Ultrahigh Thermoresistant Lightweight Bioplastics Developed from Fermentation Products of Cellulosic Feedstock

Abstract Production of bioplastics from renewable biological resources is a prerequisite for the development of a circular and sustainable society. Current bioplastics are mostly heat‐sensitive aliphatic polymers, requiring thermoresistant aromatic bioplastics. Herein, 3‐amino‐4‐hydroxybenzoic acid (AHBA) and 4‐aminobenzoic acid (ABA) are produced from kraft pulp, an inedible cellulosic feedstock, using metabolically engineered bacteria. AHBA is chemically converted to 3,4‐diaminobenzoic acid (DABA); subsequently, poly(2,5‐benzimidazole) is obtained by the polycondensation of DABA and processed into an ultrahigh thermoresistant film. The copolymerization of DABA with a small amount of ABA dramatically increases the degradation temperatures of the resulting films (over 740 °C) to yield the most thermoresistant plastic on record. Density functional theory calculations indicate that the incorporation of ABA strengthens the interchain hydrogen bonds between aromatic imidazole rings. Thus, an alternative organic molecular design is proposed for thermoresistant plastics without using heavy inorganics, although continuous aromatic heterocycles are widely considered ideal for polymer thermoresistance. This innovative macromolecular design increases thermoresistance and can be widely applied to well‐processable plastics for the production of lightweight materials and is expected to contribute to the development of a more sustainable society.