具有三苯胺結構的電致變色聚醯胺醯亞胺之合成與性質之研究

SYNTHESIS AND PROPERTIES OF ELECTROCHROMIC POLY(AMIDE-IMIDE)S WITH TRIPHENYLAMINE UNITS

李宜儒(Yi-Ju Lee)

指導教授 ： 蕭勝輝

大同大學/工程學院/化學工程學系所/碩士(2009年)

摘要

本論文包含兩部份。第一個部分探討由帶有三苯胺(triphenylamine; TPA) 結構及醯亞胺環的二羧酸和各種芳香族二胺所衍生出之新型具 TPA 結構的芳香族聚醯胺醯亞胺[poly(amide-imide)s; PAIs]的合成與特性。三種新型具有TPA 結構及雙醯亞胺環的二羧酸單體是由4,4’-diamino-2”,4”-dimethoxytriphenylamine, 4,4’-diamino-4”- methoxytriphenylamine, 4,4’-diaminotriphenylamine 和兩倍莫耳的trimellitic anhydride 縮合而得。一系列新型具電活性TPA 結構的芳香族PAI 係由這三種雙醯亞胺二羧酸與各種芳香族二胺經由亞磷酸三苯酯 (triphenyl phosphite) 催化之聚縮合反應而製得。在本論文的第二部分中，三種二胺單體4,4’-diamino-2”,4”-dimethoxytriphenylamine,4,4’-diamino-4”-methoxytriphenylamine 及4,4’-diaminotriphenylamine各別與四種含醯亞胺環的二羧酸單體聚合合成出另一系列含TPA、電 活性的新型PAI。大部分的PAI 容易溶解在許多有機溶劑中並可經由他們的溶液塗佈鑄成可撓曲性、強韌的薄膜。第一部份中的PAI 的玻璃轉移溫度(glass-tranisition temperature; Tg)在266-326 oC 之間，且在470 oC 之前沒有明顯的裂解。第二系列PAI 的Tg 則是在196-326 oC之間，他們可耐熱至高達445 oC 之溫度。塗佈在ITO 玻璃上的PAI 薄膜在氰甲烷溶液中測得的循環伏安圖顯示出一對或兩對可逆的氧化還原峰。所有含甲氧基取代的TPA 結構的PAI 比沒有甲氧基結構取代的聚合物顯現較佳的電化學穩定性。這些聚合物具有穩定的電致變色特性，他們的薄膜顏色可從中性態的無色或淡黃色轉變成氧化態 的綠色或藍色。這些陽極變色的高分子材料在氧化與還原態之間變色時大致上具有快速的應答時間及高的對比。

關鍵字

甲氧基 ； 聚醯胺醯亞胺 ； 三苯胺

並列摘要

This thesis consists of two parts. The first part deals with the syntheses and
characterization of novel triphenylamine (TPA)-containing aromatic poly(amide-imide)s (PAIs) derived from TPA-bearing, imide ring-preformed dicarboxylic acids and various aromatic diamines. Three new dicarboxylic acid monomers bearing a TPA unit and two preformed imide rings were prepared by the condensation of 4,4’-diamino-2”,4”-dimethoxytriphenylamine, 4,4’-diamino-4”-methoxytriphenylamine, and 4,4’-diaminotriphenylamine, respectively, with two molar equivalents of trimellitic anhydride. A new family of aromatic PAIs containing the electroactive TPA unit were prepared by the triphenyl phosphite activated polycondensation of these three diimide-diacids with various aromatic diamines. In the second part of this thesis, the diamine monomers, 4,4’-diamino-2”,4”-dimethoxytriphenylamine, 4,4’-diamino-4”-methoxytriphenylamine, and 4,4’-diaminotriphenylamine, were respectively reacted with four imide ring-preformed dicarboxylic acid monomers to produce another new series of TPA-containing, electroactive PAIs. Most of the PAIs were readily soluble in many organic solvents and could be solution-cast into tough and flexible polymer films. The PAIs reported in the first part exhibited glass-transition temperatures (Tgs) in the range of 266-326 oC and did not show significant decomposition before 470 oC. The second PAI series had Tgs between 196 and 298 oC and were fairly stable up to a temperature above 445 oC. Cyclic voltammograms of the PAI films cast onto an indium-tin oxide (ITO)-coated glass substrate showed one or two reversible redox pairs in acetonitrile solution. All the PAIs containing the methoxy-substituted TPA moieties exhibited an enhanced electrochemical stability as compared with their analogs without the methoxy substitution. The polymer films also revealed stable electrochromic properties, with coloration change from a colorless or pale yellowish neutral state to green or blue when fully oxidized. In general, these anodically coloring polymeric materials showed fast response time and high coloration contrast between redox states.

並列關鍵字

triphenylamine ； methoxy ； poly(amide-imide) ； PAI

參考文獻

4. Walczak, R. M.; Reynolds, J. R. Adv. Mater. 2006, 18, 1121.

5. Hsiao, S.-H.; Chang, Y.-M.; Chen, H.-W.; Liou, G.-S. J. Polym. Sci. Part A: Polym.

6. Liou, G.-S.; Hsiao, S.-H.; Chen, H.-W. J. Mater. Chem. 2006, 16, 1831.

7. Liou, G.-S.; Chang, C.-W. Macromolecules 2008, 41, 1667.

9. Liou, G.-S.; Chang, C.-W. J. Mater. Chem. 2008, 18, 5638.