A Dual Valorization Strategy of Barley Straw for the Development of High-Performance Bio-Based Polyurethane Foams

This study presents a complete and zero-waste valorization strategy for barley straw through the synthesis of bio-polyols and the concurrent utilization of its cellulose fraction as lignin-containing cellulose nanofibers (LCNF) for the development of bio-based polyurethane (PU) foams. Two types of bio-polyols were prepared: one derived from lignin isolated via biomass fractionation, named lignin bio-polyol (LBP), and another obtained directly from unfractionated barley straw, called straw bio-polyol (SBP), thereby incorporating all lignocellulosic constituents into a single reactive matrix. LCNF, produced from the same feedstock, was incorporated at different loadings to achieve full biomass utilization and reinforce the polyurethane foam structure. Foams prepared with LBP exhibited lower density and a more homogeneous structure, whereas those synthesized with SBP developed a stiffer, more crosslinked network. The incorporation of LCNF generally increased apparent density and mechanical performance, with optimal reinforcement at 3 wt.% in foams with SBP and 5 wt.% in LBP foams, corresponding to a 62.5 and 121% enhancement in compressive strength relative to their respective control foams. Moreover, the use of barley straw bio-polyol shifted some thermal degradation peaks toward higher temperatures, evidencing improved thermal resistance. Overall, this dual-route strategy provides a sustainable and versatile methodology for the comprehensive valorization of lignocellulosic biomass, enabling a systematic understanding of the role of each structural component in polyurethane foam synthesis. The resulting materials offer a renewable, low-impact pathway toward high-performance polymeric materials.