Chemical Activation of Frontal Ring-Opening Metathesis Polymerization

In this study, we present an innovative approach to frontal ring-opening metathesis polymerization (FROMP) through chemical activation. By locally concentrating Grubbs-type initiators, we accelerate exothermic polymerization at the activation site. Sufficient thermal energy initiates a polymerization front that travels through the remainder of the sample even with reduced initiator concentrations in the bulk resin. Initiation location and timing are controlled by adjusting the initiator reactivity, the properties of the transport solvent, and the air-resin interface. Our technique enables multipoint front activation, either through synchronized injection or by timing the relative reactivity of various initiators. This accessible method of chemical activation enables on-demand production of polymer and composite materials using only the thermal energy generated by the reaction, removing the need for external power sources and enabling deployment in remote or infrastructure-limited environments.