Predictive model of polymer reaction kinetics and coagulation behavior in seeded emulsion co- and ter-polymerizations

A mathematical model to describe the emulsion polymerization kinetics of co- and ter-polymerizations is developed. The model uses the well-known pseudo-homopolymerization approach together with recently developed models for radical entry and desorption in order to monitor crucial kinetic variables such as conversion and latex composition. The model includes a series of unknown parameters related to monomer-specific gel-effect coefficients, that are needed to compute the bimolecular termination reaction rates. The unknown parameters are determined through extensive calibration of the model on literature data for homo- and co-polymerizations of n-butyl acrylate (n-BA) and methyl methacrylate (MMA). The so-obtained predictive model is then applied to the modelling of the ter-polymerization of n-BA and MMA with 2-hydroxyethyl methacrylate (2-HEMA) with sodium persulphate (SPR) as initiator: predictions for the time-evolution of particle size and conversion are in excellent agreement with experimental measurements using Dynamic Light Scattering (DLS) and Gas Chromatography (GC), upon tuning the gel-effect coefficient related to 2-HEMA. The developed model is used to quantify the surfactant surface coverage of the particles as well as the total concentration of counterions in the system throughout the entire polymerization process. This key information provides a way to rationalize and control the coagulation behavior during the whole polymerization process.