具氰基芳香胺基團功能性芳香族高分子之設計、合成、性質探討及其應用

Abstract

本論文分成五個章節，第一章為總體序論。第二章以3種二胺4,4'-diamino-4'-cyanotriphenylamine、N,N-bis(4-aminophenyl)-N',N'-di(4-cyanophenyl)-1,4-phenylenediamine及 N,N'-bis(4-aminophenyl)-N,N'-di(4-cyanophenyl)-1,4-phenylenediamine與不同二酸合成三系列之新型芳香族聚(胺-醯胺)。第三章節描述了三系列之芳香族聚(胺-醯亞胺)，係以二述二胺及不同種二酸酐經一步法或二步聚合法所合成。第四章是以實驗製得之含三苯胺的雙馬來醯亞胺與市售二硫醇經Michael聚加成反應獲得聚醯亞胺硫醚。第五章節為結論及未來工作。這些含氰基芳香胺之高分子的合成、基本特性、光致發光、電學、電化學及電致變色性質皆被研究與比較。所有的高分子在極性非質子型溶劑中都有好的溶解性、出色的薄膜成形能力、高的玻璃轉換溫度、好的熱穩定性，及適當的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優良的電致變色可逆性。這些含氰基芳香胺的高分子由於適當的HOMO值、出色熱穩定性、螢光量子效率及電化學不僅能被做為電洞傳輸層和發光材料，而且也可應用於新型的電致變色元件。

This study has been separated into five chapters. Chapter 1 is general introduction. Chapter 2 includes three series of novel aromatic poly(amine-amide)s derived from synthesized diamines, 4,4'-diamino-4'-cyanotriphenylamine, N,N-bis(4-aminophenyl)-N',N'-di(4-cyanophenyl)-1,4-phenylenediamine, and N,N'-bis(4-aminophenyl)-N,N'-di(4-cyanophenyl)-1,4-phenylenediamine, and various dicarboxylic acids by direct polycondensation. Chapter 3 describes three series of aromatic poly(amine-imide)s prepared from the diamines and various tetracarboxylic dianhydrides via one-step and conventional two-step polymerization. Chapter 4 includes a series of polyimidothioethers prepared from new triphenylamine-based bismaleimides and commercial dithiols via Michael polyaddition. Chapter 5 contains conclusions and future work. The synthesis, basic characterization, photoluminescent, electrical, electrochemical, and electrochromic properties of these aromatic cyanoarylamine-based polymers were investigated and compared. All polymers revealed good solubility in many polar aprotic solvents with excellent thin-film-forming ability. In additional to high Tg values, good thermal stability, high luminecence, and proper HOMO energy levels, most of the obtained polymers also revealed good reversibility of electrochromic characteristics by the electrochemical and spectroelectrochemical methods. Thus, these cyanoarylamine-containing polymers can be considered not only as hole-transporting layer and light-emitting materials but also could be widely applied as new electrochromic devices due to their proper HOMO values, excellent thermal stability, fluorescence quantum efficiency and good electrochemical behavior.