Synthesis of colorless polyimides with high Tg from asymmetric twisted benzimidazole diamines.

[Display omitted] • Poly(benzimidazole imide) films with asymmetric and twisted structures was successfully synthesized. • These poly(benzimidazole imide)s achieved more prominent properties than traditional poly(benzimidazole imide)s. • The semi-aromatic poly(benzimidazole imide)s were expected to be expanded as heat-resistant colorless materials. • The effect of various 2′-substitutions on the properties of these poly(benzimidazole imide)s was discussed. To prepare colorless polyimide (CPI) films with high thermal properties, an effective design strategy is incorporating asymmetric and twisted structures in the polymer chain-segments. Based on this strategy, 6,4′-diamino-2′-methyl-1-methyl-2-phenylbenzimidazole (5a) and 6,4′-diamino-2′-trifluoromethyl-1-methyl-2-phenylbenzimidazole (5b) were synthesized, and two series of their polyimides (semi- and fully aromatic series) were prepared, respectively. The obtained poly(benzimidazole imide)s (PBIIs) with loosely packed but rigid backbones possessed not only high glass transition temperature (T g) but also improved optical transparency. In particular, the semi-aromatic system achieved an excellent transmittance about 80% at 400 nm and an outstanding T g exceeding 400 °C. Furthermore, the influence of various 2′-substitutions on the combination properties of these poly(benzimidazole imide)s was systematically analyzed. These data expand the poly(benzimidazole imide)s as optical materials and provide a feasible method to prepare heat-resistant colorless polymers. [ABSTRACT FROM AUTHOR]