具三甲氧基活化之三苯胺結構的新型聚醯胺及聚醯亞胺的合成與光致發光及電致變色性質研究

Synthesis, Photoluminescent and Electrochromic Properties of Novel Polyamides and Polyimides with Trimethoxy-Activated Triphenylamine Moiety

葉雅琇(Ya-Hsiu Yeh)

指導教授 ： 蕭勝輝 ； 李文福 ； 劉貴生

大同大學/工程學院/化學工程學系所/碩士(2008年)

摘要

本論文研究主題主要在探討在主鏈上含有3,4,5-trimethoxytriphenylamine 基團之新型芳香族聚醯胺及聚醯亞胺之合成與性質。一種新型含三苯胺結構的二胺單體4,4’-diamino-3,”4”,5”-trimethoxytriphenylamine是以氟化銫為媒介由3,4,5-trimethoxyaniline和4-fluoronitrobenzene 進行芳香親核取代反應，然後再以聯胺和鈀觸媒催化還原二硝基中間產物而製得。具有3,4,5-trimethoxytriphenylamine基團之非晶型及有機可溶性之聚醯胺是由各種芳香族二羧酸和上述所合成出之二胺單體進行磷酸化聚縮合反應而製得。所有的聚醯胺均很容易溶解在極性的有機溶劑中，並可經由它們的溶液塗佈鑄成可撓曲性及強軔的薄膜。這些聚醯胺具有高的玻璃態轉移溫度(Tgs)，其值約在250與288 °C之間，它們亦具備很好的熱安定性，可耐熱至400 °C以上。這些聚醯胺在紫外光區的最大吸收值介於314與379 nm之間，它們在NMP的溶液(10-5M)中的光激發光譜顯示最大放光強度的波長介於392與471 nm之間。由電化學方法可測得聚合物的初始電子轉移電位與其陽離子自由基的穩定性，塗佈在ITO玻璃上的聚醯胺薄膜，在氰甲烷溶液中的循環伏安圖顯示出在0.88-0.94伏特附近有一個強的氧化峰，而起始氧化電位約在0.65-0.68伏特左右。我們發現這些主要的氧化過程全為不可逆，當電極的電壓從0.0伏特升至 2.0伏特的過程當中，塗佈在ITO玻璃上的薄膜會顯示強的顏色變化，從無色轉化變成綠色之後轉變為紅棕色，而這些顏色的變化是不可逆的。在這些聚合物的氧化過程中似乎伴隨著某種快速、不可逆的化學反應。聚醯亞胺是由上述新合成的二胺與各種芳香族二酐先行開環聚加成反應成聚醯胺酸，再利用加熱或化學脫水劑脫水環化而得。這些聚醯亞胺具有高的玻璃態轉移溫度(Tgs) ，他們的值介於262與297 ℃之間，它們並且具有很好的熱安定性，在440 °C 之前都沒有明顯的重量損失。這些聚合物在紫外光區的最大吸收的波長值介於301與322 nm之間，最大放光強度的波長介於392與471 nm之間。塗佈在ITO玻璃上的聚醯亞胺薄膜，在氰甲烷溶液中的循環伏安圖顯示出在0.96-0.99伏特附近有一個強的氧化峰，而起始氧化電位約在0.80-0.83伏特左右。這些聚醯亞胺也同樣顯示不可逆的氧化程序。

關鍵字

聚醯胺 ； 聚醯亞胺

並列摘要

This thesis deals with the syntheses and characterization of novel aromatic poly(amine-amide)s and poly(amine-imide)s with 3,4,5-trimethoxytriphenylamine units in the backbone based on a newly synthesized diamine monomer, 4,4’-diamino-3”,4”,5”-trimethoxytriphenylamine. This diamine monomer was synthesized via the cesium fluoride-mediated N,N-diarylation of 3,4,5-trimethoxyaniline with 4-fluoronitrobenzene, followed by palladium-catalyzed hydrazine reduction of the dinitro intermediate. The poly(amine-amide)s were prepared by the phosphorylation polyamidation of the newly synthesized diamine monomer with various aromatic dicarboxylic acids. All poly(amine-amide)s were readily soluble in polar organic solvents and could be solution cast into flexible and tough films. They showed high glass-transition temperatures (Tg) between 250-288 °C and did not display significant decomposition before 400 °C. These polymers exhibited UV absorption maxima around 314-379 nm. The photoluminescence spectra of their dilute solutions (10-5 M) in N-methyl-2-pyrrolidone (NMP) exhibited a blue light emission at 392-471 nm. The initial electron-transfer and the stability of the cation radical of the polymers were studied by electrochemistry. Cyclic voltammograms (CV) of the poly(amine-amide) films cast onto an indium-tin oxide (ITO) coated glass substrate in acetonitrile solution exhibited one strong oxidation peak around 0.88-0.94 V versus Ag/AgCl with onset oxidation potential around 0.65-0.68 V. The main oxidation peak was taken as totally irreversible. During the CV scan, the cast films on the ITO electrode showed strong coloration change from colorless to pale green and then reddish-brown as the electrode potential increased from 0.0 to 2.0 V, and this color change was irreversible. A rapid, irreversible, chemical reaction seemed to occur during the oxidation process in these polymers. The poly(amine-imide)s were prepared from the newly synthesized diamine monomer with various aromatic dianhydrides via a conventional two-step procedure that included a ring-opening polyaddition to form poly(amic acid)s, followed by thermal or chemical cyclodehydration. These poly(amine-imide)s showed Tgs in the range 262-297 °C, and they were fairly stable up to a temperature above 440 °C. These polymers exhibited UV absorption maxima around 301-322 nm. The photoluminescence spectra of these polymers in N-methyl-2-pyrrolidone (NMP) solution (10-5 M) exhibited a blue light emission at 343-421 nm. Cyclic voltammograms of the poly(amine-imide) films cast onto an ITO-coated glass substrate in acetonitrile solution exhibited one strong oxidation peak around 0.96-0.99 V versus Ag/AgCl with onset oxidation potential around 0.80-0.83 V. The oxidation process was also irreversible.

並列關鍵字

Polyamides ； Polyimides

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