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胺之合成與光致發光及電致變色性質之研究

Synthesis, Photoluminescene and Electrochromic Properties of Novel Triphenylamine-based Polyamides with Adamantyl-Substituted Phenoxy Pendent Groups

潘虹吟(Hung-yin Pan)

指導教授 ： 蕭勝輝

大同大學/工程學院/化學工程學系所/碩士(2005年)

摘要

本研究首先使用 4-(1-adamantyl)-4’-aminodiphenol ether 與 1-fluoro-4-nitrobenzene，於DMSO中，以氟化銫 (CsF)為媒介，進行氮-芳香化反應（N-arylation），隨後再進行中間產物的還原反應，製得一個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。之後，再利用上述製得的二胺單體和一系列芳香族二羧酸進行磷酸化直接聚縮合反應，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胺。這些聚醯胺呈現非晶形結構，可溶在如 NMP、DMAc 和 DMF 等極性有機溶劑中，並可由它們的溶液鑄成透明且具有可撓曲性的強韌薄膜。這些聚合物的玻璃轉移溫度介於 254 到 293 oC 之間，在氮氣或空氣下的10%重量損失溫度皆在 493 oC 以上，在氮氣下加熱至 800 oC 時的焦炭殘餘率超過56％，顯示具有良好的熱安定性。這些聚醯胺的 DMAc 溶液在306~357 nm 附近具有強的 UV-Vis 吸收，它們的光激發光譜顯示會放λmax = 430~443 nm 的藍光。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 玻璃上的聚醯胺薄膜的循環伏安圖在半波電位(E1/2) 0.81~0.85 V 之間顯示一對可逆的氧化還原峰，而且這些聚醯胺薄膜在 0.0 V 及 1.0 V 連續數十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綠色。

關鍵字

金剛烷取代 ； 電致變色 ； 光機發光 ； 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 polyamides with adamantylphenoxy-substituted triphenylamino groups were prepared by the phosphorylation polyamidation of the newly synthesized diamine monomer with aromatic dicarboxylic acids. The polyamides were amorphous and soluble in polar aprotic solvents such as N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), and N,N-dimethylformamide (DMF). These polymers can be solution-cast into transparent, tough, and flexible films with good mechanical properties. The polymers showed excellent thermal stability, with high glass transition temperatures between 254 and 293 °C, 10% weight-loss temperatures in excess of 493 °C, and char yields higher than 56% at 800 °C in nitrogen. These polymers exhibited strong UV-vis absorption bands at 306–357 nm in DMAc solutions. The photoluminescence spectra showed maximum bands around 430-443 nm in the blue region. The hole-transporting and electrochromic properties are examined by electrochemical and spectroelectrochemical methods. Cyclic voltammograms of the polyamide films on an indium-tin oxide (ITO)-coated glass substrate exhibited one pair of reversible redox couples at E1/2 = 0.81~0.85 V versus Ag/AgCl in an acetonitrile solution. The polyamide films revealed excellent stability of electrochromic characteristics by continuous several cyclic scans between 0.0 and 1.0 V; the color of the films changed from the pale yellowish neutral form to the green oxidized form.

並列關鍵字

Adamantyl-Substituted ； electrochromic ； photoluminescene ； triphenylamine

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