Reactive Processing of Furan-Based Monomers via Frontal Ring-Opening Metathesis Polymerization for High Performance Materials

Frontal ring-opening metathesis polymerization (FROMP) presents an energy-efficient approach to produce high-performance polymers, typically utilizing norbornene derivatives from Diels-Alder reactions. This study broadens the monomer repertoire for FROMP, incorporating the cycloaddition product of biosourced furan compounds and benzyne, namely 1,4-dihydro-1,4-epoxynaphthalene (HEN). We conducted a computational screening of Diels-Alder products, selecting products with resistance to retro-Diels-Alder but also sufficient ring strain to facilitate FROMP. Our experiments revealed that varying substituents both modulate the FROMP kinetics and enable the creation of thermoplastic materials characterized by different thermomechanical properties. Moreover, we designed HEN-based crosslinkers to enhance the resulting thermomechanical properties at high temperatures (>200 °C). The versatility of such materials was demonstrated through direct ink writing (DIW) to rapidly produce 3D structures without the need of printed supports. This research significantly extends the range of monomers suitable for FROMP, paving the way for efficient production of advanced thermoplastic materials.