Kinetics of poly(ethylene terephthalate) glycolysis by diethylene glycol. I. Evolution of liquid and solid phases

The kinetics of uncatalysed glycolysis, at 220 degrees C, of poly(ethylene terephthalate) (PET) by diethylene glycol (DEG) in high excess has been studied. An experimental device allowing good separation, at reaction temperature, of the solid and liquid phases was set up. The results suggest that PET is initially depolymerized in the slightly swollen solid phase, by glycolysis of the amorphous interlamellar chains. This mechanism continues until a solid phase of highly crystallized polyester is obtained. The internal tensions engendered by this chemical modification cause cracks, delamination and mechanical disintegration of the polymer. The transfer towards the liquid phase is then strongly accelerated and the solvolysis of the depolymerization products continues in the liquid phase, up to equilibrium. (c) 2006 Elsevier Ltd. All rights reserved.