新型含紫精側鏈之三苯胺芳香族高分子合成與電化學及電致變色特性之研究

Abstract

本論文分成四個章節， 第一章為總體序論。第二章節包含了以 1-(2-(4-(bis(4-aminophenyl)amino)phenoxy)ethyl)-1'-ethyl-[4,4'-bipyridine] hexafluorophosphate, 4,4'-diamino-4'-methoxytriphenylamine 和 N,N'-bis(4-aminophenyl)-N,N'-di(4-methoxylphenyl)-1,4-phenylenediamine為主體與 間苯二甲醯氯利用低溫聚合法合成出一系列新型含三苯胺帶有紫精側鍊之陽極/ 陰極芳香族聚醯胺。第三章是以 1-(2-(4-(bis(4-aminophenyl)amino)phenoxy)ethyl)-1'-ethyl-[4,4'-bipyridine] hexafluorophosphate為主體與兩種不同的二酸酐合成出另一系列新型含三苯胺之 芳香族聚醯亞胺。第四章節為結論。這五個新型三苯胺帶有紫精側鍊之芳香族高 分子之合成與基本特性、電化學及電致變色性質已被研究與比較。所有的高分子 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，在空氣下高的碳殘 餘量，機械性質，較低的HOMO值。在利用電化學與光譜電化學的方法下，大部 分的高分子也展現出色可逆的電致變色特性。此外，在第二章我們比較了同聚物 與共聚物, 結果顯示若加入含有紫精基團醚鏈單元進入高分子鍊段並不影響其 氧化電位。另外在第三章的部分，兩個芳香族聚醯亞胺不論在氧化或還原上都顯 示了高顏色對比。

This study has been separated into four chapters. Chapter 1 is general introduction. Chapter 2 includes a series of novel ambipolar aramids derived from three diamine monomers,1-(2-(4-(bis(4-aminophenyl)amino)phenoxy)ethyl)-1'-ethyl-[4,4'-bipyridin e] hexafluorophosphate, 4,4'-diamino-4'-methoxytriphenylamine, and N,N'-bis(4-aminophenyl)-N,N'-di(4-methoxylphenyl)-1,4-phenylenediamine with diacid chloride IPC via low-temperature polycondensation reaction. Chapter 3 describes the other series of novel aromatic polyimides derived from 1-(2-(4-(bis(4-aminophenyl)amino)phenoxy)ethyl)-1'-ethyl-[4,4'-bipyridine] hexafluorophosphate and various commercially available tetracarboxylic dianhydrides by thermal imidization. Chapter 4 is conclusions. The synthesis, basic characterization, electrochemical and electrochromic properties of these novel triphenylamine-containing aromatic polymers with viologen pendant groups were investigated and compared. All polymers had good solubility in many polar aprotic solvents, and exhibited excellent thin-film-forming ability. In addition to high char yield in air flow, mechanical properties, and lower HOMO energy levels, most of the obtained polymers also revealed excellent reversibility of electrochromic characteristics by the electrochemical and spectroelectrochemical methods. Furthermore, in chapter 2 we compared homopolymer and copolymers, and the results showed that adding ether linkage with viologen moiety did not make influence on polymer backbone. Besides, two polyimides showed interesting electrochromic behavior with high contrast both in oxidation and reduction in chapter 3.