Diffusion‐controlled rate constant of termination reaction in radical polymerization

Abstract

AbstractSmoluchowski's theory has been modified and the improved theory was applied to diffusion‐controlled polymerization. This application proved that the rate‐controlling process is not transrational diffusion but the segmental diffusion. The segmental diffusion‐controlled rate constant was derived by the collision theory. This rate constant explains the experimental fact that the diffusion‐controlled rate constant of bimolecular termination in radical polymerization of alkyl methacrylate is inversely proportional to solution viscosity and independent of the molecular weight of the polymeric free radical.