RAFT聚合制备含有“直立”双键的聚联烯基功能聚合物

联烯是指含有累积双键的一类化合物，选择适当的方法可以选择性的在1,2位或2,3位聚合，因此得到的聚合物中含有直接以“直立”双键的形式连在聚合物主链上的活性的外亚甲基或含有取代基的外亚甲基，这种结构新颖的活性聚合物可用于制备各种功能高分子。联烯可以通过阳离子聚合、重金属Ni催化的活性配位聚合和传统的自由基聚合方法获得聚合物，然而联烯的可控自由基聚合至今未被突破，无法得到结构规整的联烯与普通乙烯基单体的嵌段共聚物，大大限制了联烯聚合物的应用。本项目拟基于课题组最新工作进展，合成多种结构的功能性联烯单体，通过筛选合适的链转移试剂，进行它们的RAFT聚合，为联烯这类具有特殊结构的单体发展非金属催化的活性聚合新方法，并获得结构规整的基于联烯的功能均聚物和嵌段共聚物。通过本项目的研究，可为高分子材料科学的发展提供新的模型聚合物，赋予现有材料以新性能，对寻找新型功能材料将有很大的促进作用。

Allenes are a class of unique compounds bearing cumulated double bonds. Regioselective polymerization of allene can be controlled in only 1,2- or 2,3-position of the cumulative double bond while employing suitable methods. Thus, a kind of polymer possessing reactive exomethylene substituents directly linked to the main chain can be obtained. This kind of novel reactive polymer can be employed for the preparation of diverse functional polymers. Allenes can be polymerized via cationic, Ni-catalyzed living coordination, and conventional radical polymerization approaches. However, controlled radical polymerization of allene monomers has not been accomplished until now so that well-defined block copolymers via allene and commercial vinyl monomer can not be obtained, which obviously limited the application of polyallene. On the basis of recent research advances in our group, various functional allene monomers will be firstly synthesized followed by RAFT polymerization via selecting suitable chain transfer agent. Thus, new metal-free living polymerization approach for allene monomers with specific structure and functionality can be developed and we can obtain well-defined allene-based functional homopolymers and block copolymers. Through this project, we can afford new model polymers and endow current material with new property for the development of polymer material science, and facilitate the seeking of new functional material.