Geomimetics for green polymer synthesis: highly ordered polyimides via hydrothermal techniques

Inspired by geological ore formation processes, we apply one-step hydrothermal (HT) polymerization to the toughest existing high-performance polymer, poly(p-phenyl pyromellitimide) (PPPI). We obtain highly ordered and fully imidized PPPI as crystalline flakes and flowers on the micrometer scale. In contrast to classical 2-step procedures that require long reaction times and toxic solvents and catalysts, HT polymerization allows for full conversion in only 1 h at 200 degrees C, in nothing but hot water. Investigation of the crystal growth mechanism via scanning electron microscopy (SEM) suggests that PPPI aggregates form via a dissolution-polymerization-crystallization process, which is uniquely facilitated by the reaction conditions in the HT regime. A conventionally prefabricated polyimide did not recrystallize hydrothermally, indicating that the HT polymerization and crystallization occur simultaneously. The obtained material shows excellent crystallinity and remarkable thermal stability (600 degrees C under N-2) that stem from a combination of a strong, covalent polymer backbone and interchain hydrogen bonding.