Theory of chain growth in chemical oxidative polymerization of aniline derivatives

[Display omitted] •An equation is derived for estimating M¯n at polymerization of aniline derivatives.•M¯n increases proportionally to monomer conversion during oxidative polymerization.•The temperature dependence of M¯n was obtained for aniline polymerization.•M¯n increases proportionally to the ratio aromatic amine/oxidizing agent.•The effect of the oxidizing agent on M¯n in aniline polymerization is predicted. A theoretical approach has been proposed for the establishment of quantitative relationship between the number-average molecular weight of products of the oxidative polymerization of aromatic amines and both reagent concentrations and temperature. The derived equation to estimate the number-average degree of polymerization was evaluated using the corresponding experimental data reported in the literature. It was demonstrated that the developed theory can adequately describe an increase in the molecular weight of aromatic amine polymers upon an increasing monomer conversion and decreasing temperature and oxidizer/monomer molar ratio. Proposed assumptions about the mechanism of chain growth in the oxidative polymerization of aromatic amines reflect the key features of influence of the ratio of reactants and acidity of the medium, as well as the structure of oxidizing agent on the number-average degree of polymerization of the resulting polymers. Predictions about the influence of various factors on the molecular weight of products of the oxidative polymerization of aromatic amines have been made.