Emulsion polymerizations. II. Kinetics, molecular weight distributions, and polymer microstructure of emulsion copolymers

The kinetics of emulsion copolymerizing systems during intervals II and III (i.e., after completion of latex particle formation) has been studied through the pseudo‐homopolymerization approach. The Smith–Ewart equations for copolymers are reduced to the corresponding equations for homopolymers by introducing suitable pseudo‐homopolymerization parameters. Analogies and differences between our results and those of previously reported treatment are critically discussed. On the grounds of the probabilistic approach developed in Part I of this series, a detailed description of the copolymer chain structure is derived for systems containing no more than one growing radical per particle. In particular explicit algebraic relationships are reported for both the two‐dimensional molecular weight distribution and the unidimensional marginal distribution functions of molecular weight and chemical composition. A complete description of the chain microstructure is also reported. Equations are derived specifying the time evolution of the monomer sequence distribution and polymer end groups.