Modeling isothermal free-radical frontal polymerization with gel effect using free volume theory, with and without inhibition

Abstract

Frontal Polymerization is a process that converts monomers into polymers by means of a propagating spatially localized reaction front. Such fronts exist with free-radical polymerization, where in the simplest case, a mixture of monomers and initiator is placed into a test tube and upon initiation of the reaction at one end of the tube, a self-sustained wave develops and propagates through the tube. Isothermal Frontal Polymerization (IFP), often referred to as interfacial gel polymerization, occurs due to the coupling of mass diffusion of the species and the gel effect. Utilizing the free volume theory of Vrentas and Duda for describing the self-diffusive behavior of the gel effect, we mathematically model and study this IFP process. We determine, both numerically and analytically, characteristics of the process including the propagation velocity of the reaction zone, the structure of the wave, and the distance traveled by the front before it breaks down due to reactions ahead of the front.