Organocatalytic Polymerization of Furfuryl Methacrylate and Post‐Diels–Alder Click Reaction to Cross‐Linked Materials

Biomass‐derived furfuryl methacrylate (FMA) has been effectively polymerized at ambient temperature by the P 4 ‐phosphazene superbase, t Bu‐P 4 , with or without i PrOH as the coinitiator, producing syndio‐rich atactic poly(furfuryl methacrylate) (PFMA). The polymerization exhibits high initiation efficiencies up to 370% and is, therefore, a catalytic polymerization system. In the polymerization by t Bu‐P 4 or t Bu‐P 4 + i PrOH, the true initiator is shown to be 2‐furfurylmethoxide, [(C 4 H 3 O)CH 2 O] − , generated from the reaction between FMA and t Bu‐P 4 or [ t Bu‐P 4 H] + [ i PrO] − during the induction period. The Diels–Alder (DA) “click” reaction has been utilized to produce two types of cross‐linked PFMA materials. The first is PFMA–C 60 , prepared from the DA reaction between the furfuryl group of PFMA and polydienophile C 60 , and the second employs a bifunctional bismaleimide (BM) to construct the cross‐linked network polymer PFMA–BM. When compared to the pristine PFMA, the cross‐linked network polymers PFMA–C 60 and PFMA–BM, especially the PFMA–BM materials with a high crosslinking density, exhibit significantly enhanced thermal stability at temperatures above 600 °C and a much higher glass‐transition temperature, as shown by the thermal and thermomechanical analyses.