Estimation of Rate Constants of Bimolecular Decomposition of Redox Initiators in Radical Polymerization

A rigorous statistical method is established to compute the rate constants of the bimolecular decomposition of redox catalysts used to initiate polymer chains. Results obtained for the systems styrene-dimethylaniline-benzoyl peroxide and acrylamide-thio-glycollic acid-potassium bromate compare favorably with those reported by other workers. The merits of this error-in-variable technique, which outperforms conventional nonlinear least-square analysis and the dead-end polymerization method, are discussed.