Hydrothermal polymerization of porous aromatic polyimide networks and machine learning-assisted computational morphology evolution interpretation

We report on the hydrothermal polymerization (HTP) of polyimide (PI) networks using the medium H 2 O and the comonomers 1,3,5-tris(4-aminophenyl)benzene (TAPB) and pyromellitic acid (PMA). Full condensation is obtained at minimal reaction times of only 2 h at 200 °C. The PI networks are obtained as monoliths and feature thermal stabilities of >500 °C, and in several cases even up to 595 °C. The monoliths are built up by networks of densely packed, near-monodisperse spherical particles and annealed microfibers, and show three types of porosity: (i) intrinsic inter-segment ultramicroporosity (48 h), also PI/SiO 2 hybrids that form through reaction with the reaction vessel. Moreover, we have developed a computational image analysis pipeline that deciphers the complex morphologies of these SEM images automatically and also allows for formulating a hypothesis of morphology development in HTP that is in good agreement with the manual morphology analysis. Finally, we upscaled the HTP of PI(TAPB-PMA) and processed the resulting powder into dense cylindrical specimen by green solvent-free warm-pressing, showing that one can follow the full route from the synthesis of these PI networks to a final material without employing harmful solvents. We report on the hydrothermal polymerization (HTP) of porous polyimide (PI) networks using the medium H 2 O and the comonomers 1,3,5-tris(4-aminophenyl)benzene (TAPB) and pyromellitic acid (PMA).