Suspension, bulk, and emulsion polymerization of vinyl chloride—mechanism, kinetics, and reactor modelling

Abstract A review of relevant microscopic processes, both chemical and physical, which occur during suspension, bulk and emulsion polymerization (both before and after pressure drop) is given. The state of the art of kinetic modelling of monomer consumption rate, reactor pressure, molecular weight and short and long chain branching development and polymer chain microstructure is illustrated. The effects of diffusion‐controlled termination and propagation reactions and the significant decrease in initiator efficiency and decomposition rate constant at high monomer conversions on the relative rates of various chemical reactions are discussed. The application of temperature programming and semibatch operation are emphasized. Finally, attempts to model polymer particle morphology are described.