Synthesis of Bio-Based Polyurethanes from Functionalized Sunflower Seed Oil

In this study, bio-based polyurethanes (PUs) were synthesized using renewable polyols derived from sunflower seed oil, aiming to develop flexible yet robust polymeric films and scaffolds. Given their composition and favorable physico-chemical properties, these materials may represent promising candidates for the design and development of advanced biomedical systems. Two distinct oil polyols were prepared via glycerol transesterification (GM) and epoxidation (EPO) with hydrogen peroxide/glacial acetic acid, respectively. These polyols, in combination with poly(tetramethylene ether) glycol (PTMEG) and/or poly(ethylene glycol) (PEG), served as diol components in a one-step reaction with 1,6-hexamethylene diisocyanate (HDI). The structure of the polyol precursors was thoroughly characterized by MALDI-TOF MS and NMR spectroscopy, confirming successful functionalization. The resulting PU films exhibited excellent flexibility (885%) and mechanical properties (23 MPa), as evaluated by ATR-FTIR, Tensile test, DSC, DMA and SEM methods. The crosslink density of the order of 10^-3 also contributes to the development of outstanding mechanical properties. Stress relaxation experiments were described using a stretched exponential (Kohlrausch-Williams-Watts) model to capture the viscoelastic behavior of the materials. In addition, stress vs. relative elongation curves revealing strain-hardening behavior were also analyzed and modeled mathematically to better describe the mechanical response under deformation. Furthermore, salt leaching techniques were employed to fabricate porous scaffolds. This work highlights the versatility of vegetable oil-based feedstocks in producing functional polyurethanes with tunable mechanical properties for applied polymer systems.