Physical properties of triglyceride estolides from lesquerella and castor oils

Abstract

Lesquerella is a developing hydroxy oilseed crop suitable for rotation in the arid Southwestern United States. The hydroxy oil of lesquerella makes it suitable for esterification into triglyceride estolides. The estolide functionality imparts unique physical properties that make this class of materials suitable for functional fluid applications. Lesquerella and castor hydroxy triglycerides were converted to their corresponding estolides by reacting the oils with saturated fatty acids (C2–C18) in the presence of a tin 2-ethylhexanoate catalyst (0.1 wt.%) and utilizing the condensation of hydroxy with corresponding anhydride or heating under vacuum at 200 °C. Two homologous series of estolides for each triglyceride were synthesized for comparison, mono-capped (one hydroxy functionality per triglyceride molecule) and full-capped (all hydroxy functionalities per triglyceride molecule). Physical properties (pour point, cloud point, viscosity, and oxidative stability) were compared for this estolide series. The longer chain saturate capped estolides (C14–C18) had the highest pour points for both mono-capped (9 °C, C18:0) and full-capped (24 °C, C18:0) lesquerella estolides. Castor mono-capped (9 °C) and full-capped (18 °C) triglyceride estolides gave similar properties. However, pour points improved linearly when the shorter saturated fatty acid capping chain lengths were esterified with the hydroxy triglycerides. Lesquerella capped with a C6:0 fatty acid had pour points of −33 °C for the mono-capped and −36 °C for the full-capped and castor had −36 and −45 °C, respectively. Oxidative stabilities of the estolides were compared for oleic, lauric and lauric-hydrogenated mono- and full-capped materials by rotating bomb oxygen test (RBOT). RBOT times for oleic and lauric capped estolides were low and similar with times centered around 15 min. However, when antioxidant (4 wt.%) was added the RBOT times increased to 688 min for the hydrogenated full-capped lesquerella lauric estolide. The antioxidant had little effect on RBOT times when 2 wt.% or less antioxidant was added for all the estolides except those that were hydrogenated. The hydrogenated estolides showed improvements in oxidative stability at all concentrations of antioxidant tested. Viscosity index ranged from 130 to 202 for all estolides with the shorter chain length capped estolides gave the lower viscosity index values. Viscosity at 100 °C ranged from 13.9 to 26.6 cSt and the 40 °C viscosity ranged from 74.7 to 260.4 cSt where the longer chain length capped estolides gave the highest viscosities.