On the contribution of covalent and ionic species to the chain growth. Monte Carlo simulations and theoretical considerations

Abstract Contributions of the covalent and ionic species to the chain building in cationic reversible polymerizations are analyzed by means of Monte Carlo simulations and by solving the formulated set of equations. The validity of the equation for the contribution of covalent propagation, derived for reversible polymerization with simplifying assumptions, is discussed. It is shown that repeating units incorporated into the chain by covalent propagations are distributed uniformly only when direct monomer insertion into covalent bonds is not possible, or when intramolecular interconversion of covalent and ionic species is very fast in comparison with propagation.