含三蝶烯結構之聚(醯胺-醯亞胺)及 聚(醯胺-三芳香胺)的合成與性質研究

具有三蝶烯結構之二胺化合物1,4-bis(4-aminophenoxy)triptycene與苯偏三酸酐(trimellitic anhydride)進行縮合反應製成為一具有兩個醯亞胺環的二羧酸單體1,4-bis(4-trimellitimidophenoxy)triptycene。一系列含三蝶烯之聚醯胺醯亞胺[poly(amide-imide)s; PAIs]是由此二醯亞胺二羧酸單體與數種芳香族二胺進行Yamazaki磷酸化聚縮合反應而製得。此系列PAIs之固有黏度值介於0.38-0.61 dL/g之間，大部分的PAIs可溶於多種常見的有機溶劑中並可鑄成強軔的薄膜。這些PAIs的玻璃轉移溫度（Tg）約在274-305℃之間，在氮氣環境下加熱到500℃ 時仍不會產生明顯的熱分解，顯示它們具有優良的熱穩定性。若與不含三蝶烯結構的PAI相比，此系列PAIs展現較佳的溶解度，低的結晶性以及較好的可成膜性。此外，含三蝶烯結構之二胺化合物1,4-bis(4-aminophenoxy)triptycene與二羧酸化合物1,4-bis(4-carboxyphenoxy)triptycene 分別與具有三苯胺 (triphenylamine; TPA) 或咔唑 (carbazole) 基團的單羧酸及單胺化合物縮合成分子中央具有三蝶烯結構及尾端具有三苯胺或咔唑基團的二醯胺化合物，這些二醯胺化合物的電化學及電聚合反應將在本論文中加以探討。藉由電聚合反應在ITO導電玻璃表面上生成的聚(醯胺-三芳香胺)[poly(amide-triarylamine)s]薄膜具有可逆的電化學氧化還原反應及明顯的電致變色現象，我們並以光譜電化學及多次開關測試探討電聚合薄膜的電致變色特性。

關鍵字

三蝶烯；聚醯胺醯亞胺；熱性質；溶解度；電聚合；電致變色；電化學；光譜電化學

並列摘要

First, a diimide-diacid monomer bearing the triptycene unit, namely 1,4-bis(4-trimellitimidophenoxy)triptycene, was synthesized from the condensation reaction of 1,4-bis(4-aminophenoxy)triptycene and two equivalent amount of trimellitic anhydride. A series of new poly(amide-imide)s (PAIs) with triptycene units in the main chain were prepared by the phosphorylation polyamidation reactions from the diimide-diacid monomer with several aromatic diamines including commercially available diamines and 1,4-bis(4-aminophenoxy)triptycene. All the resulting PAIs were readily soluble in many organic solvents and could be solution-cast into tough and flexible polymer films. These PAIs exhibited glass-transition temperatures (Tgs) in the range of 274-305 °C, and they did not show significant weight-loss before 500 oC. In comparison with the structurally similar PAIs without the triptycene unit, the present PAIs exhibited higher solubility, lower crystallization tendency, and better film formability. In addition, four diamide derivatives featuring a triptycene as an interior core and terminal electroactive triphenylamine (TPA) or carbazole groups were prepared by the condensation reactions from 1,4-bis(4-aminophenoxy)triptycene with 4-carboxytriphenylamine and N-(4-carboxyphenyl)carbazole, respectively, and from 1,4-bis(4-carboxyphenoxy)triptycene with 4-aminotriphenylamine and N-(4-aminophenyl)carbazole, respectively. The electrochemistry and electropolymerization of these diamide derivatives were investigated. The electrogenerated poly(amide-triarylamine) films exhibited reversible electrochemical oxidation processes and strong color changes upon electro-oxidation, which can be switched by potential modulation. The electrochromic properties of the films were evaluated by the spectroelectrochemical and electrochromic switching studies.

並列關鍵字

triptycene ； poly(amide-imide)s ； thermal properties ； solubility ； electropolymerization ； electrochromism ； electrochemistry ； spectroelectrochemistry

參考文獻

18. Yamazaki, N.; Matsumoto, M.; Higashi, F., Studies on Reactions of the N-Phosphonium Salts of Pyridines XIV. Wholly Aromatic Polyamides by the Direct Polycondensation Reaction by Using Phosphites in the Presence of Metal salts. J. Polym. Sci. Polym. Chem. 1975, 13, 1373-1380.

1. (a) Mittal, K. L., Polyimides: Synthesis, Characterization and Application. Plenum: New York, 1984; (b) Wilson, D.; Stenzenberger, M. D., Polyimides. Chapman & Hall: New York, 1990; (c) Sroog, C. E., Polyimides. Prog. Polym. Sci. 1991, 16 (4), 561-694.

3. Walsh, C. J.; Mandal, B. K., A New Class of Aromatic Dianhydrides for Thermostable Polyimides. Chem. Mater. 2001, 13, 2472-2475.

7. Yang, J. S.; Yan, J. L., Central-ring functionalization and application of the rigid, aromatic, and H-shaped pentiptycene scaffold. Chem Commun (Camb) 2008,(13), 1501-12.

8. Bartlett, P. D.; Ryan, M. J.; Cohen, S. G., Triptycene (9,10-o-Benzenoanthracene). J. Am. Chem. Soc. 1942, 64, 2649-2653.

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含三蝶烯結構之聚(醯胺-醯亞胺)及聚(醯胺-三芳香胺)的合成與性質研究

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