新型具三苯胺側鏈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

Synthesis, Stable Electrochemical and Electrochromic Properties of New Aromatic Polymers Bearing Pendent Triphenylamine Groups

鍾承憲(Chen-Hsien Chung)

指導教授 ： 劉貴生

國立暨南國際大學/科技學院/應用化學系/碩士(2007年)

摘要

4-amino-4’,4”-dimethyltriphenylamine是由對碘甲苯與對硝基苯胺進行Ullma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使致二個新型含三苯胺的二胺N,N-bis(4-aminophenyl)-N’,N’-di(4-methylphenyl)-1,4-phenylenediamine和二羧酸N,N-bis(4-carboxyphenyl)-N’,N’-di(4-methylphenyl)-1,4-phenylenediamine單體化合物的產生。本論文分成兩個部分，第一部分為研究N,N-bis(4-aminophenyl)-N’,N’-di(4-methylphenyl)-1,4-phenylenediamine為主體所合成出新型含三苯胺之芳香族聚(胺-醯胺)，第二個部分為研究以N,N-bis(4-carboxyphenyl)-N’,N’-di(4-methylphenyl)-1,4-phenylenediamine為主體所合成出的新型含三苯胺之芳香族聚(胺-醯胺)。這兩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，好的熱穩定性和機械性質，較低的HOMO能階。在利用電化學與光譜電化學的方法下，所有的高分子相對於對位無取代基保護的聚(胺-醯胺)也展現出色可逆的電致變色特性。如此，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P-LED當電洞傳輸層和電致變色的材料。

關鍵字

三苯胺 ； 電化學 ； 電致變色 ； 穩定性.

並列摘要

4-Amino-4’,4”-dimethyltriphenylamine was synthesized by Ullman reaction between 4-iodotoluene and 4-nitroanilne, followed by palladium-catalyzed hydrazine reduction. Further amination reaction between 4-aminotriphenylamine 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, N,N-bis(4-aminophenyl)-N’,N’-di(4-methylphenyl)-1,4-phenylenediamine and N,N-bis(4-carboxyphenyl)-N’,N’-di(4-methylphenyl)-1,4-phenylenediamine, respectively. This study consists of two parts. Part I investigates the synthesis and properties of a series of novel aromatic, poly(amine-amide)s based on N,N-bis(4-aminophenyl)-N’,N’-di(4-methylphenyl)-1,4-phenylenediamine. The second part investigates the novel aromatic poly(amine-amide)s derived from N,N-bis(4-carboxyphenyl)-N’,N’-di(4-methylphenyl)-1,4-phenylenediamine were summarized in Part II. The synthesis, basic characterization, electrochemical and electrochromic properties of two 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 values, good thermal stability, and lower HOMO energy levels, all the obtained polymers also revealed batter reversibility of electrochromic characteristics in comparison with structurally similar polyamides without the methyl substituent. Thus, these triphenylamine-containing polymers may find applications in P-LED as hole-transporting layer and electrochromic materials due to their proper HOMO values, excellent electrochemical and thermal stability.

並列關鍵字

triphenylamine ； electrochemical properties ； electrochromic characteristics ； stability.

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