The stochastic kinetics of intramolecular reactions in linear polymers

Abstract

AbstractThis paper deals with the kinetics of reactions of linear flexible macromolecules in solution possessing initially several reactive sites per macromolecule. It is assumed that the reactive sites interact with each other encounter‐controlled and that both intra‐ and intermolecular reactions are possible. On the basis of the theory of stochastic kinetics in microsystems, equations were derived, describing the kinetics of intramolecular reactions as a function of the molecular weight distribution. An important application of this theoretical treatment pertains to the distribution between inter‐ and intramolecular reactions. A demonstration for typical reaction conditions reveals the influence of rate parameters and of the average number of reactive sites per macromolecule r̄(0) on the proportionate distribution expressed by fA = f (r̄(0)); (fA = fraction of intramolecular reactions). This function is only weakly influenced by varying the width parameter β in the case of Schulz‐Zimm molecular weight distributions from β = 1 to → ∞.