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Synthesis of novel polymers based on monomers of the diallylamine series : Mechanistic and kinetic study

By the use of semi-empirical quantum-chemical calculations, potential-energy profiles of model radical reactions of chain propagation and chain transfer to monomer were computed for the polymerization of monomers of the diallylmethylamine series; based on these data, an approach to preparing high-molecular-mass polymers starting from compounds of the allyl and diallylamine series in the nonquaternized form was developed. New monomer systems-equimolar trifluoroacetate salts of diallylmethylamine and diallylamine-were synthesized. It was demonstrated that, in solutions of these salts, monomer molecules occur in the protonated form. Novel polymers, secondary and tertiary polyamines-polydiallylammonium salts and their polybases with M w = (3-6) x 104 and higher-were prepared by radical polymerization. Mechanisms and kinetics of polymerization processes were examined; it was established that chain termination proceeds according to the bimolecular mechanism and -the degradative chain transfer to monomer is transformed into the effective chain transfer.