模板单体的阴离子聚合

项目名称： 模板单体的阴离子聚合

项目编号： No.21474016

项目类型： 面上项目

立项/批准年度： 2015

项目学科： 数理科学和化学

项目作者： 何军坡

作者单位： 复旦大学

项目金额： 92万元

中文摘要： 本项目拟通过模板单体的阴离子聚合，实现对高分子链的键接结构、序列结构、电子结构和聚合度及其分布的多尺度控制。以2,3(A,B)-二取代-1,3-丁二烯及其衍生物为模板单体，用丁基锂引发进行活性阴离子聚合，所得聚合物既可氢化制备饱和主链聚合物，又可脱氢制备具有共轭主链的取代聚乙炔。在饱和主链结构中，若取代基A和B相同, 即为纯头头连接聚合物；若A和B不同，则为严格交替序列共聚物。在共轭聚乙炔中，亦可同样控制其链结构。同时，利用阴离子聚合的活性特点，还可以制备聚乙炔衍生物和富勒烯、聚硅烷以及聚硅氧烷的杂化材料、含聚乙炔的嵌段共聚物以及聚乙炔基网状结构。最后，设计1,2,3-三取代的丁二烯单体，并通过其与1,1-二苯基乙烯的共聚，还可制更长特定序列的聚合物。这些工作将会拓展阴离子聚合的应用研究，为聚合物结构的精密控制合成提供新的方法。

中文关键词： 阴离子聚合；共轭高分子；聚乙炔；序列控制

英文摘要： The general purpose of the project is to control simultaneously the regio-structure, sequence, electronic structure as well as the degree of polymerization and distribution of polymers through anionic polymerization of template monomers. For butyllithium initiated polymerization of 2,3(A, B)-disubstituted-1,3-butadiene, the resulting polymer product possesses residual double bond in the main chain, thus capable of being hydrogenated or dehydrogenated to yield saturated polymers or conjugated polyacetylenes, respectively. For the case of substituents A and B being equal, the resulting polymers are regarded as head-to-head structures. Whereas if A and B are different, the products are alternating polymers. Owing to the reactivity of polymer anions, it is easy to synthesize polyacetylenes end-capped with fullerene, block copolymers and organic and inorganic hybrid materials containing polyacetylene segments, as well as polyacetylene-based networks. In addition, it may also possible to synthesize polymers with ABC or ABCD sequences using 1,2,3-trisubstituted-1,3-butadienes. These research will provide new way for the application of anionic polymerization in the precise synthesis of polymers.

英文关键词： Anion polymerization;conjugated polymer;polyacetylene;sequence control