Isothermal frontal polymerization: Confirmation of the isothermal nature of the process and the effect of oxygen and polymer seed molecular weight on front propagation

Isothermal frontal polymerization is a directional polymerization that utilizes the Norish-Trommsdorff (gel) effect to produce optical gradient materials. When a solution of methyl methacrylate and thermal initiator contacts a polymer seed (a small piece of poly(methyl methacrylate), a viscous region is formed in which the polymerization rate is faster than in the bulk solution. We obtained definitive evidence of the isothermal nature of the process by placing thermocouples above the propagating front. Using the optical technique of laser line deflection (Weiner's method), we studied the front propagation to determine the induction period, and the maximum distance propagated as a function of the molecular weight of the seed. We determined that the polymer seed must have a minimum molecular weight to initiate a front. We also determined that oxygen would act as a bulk polymerization inhibitor and increase the front propagation distance, but after purging the monomer-initiator solution with oxygen for several hours, the distance was shortened. We ascribed this behavior to the formation of peroxy radicals from the slow decomposition of the initiator and subsequent reaction with oxygen. (c) 2006 Wiley Periodicals, Inc.