具三苯胺或咔唑基團之有機可溶性芳香族正型共軛高分子之合成與性質

中文摘要本論文共分成三部份，第一部分包含以N-(4-nitrophenyl)-4’,4”-bisformyl-diphenylamine 為主體所合成之一系列芳香族聚甲亞胺，而分別以N,N-diphenyl-4-methoxyphenylamine和 N-(4-methoxyphenyl)-carbazole為主體所合成出的poly[N,N-diphenyl-4-methoxyphenylamine-4’,4”-diyl] 和bis[N-(4-methoxyphenyl)-9H-carbazole-3-yl] 則被歸納在第二和第三部份。N-(4-nitrophenyl)-4’,4”-bisformyl-diphenylamine為N-(4-nitrophenyl)-diphenylamine化合物經由 Vilsmeier-Haack 反應得到。可溶性的聚甲亞胺於溶液中聚縮合，經由N-(4-nitrophenyl)-4’,4”-bisformyl-diphenylamine和芳香族的二胺以NMP為溶劑於室溫和低壓狀態下製備。而PMeOTPA由氧化聚合法製備，其藍光(435nm)螢光量子效率高達79%。PMeOTPA於場效電晶體的實驗，顯示出正型的特徵。另外，也成功製備了包含N-(4-methoxyphenyl)-carbazole重複單位的陽極電變色材料DMeOPCz。這三個系列芳香族高分子或二聚物之合成與基本特性、電化學及光學性質性已被說明與討論。所有的高分子或二聚物在極性非質子型溶劑中有好的溶解性，出色的薄膜成形能力，高的玻璃轉移溫度，好的熱穩定性。再利用光學或電化學的方法下，所有的高分子或二聚物展現好的螢光和電變色特性。如此，這些材料也許能被廣泛應用於有機電子元件。

關鍵字

可溶性；芳香族高分子

並列摘要

ABSTRACT This study has been separated into three parts. Part I includes a series of aromatic poly(azomethine)s (PAMs) based on N-(4-nitrophenyl)-4,4’-bisformyl-diphenylamine. The other poly[N,N-diphenyl-4-methoxyphenylamine-4’,4”-diyl] (PMeOTPA) and bis[N-(4-methoxyphenyl)-9H-carbazole-3-yl] (DMeOPCz) derived from N,N-diphenyl-4-methoxyphenylamine and N-(4-methoxyphenyl)-carbazole, respectively, were summarized in Part II and III. N-(4-nitrophenyl)-4’,4”-bisformyl-diphenylamine was synthesized from N-(4-nitrophenyl)-diphenylamine by the Vilsmeier-Haack reaction. Soluble PAMs were prepared by the solution polycondensation of N-(4-nitrophenyl)-4’,4”-bisformyl-diphenylamine and aromatic diamine in NMP at room temperature under reduced pressure. Poly[N,N-diphenyl-4-methoxyphenylamine-4’,4”-diyl] (PMeOTPA), with blue light (435 nm) fluorescence quantum efficiency up to 79 % was easily prepared by oxidative coupling polymerization. The PMeOTPA based field effect transistor showed p-type characteristics with significant temperature dependence. And, an anodic electrochromic material of DMeOPCz with N-(4-methoxyphenyl)-carbazole repeating units was successfully prepared. The synthesis, basic characterization, electrochemical and optical properties of three series of aromatic polymers or dimer were investigated. All polymer or dimer had good solubility in many polar aprotic solvents, and exhibited excellent thin-film-forming ability. In additional to high Tg values, good thermal stability, all the obtained polymers or dimer also good emitting or electrochromic characteristics by the optical or electrochemical methods. Thus, these materials may be widely applied in organic electronics.