含三蝶烯結構之聚(醯胺-醯亞胺)及 聚(醯胺-三芳香胺)的合成與性質研究

Abstract

First, a diimide-diacid monomer bearing the triptycene unit, namely 1,4-bis(4-trimellitimidophenoxy)triptycene, was synthesized from the condensation reaction of 1,4-bis(4-aminophenoxy)triptycene and two equivalent amount of trimellitic anhydride. A series of new poly(amide-imide)s (PAIs) with triptycene units in the main chain were prepared by the phosphorylation polyamidation reactions from the diimide-diacid monomer with several aromatic diamines including commercially available diamines and 1,4-bis(4-aminophenoxy)triptycene. All the resulting PAIs were readily soluble in many organic solvents and could be solution-cast into tough and flexible polymer films. These PAIs exhibited glass-transition temperatures (Tgs) in the range of 274-305 °C, and they did not show significant weight-loss before 500 oC. In comparison with the structurally similar PAIs without the triptycene unit, the present PAIs exhibited higher solubility, lower crystallization tendency, and better film formability. In addition, four diamide derivatives featuring a triptycene as an interior core and terminal electroactive triphenylamine (TPA) or carbazole groups were prepared by the condensation reactions from 1,4-bis(4-aminophenoxy)triptycene with 4-carboxytriphenylamine and N-(4-carboxyphenyl)carbazole, respectively, and from 1,4-bis(4-carboxyphenoxy)triptycene with 4-aminotriphenylamine and N-(4-aminophenyl)carbazole, respectively. The electrochemistry and electropolymerization of these diamide derivatives were investigated. The electrogenerated poly(amide-triarylamine) films exhibited reversible electrochemical oxidation processes and strong color changes upon electro-oxidation, which can be switched by potential modulation. The electrochromic properties of the films were evaluated by the spectroelectrochemical and electrochromic switching studies.