Kinetic Relationships in Radical Polymerization

Abstract

The general features of free radical polymerization have been known and understood for at least 30 years. The acceptance of a simple chain mechanism is universal and is the basis of the controlled industrial production of most vinyl polymers. Consequently the kinetics of radical polymerization is often assumed to be a closed subject. In many systems, however, polymerization rate data does not conform to the expected pattern. These observations suggest that complications occur in the chain process, the exact nature of which remains to be fully ascertained. In this brief review, current speculation on the detailed mechanism of radical polymerization, based on observed kinetic relationships, is summarized.