The Aqueous Barbier Polycondensation of Biomass‐Derived 5‐Chloromethylfurfural: A Proof of Concept Study to Access Functional Polymers

The versatility of the zinc‐mediated aqueous Barbier reaction in functional polymer synthesis is demonstrated in instance of a biomass‐derived bifunctional monomer, 5‐chloromethylfurfural (CMF). CMF is a renewable furan derivative that can be directly obtained from various sugars and cellulose in high yields and is a versatile precursor that can be converted into several valuable building blocks. In this study, CMF is utilized as a monomer in metal‐catalyzed conditions to access both furan and hydroxyl functional polymers. The effect of different reaction conditions on polymerization is explored. Polymers through Barbier polycondensation of bifunctional monomer are obtained with moderately good polymer conversions (54–89%) and molecular weights (8.7–15.1 kDa). The crosslinking of obtained functional polymers is studied by employing bismaleimide and dianhydride crosslinkers for possible application of synthesized polymers as hydrophilically modified membrane materials. The crosslinked materials are obtained by reaction of furan and alcohol groups through Diels–Alder and ester formation reactions, respectively. Synthesis and characterization procedures of linear and crosslinked polymers are described. The reported proof of concept study demonstrates the efficiency of aqueous Barbier reaction in functional polymer synthesis. The zinc‐mediated aqueous Barbier polycondensation is demonstrated as an efficient polymerization method to access functional materials. The method employs the metal‐catalyzed polymerization of monomers carrying alkyl halide and carbonyl groups in aqueous reaction medium.