Abstract
This chapter aims at discussing the factors that determine the rate and course of radical reactions. It focuses on reactions that are most frequently encountered in radical polymerization. The misconceptions regarding radical reactions in early years of research are discussed. The fact that radical reactions are under kinetic, rather than thermodynamic control, is now proven and widely accepted. The chapter goes on to discuss the properties, structures, and the stability of radicals. The detection of radicals is also discussed. Addition reactions to carbon-carbon double bonds are described in the next section, including information on bond strengths, entropic considerations, and theoretical treatments. Hydrogen atom transfer is discussed with a focus on bond dissociation energies, steric factors, polar factors, stereo-electronic factors, reaction conditions, and abstraction vs. addition. Radical-radical reactions are described including information on pathways for combination, disproportionation, and combination vs. disproportionation.
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