Solvent effects on free-radical polymerization, 5. Analysis of homopolymerization rate on the basis of the reactant-solvent complex model

The rate of polymerization was described as a function of the monomer concentration of 36 monomer/solvent systems in terms of the reactant-solvent complex (RSC) model. One-, two-and three-parameter optimization procedures were used to fit the rate function to experimental data. Fitting increments were the complex equilibrium constant K and the relative monomer reactivity parameter r₁₁. Irrespective of the optimization procedure, K and r₁₁, were found to correlate with the monomer exponent n and to be K = 0 and r₁₁, = 1 at n = 1. In these cases the RSC model reduces to the classical rate model. Despite the weak character of the monomer (radical)/solvent complexation, this interaction should not be neglected in rate modelling. The RSC model is a convenient tool to describe the chain propagation separately.