Activaton energies for backbiting and β-scission reactions for the polymerization of n-BA were determined by fitting experimental data to a mathematical model. The activation energy for backbiting was higher and that for β-scission lower than those accepted in the literature.

The kinetic Monte Carlo simulation was used to predict the characteristics of the polymer network formation during pre-and postgelation regimes of free-radical cross-linking copolymerization. The simulation naturally considers the presence of multiradicals, primary and secondary cyclization with no preassumptions. The simulation was first validated in the pregel regime by comparing the microstructure with that given by a meanfield model. The Monte Carlo simulation was then used to predict the kinetics and development of the polymer microstructure of the sol and gel fractions up to full conversion, including the complete molecular weight distribution, cross-linking and pendant double bond densities, primary and secondary cyclization and the molecular weight distribution between crosslinking points. The simulation also allows studying the presence and evolution of multiradicals along the polymerization.

Transfer to polymer in the radical polymerization of acrylic monomers results in chain branching and has significant implications for both reaction kinetics and the microstructure of the resulting polymer. While intramolecular transfer to polymer is more prevalent than the intermolecular pathway, intermolecular transfer to polymer is of particular importance for understanding polymer microstructures. Despite this, the magnitude of the rate coefficient is uncertain, and therefore, predicting the effects of intermolecular transfer remains a challenge. Herein, we seek to provide an estimate of the rate of intermolecular transfer of butyl acrylate by conducting reversible addition−fragmentation chain transfer (RAFT) polymerizations in the presence of a low molecular weight dead polymer. In these experiments, intermolecular transfer to polymer yields a characteristic low molecular shoulder in the polymer detected by UV in the SEC. We obtain a value significantly higher than those previously estimated and discuss the implications this has on branch formation, molecular weight and gel formation in radical polymerization of acrylic monomers as well as the formation of dead chains in controlled radical polymerization.

Please cite this article as: S. Hamzehlou, J.R. Leiza, J.M. Asua, A new approach for mathematical modelling of the dynamic development of particle morphology, Chemical Engineering Journal (2016), doi: http://dx. AbstractA new model for the dynamic evolution of the morphology of polymer-polymer latex particles has been developed. This model overcomes the limitations of the existing methodologies that were only able to provide the morphology of a single particle, which is only a restricted view of the real system that contains a distribution of particle morphologies. Taking into account the relevant kinetic and thermodynamic effects, the new model calculates the distribution of morphologies for the whole population of polymer particles with less computational effort than that needed by the previous models to calculate the morphology of a single particle. The model was validated by fitting the evolution of particle morphology of composite particles during polymerization of methyl methacrylate on a polystyrene seed. Furthermore, the ability of the model to predict the evolution of the particle morphology for different cases was explored.