具咔唑及三苯胺結構之芳香族聚醯胺、聚醯亞胺及電聚合高分子的合成及光電特性研究

Synthesis and Optoelectronic Properties of Aromatic Polyamides, Polyimides and Electrosynthesized Polymers Containing Carbazole and Triphenylamine Moieties

王惠民(Hui-Min Wang)

指導教授 ： 蕭勝輝

國立臺北科技大學/工程學院/工程科技研究所/博士(2013年)

摘要

本論文分成五個章節，第一章為總體序論。第二章以新製得的二胺單體4,4’-diamino-4’’-(3,6-dimethoxycarbazol-9-yl)triphenylamine與不同的芳香族二羧酸合成一系列之芳香族聚醯胺。第三章描述了在咔唑基團的活性位置有著不同取代基之三系列芳香族聚醯亞胺，係以三種二胺與不同的芳香族二酸酐經兩步驟法所合成。所有的高分子在多種極性的有機溶劑中展現良好的溶解性，並可經由溶液塗佈法鑄成強韌的薄膜。除了具備高的玻璃轉移溫度及良好的熱穩定性，所得到的高分子薄膜均展現優良的電化學與電致變色穩定度，並伴隨多顏色的色彩變化。當咔唑基的活性位置具有推電子的甲氧基取代時，這些聚合物會展現明顯較佳的電化學穩定性及良好的電致變色特性。第四章則合成兩個具咔唑及三苯胺結構的電活性單體4-(carbazol-9-yl)triphenylamine和4,4’-dimethoxy-4’’-(carbazol-9-yl)triphenylamine，並經由他們的電化學反應各別得到一個高分子及一個二量體。這個高分子膜具有可逆的電化學氧化還原反應，而且會伴隨明顯的電致變色現象，顏色可由無色轉變至黃色、綠色、深藍色。二量體則具有獨特的綠色/紅色陽極電致變色的行為。此外，它們製備成電致變色元件後，都展現良好的性能。第五章則探討兩個由1,3,5-亞苯基為核心，末端含三苯胺及咔唑結構之星狀電聚合單體的合成與電化學。其中一個單體可以經由咔唑基團的活性位置電聚合形成交聯高分子。這高分子膜具有可逆的電化學氧化反應，而伴隨明顯的顏色變化可由無色轉變至橘色、綠色、藍色，同時在可見光及紅外光區展現出高的光學對比度。

關鍵字

咔唑 ； 三苯胺 ； 聚醯胺 ； 聚醯亞胺 ； 電致變色 ； 電聚合、光激發光

並列摘要

This study has been separated into five chapters. Chapter 1 is general introduction. Chapter 2 reports the synthesis and properties of a series of aromatic polyamides by the phosphorylation polycondensation reactions from a newly synthesized diamine, namely 4,4’-diamino-4’’-(3,6-dimethoxycarbazol-9-yl)triphenylamine, with various aromatic dicarboxylic acids. Chapter 3 describes three series of aromatic polyimides with different substituents at the active sites of the carbazole unit from the corresponding diamines and various tetracarboxylic dianhydrides via conventional two-step polymerization. All polymers were readily soluble in many organic solvents and could be solution-cast into tough and amorphous films. In addition to high Tg and good thermal stability, the resulting polymers revealed high electrochemical and electrochromic stability along with multi-electrochromic behavior. By incorporation of the electrochemically active C-3 and C-6 sites of the carbazole unit with electron-donating methoxy groups, the new polymers exhibit greatly enhanced electrochemical stability and electrochromic performance in comparison with previously reported analogs without methoxy substituents on the carbazole unit. In Chapter 4, 4-(carbazol-9-yl)triphenylamine and 4,4’-dimethoxy-4’’-(carbazol-9-yl)triphenylamine were synthesized and electrochemically reacted to give a polymer and a dimer, respectively. The electrogenerated polymer film exhibited reversible redox behavior with coloration change from colorless to yellow or green and then to dark blue. The dimer showed unique anodic green/red electrochromic behaviors. Furthermore, the polymer film and dimer can be fabricated as electrochromic cell which has good performance. Chapter 5 describes the synthesis and electrochemical properties of two star-shaped electropolymerizable monomers featuring a 1,3,5-phenylene units as an interior core bridged via an amide linker to terminal electroactive N-phenylcarbazole and triphenylamine groups. One of the monomers produced a cross-linked polymer through electrodimerization occurring at the C3 and C6 positions of the carbazole group. The polymer film showed reversible electrochemical oxidation with stable color changes from colorless to orange and then to green or blue, which exhibited high contrast ratio both in the visible and NIR ranges.

並列關鍵字

carbazole ； triphenylamine ； polyamide ； polyimide ； electrochromism ； electropolymerization ； photoluminescence

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