Sustainable Design of High-Performance Polyurethanes Using Medium-Chain-Length Polyhydroxyalkanoates

The transition toward a circular economy is accelerating the development of high-performance, sustainable polymeric materials derived from renewable resources. Medium-chain-length polyhydroxyalkanoates (mcl-PHAs) represent a versatile class of biodegradable polyesters with inherent flexibility and tunable side-chain chemistry, making them attractive candidates for advanced polymer applications. Here, we report a novel class of bio-based polyurethanes (PUs) incorporating mcl-PHAs as soft segments, marking their first application in polyurethane synthesis and shifting towards greener PU synthesis. Polyurethane networks were prepared using castor oil (CO) and mcl-PHAs as polyols, with hexamethylene diisocyanate (HMDI) as a hard segment. Material properties were systematically tuned by varying the mcl-PHA/CO ratio (100/0 to 0/100), enabling precise control over structure-property relationships. Comprehensive characterization confirmed urethane bond formation and revealed predominantly amorphous materials with tunable thermal and mechanical behavior. Increasing mcl-PHA content enhanced elasticity and influenced phase organization, underscoring its role as a flexible, bio-derived soft segment. The resulting materials exhibited competitive mechanical performance alongside adjustable swelling behavior and morphology. Importantly, in vitro biocompatibility (MRC-5 fibroblasts) and eco-toxicological evaluation (Caenorhabditis elegans) confirmed the absence of toxicity. These findings highlight the potential of mcl-PHAs as sustainable building blocks for advanced polyurethane systems.