Rate of copolymerization in strongly alternating systems: The evidence for the involvement of monomer complexes

Abstract Work on typical strongly alternating radical copolymerizations is reviewed. Emphasis is placed on measurements of rates of copolymerization as functions of monomer feed ratio, overall monomer concentration and solvent type. Particular attention is paid to the question of whether or not rate measurements can throw light on the detailed mechanisms of alternating radical copolymerizations and especially on whether or not they provide evidence for significant propagation via monomer‐monomer donor‐acceptor complexes. It is concluded that rate measurements alone are not necessarily a good guide to copolymerization mechanisms. A semi‐empirical method is proposed for assessing the likely reactivities of monomer‐monomer complexes; it is shown that this method predicts reactivities for monomer‐monomer complexes which are comparable with some calculated from rate and other data.