A kinetic study of the hydrolytic degradation of polyethylene terephthalate at high temperatures

Abstract The hydrolytic depolymerization of molten PET in excess water was studied using a 2 L stirred pressure reactor at temperatures of 250, 265, and 280°C. Rate constants for hydrolysis are calculated from the initial rate data. At initial water: PET charge ratios (w/w) exceeding 5.1, essentially complete depolymerization to monomer is possible at 265°C. At lower water: PET initial charges, an equilibrium is established. The equilibrium constants are calculated for 2 g water/g PET at three temperatures. A kinetic model is proposed to describe the hydrolysis reaction. The model is shown to fit experimental data and to yield good predictions for the equilibrium concentration of carboxyl groups. Carboxyl‐group concentrations are measured using an end‐group analysis technique. Potentiometric titrations are carried out in one of two solvent systems, dimethylphenol:chloroform or dimethylsulfoxide, depending on the extent of hydrolysis. © 1993 John Wiley & Sons, Inc.