Kinetics of Radical Copolymerization. XII. Investigation of the Rate of Polymerization of the System Styrene-Butyl Acrylate-Benzene

Abstract

The classical copolymerization rate equation does not describe the copolymerization rate in the styrene-butyl-acrylate-azoiso-butyronitrile-benzene-50°C system appropriately. The cross-termination coefficient (Π), calculated according to the classical rate equation, shows a strong monomer and solvent concentration dependence. The experimental results cannot be interpreted by the diffusion theory, penultimate effect, or the theory of charge transfer complexes. However, Π was found to be constant over the whole concentration range by the hot radical theory. Our kinetic data were consistently described by this theory, and its 13 parameters, characteristic of the copolymerization, were determined.