Mechanism of interaction of diallylmethylamine and its protonated and quaternary forms with their own radicals in solvent

The potential energy profiles of reactions of diallylmethylamine and its protonated and quaternary forms with their own radicals were calculated by the semiempirical MNDO-MP3 method taking into account electrostatic solvation effects in the framework of the selfconsistent reaction field model. The reactions studied simulate chain propagation and chain transfer to monomer in radical polymerization of the above monomers in dilute solutions with different dielectric permittivities of the solvents. The conformations of monomers in the gas phase and in solvent were studied. It was found that protonation and quaternization lead to successive increase in the activation energy of mobile allyl hydrogen atom abstraction and to increase in the difference between the activation barriers to competing reactions of chain transfer and propagation. The results obtained make it possible to predict the conditions of the synthesis of high-molecular-weight polymers based on diallylamine monomers. The mechanisms of reactions studied are discussed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 865–872, May, 1999.