Evolution of Chain Microstructure and Kinetics of Reaching Equilibrium in Living Reversible Copolymerization

Abstract

Theoretical considerations and Monte Carlo simulations have proved that the microstructure of copolymer chains in living reversible copolymerization can be effectively described by the first‐order Markov chain process only when the system space of this process reaches chain lengths above the number‐average degree of polymerization (DPn). The time scale of equilibration depends mostly on DPn of the product, rate constants of depropagation, as well as on the equilibrium microstructure of copolymer. During the process, evolution encompasses, besides the chain‐length distribution like in homopolymerization, also the chain microstructure. The kinetically determined microstructure (gradient, alternate, etc.) observed in the first stage of copolymerization is related to reactivity ratios. It evolves into the equilibrium microstructure, determined exclusively by the equilibrium constants and initial conditions. Discussion of this evolution together with the statistical description of the reversible binary copolymerization systems at various stages of equilibration is given. image