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 r 11 . Irrespective of the optimization procedure, K and r 11 , were found to correlate with the monomer exponent n and to be K = 0 and r 11 , = 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.