On the connection between microstructure and kinetics of (pseudo)copolymerization

The connection between microstructure and kinetics in the case of irreversi ble growth of long (pseudo)copolymers has been discussed, extended and esta blished. The theoretical results have been cast in simple matrix equations which enable one to compute the probability to find any given sequence in t erms of ratios of kinetic constants, rather than in terms of stochastic par ameters. As an application, the case of regioregular polymerization of viny l monomers by C-1-symmetric coordination catalysts has been considered. In addition to propagation, first order in monomer concentration, chain and si te epimerization, both zeroth-order in monomer concentration, have been tak en into account. The resulting equations have been tested against a set of literature data obtained by five different catalysts, each operated at five different concentrations, resulting in the evaluation of ratios of kinetic constants. For all catalysts the quantitative analysis of the kinetics con firms that the contribution of chain epimerization is small or negligible i n the concentration range examined.