側鏈含金剛烷基取代之苯氧基及主鏈具三苯胺結構的新型聚醯亞胺之合成及其性質之研究

Synthesis and Properties of Novel Triphenylamine-based Polyimides with Adamantyl-Substituted Phenoxy Pendent Groups

郭珍華(Chen-hua Kuo)

指導教授 ： 蕭勝輝

大同大學/工程學院/化學工程學系所/碩士(2007年)

摘要

一種新型具有三苯胺結構的芳香族二胺單體 4-[4-(1-adamantyl)- phenoxy]-4’,4”-diaminotriphenylamine是使用 4-(1-adamantyl)-4’- aminodiphenol ether 與 1-fluoro-4-nitrobenzene，於DMSO中，以氟化銫 (CsF)為觸媒，進行氮-芳香化反應（N-arylation），隨後再進行二硝基中間產物的還原反應而得。之後，再利用上述製得的二胺單體和一系列市售之芳香族二酐經由熱閉環法或化學閉環法，製備一系列新型、具有金剛烷基苯氧基取代的三苯胺結構的芳香族聚醯亞胺。這些聚醯亞胺呈現非結晶結構，並可製成具有可撓曲性及良好機械性能的薄膜。這些聚合物具有優秀的熱安定性，玻璃轉移溫度介於 273 到 310 oC 之間，10%的重量損失溫度皆在 527 oC 以上，在氮氣下加熱至 800 oC 時的焦炭殘餘率超過52％。此外，我們也利用電化學及光譜電化學來探討它們的電動傳輸及電致變色的特性。塗佈在 ITO 玻璃上的聚醯亞胺薄膜的循環伏安圖在半波電位(E1/2) 1.12~1.13 V 之間顯示一對可逆的氧化還原峰，而且這些聚醯亞胺薄膜在 0.0 V 及 1.4 V 連續數次的變換施加電壓後，仍呈現良好穩定的電致變色特性，顏色會從中性態的淺黃色變化成氧化態的藍色。

關鍵字

電致變色 ； 聚醯亞胺 ； 苯氧基 ； 金剛烷 ； 三苯胺

並列摘要

A new triphenylamine-containing aromatic diamine monomer, 4-[4-(1-adamantyl)phenoxy]-4’,4”-diaminotriphenylamine, was synthesized from cesium fluoride-mediated N-arylation of 4-(1-adamantyl)-4’-aminodiphenyl ether with 1-fluoro-4-nitrobenzene and subsequent reduction of the dinitro intermediate. A series of novel aromatic polyimides with adamantylphenoxy-substituted triphenylamino groups were prepared from the newly synthesized diamine monomer with aromatic tetracarboxylic dianhydridess. The polyimides were amorphous and could afford transparent, tough, and flexible films with good mechanical properties. The polymers showed excellent thermal stability, with high glass transition temperatures between 273 and 310 °C, 10% weight-loss temperatures in excess of 527 °C, and char yields higher than 52% at 800 °C in nitrogen. The hole-transporting and electrochromic properties are examined by electrochemical and spectroelectrochemical methods. Cyclic voltammograms of the polyimide films on an indium-tin oxide (ITO)-coated glass substrate exhibited one pair of reversible redox couples at E1/2 = 1.12~1.13 V versus Ag/AgCl in an acetonitrile solution. The polyimide films revealed excellent stability of electrochromic characteristics by continuous several cyclic scans between 0.0 and 1.4 V; the color of the films changed from the pale yellowish neutral form to the blue oxidized form.

並列關鍵字

adamantane ； triphenylamine ； electrochromism ； phenoxy

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