ABSTRACT

2The mechanism of the initial stages of oxidative polymerization of aniline (An) and its derivatives with the formation of conductive polymers with the system of conjugated π-bonds has been analyzed. It is shown that both during chemical (in the presence of peroxydisulfate anions) and electrochemical polymerization, the process is initiated by the cation-radicals of the initial monomer, which then recombine in accordance with the type “head to tail.” The obtained dimers represent by themselves the structural units of the future polymeric chain, and then they can take part in similar chain of the transformations. In the process of polymeric chain propagation, the molecules with varying polymerization degree can participate, because their reactivity is determined by the presence of the end amino-groups, and, therefore the oxidative polymerization is typical polyaddition process. On example of nitro-and oxymethyl-derivatives, the impact and position of the substituent in the aromatic ring on the reactivity of the aniline derivatives in the reaction of oxidative polymerization were evaluated. On the basis of spectral studies and elemental analysis, the most likely structures of the obtained polymeric anilines, including the polyluminol, were determined. It was shown that in the case of polyanilines (PAn) obtained by chemical method, regardless of the nature of the initial monomer the final product represents by itself a form of emeraldine salt.