Sustainable Polyurea Greases Based on Epoxidized Soybean Oil: Influence of Ureido Structure on Performance

In this study, sustainable polyurea greases were prepared using epoxidized soybean oil (ESO) as bio-based base oil, with octadecylamine (ODA) reacted with three diisocyanates: 4,4'-diphenylmethane diisocyanate (MDI), 1,6-hexamethylene diisocyanate (HDI), and toluene diisocyanate (TDI). The diisocyanate structure dominated the thickener microstructure: MDI-ODA formed a compact short-rod fibrillar network with strong hydrogen bonding and π-π stacking, endowing the grease with the highest consistency (256), dropping point (262 °C), lowest oil separation (2.7%), and optimal thermal stability (T5% = 278 °C). HDI-ODA showed a lamellar structure with moderate performance, while TDI-ODA presented a loose porous network. Rheological tests confirmed MDI-ODA/ESO possessed the highest yield stress and structural recovery (79.5%). Tribological tests showed MDI-ODA/ESO delivered the lowest friction coefficient and wear scar diameter. Compared with non-epoxidized soybean oil (SO), ESO significantly enhanced grease performance. This improvement is attributed to the ring-opening reaction between the N-H of the ureido group and the epoxy groups of ESO, which improves thickener-oil compatibility. In addition, the polar epoxy groups promote the formation of stable lubricating films. This work verifies that diisocyanate structure and base oil epoxidation are critical for high-performance sustainable polyurea greases.