具基取代三苯胺基團之新型芳香族聚合物的合成與光致發光及電致變色性質之研究

Synthesis, Photoluminescence and Electrochromism of Novel Aromatic Polymers with N-indolyltriphenylamine Moiety

黃儀芬(Yi-Fen Huang)

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

本論文包含三個研究主題， 第一部分在描述在主鏈上含有 N-indolyltriphenylamine 基團之新穎芳香族聚醯胺及聚醯亞胺之合成與 性質。一種由(indole)所衍生的新型含三苯胺結構的二胺單體 4-(N-indolyl)-4’,4”-diaminotriphenylamine 是在氟化銫共存下由 N-(4-aminophenyl)indole 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 N-indolyltriphenylamine 基團之非晶型及有機可溶性之聚醯胺是由芳香 族二羧酸和上述所合成出之二胺進行磷酸化聚縮合反應而製得。聚醯亞 胺是由二胺與二酐先行開環聚加成反應成聚醯胺酸後再利用加熱或化 學脫水劑脫水環化而得。所有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。聚醯亞胺薄 膜則可經由他們的聚醯胺酸[poly(amic acid)s] 薄膜加熱脫水環化而製 得。這些聚合物具有高的玻璃態轉移溫度(Tg)，其值約在296與316 ℃之 間，它們亦具備很好的熱安定性，聚醯胺可耐熱至500 ℃以上，聚醯亞 胺可耐熱至600 ℃以上。這些聚合物的氧化還原行為是用循環伏安法 (cyclic voltammetry; CV)測定之，大部分的聚合物具有一個可逆的氧化程 序，部分的聚醯胺顯示另一個不可逆的氧化程序。此外，這些聚合物大 致上均具有良好的電致變色特性，它們的薄膜顏色可從中性態的淡黃色轉變成氧化態的綠色或藍色。 本論文的第二部分是在探討一種含有 N-indolyltriphenylamine結構 的二羧酸所衍生出的新穎芳香族聚醯胺之合成與性質。一種新型二羧酸 單體4,4'-dicarboxy-4"-(N-indolyl)triphenylamine 是以氫化納當鹼由 N-(4-aminophenyl)indole和4-fluorobenzonitrile進行芳香親核取代反應，然 後再將二中間產物鹼性水解而製得。一系列固有黏度介於0.75-1.28 dL/g的聚醯胺是由此二羧酸單體與一些芳香族二胺以Yamazaki直接磷酸 化聚縮合反應製備而得。所有的聚醯胺都可溶於多數的有機溶劑並可經 溶液鑄成強韌的薄膜。這些聚醯胺具有高的Tg (254–305 ℃)，它們在氮氣 下分解掉10 %的熱重量損失溫度值可在 516 ℃以上，顯示出不錯的熱穩 定性。這些聚合物的 NMP 溶液 (10-5 M) 的光激發光譜顯示它們的最 大放光強度的波長 449-465 nm 之間，屬於藍光區，其螢光效率 (ΦF) 最 高可達15.0 %。 本論文最後一部分係探討以 4,4'-dicarboxy-4"-(N-indolyl)triphenylamine 為主體的新穎含基的 poly(amine-hydrazide)s 及poly(amine-1,3,4-oxadiazole)s 之合成與性質。 新穎之芳香族poly(amine-hydrazide)s是由上述之二羧酸與市售之芳香族 二醯及4- 胺基苯醯經由Yamazaki 磷酸化反應而製得。這些 poly(amine-hydrazide)s 可經熱脫水環化成 poly(amine-1,3,4-oxadiazole)s。這些聚合物溶在NMP的溶液中的UV/Vis 吸收光譜波長介於302-386 nm，而其光激發光譜顯示在藍光至綠光區， 波長在431-528 nm之間有最大放射強度，其量子效率最高可達33 %。 這 些聚合物的薄膜的循環伏安圖會顯示出含一對陽極氧化峰，其Eonset值介 於0.93與1.40 V之間，而在陰極亦會出現可逆的還原峰，Eonset值介於-1.39 至 -1.55 V 之間。

關鍵字

電致變色

並列摘要

This thesis consists of three parts. The first part deals with the syntheses and characterization of novel aromatic poly(amine amide)s and poly(amine imide)s bearing a N-indolyltriphenylamine unit on the main chian. A new triphenylamine-based diamine monomer, 4-(N-indolyl)-4’,4”-diaminotriphenylamine (4) was synthesized via the cesium fluoride-mediated N,N-diarylation of N-(4-aminophenyl)indole with 4-fluoronitrobenzene, followed by palladium-on-charcoal-catalyzed hydrazine reduction of the dinitro intermediate. Amorphous and organosoluble poly(amine-amide)s were prepared by the phosphorylation polyamidation of the newly synthesized diamine monomer (4) with various aromatic dicarboxylic acids. Poly(amine imide)s were prepared in conventional two-step method by the reaction of diamine 4 with various aromatic dianhydrides to form poly(amic acid)s, followed by thermal or chemical cyclodehydration. Basic properties of these poly(amine amide)s and poly(amine imide)s, such as inherent viscosity, molecular weights, film-forming ability, mechanical properties, crystallinity, solubility, thermal properties, optical and electrochemical properties were investigated and compared with those of parent poly(amine amide)s and poly(amine imide)s derived from 4,4’-diaminotriphenylamine with the same aromatic diacids and dianhydrides.
The second part of this thesis describes the synthesis and properties of novel poly(amine-amide)s on the basis of 4,4'-dicarboxy-4"-(N-indolyl)triphenylamine (7). The
new triphenylamine-containing dicarboxylic acid monomer 8, was synthesized via the double N-arylation of 4-fluoroaniline with N-(4-aminophenyl)indole, followed by alkaline hydrolysis of the dinitrile intermediate. A new family of poly(amine amide)s with inherent viscosities of 0.75-1.28 dL/g were prepared by the direct phosphorylation polycondensation from the diacid monomer 7 with various aromatic diamines. All of the poly(amine amide)s were readily soluble in a variety of organic solvents and formed strong and tough films via solution casting. The wholly aromatic poly(amine-amide)s have useful levels of thermal stability associated with moderately high glass transtion temperatures (254–305 ℃) and 10 % weight loss temperatures in excess of 516 ℃ in nitrogen. The photoluminescence (PL) spectra of these polymers in N-methyl-2-pyrrolidone (NMP) solution (10-5M) exhibited a strong emission in the blue region at 449-465 nm.
The final part of this thesis reports the synthesis and properties of novel N-indoly poly(amine-hydrazide)s and poly(amine-1,3,4-oxadiazole)s based on 4,4'-dicarboxy-4"-(N-indolyl)triphenylamin. Novel wholly aromatic poly(amine -hydrazide)s were synthesized via the Yamazaki phosphorylation reaction from the diacid and various commercially available aromatic dihydrazides, followed by thermal cyclodehydration to poly(amine-1,3,4-oxadiazole)s. All aromatic polymers exhibited strong UV-Vis absorption bands at 302-375 nm in NMP solution. The photoluminescence spectra showed maximum bands around 453-490 nm in the blue and green region. The hole-transporting and electrochromic properties were examined by electrochemical and spectroelectrochemical methods. For a comparative study, analogous poly(amine-hydrazide)s and poly(amine-1,3,4-oxadiazole)s based on 4,4’-dicarboxytriphenylamine were also prepared and characterized.

並列關鍵字

Electrochromism

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