聚（3,4-乙撑二氨基噻吩）及其衍生物的合成与热电性能研究

The thermoelectric functional materials, as a kind of green energy materials which can convert heat and electrical energy, have attracted a great deal of research interests. Due to their many advantages, such as light weight, low thermal conductivity and good processability, the conductive polymers display broader application prospects in the field of organic thermoelectric materials. However, the very few structural types and low power factor of the known conductive polymers hamper seriously the study and application of organic thermoelectric materials. So the project will design and synthesize a novel kind of easily modified and polymerized monomer 3,4-ethylenediaminothiophene (EDAT) based on the analysis of the molecular structure of high conductive poly(3,4-ethylenedioxythiophene) (PEDOT). The high conductive poly(3,4-ethylenediaminothiophene) (PEDAT) can be obtained after optimizing polymeric and doping conditions. By comparing the thermoelectric performance of this polymer with that of PEDOT, we can reveal the influence rule and machanism of the structures on the properties of polymers. Meanwhile, through modifying nitrogen atom of EDAT, we can also summarize the relation between different substituent and thermoelectric performance of according polymer. This will further guide the rational design of high performance thermoelectric materials. Consequently, we can realize the successful development of a new class of high performance organic thermoelectric materials with good workability, high stability and tunable electrical conductivity and thermoelectric performance. The results of the present project may open up a new branch of the organic thermoelectric materials.

热电功能材料作为一类可以将热能和电能相互转化的绿色能源材料，吸引了人们极大的研究兴趣。导电聚合物由于其质轻、热导率低及可加工性强等优点在有机热电材料领域显示出广阔的应用前景。然而，已知导电聚合物屈指可数的结构类型和它们的低功率因子等严重制约了有机热电材料的研究与应用。基于此，本项目将通过对具有高电导率的PEDOT结构剖析，设计合成一种结构新颖、可修饰性强且容易聚合的新型单体乙撑二氨基噻吩；通过对单体聚合及掺杂条件的优化，获得高电导率的聚（乙撑二氨基噻吩），并将其热电性能与PEDOT进行对比，揭示聚合物结构对性能的影响规律和机理；同时，通过对乙撑二氨基噻吩单体氮原子的修饰，总结不同取代基与相应聚合物热电性质之间的相互关系，进一步指导高性能热电材料结构的理性设计，实现一类具有全新结构的可加工性强、稳定性高、电导率及热电性能可调的高性能有机热电材料的成功开发，为有机热电材料开辟一个新的研究分支。

热电功能材料作为一类可以将热能和电能相互转化的绿色能源材料，吸引了人们极大的研究兴趣。由于复合热电材料可以将有机热电材料和无机热电材料的优势进行有机结合，因而成为当今热电材料领域研究的热门课题。然而，尽管有机化合物可设计性强，结构多样，但是目前用于复合热电材料的有机化合物屈指可数。究其原因主要可归纳为两个方面。其一，多数新型有机共轭聚合物的结构复杂，大量合成的实验可操作性不强；其二，有机小分子化合物普遍存在溶解性较好，且须在特定的有机合成反应条件下进行，不利于其与无机粒子的充分复合。基于此，本项目在高电导性碳纳米管（SWCNT）存在下，通过分子设计，原位制备并调查了低溶解性，低带隙，高稳定性的小分子噻吩并吡嗪双氮氧化物（TPNO）包覆SWCNT的复合热电材料。通过 “一步缩合法发”，发展了具有可螯合单元N=C-C=N（DAB）的席夫碱共轭聚合物/SWCNT复合热电材料，并利用席夫碱聚合物的螯合性质与过渡金属离子配位，衍生了一类新型的三元复合热电材料。将具有“机械变色”性质的金属有机化合物苯乙炔亚铜(PhCCCu)纳入复合热电材料中，发展了新型的多功能热电复合材料。该项目的研究工作将为开发新型高性能热电材料提供一定的理论借鉴和实践指导，有望为热电材料的发展开辟新的研究分支。