项目名称： 高选择性直接芳基化缩合聚合反应研究及应用

项目编号： No.21504019

项目类型： 青年科学基金项目

立项/批准年度： 2016

项目学科： 数理科学和化学

项目作者： 王晓晨

作者单位： 国家纳米科学中心

项目金额： 21万元

中文摘要： 直接芳基化缩合聚合(DAP)反应直接利用芳基碳-氢键进行聚合反应，不需要进行聚合单体的预活化，合成提纯简单，聚合反应过程环境友好。从学术、产业、环境和经济效益等诸方面考量，DAP反应都是非常具有吸引力的新型共轭聚合物合成方法。但目前，DAP反应选择性较差，合成的共轭聚合物缺陷严重。本项目立足于聚合反应的特性和要求，通过小分子模型化合物检验各反应因素对直接芳基化偶联反应的反应活性和选择性的影响规律。重点研究催化剂与配体空间结构和电子效应对直接芳基化偶联反应选择性的影响，筛选出适用于共轭聚合物合成的直接芳基化偶联反应条件。以几个共轭聚合物明星分子为例，探讨DAP反应与传统的偶联缩合聚合反应的特性差异，进一步提高反应选择性，尽可能抑制反应中副反应的发生，获得少缺陷，高质量的共轭聚合物材料。这一研究工作将对直接芳基化偶联反应的研究和推动共轭聚合物制备与大规模应用产生积极的作用。

中文关键词： 共轭聚合物；聚合反应；直接芳基化；碳氢活化

英文摘要： The direct arylation reaction as a carbon–hydrogen (C–H) bond activation method enables a coupling reaction between arenes and aryl(pseudo)halides. Direct arylation cross-coupling offers advantages over traditional couplings such as fewer synthetic steps, safer and more convenient operation. As a result, direct arylation polymerization (DAP) makes it possible to synthesize conjugated polymers via an economically efficient, safe and environment-friendly approach. Despite these advantages, regioselectivity of DAP is still not a patch on traditional coupling reaction. In this project, considering the characteristics and demand of polymerization, we will systematically study, based on meticulously selected model molecules, the effect of different reaction factors on the selectivity and activity of direct arylation coupling reaction, especially the stereoscopic structure and electronic effect of catalysts and ligands on the regioselectivity. The superior combination will be screened and applied in preparing conjugated polymers. Several star conjugated polymers will be polymerized by the optimized direct arylation cross-coupling reaction. The chemical structures and properties of the polymers prepared by the optimized DAP will be thoroughly studied and compared with the polymers prepared by traditional coupling reaction or commercial products. This synthetic strategy will enable the facile and efficient synthesis of conjugated copolymers with better C–H selectivity. From a broad perspective, this work will expand the scope of direct arylation coupling reactions and enable the synthesis of high-quality conjugated polymers by exclusive direct arylation coupling reactions via fewer synthetic steps and without using flammable, nonstable and toxic organometallic reagents.

英文关键词： conjugated polymer;polymerization;direct arylation;C-H activation