含蒽醌結構之聚醚醯亞胺與聚胺酯之合成與性質研究

本論文分成兩個部分，第一部分在探討以一新製得的二胺單體，名為2,6-Bis(4-amino-2-trifluoromethylphenoxy)anthraquinone，與各式芳香族二酸酐先進行開環加成聚合得到聚醯胺酸，然後再經由化學閉環或熱閉環方式得到具蒽醌結構之含氟聚醚醯亞胺。這一系列的含氟聚醚醯亞胺比相似結構不含CF3取代基團的聚醚醯亞胺具有較高的溶解性以及光學透明性。除此之外，這一系列含氟聚醚醯亞胺展現出優異的熱穩定性，它們的玻璃轉移溫度介於263-312 ℃之間， 500 ℃以上才會產生明顯的熱分解。我們也對這些聚醚醯亞胺進行了循環伏安及光譜電化學研究，初步結果顯示這些具蒽醌結構之聚醚醯亞胺是一種潛在的紅色陰極變色材料。第二部分在探討兩種以蒽醌作為核心結構並含兩個三苯胺封端或咔唑封端的酯類衍生物的合成及其電化學和電聚合反應。將單體溶在具有電解質的溶液中，經過循環伏安法重複的掃描數圈後，聚胺酯薄膜會在ITO玻璃表面上逐漸生成，這些塗佈在ITO玻璃表面的高分子薄膜，擁有可逆的電化學氧化還原且伴隨著明顯的顏色變化。這些高分子薄膜的電致變色行為可藉由光譜電化學清楚地解釋，多次開關測試研究則用來評估電聚合薄膜的電致變色穩定性。

關鍵字

蒽醌聚醚醯亞胺；聚胺酯；三苯胺；咔唑；電致變色；電聚合

並列摘要

This study has been separated into two parts. In the first part of this thesis, a novel class of the fluorinated poly(ether-imide)s (PEIs) with anthraquinone (AQ) units were prepared from the polycondensation reactions of a newly synthesized AQ-dietheramine monomer, namely 2,6-bis(4-amino-2-trifluoromethylphenoxy)- anthraquinone, with aromatic tetracarboxylic dianhydrides via a conventional two-step technique. The fluorinated poly(ether-imide)s exhibited enhanced solubility and optical transparency because of increased free volume caused by the CF3 substituents. Furthermore, these PEIs showed high thermal stability, with glass-transition temperatures of 263-312 ℃ and decomposition temperatures in excess of 500 ℃. These PEIs were also investigated by cyclic voltammetry and spectroelectrochemistry. Preliminary results reveal that these AQ-based PEIs are potentially useful as cathodically coloring red electrochromes. In the second part of this thesis, two ester derivatives featuring anthraquinone (AQ) as an interior core and terminal electroactive triphenylamine (TPA) or carbazole (Cz) groups were prepared by the esterification of 2,6-dihydroxyanthraquinone with 4-(diphenylamino)benzoyl chloride and 4-(9H-carbazol-9-yl)benzoyl chloride, respectively. The electrochemistry and electropolymerization of these monomers were investigated. The polymeric films were built onto ITO/glass surface by repetitive cyclic voltammetry (CV) scanning of the monomer solutions containing an electrolyte. The electrogenerated poly(amine-ester) films exhibited reversible electrochemical processes and strong color changes upon electro-oxidation or electro-reduction, which can be switched by potential modulation. The remarkable electrochromic behavior of the film was clearly interpreted on the basis of spectroelectrochemical studies, and the electrochromic stability was evaluated by the electrochromic switching studies.

並列關鍵字

anthraquinone ； poly(ether-imide)s ； poly(amine-ester)s ； triphenylamine ； carbazole ； electrochromism ； electropolymerization

參考文獻

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含蒽醌結構之聚醚醯亞胺與聚胺酯之合成與性質研究

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