主鏈含三苯胺結構及側鏈帶有3,6-雙(第三丁基)咔唑基團之新型芳香族聚醯胺及聚醯亞胺的合成與光電性質

Synthesis and Optoelectronic Properties of Novel Aromatic Polyamides and Polyimides Having Triphenylamine Units in The Main Chain and 3,6-Bis(tert-butyl)carbazole Pendent Groups

廖士和(Shih-Ho Liao)

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

本論文包含兩個研究主題，第一部分在描述主鏈含三苯胺結構及側鏈帶有3,6-bis(tert-butyl)carbazole基團之新型芳香族聚醯胺的合成與光電性質。一種由咔唑所衍生的新型含三苯胺結構的二胺單體4,4’-diamino-4’’-(3,6-di-tert-butylcarbazol-9-yl)triphenylamine是由3,6-di-tert-butyl-9-(4-aminophenyl)carbazole 和4-fluoronitrobenzene進行氟化銫-芳香親核取代反應，隨即再以聯胺和Pd/C催化還原二硝基中間產物而得到。具有非晶型和有機可溶性之聚醯胺是由芳香族二羧酸和上述之二胺進行磷酸化聚縮合反應而製得。所有聚醯胺很容易溶解在極性的有機溶劑中，並可經由他們的溶液塗佈鑄成可撓曲性強韌的薄膜，這些聚合物具有高的玻璃轉移溫度(Tg)，其值約在291與321 ℃之間，他們亦具備很好的熱安定性，聚醯胺可耐熱至400 ℃以上。聚合物的氧化還原行為是用循環伏安法(cyclic votammetry ; CV)測定之，這些的聚合物均具有兩個可逆的氧化程序。此外，這些聚合物具有良好的電致變色特性，他們的薄膜顏色可從中性態的淡黃色轉變成氧化態的綠色及藍色。
　　本論文的第二部分是在探討主鏈含三苯胺結構及側鏈帶有3,6-bis(tert-butyl)carbazole基團之新型芳香族聚醯亞胺的合成與光電性質。聚醯亞胺是由上述新合成的二胺與二酐先行開環聚加成反應，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。大部份的聚醯亞胺很容易溶解在極性的有機溶劑中，並可經由他們的溶液塗佈鑄成可撓曲性強韌的薄膜。它們具有高的玻璃轉移溫度(Tg)，其值約在320與346 ℃之間，他們在500 ℃以前沒有明顯的分解。聚醯亞胺的氧化還原行為是用循環伏安法測定，它們均具有兩個可逆的氧化程序。這些聚合物具有良好的電致變色特性，他們的薄膜顏色可從中性態的淡黃色轉變成第一個氧化態的綠色及全氧化態的藍色。

關鍵字

聚醯亞胺 ； 聚醯胺 ； 咔唑 ； 電致變色

並列摘要

This thesis consists of two parts. The first part deals with the syntheses and optoelectronic properties of novel poly(amine-amide)s bearing main-chain triphenylamine units and 3,6-bis(tert-butyl)carbazole pendent groups. A new carbazole-derived triphenylamine-cotaining diamine monomer, 4,4’-diamino-4’’-(3,6-di-tert-butylcarbazol-9-yl)triphenylamine was synthesized via the cesium fluoride-mediated N,N-diarylation of 3,6-di-tert-butyl-9-(4-aminophenyl)carbazole with 4-fluoronitrobenzene, followed by palladium-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 with various dicarboxylic acids. All poly(amine-amide)s were readily in organic solvents and could be solution cast into flexible and tough films. All poly(amine-amide)s showed high glass-transition temperature (Tg) between 291-321 ℃, and they were fairly stable up to a temperature above 400 ℃. The redox behaviors of the polymer were examined by cyclic votammetry (CV), and all the polymers showed two reversible oxidation processes. In addition, these polymers revealed good electrochromic characteristics, with coloration change from a pale yellowish state to deep green and deep blue oxidized states.
The second part deals with the syntheses and optoelectronic properties of novel aromatic poly(amine-imide)s with main-cain triphenylamine and pendent 3,6-bis(tert-butyl)carbazole units. 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. Most of the poly(amine-imide)s were readily in organic solvents and could be solution cast into flexible and tough films. They exhibited high Tg of 320-346 ℃ and did not show significant thermal decomposition before 500 ℃. In addition, cyclic voltammograms of the poly(amine-imide) films on ITO-glass exhibited two reversible redox process. The polymer films revealed excellent stability of electrochromic characteristics and coloration change from yellow in the neutral state, green as a radical cation, and deep blue when fully oxidized.

並列關鍵字

carbazole ； triphenyl(anine-amide)s ； triphenyl(anine-imide)s ； electrochromic

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