Kinetics of vinyl polymerization initiated by ceric ion in aqueous solution

Abstract A systematic kinetic study of the thermal polymerization of methyl methacrylate, methyl acrylate, and acrylonitrile initiated by ceric ion in aqueous perchloric, nitric, and sulfuric acid solutions, has been made. The polymerization experiments were conducted in the dark at 35°C. under conditions of negligible oxidation of water by ceric ion. The polymerization was found to proceed without an induction period, and the steady‐state rate was attained in a short time. The rate of monomer disappearance (followed by gravimetry) was found to bear a square dependence on monomer concentration and is independent of both the ceric and hydrogen ion concentrations. The rate of ceric disappearance (followed by titrimetry or spectrophotometry) was found to be directly proportional to the ceric, monomer, and hydrogen ion concentrations. The chain lengths of the polymers (determined viscometrically) were directly proportional to the monomer concentration and inversely to the ceric and hydrogen ion concentrations. Initially added cerous ion had negligible effect on the rates. Increase in ionic strength caused a slight increase in the rates. From experiments conducted at different temperatures, the activation energies for the various processes in the reaction were calculated. Most of the experimental results were suitably explained by a kinetic scheme involving initiation and termination by ceric ion in the unhydrolyzed Ce 4+ form.