The mechanochemical synthesis of polyanilines (PANIs), made by oxidative polymerization of anilines, is reviewed. First, previous knowledge of the polymerization reaction in solution is discussed to understand the effect of different parameters: oxidant/monomer ratio, added acid, oxidant, temperature and water content on the properties of the conducting polymers (molecular weight, degradation, doping/oxidation level, conductivity, and nanostructure). The work on mechanochemical polymerization (MCP) of anilines is analyzed in view of previous data in solution, and published data are critically reconsidered to clarify the interpretation of experimental results. A key factor is the production of acids during polymerization, which is often overlooked. The production of gaseous HCl during MCP of aniline hydrochloride is experimentally observed. Since some experiments involves the addition of small amounts of water, the kinetics and heat balance of the reaction with concentrated solutions were simulated. A simple experiment shows fast (<2 min) heating of the reaction mixture to the boiling point of water and temperature increments are observed during MCP in a mortar. The form and sizes of PANI nanostructures made by MCP or solution are compared. The extensive work on the production of nanocomposites by MCP of anilines together with different nanomaterials (porous clays, graphene, carbon nanotubes, metal, and oxide nanoparticles) is also described.
Keywords: conductive polymers; mechanochemistry; nanocomposites; polyanilines.