MNDO-PM3 study of the early stages of the chemical oxidative polymerization of aniline

The theoretical approach to the study of aniline polymerization mechanism has been based on the MNDO-PM3 semi-empirical quantum chemical computations of the heat of formation of aniline dimer and trimer intermediates. The oxidation in aqueous medium without added acid is analyzed. The aniline nitrenium cation is proposed to be the reactive electrophilic species generated by the oxidation of aniline with a two-electron oxidant, ammonium peroxydisulfate, in the initiation phase. 4-Aminodiphenylamine and its fully oxidized form, N-phenyl-1,4-benzoquinonediimine, are the main dimeric products. 2-Aminodiphenylamine and its fully oxidized form, N-phenyl-1,2-benzoquinonediimine, are the most important side products of aniline dimerization. The influence of protonation on the oxidizability of aniline and reaction intermediates was studied. The dominant aniline oligomers have been shown to be linear as well as branched. The importance of reactivity difference between fully oxidized aniline oligomers composed of odd or even numbers of constitutional aniline units is pointed out. The species with odd numbers of aniline units, having nitrenium cationic nature, are much more reactive. The oxidation combined with intramolecular cyclization reaction pathways leads to substituted phenazines, characteristic of two-dimensional PANI chain-growth.