Biodegradable polycarbonates from lignocellulose based 4-pentenoic acid and carbon dioxide

The production of biodegradable polycarbonate by copolymerizing CO₂ with epoxides has emerged as an effective method to utilize CO₂ in response to growing concerns about CO₂ emissions and plastic pollution. Previous studies have mainly focused on the preparation of CO₂-based polycarbonates from petrochemical-derived propylene oxide (PO) or cyclohexene oxide (CHO). However, to reduce dependence on fossil fuels, the development of 100% bio-based polymers has gained attention in polymer synthesis. Herein, we reported the synthesis of glycidyl 4-pentenoate (GPA) from lignocellulose based 4-pentenoic acid (4-PA), which was further copolymerized with CO₂ using a binary catalyst SalenCoCl/PPNCl to produce bio-based polycarbonates with vinyl side chains and molecular weights up to 17.1 kg/mol. Introducing a third monomer, PO, allows for the synthesis of the GPA/PO/CO₂ terpolymer, and the glass transition temperature (T ) of the terpolymer can be adjusted from 2°C to 19°C by controlling the molar feeding ratio of GPA to PO from 7:3 to 3:7. Additionally, post-modification of the vinyl side chains enables the production of functional polycarbonates, providing a novel approach to the preparation of bio-based materials with diverse side chains and functions.