Temporally Stable Supramolecular Polymeric Salts Enabling High‐Performance 3D All‐Aromatic Polyimide Lattices

Abstract Vat photopolymerization (VP) Additive Manufacturing (AM), in which UV light is selectively applied to cure photo‐active polymers into complex geometries with micron‐scale resolution, has a limited selection of aliphatic thermoset materials that exhibit relatively poor thermal performance. Ring‐opening dianhydrides with acrylate‐containing nucleophiles yielded diacrylate ester‐dicarboxylic acids that enabled photo‐active polyimide (PI) precursors, termed polysalts, upon neutralization with an aromatic diamine in solution. In situ FTIR spectroscopy coupled with a solution and photo‐rheological measurements revealed a previously unknown time‐dependent instability of 4,4′‐oxydianiline (ODA) polysalts due to an aza‐Michael addition. Replacement of the electron‐donating ether‐containing diamine with an electron withdrawing sulfone‐containing monomer, e.g., 4,4′‐diaminodiphenyl sulfone (DDS), prohibited the aza‐Michael addition of the aromatic amine to the activated acrylate double bond. Novel DDS polysalt photocurable solutions are similarly analyzed and validated long‐term stability, which enabled reproducible printing of polyimide organogel intermediates. Subsequent VP AM afforded 3‐dimensional (3D) structures of intricate complexity and excellent surface finish, as demonstrated with scanning electron microscopy. In addition, the novel PMDA‐HEA/DDS solution enabled the production of the first beam latticed architecture comprised of all‐aromatic polyimide. The versatility of a polysalt platform for multi‐material printing is further demonstrated by printing parts with alternating polysalt compositions.