Sevim Z. Erhan

Epoxidized soybean oil as a potential source of high-temperature lubricants

Development and application of biocompatible lubricants are increasing daily as a result of stringent regulations imposed on mineral oil-based lubricants with their non-biodegradable toxic wastes. Before consumer acceptance of vegetable oil-based lubricants, they must overcome certain poor performance characteristics such as thermal and oxidative instabilities. This work demonstrates the improved performance of epoxidized soybean oil (ESBO) over soybean oil (SBO) and genetically modified high oleic soybean oil (HOSBO) in certain high temperature lubricant application. We validated the thermal and deposit forming tendencies of these oils using micro-oxidation and differential scanning calorimetry in conjunction with identification of oxidized products by infrared spectroscopy and also discussed the function of a phenolic antioxidant in these oils. Boundary lubrication properties under high load and low speed were determined and the variations explained based on the structural differences of these vegetable oils.

Lubricant basestocks from vegetable oils

Abstract Compared to the lubricants made of petroleum, vegetable-based lubricants are much more biodegradable but inferior in many other technical characteristics. The basestock typically contributes to more than 80% of lubricant and must meet performance criteria in such aspects as cleanliness, viscometric properties, volatility, oxidative and hydrolytic stability, deposit forming tendencies, solvency, miscibility or compatibility with system elastomers and other. For vegetable-based lubricants, oxidative stability and low temperature problems are considered the most critical. Thin film oxidation test was used to compare oxidative stabilities. Vegetable oils appear an order of magnitude less stable than mineral oils or synthetic biodegradable basestocks, such as isoalkyl adipates or poly alphaolefins. Low temperature performance of vegetable oils, namely pour points and cold storage, was also problematic. These problems can only partially be relieved by lubricant additives, thus vegetable oils have to be modified chemically to eliminate sites susceptible to oxidation and to disrupt formation of crystals at low temperatures.

Lubricant base stock potential of chemically modified vegetable oils.

The environment must be protected against pollution caused by lubricants based on petroleum oils. The pollution problem is so severe that approximately 50% of all lubricants sold worldwide end up in the environment via volatility, spills, or total loss applications. This threat to the environment can be avoided by either preventing undesirable losses, reclaiming and recycling mineral oil lubricants, or using environmentally friendly lubricants. Vegetable oils are recognized as rapidly biodegradable and are thus promising candidates as base fluids in environment friendly lubricants. Lubricants based on vegetable oils display excellent tribological properties, high viscosity indices, and flash points. To compete with mineral-oil-based lubricants, some of their inherent disadvantages, such as poor oxidation and low-temperature stability, must be corrected. One way to address these problems is chemical modification of vegetable oils at the sites of unsaturation. After a one-step chemical modification, the chemically modified soybean oil derivatives were studied for thermo-oxidative stability using pressurized differential scanning calorimetry and a thin-film micro-oxidation test, low-temperature fluid properties using pour-point measurements, and friction-wear properties using four-ball and ball-on-disk configurations. The lubricants formulated with chemically modified soybean oil derivatives exhibit superior low-temperature flow properties, improved thermo-oxidative stability, and better friction and wear properties. The chemically modified soybean oil derivatives having diester substitution at the sites of unsaturation have potential in the formulation of industrial lubricants.

Ester hydroxy derivatives of methyl oleate : Tribological, oxidation and low temperature properties

Five branched oleochemicals were prepared from commercially available methyl oleate and common organic acids; and their lubricant properties were determined. These branched oleochemicals are characterized as 9(10)-hydroxy-10(9)-ester derivatives of methyl oleate. These derivatives show improved low temperature properties, over olefinic oleochemicals, as determined by pour point and cloud point measurements. The derivatization also increased thermo-oxidative stability, measured using both pressurized differential scanning calorimetry (PDSC) and thin film micro oxidation (TFMO) methods. Branched oleochemicals were used as additives both in soybean oil and in polyalphaolefin. Their lubrication enhancement was evaluated by both four-ball and ball-on-disk wear determinations. These derivatives have good anti-wear and friction-reducing properties at relatively low concentrations, under all test loads. Their surface tensions were also determined and a trend was observed. The materials with larger side chain branches had lower surface tension than those containing smaller side chain branches. An exception to this trend was found when studying the compound with the carbonyl containing levulinic acid side chain, which had the highest surface tension of the branched oleochemicals studied. Overall, the data indicate that some of these derivatives have significant potential as a lubricating oil or fuel additives.

One-pot synthesis of chemically modified vegetable oils.

Vegetable oils are promising candidates as substitutes for petroleum base oils in lubricant applications, such as total loss lubrication, military applications, and outdoor activities. Although vegetable oils have some advantages, they also have poor oxidation and low temperature stability. One of the ways to address these issues is chemical modification of fatty acid chain of triglyceride. We report a one-pot synthesis of a novel class of chemically modified vegetable oils from epoxidized triacylglycerols and various anhydrides. In an anhydrous solvent, boron trifluoride etherate is used as catalyst to simultaneously open the oxirane ring and activate the anhydride. The reaction was monitored and products confirmed by NMR, FTIR, GPC, and TGA analysis. Experimental conditions were optimized for research quantity and laboratory scale-up (up to 4 lbs). The resultant acyl derivatives of vegetable oil, having diester substitution at the sites of unsaturation, have potential in formulation of industrial fluids such as hydraulic fluids, lubricants, and metal working fluids.

The improved synthesis of carbonated soybean oil using supercritical carbon dioxide at a reduced reaction time

We have demonstrated an improved synthesis of a cyclic carbonate of soybean oil (CSO) utilizing supercritical carbon dioxide (CO2) as the solvent. Because the mutual solubility of supercritical CO2 and soybean oil is significantly higher than that of gaseous CO2 and soybean oil, our method synthesizes the material in ∼1/3 of the reaction time reported in the literature. We have also demonstrated a catalyst removal method for our system based on the simple Hofmann elimination reaction, reducing the need for organic solvent extraction. CSO is a potential petroleum replacement, and may be useful in the synthesis of polymers based on bio-resources.

Wax appearance temperatures of vegetable oils determined by differential scanning calorimetry: effect of triacylglycerol structure and its modification

Abstract Crystallization and wax appearance temperatures of a series of vegetable oils (natural, genetically and chemically modified) were studied using differential scanning calorimetry (DSC). The fatty acid chains of a triacylglycerol molecule have a bend ‘tuning fork’ conformation and undergo molecular stacking during the cooling process. Wax crystallization at low temperature is controlled by steric and geometrical constrains in these molecules. This study describes an approach to quantify and predict wax appearance temperature of vegetable oils based on the statistical analysis of DSC and NMR data. A molecular modeling program was used to design triacylglycerol molecules with different fatty acid (e.g. oleic and linoleic) chains to illustrate their effect on the crystallization process. Effect of pour point depressant (PPD) additives on vegetable oil crystallization is also discussed.

Polymerization of vegetable oils and their uses in printing inks

Ink vehicles were prepared by the polymerization of vegetable oils. By controlling the polymerization conditions, the desired viscosity, color and molecular weight could be achieved for a variety of vegetable oils with a broad range of iodine values and fatty acid compositions. The effect of temperature and catalyst on polymerization rates were evaluated, and polymerization rate constants were calculated. Of the oils tested, the polymerization rate constant of safflower oil was the highest, followed by soybean, sunflower, cottonseed and canola oils in decreasing order. Use of a catalyst shortened the heating time by about 25–50% or lowered the polymerization temperature requirement by 25–30°C.

Lithographic and letterpress ink vehicles from vegetable oils

Our objectives for this study were to produce vegetable oil-based printing ink vehicles that did not require any petroleum components, which meet or exceed industry standards for rub-off resistance, viscosity and tackiness for a variety of printing applications. These objectives were satisfactorily met. Vehicles were completely compatible with carbon black, making them suitable for black ink formulations. In addition, the resulting vehicles had exceptionally light colors, and permitted formulations of colored inks that had substantially reduced pigment levels compared to industry standards.

Azide Derivatives of Soybean Oil and Fatty Esters

An environmentally friendly water-based pathway to form the azide derivatives of soybean oil and fatty esters is reported. This entails first the formation of epoxides and then the azidization of the epoxides. The azidization reaction is carried out at high yields in water with only a small amount of an ionic liquid as a catalyst. The distribution of azide and alcohol functionalities on the fatty acid moiety is approximately random. This reaction has been applied to methyl oleate, methyl linoleate, soybean oil, and methyl soyate. The resulting structures have been studied by NMR.