Frontal ring-opening metathesis polymerization (FROMP) is a promising technique for rapid, energy-efficient production of materials. The highly exothermic FROMP reaction is driven by the release of ring strain in dicyclopentadiene (DCPD) monomer during polymerization in the presence of a ruthenium-based second generation Grubbs’ catalyst (GC2). A local thermal stimulus activates latent catalyst in neat DCPD, initiating polymerization and releasing heat, thus activating additional catalyst. This chain reaction results in a self-propagating polymerization front which rapidly converts all available monomer into a fully cured cross-linked polymer. One of the principal limitations of previous FROMP systems was pot life. We recently discovered that alkyl phosphites serve as effective inhibitors for GC2 in the FROMP of DCPD, increasing pot life up to 140× while still allowing frontal polymerization at relatively high frontal velocities. The increased working time has enabled significant advances in the manufacturing of polymers and composites via frontal polymerization. Fiber-reinforced polymer composites with mechanical properties comparable to conventionally manufactured aerospace-grade bisphenol A epoxy composites were manufactured with significantly less energy and time input. FROMP manufacturing can reduce the energy required to fully cure large components by more than ten orders of magnitude while simultaneously reducing the curing time by more than two orders of magnitude. Experimental and computational studies are ongoing to elucidate the physical and chemical factors that affect the required energy input and curing time.

Frontal ring-opening metathesis polymerization for rapid curing of fiber-reinforced composites

255th National Meeting (2018)

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