A model for extent and rate of reaction of polymer substituents

Abstract

A general model has been examined in which neighbouring pairs of polymer substituents react at random with, e.g., elimination or ring formation. Equations are derived which give (a) the number N_x of sequences containing x unreacted substituents, (b) the extent ξ of reaction and (c) the rate [graphic omitted] of reaction as functions of time and of initial number m of substituents. At t=∞ the values found for N₁ and ξ agree with Flory's independent calculation of final values. The results of computations based on exact equations are compared with those from concise analytical expressions valid for large m. Previous experimental measurements of the time-dependence of ξ for the dechlorination of PVC by zinc in dioxan solution are in fair agreement with the present results for large m.