Towards Predictive Models of Acrylates Free Radical Polymerization in Solution: The Key Role of Solvent-induced Cage Effects

The rate constant of poly-butyl acrylate backbiting in the temperature range 310-510 K is investigated through Born Oppenheimer molecular dynamics in the gas phase, in polar and nonpolar solvents. The Arrhenius parameters so determined are introduced in a mechanistic kinetic mechanism of butyl acrylate polymerization in bulk and solution. The results are compared with the experimental data available for bulk and solution polymerization in the temperature range 350-430 K, allowing to explain how polymerization rate is affected by backbiting reactions of poly-butyl acrylate in different solvents. This work opens the possibility of developing detailed kinetic models in the condensed phase by using kinetic parameters determined a priori from molecular-scale simulations, widening their range of applicability beyond the one experimentally accessible.