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

Baumgartner, Bettina; Bojdys, Michael J.; Unterlass, Miriam M.

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 °C, in nothing but hot water. Investigation of the crystal growth mechanismviascanning electron microscopy (SEM) suggests that PPPI aggregates formviaa 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 °C under N2) that stem from a combination of a strong, covalent polymer backbone and interchain hydrogen bonding.
Published in: Polymer chemistry, 10.1039/c4py00263f, Royal Society of Chemistry
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