具二甲胺基取代的三苯胺結構之芳香族聚醯亞胺之合成與其性質之研究

Synthesis and Properties of Aromatic Polyimides with Dimethylamino- substituted Triphenylamine Groups

池鈺雯(Yu-Wen Chih)

指導教授 ： 郭文正 ； 蕭勝輝

國立臺北科技大學/工程學院/化學工程研究所/碩士(2009年)

摘要

本研究利用N,N- dimethyl-p-phenylenediamine與4-fluoronitrobenzene，於DMSO溶劑中，以氟化銫（CsF）為媒介進行芳香性親核取代反應，得到4,4′-Dinitro- 4′′-(dimethylamino)triphenylamine，隨後再進行聯胺和Pd/C催化還原反應，進而製得一種新型具有三苯胺結構的芳香族二胺單體4,4′-diamino-4′′-(dimethylamino)- triphenylamine。之後，再利用上述製得的二胺單體和一系列芳香族二酐進行聚縮合反應，製備一系列新型、具有二甲胺基取代的三苯胺結構芳香族聚醯亞胺。這些聚合物具有優異的耐高溫特性，它們的玻璃轉移溫度介於299∼324 ℃之間，它們在500 ℃之前不會產生明顯的熱裂解，在氮氣中分解5%的熱損失溫度為425 ℃以上，而在空氣中分解5%的熱損失溫度為442 ℃以上。塗佈在ITO玻璃上的聚合物薄膜，其循環伏安（CV）圖皆顯示出二對可逆的氧化還原峰，聚醯亞胺的第一半波氧化電位約在0.49∼0.59 V附近，第二半波氧化電位約在0.93∼0.96 V之間。這些聚合物具有良好的電致變色特性，他們在中性態為淡黃色，在一階氧化態時呈現綠色，二階氧化態會呈現藍紫色。

關鍵字

三苯胺 ； 芳香族聚醯亞胺 ； 電化學 ； 電致變色

並列摘要

4,4′-Diamino-4′′-(dimethylamino)triphenylamine was synthesized by the cesium fluoride (CsF)-mediated nucleophilic displacement reaction of 1-fluoro-4-nitrobenzene with N,N-dimethyl-p-phenylenediamine in dimethyl sulfoxide, followed by palladium- catalyzed hydrazine reduction of the intermediate compound 4,4′-dimitro- 4′′-(dimethylamino)triphenylamine. This newly synthesized diamine monomer was polycondensed with various aromatic tetracarboxylic dianhydrides to produce a series of novel triphenylamine-based polyimides with pendent dimethylamino substituents. These polymers showed high glass transition temperatures between 299 and 324 ℃, and they were stable up to a temperature above 500 ℃. The 5 % weight-loss temperatures of these polymers in nitrogen and air were higher than 425 and 442 ℃, respectively. Cyclic voltammograms of the polyimides showed two reversible redox waves with half-wave oxidation potentials (E1/2) of 0.49-0.59 V and 0.93-0.96 V (versus Ag/AgCl), respectively, in an acetonitrile solution. The polyimide films revealed good stability of electrochromic characteristics, with a coloration change of the film from the pale yellow neutral form to the green semioxidized form, and the purple-blue fully oxidized state. The coloration change was followed by UV-Vis spectroscopy.

並列關鍵字

Triphenylamine ； Aromatic Polyimides ； Electrochemistry ； Electrochromism

參考文獻

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