Novel heterocyclic poly(pyridine‐imide)s with unsymmetric carbazole substituent and noncoplanar structure: High thermal, mechanical and optical transparency, electrochemical, and electrochromic properties

Abstract

ABSTRACTA diamine containing heterocyclic pyridine and unsymmetrical carbazole substituents, 4‐(9‐ethyl‐3‐carbazole)‐2,6‐bis(4‐aminophenyl)pyridine (CBAPP), was prepared for use in the synthesis of poly(pyridine‐imide)s PI‐1–8 by direct polycondensation with dianhydrides in N,N‐dimethylacetamide (DMAc). The poly(pyridine‐imide)s derived from the diamine are highly soluble in solvents such as N‐Methyl‐2‐pyrrolidone (NMP) and DMAc at room temperature. Noncoplanar polyimide (PI‐1) showed excellent solubility, high transparency, and high‐performance mechanical properties. These polymers had relatively high glass transition temperatures and exhibited good thermal stability in both nitrogen (Td10 > 470 °C) and air (Td10 > 450 °C). The PI‐3∼5 cannot form flexible and tough films due to the unsymmetrical carbazole moiety, rigid structure, and polar–polar interaction. However, through copolymerization technique these polymers (PI‐6∼8) could be enhanced through the solubility, mechanical, and thermal properties. The optical properties included a strong orange fluorescence (540 nm) after protonation with acid. When the HCl concentration was increased, a new absorption band at approximately 350 nm appeared, and the intensity of the fluorescent peak at 380 nm observed in the neutral polymer solution decreased, along with the appearance of the new fluorescent peak at 540 nm. The poly(pyridine‐imide)s presented here showed only slight fluorescence quenching in the presence of methanol. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 405–412