Consistent values of rate parameters in free radical polymerization systems. II. Outstanding dilemmas and recommendations

Abstract

Abstract The problems of determining reliable, well‐characterized values of kinetic parameters in free‐radical polymerizations are discussed. The origins of the fact that experimental determinations of rate coefficients of ostensibly identical systems often result in quite different values being reported can be ascribed to subtle mechanistic assumptions made in data interpretation, which are considered in detail. A series of recommendations to assist in overcoming these problems, and to highlight their origins, are presented, with emphasis placed on new techniques including those employing laser photolysis and EPR.