α,ω-Diene Furans from Renewable Feedstocks as monomers for Tunable Bio-based polymers

The increasing interest in utilizing renewable resources for the production of polymeric materials is primarily driven by environmental concerns and the need for sustainable solutions to the challenges faced by the current generation. Consequently, the plastic industry is shifting toward more sustainable methods for developing new monomers and materials. Among these innovations, furan-based polymers derived from renewable sources have garnered significant scientific attention in recent years. However, their use remains limited, with the majority of research focusing on polymers derived from 2,5-furandicarboxylic acid (FDCA). To date, the few furan-derived polymers that have been synthesized typically utilize polycondensation methods, which often require harsh reaction conditions, involving environmentally hazardous procedures, and providing limited control over the polymer structure. In contrast, there are other polymerization techniques – namely Acyclic Diene Metathesis (ADMET) polymerization and Thiol-ene photopolymerization – that allow for the synthesis of polymeric materials with more control over polymer structures under milder conditions. These technique have been extensively used in the synthesis of bio-based polymers, however, despite the ever-growing interest in furan-based monomers, the application on these compounds is still scarcely explored. In this study, we present the development of novel furan bio-monomers derived from D-fructose, specifically 2,5-bis(hydroxymethyl)furan (BHMF), and galactaric acid, namely dimethyl furan-2,5-dicarboxylate (FDME). Through transcarbonylation and transesterification reactions different lengths aliphatic chains with terminal olefins were incorporated in BHMF and FDME respectively. These new furan-based α,ω-diene monomers are then polymerized via ADMET polymerization and Thiol-ene photopolymerization, allowing for the production of a variety of both homo and co-, polycarbonates and polyesters with a wide range of thermal properties under mild conditions. Overall, this work underscores the importance of integrating renewable feedstocks with sustainable synthetic strategies when developing novel polymeric materials. The versatility and tunability of the furanic monomers presented here highlight their promise for future applications across diverse fields, including coatings, packaging, among others.