Synthesis and electrochromic properties of aromatic polyimides bearing pendent triphenylamine units

摘要

A series of aromatic polyimides with pendent triphenylamine group were synthesized from equimolar mixtures of 4,4'-oxydianiline (ODA) and 4-(3,5-diaminobenzamido)triphenylamine (4),4-(3,5-diaminobenzamido)-4',4"-di-tert-butyltriphenylamine (t-Bu-4) or 4-(3,5-diaminobenzamido)-4',4"-dimethoxytriphenylamine (MeO-4) with two aromatic tetracarboxylic dianhydrides (DSDA or 6FDA) via a conventional two-step procedure that included a ring-opening polyaddition to give poly(amic acid)s, followed by chemical imidization. These polyimides exhibited good solubility in polar organic solvents and could be solution-cast into flexible and strong films. They showed excellent thermal stability, with T_g values in the range of 284-309 °C. The polyimides derived from diamines t-Bu-4 and MeO-4 exhibited reversible electrochemical oxidation, accompanied by strong color changes with high contrast ratio and electrochromic stability. For the polyimides derived from diamine 4,the coupling reaction between the triphenylamine radical cations occurred during the oxidative process forming a tetraphenylbenzidine structure, which resulted in an additional oxidation state and color change together with enhanced near-IR absorption at fully oxidized state.