Synthesis, characterization, effect of triaryl ring Substituents groups on thermal and spectral properties of New soluble triphenylamine-based aromatic polyamides

FTIR, 1H and 13C NMR spectroscopic techniques were used to identify the chemical structures of the dicyano intermediates, the carboxylic acid monomer and the resultant poly(amine-amide)s. These aromatic poly(amine-amide)s were found to be readily soluble in a variety of organic solvents and could afford strong and tough films via solution casting. They exhibited excellent thermal stability associated with high glass transition temperatures (Tg＝248.32-290.46℃) and 10 % weight loss temperatures in excess of 522℃ in nitrogen. In dilute NMP solution, these polymers exhibited a medium to strong photoluminescence in the blue region at (425-443) nm. Cyclic voltammetry of the poly(amine-amide)s films cast onto an ITO-coated glass substrate in dry acetonitrile containing 0.1 M of Tetrabutylammonium perchlorate(TBAP) as an electrolyte exhibited one oxidation redox couples (Eonset) at (1.30-1.37) V vs Ag/AgCl , and revealed electrochromic characteristics with a color change from pale yellow to blue at applied potentials switched between 0.0 and 1.6 V.

本研究采用傅里叶变换红外光谱（FTIR）、氢核磁共振波谱（1H NMR）及碳核磁共振波谱（13C NMR）技术，对二氰基中间体、羧酸单体及所得聚（胺-酰胺）的化学结构进行了表征与鉴定。该类芳香族聚（胺-酰胺）易溶于多种有机溶剂，可通过溶液浇铸法制备出强韧的薄膜。其具备优异的热稳定性，玻璃化转变温度（Tg）介于248.32~290.46℃之间，氮气氛围下10%热失重温度超过522℃。在稀N-甲基吡咯烷酮（NMP）溶液中，该类聚合物在425~443 nm的蓝光区域表现出中等到较强的光致发光性能。以0.1 M高氯酸四丁基铵（TBAP）为电解质的无水乙腈体系中，对涂覆于氧化铟锡（ITO）玻璃基底上的聚（胺-酰胺）薄膜进行循环伏安测试，结果显示其存在一组氧化还原对，起始氧化电位（Eonset）为1.30~1.37 V（相对于Ag/AgCl参比电极）；当施加电位在0.0~1.6 V区间切换时，该薄膜可实现从浅黄色到蓝色的颜色变化，表现出典型的电致变色特性。