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Location: Bio-oils Research

2011 Annual Report

1a. Objectives (from AD-416)
The long term objective of this project is to develop new value-added, non-food, non-fuel industrial products from vegetable oil using chemical methods. Objective 1: Develop new technologies that enable the commercial polymerization of vegetable oils into high value products. Objective 2. Develop commercially preferred industrial/automotive lubricants based on vegetable oil. Objective 3. Develop technologies that enable new, commercially-viable chemical processes for producing superior vegetable oil-based surfactants.

1b. Approach (from AD-416)
The approach to objective 1 will involve the use of a two step process. Strong acid polymerization catalyst used at relatively high temperatures will cause intermolecular polymerization of the double bonds of soybean oil. Catalyst studied will include trifluorsulfonic acid and fluorosulfuric acid, strong Lewis acids, such as aluminum trichloride, and heterogeneous catalysts such as aluminum doped titania or sulfated treated zirconia. In the second polymerization step, appropriate cross-linking agents will be used to expand the range of available materials to solid materials such as hard resins for composite panels, hydrogels and elastomeric materials for energy absorbing packaging. These polymers will be characterized by techniques such as NMR spectroscopy in order to find a large range of applications. The approach to objective 2 will involve a strategic combination of chemical modification, blending, and additive packages will produce vegetable oil-based lubrication fluids with properties superior to petroleum-based lubricants. The low stability of vegetable oil towards oxidation will be addressed by chemical modifications which remove the bis-allylic protons of the molecule while, at the same time, improve the poor low temperature flow properties of the oil. Nucleophilic addition of heteroatom-containing compounds will be performed on the activated substrates with the use of appropriate catalysts. For example, di-butyl phosphate can be added to epoxidized methyl oleate using zirconium doped titania as a ring opening catalyst, and aniline can be added to the same starting material. The approach to objective 3 will involve the formation of a new type of structure of branched surfactants which has not been previously reported in the literature. A sugar moiety will initially be connected to the fatty material by a precedented tosylation reaction which will be updated to a modern catalytic reaction. It will have hydrophile-lipophile balances suitable for use in water in oil emulsification and as wetting agents. Functional groups will be added to the surfactant using epoxidation and ring opening addition. This will change the suitability of these surfactants leading to potential application in dispersants and coating products. This surfactant material will have significant advantages over the currently used ethylene oxide based surfactants because traces of un-reacted ethylene oxide or dioxin byproducts will not be an issue. Also, because the soy-based monomer is large compared to ethylene oxide, a narrow range of molecular weight surfactants will be synthesized.

3. Progress Report
This is the first year of project 3620-41000-159-00D, which was certified in September of 2010, building on the research of the previous plan. There has been a significant amount of progress on this project during the year towards all three objectives. Three provisional patent applications were filed, primarily in the area of lubrication additives. Material from one of those patent applications is being marketed to lubricant formulators by a Cooperative Research and Development Agreement (CRADA) partner. This material has the promise of improving the wear reduction ability in lubricating oil without the use of metal ions, phosphorous, or sulfur. Other research in the lubrication area uncovered errors in the understanding of the heat treatment of soybean oil, an important process. In the polymer area, new reaction procedures have been developed in order to invent new soybean oil based materials that range in properties from thick liquids to solid powders. A gum material has been produced in a collaborative effort with a large company in order to make a suitable product. Other fundamental work, including the study of the diffusion of water in a gel and how oil from a new crop performs under known reaction conditions, was conducted.

4. Accomplishments
1. Soybean oil and phosphorous compound useful for industrial lubricant applications. All major industrial processes require some type of lubricant. From metal rolling sprays, to wheel bearing grease, and fire resistant hydraulic fluids, to the familiar motor oil in a car engine, complicated formulations are needed to meet the performance standards. In lubricants with either a mineral or soybean oil base, additives are needed to help protect against wear. A currently used additive is called zinc dialkyldithiophosphate. This benchmark additive is effective when used in mineral oil based lubricants, but must be used in unrealistic concentrations to make good soybean oil lubricants. However, scientists at the ARS National Center for Agricultural Utilization Research (NCAUR), Peoria, IL, devised a way to make a more effective additive by chemically combining a soybean oil derived starting material with a chemical phosphate. This new additive is effective, and only uses a small fraction of the phosphorous present in the dialklydithiophosphate compound. Another advantage is the lack of sulfur and metal ions in this product, a big positive in some applications. This additive is one of the many developments necessary for the expansion of biobased lubricants into the petroleum dominated lubricant industry.

Review Publications
Xu, Q., Nakajima, M., Liu, Z., Shiina, T. 2011. Biosurfactants for microbubble preparation and application. International Journal of Molecular Sciences. 12:462-475.

Biswas, A., Sharma, B.K., Doll, K.M., Willett, J.L., Erhan, S.Z., Vermillion, K., Cheng, H. 2009. Synthesis of an amine-oleate derivative using an ionic catalyst. Journal of Agricultural and Food Chemistry. 57(1):8136-8141.

Sharma, B.K., Doll, K.M., Erhan, S.Z. 2011. Chemically modified fatty acid methyl esters: their potential for use as lubrication fluids and surfactants. In: Biresaw, G., Mittal, K.L., editors. Surfactants in Tribology. Vol 2. Boca Raton, FL: Taylor & Francis. p. 387-408.

Doll, K.M., Sharma, B.K. 2011. Surfactant effects on bio-based emulsions used as lubrication fluids. In: Biresaw, G., Mittal, K.L., editors. Surfactants in Tribology. Vol 2. Boca Raton, FL: Taylor & Francis. p. 173-190.

Doll, K.M., Sharma, B. 2011. Emulsification of chemically modified vegetable oils for lubricant use. Journal of Surfactants and Detergents. 14:131-138.

Doll, K.M., Erhan, S.Z. 2011. Evaluation of a sugar based edible adhesive utilizing a tensile strength tester. Journal of the Association for Laboratory Automation. 16(2):153-156.

Liu, Z., Rempel, G.L. 2011. Removal of transition metals from dilute aqueous solution by carboxylic acid group containing absorbent polymers. Hydrology: Current Research. 2(1):1-6.

Liu, Z., Biresaw, G. 2011. Synthesis of soybean oil-based polymeric surfactants in supercritical carbon dioxide and investigation of their surface properties. Journal of Agricultural and Food Chemistry. 59:1909-1917.

Xu, Q., Nakajima, M., Liu, Z., Nakamura, N., Shiina, T. 2011. Evaluation of a novel soybean oil-based surfactant for fine emulsion preparation. Household and Personal Care Today. p. 13-15.