Abstract
General kinetic features of radical and ionic polymerization processes accompanied by reversible chain termination reactions are considered. Special attention is paid to the conditions of applicability of the steady-state approximation usually employed to analyze the kinetics of radical polymerization. It is shown that the steady-state concentration of radicals is attained at practically the very beginning of the reaction, while the steady-state concentration of a reversible termination agent is reached with a certain delay. A kinetic explanation of the reversible termination reaction effect on the pattern of the molecular-mass distribution is suggested. Conditions providing the obtainment of a polymer with a narrow molecular-mass distribution in processes with reversible termination are formulated.
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