Kinetic Model for the Homogeneously Catalyzed Polyesterification of Dicarboxylic Acids with Diols

A generally applicable stoichiometric and kinetic model was developed for the polyesterification of unsaturated dicarboxylic acid with diols in the presence of a homogeneous acid catalyst. The model also incorporates, besides the esterification, the cis−trans isomerization and the double-bond saturation reactions. Rate equations based on plausible mechanistic reaction steps were derived, and the parameters of the rate equations were determined with nonlinear regression analysis using the polyesterification of maleic acid with propylene glycol at 150−190 °C as a demonstration system. Comparisons of the model predictions with the experimental data showed that the approach is useful in predicting the polyesterification kinetics and the product distribution.