Synthesis and characterization of soluble pyridinium-containing copolyimides†

Novel ionene-type cationic copolyimides based on 4,4′-oxydiphthalic anhydride (ODPA), 4,4′-(1,4-phenylenediisopropylidene)bisaniline (BIS P), and 2,6-diaminopyridine (DAP) were synthesized. The copolyimides were obtained in two stages: first, the copolyimides with the 0/1, 0.2/0.8, 0.3/0.7, 0.5/0.5, 0.6/0.4 and 1/0 DAP/Bis P ratios were obtained through thermal imidization, and then quaternization of soluble copolyimides with methyl iodide was conducted for 24 or 48 h. The samples were characterized via FTIR, NMR and EDX methods to confirm their structure and composition. The cationic copolyimides with a DAP content of less than 0.3 showed initial weight loss (onset) at about 250 °C, according to TGA results and demonstrated solubility in chloroform. The highest ionic conductivity value of 0.234 S cm⁻¹ was showed by the sample with 0.3 DAP content and 0.15 degree of quaternization. The stability of the membranes in alkaline media was evaluated using FTIR and TGA. It was shown that samples with a DAP content of more than 0.3 lost their integrity probably owing to partial hydrolysis of imide rings, while copolyimides with a DAP content of 0.2 and 0.3 remained stable.