross-linked polyacetylene will be prepared. We will also synthesize rod-coil block copolymers and star copolymers containing substituted polyacetylene segment by combination of Mizoroki-Heck coupling with living anionic polymerization. Mizoroki-Heck coupling reaction in emulsion or suspension using various Pd catalytic systems will lead to the synthesis of substituted polyacetylene particles. We will seek the possibility to achieve living polycondensation through appropriate choice of catalysts and additives. Finally, the effects of UV or visible light on all polymerization systems will be studied in order to improve the polymerization efficiency.

本项目计划探索一条通过Mizoroki-Heck偶联反应进行聚乙炔分子设计的路线。以乙烯基卤化物为单体，合成带有不同侧基的线形取代聚乙炔、超支化聚乙炔以及交联网状聚乙炔，并选择合适的催化剂以及添加剂研究缩聚反应的可控性；通过与阴离子聚合相结合的方式制备含取代聚乙炔链段的刚柔嵌段共聚物和星状共聚物；计划考察各种Pd催化体系，通过乳液或分散聚合制备取代聚乙炔粒子，通过使用带有特殊官能团的单体或者后聚合改性的方法制备功能性的聚合物粒子；研究这些聚合产物的结构与性能之间的关系。同时研究本项目所有合成体系中紫外或可见光的影响，找到光辅助促进聚合反应效率的方法。

本项目发展了一种通过Mizoroki-Heck偶联反应制备取代聚乙炔的新方法。通过对α-溴苯乙烯类单体结构的设计，合成了一系列带有不同取代基的线形聚乙炔，并在此基础上合成了支化、高度支化、交联网状、以及端基官能化取代聚乙炔。研究了包括Pd催化体系、单体结构和反应条件如溶剂、温度等对聚合反应的影响。对合成的聚合物结构进行了表征，并测试了其非线性光学性质，探讨了其作为光限幅材料的应用潜力。同时，也对可见光催化的Mizoroki-Heck偶联聚合反应动力学和机理进行了深入研究。