Mechanochemically‐Assisted Synthesis of Polyimides

Polyimides were obtained in 99 % yield in under 1 h through the "beat and heat" approach, involving solvent-free vibrational ball milling and a thermal treatment step. The influence of a plethora of additives was explored, such as Lewis acids, Lewis bases, and dehydrating agents, and the mechanochemical reaction was identified to run via a polyamic acid intermediate. The protocol was adopted to a range of substrates inaccessible through solution-based processes, including perylene tetracarboxylic acid dianhydride and melamine. Furthermore, quantum chemical calculations were conducted to identify the water removal as the crucial step in the reaction mechanism. The presented method is substantially faster and more versatile than the solution-based process.