自由基引发的新型逐步聚合反应及用于光电功能高分子高效率合成研究

Photoelectric functional polymers have been widely applied in organic electronics with prosperous and tremendous economic benefit. However, synthesis of these polymers remains many challenges, that it is sensitive to water or oxygen and difficult to inhibit the side reaction and define the polymer structure, and need the catalyst with toxic and high price. These problems may not only seriously affect the photoelectric performance of polymers, but also increase production costs. Highly efficient synthesis of well-defined photoelectric functional polymers is of significance. This proposal will develop a controlled radical initiated novel step polymerization for highly efficient synthesis of photoelectric functional polymers. Typical photoelectric functional monomer has functional building blocks and at least two carbazyls, which can react with other carbazyls of monomers, oligomers or polymers during step growth polymerization, and form 3,3'-dicarbazyl as a connection via both chemical and electrochemical initiations at room temperature and open air in present of FeCl3 for chemical polymerization and anionic salt as supporting electrolyte for electrochemical polymerization. This polymerization is simple, versatile, atom-economic, environment-friendly and highly efficient approach to straightforward synthesize photoelectric functional polymer with well-defined structures without distinct byproducts. It will attract interest of researchers, who are working on polymer and materials science.

光电功能高分子已经被广泛应用于有机电子领域，具有巨大的市场经济前景。光电功能高分子通常的合成反应体系复杂、产物结构不够明确、催化剂除去困难、需要价格较贵且有毒的有机金属催化剂、对水或氧气敏感，这不仅影响光电高分子性能而且也提高了生产成本。因此，具有明确结构的光电功能高分子的高效率合成亟待发展新型的合成方法。本项目将发展可控自由基引发的新型逐步聚合方法制备光电功能高分子。利用咔唑的C-H键活化偶联生成3,3'‒二聚咔唑脱氢的可控自由基反应，咔唑修饰的各种不同尺度和种类（小分子、配合物、聚合物、纳米粒子）的光电功能单元可以通过咔唑偶联自身或相互反应，高效率合成可多功能深化和调控光谱的，具有特定序列结构的光电功能高分子。最终向国内外光电功能高分子合成工作者提供一种体系简单（光电功能单体 + 1种无机盐）、条件温和（室温、敞开体系）、原子经济且环境友好(易提纯、后处理简单)的合成方法。

独特或不可替代的合成方法最有可能是聚合物新体系创造的源泉。电化学聚合是外电场调控的合成和开发导电高分子的传统重要方法，作为非常规方法可能实现独辟蹊径高分子合成方法和材料的创新。申请人利用电化学刺激的动力学加速本质与电化学选择性活化反应，发展了新型的逐步聚合方法，实现了拓扑和序列结构可控的电化学合成和精确合成。特别地，电化学迭代合成可以在制备宏观表面规整的晶态聚合物分子单层，建立了新一类光电功能聚合物材料研究模型。具体成果例如：（1）电化学还原聚合方法可以制备氧敏感材料。（2）发现咔唑可控氧化反应，修正了存在了近50年的咔唑电化学氧化机理。（3）拓扑结构可控的新型逐步聚合使得高分子具有二次合成与加工能力。（4）发展了新型且不可替代的电化学迭代合成方法，实现了序列可控合成和精确电化学聚合。