Novel semi-N-methyl substituted bisbenzimidazole based polyimide films with low coefficient of thermal expansion and high Tg

Herein, novel isomeric diamines containing semi-N-methyl substituted bisbenzimidazole and derived polyimides (PIs) were successfully synthesized. Experimental data showed that the obtained PIs exhibited outstanding heat resistance and dimensional stability, including 5 % thermal weight loss temperature (Td5 %) of 547 ~ 557 °C, high glass transition temperature (Tg) of 407 ~ 423 °C, and low coefficient of thermal expansion (CTE) of 2.2 ~ 17.6 ppm/°C. The influence of molecular structure of isomeric diamines, including para and ortho substituted N-methyl, on the molecular packing and properties of polymer was discussed. As a result, the novel PIs showed lower CTE than traditional PABZ (5-amino-2-(4-aminobenzene)-benzimidazole) based PIs without bringing high water absorption. These high-performance PI films with matching CTE of copper have potential applications in flexible display substrates and printed circuit boards.