The renewable feedstock levoglucosenone as a building block for the development of bio-derived, functional acrylic polymers

Abstract

As the world seeks to reduce its reliance on petrochemicals, the search for renewable polymers with equal or enhanced performance compared to conventional fossil fuel-based materials is crucial. In this study we utilized the readily accessible platform molecule levoglucosenone (LGO) as a renewable feedstock for the synthesis of bio-derived acrylic polymers. LGO, was used in the preparation of the bio-based monomer LGO-acrylate (LGOA), possessing an internal unsaturated carbon–carbon bond within the LGO ring. The as-synthesized monomer was subject to PET-RAFT polymerization with 95% conversion of the acrylate group in 6 hours, with only a small fraction of the internal unsaturated bond in the LGO bicyclic ring pendant group consumed during the course of the polymerization. The homopolymer possessed a high glass transition temperature (up to 118 °C) and excellent thermal stability, and was successfully copolymerized with n-butyl acrylate (BA) both in the bulk and in emulsion, to form polymers with glass transitions below room temperature. Thiol–ene ‘click’ chemistry as a post-polymerization modification approach was performed using the double bonds within LGO pendant groups, enabling convenient polymer functionalization and the formation of crosslinked networks and films via a post-polymerization approach. The formation of thiol functionalized and crosslinked polymers demonstrates the ability to produce tailorable bio-derived polymer networks, identifying LGO as an attractive scaffold for the synthesis of polymers from renewable starting materials.