A novel diamine named (2,2′-bibenzoxazole)-5,5′-diamine (DBOA) and derived polyimides (PIs) were successfully synthesized. The rigid, linear, symmetrical molecular structure and the strong charge transfer complex (CTC) were considered to be the reasons for the improved molecular packing and enhanced thermal properties of the polymers. These DBOA based PIs exhibited a higher glass transition temperature (Tg) and lower coefficient of thermal expansion (CTE) than traditional benzoxazole (BOA) based PIs. Meanwhile, the PI derived from DBOA and BPDA (3,3′,4,4′-biphenyltetracarboxylic dianhydride) exhibited high Tg (395 °C) and low CTE (8.9 ppm per °C), and is expected to be applied in organic light-emitting diode (OLED) displays.
