Kinetics of the thermal degradation of poly(1,4-cyclohexylenedimethylene terephthalate)

The kinetics for the thermal degradation of poly (1,4-cyclohexylenedimethylene terephthalate) (PCHDT) were evaluated by means of a melt extruder. The effects of temperature, residence time, and oxygen content of the gas blanketing the polymer during storage on degradation of PCHDT were determined. The rate of thermal degradation was measured in terms of the rate of decrease of inherent viscosity and the rate of increase of carboxyl end group concentration. Residence time, temperature, and their interaction all contributed significantly to the degradation. For the conditions investigated, the oxygen content of the blanketing gas had no measurable effect on degradation. Analysis of the kinetic data yielded equations based on a random chain scission mechanism. These equations enabled the prediction of inherent viscosity and carboxyl end group concentration as functions of temperature and residence time and the inherent viscosity and carboxyl end group concentration of the original polymer. The activation energies for decrease in inherent viscosity and increase in carboxyl end group concentration of poly (1,4-cyclohexylenedimethylene terephthalate) were determined as 38.7 kcal/mole, respectively.