Simulating acrylate polymerization reactions:: Toward improved mechanistic understanding and reliable parameter estimates

It is well accepted that free-radical acrylate polymerizations are governed by a complex coupled kinetic mechanism consisting of propagation, termination and inter-molecular transfer to small species such as monomer or modifiers, together with intra- and inter-molecular transfer reactions to polymer. Propagation, P-scission or termination of the transient secondary/tertiary radicals formed following transfer to polymer is possible. This reaction cascade strongly affects the micro-structural characteristics of the polymer and its application properties. Individual parts of this mechanism have been discussed on many occasions. However, a general approach for determining the rate coefficients for the full kinetic scheme has been missing. Such an approach is developed in this communication.