Polydicyclopentadiene (PDCPD) is a polymer of growing importance in industrial applications. Frontal ring-opening metathesis polymerization (FROMP) offers a means to rapidly cure PDCPD with minimal input energy owing to a propagating reaction wave sustained by the exothermic polymerization. Previous examples of FROMP have required the use of relatively high concentrations of costly ruthenium catalyst, negating many of the benefits of FROMP synthesis. In this contribution, we demonstrate that by using the highly reactive exo-dicyclopentadiene isomer for FROMP the concentration of catalyst is reduced over 3-fold, while maintaining a high frontal velocity. Reducing the amount of ruthenium required for FROMP makes this technique attractive for the production of large PDCPD structural components.

Frontal polymerization (FP), a propagating reaction wave driven by exothermic polymerization, is increasingly considered for the rapid fabrication of fiber-reinforced composites. However, the effect of the fibers on the FP reaction has not yet been explored. In this contribution, we demonstrate that thermally conductive continuous elements accelerate FP using an experimental model system and finite-element-based numerical simulations. Furthermore, the degree of acceleration is shown to be affected by the amount of available monomer in the system. These results suggest that thermally conductive carbon fiber reinforcement may facilitate FP for composite manufacturing.

A hybrid microcapsule–microvascular system is introduced to regenerate the multiscale damage that results from impact puncture of vascularized polymeric sheets. Microvascular delivery of a two‐stage healing agent restores lost damage volume (puncture) to recover impact energy absorption, while embedded microcapsules heal microcracks to facilitate sealing. Modulation of the mechanical properties (1.4 GPa to 1.1 MPa stiffness) of the healing agent after curing is achieved by selection of compatible reactive acrylate monomers. Specimens are punctured and the impacted hole and surrounding damaged volume is restored by delivering the two‐stage healing agents to the site of damage via a microvascular network. Rapid gelling of two‐stage healing agents enables their retention in the damage region, while subsequent polymerization recovers structural performance. Impact recovery efficiency is assessed in terms of energy absorption, comparing reimpacted specimens to the initial impact. Recovery of impact energy absorption as high as 100% is observed for the optimal specimen design. Specimens are tested for sealing under static pressurization to monitoring leakage through the restored damage. A hybrid system incorporating both microvascular delivery of the two‐stage healing agents and microcapsules containing solvated epoxy enables sealing of 100% of specimens.

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