設計與合成基於芳香胺的苯乙烯-馬來酸酐（SMA）共聚物用於電致變色裝置應用

Abstract

本研究使用簡單的方法來合成熱固性材料，採用的材料是苯乙烯-馬來酐酸酐（SMA）共聚物，其中含有不同的三芳胺基團以調整熱固性材料中鏈與鏈之距離。本研究旨在全面探討這些材料的性質，並且我們還使用了離子交換修飾來研究其在電化學反應過程中對陰離子擴散動力學的影響。本研究採用了商用的SMA與三種芳胺基雙胺單體進行反應，分別為4,4'-二胺基-4''-甲氧基三苯胺（3Ph）、N,N'-雙(4-氨基苯基)-N,N'-雙(4-甲氧基苯基)-1,4-苯二胺（5Ph）和4,4'-雙[4-氨基苯基(4-甲氧基苯基)氨基)]-4''-甲氧基三苯胺（7Ph），形成無色的熱固性聚合物薄膜，具有不同的分子鏈間距。此外，還使用三乙胺（Et3N）在形成聚醯胺酸（PAA）後進行離子交換方法，以改善抗衡離子的遷移。研究發現，增大分子鏈間距和在聚合物基質中進行離子交換導致抗衡離子擴散動力學和電致變色性質的協同增強，包括更快的響應時間，提高的響應速度和更高的著色效率（ηCE），高達540 cm2/C。

A facile approach was employed to produce thermosets of styrene-maleic anhydride copolymers (SMA) containing three kinds of triarylamine moieties to elucidate electrochromic (EC) behaviors comprehensively, and an additional ionization modification was also applied to explore the effect on counter-ion diffusion kinetics during the electrochemical process. The commercially available SMA was chosen as the starting material to coupling with three triarylamine-based diamine monomers, 4,4'-diamino-4''-methoxytriphenylamine (3Ph), N,N'-bis(4-aminophenyl)-N,N'-di(4-methoxylphenyl)-1,4-phenylenediamine (5Ph), and 4,4'-bis[4-aminophenyl(4-methoxyphenyl)amino)]-4''-methoxytriphenylamine (7Ph), respectively, resulting in colorless and transparent thermoset polymer films with different interchain distance. Furthermore, the precursors of these polyamic acids (PAAs) could be reacted with triethylamine (Et3N) to form the related triethylammonium-containing PAA complexes, which could facilitate the migration of counter-ion during redox procedures. After evaluating the electrochemical and EC behaviors, we demonstrate that the merge of enlarging interchain distance and ionization modifications in the triarylamine-coupling SMA copolymer matrixes leads to synergistic effects in the diffusion dynamics of the electrolyte counter-ion and could effectively enhance higher diffusion rates (D) of the counter-ion in the polymer matrix with more than 2,400 times larger (iS5Ph: 96.73 cm2 s-110-18) than the triphenylamine-based linear type polyimide, L3Ph (0.04 cm2 s-110-18), and the prepared electrochromic device (ECD) properties revealed faster coloration response speed (υc) 43.7 % s-1 and outstanding coloration efficiency (ηCE) up to 540 cm2/C.