镍络合物催化的共轭高分子与联烯的嵌段共聚

项目名称： 镍络合物催化的共轭高分子与联烯的嵌段共聚

项目编号： No.21304027

项目类型： 青年科学基金项目

立项/批准年度： 2014

项目学科： 数理科学和化学

项目作者： 刘娜

作者单位： 合肥工业大学

项目金额： 25万元

中文摘要： 高分子合成方法学是高分子科学的基础和研究核心。新的合成方法的建立，通过产生新的结构，促进新性质和新功能的发现，从而促进相关学科和研究领域的发展。我们前期预研工作揭示，镍封端聚噻吩可以和烷氧基联烯单体嵌段共聚，生成聚噻吩-聚联烯二嵌段共聚物。本项目提出系统地研究这种镍封端的共轭高分子与联烯的嵌段共聚反应，研究共聚物结构和分子量的可控性及聚合反应的动力学。揭示共聚合反应的机理。进一步研究镍封端的聚联烯与芳香单体的共聚反应，研究单体的聚合顺序对共聚合反应和聚合物结构的影响。探索这种共聚合反应的普适性。通过在共轭高分子嵌段链和聚联烯嵌段链上引入不同性质的取代基，调控这种"刚-柔"二嵌段共聚物在不同溶剂中的溶解性，研究这类共聚物的自组装性质。通过本项目的研究，我们将建立利用镍络合物为催化剂，基于不同的聚合机理，顺序聚合两种单体，一步合成共轭高分子与聚联烯二嵌段共聚物的新的合成方法。

中文关键词： 嵌段共聚物；活性聚合；聚噻吩；聚联烯；镍配合物

英文摘要： Polymer synthetic chemistry is the basic research field of polymer science. The establishment of new synthetic methods would enable the synthesis of new polymers and thus lead to the creation of new structures and functions. We recently revealed that Ni(II)-terminated polythiophene could copolymerize with alkoxyallenes to afford a well-defined block copolymer of polythiophene-b-polyallene. On the base of this finding, in this project we propose to systemically study the copolymerization of Ni(II)-terminated conjugated polymers with allenes and explore the conditions for the control of the structures and molecular weights of the block copolymers, and the kinetics of the copolymerization process. We will also study the copolymerization of Ni(II)-terminated polyallenes with aromatic monomers and investigate the effect of monomer polymerization sequence on the block copolymerization. Through the above researches, we hope to establish a general approach to the synthesis of block polymers containing conjugated polymers and polyallenes in a single pot. By introducing discrete groups to the two block chains to modulate the solubility of each block, we will also investigate the self-assembly of the new rod-coil block polymers.

英文关键词： block copolymer；living polymerization；polythiophene；polyallene；Ni(II) complex