Isothermal frontal polymerization: Confirmation of the mechanism and determination of factors affecting the front velocity, front shape, and propagation distance with comparison to mathematical modeling

Isothermal frontal polymerization (IFP) is a directional polymerization that uses the Trommsdorff, or gel, effect to produce gradient materials for optical applications. When a solution of methyl methacrylate and a thermal initiator contacts a polymer seed (a small piece of polymer), a viscous region is formed in which the polymerization rate is faster because of the Trommsdorff effect. Using the optical techniques of laser line deflection (Weiner's method) and shadowgraphy along with controls, we obtained definitive experimental evidence of IFP. Moreover, we were able to measure accurately and precisely the front position and front concentration profile as a function of time by monitoring IFP systems and controls of various initiator concentrations and cure temperatures. The experimental data were compared with theoretical predictions from a model using mass‐diffusion and radical polymerization kinetics. The model reproduced the decrease of the propagation time and showed an increase in the propagation velocity for an increase in the initiator concentration and/or cure temperature.