新型具4-甲氧基三苯胺基團之芳香族高分子之合成與電化學及電致變色性質之研究

第一個4,4’-diamino-4”-methoxytriphenylamine單體化合物的產生，是由對氟硝基苯與對甲氧基苯胺進行親核性取代反應生成硝基化合物，接著再用聯胺與鉑金屬催化還原而被合成出。另二個新型含三苯胺的二胺N,N-bis(4-aminophenyl)-N’,N’-di(4-methoxyphenyl)-1,4-phenylenediamin 和二羧酸N,N-bis(4-carboxyphenyl)-N’,N’-di(4-methoxyphenyl)-1,4-phenylenediamine單體化合物的產生。首先合成4-amino-4’,4’’-dimethoxytriphenylamine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，接著再用聯胺與鉑金屬催化還原而被合成出。更進一步的分別與對氟硝基苯和對氟苯腈進行胺基化反應，隨後將二硝和二腈中間物分別還原和鹼性水解而產生。本論文分成七個章節，第一章為總體序論。第二和三章節包含了以4,4’-diamino-4”-methoxytriphenylamine為主體所合成出的二個系列新型含三苯胺之芳香族聚(胺-醯胺)和聚(胺-醯胺-醯亞胺)，第四和第五章節是以N,N-bis(4-aminophenyl)-N’,N’-di(4-methoxyphenyl)-1,4-phenylenediamine和 N,N-bis(4-carboxyphenyl)-N’,N’-di(4-methoxyphenyl)-1,4-phenylenediamine 為主體所合成出的二個系列新型含三苯胺之芳香族聚(胺-醯胺)和(胺-醯胺)，第六章節包含了以4,4’-diaminotriphenylamine, 4,4’-diamino-4”-methoxytriphenylamine, N,N-bis(4-aminophenyl)-N’,N’-diphenyl-1,4-phenylenediamine和N,N-bis(4-aminophenyl)-N’,N’-di(4-methoxyphenyl)-1,4-phenylenediamine為主體所合成出的一個系列新型含三苯胺之芳香族聚(胺-醯亞胺)。第七章節為結論。這五個系列新型具三苯胺側鏈基團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，高的玻璃轉換溫度和軟化溫度，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，所有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。

關鍵字

三苯胺；聚(胺-醯胺) ；聚(胺-醯胺-醯亞胺) ；電致變色；電化學

並列摘要

First compound, 4,4’-diamino-4”-methoxytriphenylamine was synthesized by the nucleophilic fluoro-displacement reaction of 4-fluoronitrobenzene with p-anisidine, followed by palladium-catalyzed hydrazine reduction. Another two novel compounds, N,N-bis(4-aminophenyl)-N’,N’-di(4-methoxyphenyl)-1,4-phenylenediamine and N,N-bis(4-carboxyphenyl)-N’,N’-di(4-methoxyphenyl)-1,4-phenylenediamine were synthesized. First 4-amino-4’,4’’-dimethoxytriphenylamine was synthesized by the nucleophilic fluoro-displacement reaction of 4-nitroaniline with 4-iodoanisole, followed by palladium-catalyzed hydrazine reduction. Further amination reaction between 4-amino-4’,4’’-dimethoxytriphenylamine with 4-fluoronitrobenzene and 4-fluorobenzonitrile, subsequent reduction and alkaline hydrolysis of the dinitro and dinitrile intermediate led to two new triphenylamine-containing aromatic diamine and dicarboxylic acid. This study has been separated into seven chapters. Chapter 1 is general induction. Chapter 2 and 3 include two series of novel aromatic, poly(amine-amide)s and poly(amine-amide-imide)s based on 4,4’-diamino-4”-methoxytriphenylamine. The Chapter 4 and 5 include two series of novel aromatic poly(amine-amide)s and poly(amine-amide)s derived from and N,N-bis(4-aminophenyl)-N’,N’-di(4-methoxyphenyl)-1,4-phenylenediamine and N,N-bis(4-carboxyphenyl)-N’,N’-di(4-methoxyphenyl)-1,4-phenylenediamine, respectively. The lastest series of novel aromatic poly(amine-imide)s derived from 4,4’-diaminotriphenylamine, 4,4’-diamino-4”-methoxytriphenylamine, N,N-bis(4-aminophenyl)- N’,N’-diphenyl-1,4-phenylenediamine and N,N-bis(4-aminophenyl)-N’,N’-di(4-methoxyphenyl)-1,4-phenylenediamine were summarized in Chapter 6. Chapter 7 is conclusions. The synthesis, basic characterization, electrochemical and electrochromic properties of five series of novel aromatic polymers bearing pendent triphenylamine groups were investigated and compared. All polymers had good solubility in many polar aprotic solvents, and exhibited excellent thin-film-forming ability. In additional to high Tg or Ts values, good thermal stability, mechanical properties, and lower HOMO energy levels. All 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.