Frontal Polymerizations: From Chemical Perspectives to Macroscopic Properties and Applications.

The synthesis and processing of most thermoplastics and thermoset polymeric materials rely on energy-inefficient and environmentally burdensome manufacturing methods. Frontal polymerization is an attractive, scalable alternative due to its exploitation of polymerization heat that is generally wasted and unutilized. The only external energy needed for frontal polymerization is an initial thermal (or photo) stimulus that locally ignites the reaction.

Controllable Frontal Polymerization and Spontaneous Patterning Enabled by Phase-Changing Particles.

Frontal polymerization provides a rapid, economic, and environmentally friendly methodology to manufacture thermoset polymers and composites. Despite its efficiency and reduced environmental impact, the manufacturing method is underutilized due to the limited fundamental understanding of its dynamic control. This work reports the control and patterning of the front propagation in a dicyclopentadiene resin by immersion of phase-changing polycaprolactone particles.

Manipulating Frontal Polymerization and Instabilities with Phase-Changing Microparticles.

Recently presented as a rapid and eco-friendly manufacturing method for thermoset polymers and composites, frontal polymerization (FP) experiences thermo-chemical instabilities under certain conditions, leading to visible patterns and spatially dependent material properties. Through numerical analyses and experiments, we demonstrate how the front velocity, temperature, and instability in the frontal polymerization of cyclooctadiene are affected by the presence of poly(caprolactone) microparticles homogeneously mixed with the resin. The phase transformation associated with the melting of the microparticles absorbs some of the exothermic reaction energy generated by the FP, reduces the amplitude and order of the thermal instabilities, and suppresses the front velocity and temperatures.

Spontaneous Patterning during Frontal Polymerization.

Complex patterns integral to the structure and function of biological materials arise spontaneously during morphogenesis. In contrast, functional patterns in synthetic materials are typically created through multistep manufacturing processes, limiting accessibility to spatially varying materials systems. Here, we harness rapid reaction-thermal transport during frontal polymerization to drive the emergence of spatially varying patterns during the synthesis of engineering polymers.