新型具雙三苯胺醚或三甲基取代三苯胺基團之芳香族高分子合成、電化學、電致變色與 氣體穿透特性之研究

Abstract

第一個4,4’-diamino-2’’,4”,6’’-trimethyltriphenylamine單體化合物的合成，是由對氟硝基苯與2,4,6-三甲基苯胺進行親核性取代反應生成二硝基化合物，接著再用聯胺與鉑金屬催化還原而被合成出。另一個新型含三苯胺的二胺bis(4-amino-4’-methoxytriphenylamine)ether首先合成 bis(N-4-methoxyphenyl- N-4-nitrophenyl-4-aminophenyl)ether由對甲氧基碘苯與對硝基苯胺進行親核性取代反應生成硝基化合物，接著再用氫氣與鉑金屬催化還原而被合成出。本論文分成五個章節，第一章為總體序論。第二和三章節包含了以4,4’-diamino-2’’,4”,6’’-trimethyl-triphenylamine、4,4’-diamino-,4’’-methyl-triphenyl- amine和bis(N-4-aminophenyl-N-4-methoxyphenyl-4-aminophynyl)ether為主體所合成出的三個系列新型含三苯胺之芳香族聚(胺-醯胺)，第四章是以4,4’-diamino-2’’,4”,6’’-trimethyltriphenylamine、4,4’-diamino-,4’’-methyl- triphenylamine和bis(N-4-aminophenyl-N-4-methoxyphenyl-4 -aminophenyl)ether 為主體所合成出的三個系列新型含三苯胺之芳香族聚(胺-醯亞胺)。第五章節為結論。這五個系列新型三苯胺衍生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，高的玻璃轉換溫度，好的熱穩定性和機械性質，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。這些含三苯胺的高分子由於HOMO值和出色的電化學及熱穩定性也許能被廣泛的應用在電致變色和氣體分離薄膜的材料。

First compound, 4,4’-diamino-2’’,4”,6’’-trimethyltriphenylamine was synthesized by hydrazine Pd/C-catalyzed reduction of the dinitro compound 4,4’-dinitro-2’’,4”,6’’-trimethyltriphenylamine resulting from the sodium hydride-mediated aromatic nucleophilic substitution reaction of 2,4,6-trimethylaniline with 4-fluoronitrobenzene. Another novel compound, bis(N-4-aminophenyl-N-4-methoxyphenyl-4-aminophenyl)ether was synthesized by hydrogen Pd/C-catalyzed reduction of the dinitro compound bis(N-4-methoxyphenyl-N-4-nitrophenyl-4-aminophenyl)ether resulting from the potassium carbonate-mediated aromatic nucleophilic substitution reaction of bis(N-4-nitrophenyl-4-aminophenyl)ether with 4-iodoanisole. This study has been separated into five chapters. Chapter 1 is general induction. Chapter 2 and 3 include three series of novel aromatic, poly(amine-amide)s based on 4,4’-diamino-2’’,4”,6’’-trimethyltriphenylamine, 4,4’-diamino-,4’’- methyltriphenylamine and bis(N-4-aminophenyl-N-4-methoxyphenyl-4 -aminophenyl)ether, respectively. The Chapter 4 include three series of novel aromatic poly(amine-imide)s and derived from 4,4’-diamino-2’’,4”,6’’-trimethyltriphenylamine, 4,4’-diamino-,4’-methyltriphenylamine and bis(N-4-aminophenyl-N-4 -methoxyphenyl-4-aminophenyl)ether, respectively. Chapter 5 is conclusions. The synthesis, basic characterization, electrochemical and electrochromic properties of six series of novel aromatic triphenylamine-derived polymers 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 Tg values, good thermal stability, 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. Thus, these triphenylamine-containing polymers may be widely applied in electrochromic materials and membrane of gas separation due to their proper HOMO values, excellent electrochemical and thermal stability.