Facile Synthesis\nof a Novel Furanic Monomer and Its\nADMET Polymerization toward Fully Renewable Functional Polymers

Efficient and sustainable transformation of biomass-derived\nchemicals\nto materials with the potential to replace conventional fossil-derived\npolymers is considered a major challenge. In this work, we disclose\nthe synthesis of a novel furan-based α,ω-diene monomer\nfollowing a facile, green, and energy-efficient process from fully\nrenewable starting materials. The multifunctional monomer was produced\nby the base-catalyzed cross-aldol condensation of 10-undecenal (UA)\nand 2,5-diformylfuran (DFF) under mild conditions, providing the desired\nproduct in good yields. By employing the new monomer, fully biobased\npolymers were prepared in good molecular weights (<i>M</i><sub>n</sub> up to 31 kg/mol) by acyclic diene metathesis (ADMET)\npolymerization using Grubb’s second-generation catalysts. The\nstructure–property investigation of the polymers revealed <i>T</i><sub>g</sub> in the range of −16 to 5 °C, high\nthermal stability, good hydrophobicity, and photoactive properties.\nOwning to the presence of amenable functional groups, the resultant\npolymer was also subjected to postpolymerization modifications. The\neffect of these modifications on the polymer properties showed enhanced\ncrystallization attributed to hydrogen bonding interactions. This\nwork demonstrates a scalable and environmentally benign approach to\naccess structurally novel and versatile materials exhibiting interesting\nproperties from 100% biobased resources.