Reactivity of Allyl Monomers in Radical Polymerization

Abstract It was shown that the difference in the polymerizability of a series of allyl monomers, e. g., vinylacetic acid, allyl acetate, dimethylvinylcarbinol, diallyl ether, allyl alcohol, dimethyl-allylamine, diallylamine, and allylamine is related to the polar effects of the functional groups, whose influence determines the relative stability of the C-H bond at the α-position and thus the rate of the chain transfer to the monomer (degradative chain transfer) as the result of this effect. The initial polymerization rates obey the Hammett-Taft equation, log (1/V0) = const + ρσ°, where ρ is equal to −2. The study of the effect of different acids on polymerization kinetics of allyl monomers and molecular weights of products has revealed that the increase in polymerization rate depends on the nature of monomer, molar ratio of acid and monomer, and the nature, functionality, strength, and concentration of the acid. A kinetic scheme was proposed to determine the contribution of different factors into the over...