Multicomponent free‐radical polymerization in batch, semi‐ batch and continuous reactors

Abstract A practical methodology for the computer modelling of multicomponent free radical polymerizations for solution and emulsion systems has been developed. The approach is general providing a common model framework which is applicable to many comononer systems. Model calculations include conversion of the monomers, multivariable distributions of concentrations of monomers bound in the polymer chains and molecular weights, long and short chain branching frequencies, chain microstructure and crosslinked gel content when applicable. Diffusion‐controlled termination and propagation reactions are accounted for using the free‐volume theory. When necessary, chain‐length‐dependent diffusion‐controlled termination may be employed. Kinetic parameters have been measured and are available for the following binary comonomer systems: styrene/acrylonitrile, p‐methylstyrene/acrylonitrile, p‐ methylstyrene/styrene, p‐methylstyrene/methyl methacrylate and styrene/butadiene. Various comononer systems will be used to illustrate the development of practical semi‐batch and continuous reactor operational policies for the manufacture of copolymers with high quality and productivity. It should be mentioned that these comprehensive polymerization models may be used by chemists and chemical engineers to reduce the time required to develop new polymer products and advanced production processes for their manufacture.