丁二炔类材料拓扑化学聚合行为  

Topochemical polymerization of diacetylenes

作　　者：李清源[1,2] 姚奕帆[2] 仇格 张盼[1,2] 董焕丽[2] 胡文平[2,3] 

机构地区：[1]首都师范大学化学系光功能材料与器件北京市重点实验室,北京100048 [2]中国科学院化学研究所中国科学院有机固体重点实验室,北京100190 [3]天津大学理学院化学系天津化学化工协同创新中心,天津300072

出　　处：《科学通报》2016年第24期2688-2706,共19页Chinese Science Bulletin

基　　金：国家自然科学基金(51222306;91433115;51203094);北京市科技新星(Z131101000413038);北京市属高校创新团队建设提升计划(IDHT20140512);北京市自然科学基金-北京市科学技术研究院联合项目(L140005)资助

摘　　要：丁二炔类材料(diacetylenes)由于其独特的聚合方式(即拓扑化学聚合,topochemical polymerization)以及聚合后形成的共轭高分子材料表现出优异的电学、非线性光学等特性,很早就受到了人们的广泛关注.当然,不是所有的丁二炔类化合物都能发生晶体内的拓扑化学聚合反应,这需要丁二炔单体分子在固态下首先要满足一定的分子堆积结构,同时还需要有合适的外界条件,譬如加热、光照、?射线辐射等条件来刺激该反应的发生.本文从分子结构的设计合成和超分子化学结构的构建两个角度出发,系统总结了能够实现丁二炔类材料发生晶体内拓扑化学聚合的各种策略,讨论了相关丁二炔类化合物的反应特性及反应后的分子结构特征,最后简要介绍了聚丁二炔类共轭高分子材料在光、电、传感等领域的潜在应用.通过本文对丁二炔类材料拓扑化学聚合行为研究的系统总结,希望能够再次激起化学工作者对于利用拓扑化学聚合反应来制备共轭高分子材料的研究兴趣,从化学合成的角度进一步发展一些新的可发生拓扑化学聚合反应的单体分子结构单元,丰富该类材料体系,促进相关研究的发展.Since the discovery of conducting polymers, they have received considerable attention both from academic and industry due to their attractive advantages of light weight, low cost, and easy processing, which make them demonstrate a wide range of applications. Over the past decades, significant advances have been achieved in this field with the development of high performance polymeric semiconductors and device fabrication techniques. However, there are still many scientific questions existing in this field, such as the unclear charge transport physics in conjugated polymers due to disordered molecular structures in the widely investigated films. Compared to thin films, single crystals possess long-range molecular order, no grain boundaries and no defects, which are seen as the best candidates for revealing the intrinsic charge transport of materials. However, it has been a big challenge for the crystallization of polymers directly from solution, and even is elusive for the conjugated polymers due to their intrinsic electron-rich conjugated backbone structures. Topochemical polymerization where under a certain reaction condition, the preorganized monomer crystals could be directly changed to their corresponding polymer crystals with a minimum amount of atomic and molecular movement, that is realizing the single-crystal-to-single-crystal transformation would provide us a promising solution. Compared to traditional solution process, with this method, we can possibly realize two goals：（1） the controllable synthesis because the first crystal growth process is from the monomer molecules;（2） the possible obtainment of higher molecule-weight polymer chains because we do not need consider their solubility problem like that from solution synthesis. However, to date, very few polymer systems could be prepared through this topochemical polymerization process. Polydiacetylenes（PDAs） are the first and also the only known class of conjugated polymers which could be produced in pure form, large-size single crystals

关 键 词：丁二炔衍生物 拓扑化学聚合 固体聚合活性 超分子工程 聚丁二炔类共轭高分子材料 

分 类 号：O631.5[理学—高分子化学]