Kinetic study of dissolution of poly(vinyl chloride) in cyclohexanone

The kinetics of dissolution of five fractions of commercial poly(vinyl chloride) in cyclohexanone was studied at temperatures from 20 to 70°C. Good agreement was observed between the experimental results and equations expressing the dependence of the induction periods and the rates of dissolution on temperature and molecular weight. It was found that the apparent activation energy for the swelling process lies in the range 9–14 kcal/mole and the apparent activation energy for the dissolution diffusion process in the range 8–12 kcal/mole. The apparent dependence of activation energies on number-average molecular weight indicates that the chain ends are more important in determining the dissolution rate than the centers of the polymer chains.