Some features of radical polymerization of acrylic and methacrylic acid salts in aqueous solutions

Abstract The kinetics of radical polymerization of acrylic and methacrylic acids and their salts in aqueous solutions have been studied. A considerable increase in the polymerization rate at an increase in pH in the alkalinity area has been detected, the general trend of the rate‐enhancement being specifically dependent on the type of cation present in the solution. On the basis of the set of the experimental data an assumption was made on the kinetic role of ion pairs in the radical polymerization of ionizable monomers. Formation of ion pairs results in the increase of the elementary propagation rate constant K p . Rotating sector measurements for individual kinetic constant confirmed the advanced hypothesis. The importance of the conformational state of polyelectrolyte growing chains in the kinetics of radical polymierzation of ionizable monomers has been shown. Participation of ion pairs in the propagation step leads to marked stereochemical effects and, in certain cases, to the formation of practically stereospecific polymers.