Polyurethanes (PUs) are one of the most versatile polymeric materials, making them suitable for a wide range of applications. Currently, petroleum is still the main source of polyols and isocyanates, the two primary feedstocks used in the PU industry. However, due to future petroleum price uncertainties and the need for eco-friendly alternatives, recent efforts have focused on replacing petrol-based polyols and isocyanates with counterparts derived from renewable resources. In this study, waste cooking oil was used as feedstock to obtain polyols (POs) for new sustainable polyurethane foams (PUFs). POs with various hydroxyl numbers were synthesized through epoxidation followed by oxirane ring opening with diethylene glycol. By adjusting reagent amounts (acetic acid and H2O2), epoxidized oils (EOs) with different epoxidation degrees (50–90%) and, consequently, POs with different OH numbers (200–300 mg KOH/g) were obtained. Sustainable PUFs with high bio-based content were produced by mixing the bio-based POs with a commercial partially bio-based aliphatic isocyanate and using water as the blowing agent in the presence of a gelling catalyst and additives. Various water (4, 8, 15 php) and gelling catalyst (0, 1, 2 php) amounts were tested to assess their effect on foam properties. PUFs were also prepared using EOs instead of POs to investigate the potential use of EOs directly in PUF production. Characterization included morphological, chemical, physical, thermal, and mechanical analyses. The rigid PUFs exhibited high density (150–300 kg/m³) and stability up to 200 °C. The combined use of bio-based polyols with partially bio-based isocyanate and water enabled PUFs with a bio-based content of up to 77 wt.%. EOs demonstrated potential in PUF production by bypassing the second synthesis step, enhancing sustainability, and significantly reducing energy and costs; however, PUF formulations with EOs require optimization due to lower epoxy ring reactivity.
