Reactivity of monomers in copolymerization

An investigation of the copolymerization of many monomer pairs induced by benzoyl peroxide has shown that an order of monomer reactivity with radicals exists. By utilizing the data available, it was possible to make a semiquantitative arrangement of many monomers according to their relative rates of reaction with radicals. A symmetrical selectivity factor is assumed to account for deviations from the order in copolymerization reactions. This selectivity may be attributed to (1) complex formation between monomers or to (2) dipole, steric, or other factors which are independent of concentration. Copolymerization equations have been derived for each case and application of them to styrene–methyl methacrylate mixtures has indicated that selectivity due to (2) is most important in this system. The equation for case (2) has been applied to other copolymer systems.