Investigation of cooperative kinetics on reactions of functional groups on polymer chains

Abstract

Abstract The kinetics of aminolysis of 1,2;3,4‐ meso ‐erythritol dicarbonate and 1,2;3,4;5,6‐mannitol, sorbitol, and dulcitol tricarbonates by n ‐butylamine in dimethylformamide solution was investigated. The dicarbonate and tricarbonates are considered respectively as models of dyads and triads in the poly(vinylene carbonate) chain. The theoretical kinetic curves for the dimer and the trimers were calculated by solution of kinetic equations and close agreement with experiment was obtained. A version of the Monte‐Carlo method was developed to provide a model for the reaction process by a computer calculation including the neighboring group effect in enhancing reactivity. The theoretical curve for a trimer coincides with the experimental one. These results confirm the accelerating influence of the unreacted neighboring groups. For the polymeric chain the experimental and calculated curves deviate for conversions beyond 10%. This indicates an additional polymer effect, which is as yet unexplained.