Facile Synthesis of a Novel Furanic Monomer and Its ADMET Polymerization toward Fully Renewable Functional Polymers

Efficient and sustainable transformation of biomass-derived chemicals to materials with the potential to replace conventional fossil-derived polymers is considered a major challenge. In this work, we disclose the synthesis of a novel furan-based α,ω-diene monomer following a facile, green, and energy-efficient process from fully renewable starting materials. The multifunctional monomer was produced by the base-catalyzed cross-aldol condensation of 10-undecenal (UA) and 2,5-diformylfuran (DFF) under mild conditions, providing the desired product in good yields. By employing the new monomer, fully biobased polymers were prepared in good molecular weights (<i>M</i> _n up to 31 kg/mol) by acyclic diene metathesis (ADMET) polymerization using Grubb's second-generation catalysts. The structure-property investigation of the polymers revealed <i>T</i> _g in the range of -16 to 5 °C, high thermal stability, good hydrophobicity, and photoactive properties. Owning to the presence of amenable functional groups, the resultant polymer was also subjected to postpolymerization modifications. The effect of these modifications on the polymer properties showed enhanced crystallization attributed to hydrogen bonding interactions. This work demonstrates a scalable and environmentally benign approach to access structurally novel and versatile materials exhibiting interesting properties from 100% biobased resources.