5-Hydroxymethylfurfural Derived Epoxy Monomers Reactions With COS: Synthesis of Polymeric Thiocarbonates with Pendant...

The shift toward eco-friendly polymers is undeniably exciting and necessary, especially as industries strive to reduce their reliance on petroleum-based materials. In this communication, we have showcased the synthesis of epoxy monomers derived from biobased platform chemicals, specifically 5-hydroxymethyl-2-furfural (5-HMF) and epichlorohydrin (ECH), used as starting materials. The study of its coupling reactions with CO₂ and its sulfur congener COS has been evaluated utilizing a well-defined binary (salen)MX/PPNX catalyst system. It was found that the reactions with CO₂ predominantly produced cyclic products, while the more reactive COS led to the formation of aldehyde functional poly(monothiocarbonate)s (PMTC) in a regioselective manner at ambient temperature. Furthermore, the post-polymerization reactions of aldehydes with primary amines bearing alkene, alkyne, and radical functional groups led to the production of corresponding imine derivatives, thereby providing a pathway to well-defined, highly modifiable polymers. This process has the potential to promote a more sustainable approach for transforming a wide array of polymeric materials while introducing desirable features such as (bio)degradability for various applications.