Prediction of molecular weight distributions by probability generating functions. Application to industrial autoclave reactors for high pressure polymerization of ethylene and ethylene‐vinyl acetate

We develop a mathematical model able to describe the complete molecular weight distributions of polyethylene and elhylene‐vinyl acetate copolymers obtained in high pressure autoclave reactors. We apply probability generating function definitions to the mass balances of radical and polymer species in the reacting medium. We use three different definitions of probability generating functions, each one directly applicable either to the number, weight or chromatographic distributions. These probability generating functions are numerically inverted to obtain the corresponding calculated molecular weight distribution. The capabilities of two different inversion methods are compared. Predictions are compared with experimental data obtained in an industrial reactor; good agreement is obtained. The approach presented here is applicable to other types of polymerization reactors and post‐polymerization processes.