Regioselectivity of the Radical Cation Recombination in the Aniline Polymerization

Abstract

The regioselectivity of the fast stages of the aniline polymerization mechanism is considered. Using the AM1 method, the approaching of the radical cation of an aniline trimer to the aniline radical cation with chloride counterions, as well as the radical cations of the monomer to each other is simulated. It is shown that on passing from the recombination of the aniline radical cations with each other to the recombination of the aniline radical cations with the radical cations of an aniline trimer, the main approaching direction changes from C/N to N/N, which is followed by the semidine rearrangement. The high para-selectivity of the aniline polymerization is explained and the ratio of the rate constants of various recombination routes of the radical cations is evaluated.