Hierarchical Polyimide Microparticles with Controllable Morphology

Abstract Hierarchical polyimides (PIs) not only show outstanding thermal stability and high mechanical strength but also have great advantages in terms of microstructure and surface area, which makes them highly valuable in various fields such as aerospace, microelectronics, adsorption, catalysis, and energy storage. However, great challenges still remain in the synthesis of hierarchical PIs with well‐defined microstructure. Herein, polyamide acid salts (PAAS) with tunable ionization degree are synthesized first via the polymerization of dianhydride and diamine monomers in deionized water with 1,2‐dimethylimidazole (DMIZ). Then cationic cetyltrimethylammonium chloride (CTAC) is added to the PAAS aqueous solution to induce the formation of polyelectrolyte‐surfactant complexes based on electrostatic interaction. After a typical hydrothermal reaction (HTR) procedure, hierarchical PIs with different microstructures such as urchin‐like PI microparticles, flower‐like PI microparticles, and lamellar PI petals can be fabricated simply by changing the additive amount of DMIZ and CTAC. The nanostructure self‐assemblies of PAAS are dominated by the charges on macromolecular chains and the formation of hierarchical structures of polymers is ascribed to a geometrical selection process during crystal growth. This work provides valuable insights into the self‐assembly behaviors of polyelectrolyte systems for synthesizing well‐defined hierarchical polymers.