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United States Department of Agriculture

Agricultural Research Service

Research Project: Functionalization of Vegetable Oils for Use in the Polymer, Oleochemical, and Lubricant Industries

Location: Bio-oils Research Unit

2013 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. Biosafety exempt.


3.Progress Report:
This is the third year of the project which was certified by the Office of Scientific and Quality Review (OSQR) in 2010. During this year, research has been performed by ARS scientists in the Bio-Oils Research Unit at the USDA-ARS National Center for Agricultural Utilization Research (NCAUR), Peoria, Illinois, which pertains to each of the objectives. New catalytic systems have been developed. The first is a new system for the formation of polymers from vegetable oils with benign catalysts opening up potential applications in the food and medical areas. This new method gives performance materials similar to a previous invention, but can be more conveniently employed. A second catalyst will chemically remove the oxygen-containing groups from a vegetable oil material and produce a chemical similar to that which can be made from petroleum. The possibilities for this technology are wide, and a patent application has been filed to cover this invention. In other work, a further study was made on a lubricant additive based on boron, which is effective in reducing wear and oxidation. The development of soybean oil-based gels and surfactants was also continued with collaborators, resulting in further publications. In a final project, in collaboration with other projects, a vegetable oil with chemically added sulfur was used to remove metal ions from a water solution.


4.Accomplishments
1. Natural oil polymer synthesis. Natural oils, such as euphorbia oil and tung oil, contain structures that are easily modified through chemistry, a trait shared by the much more expensive veronia oil. ARS scientists in the Bio-Oils Research Unit at the USDA-ARS National Center for Agricultural Utilization Research (NCAUR), Peoria, Illinois, have developed a route to take advantage of these naturally-occurring groups. The new material is a polymer whose properties can be changed by varied reaction time, temperature, and catalyst amount. An additional advantage is that this chemistry utilizes liquid carbon dioxide instead of environmentally harmful organic solvent. The solid powder material was analyzed to determine the chemical and physical properties. This material may provide a less expensive alternative suitable for many applications. Possibilities are the formation of a soap or a gel, useful in cosmetic or detergent formulations.


Review Publications
Doll, K.M., Biswas, A. 2013. A biobased nitrogen-containing lubricant additive synthesized from expoxidized methyl oleate using an ionic liquid catalyst. In: Biresaw, G., Mittal, K.L., editors. Surfactants in Tribology. Volume 3. Boca Raton, FL: CRC Press. p. 131-145.

Doll, K.M., Bantchev, G.B., Murray, R.E. 2013. Bismuth(III) trifluoromethanesulfonate catalyzed ring opening reaction of mono epoxy oleochemicals to form keto and diketo derivatives. ACS Sustainable Chemistry & Engineering. 1:39-45.

Liu, Z., Biswas, A. 2013. Fluoroantimonic acid hexahydrate (HSbF6-6H2O) catalysis: The ring-opening polymerization of epoxidized soybean oil. Applied Catalysis A: General. 453:370-375.

Liu, Z., Knetzer, D.A. 2013. Catalyzed ring-opening polymerization of epoxidized soybean oil by hydrated and anhydrous fluoroantimonic acids. Green Materials. 1:87-95.

Doll, K.M., Sharma, B.K., Pereira, M.S., Santos, G.F., Suarez, P.A., Erhan, S.Z. 2012. Production of phosphorous-containing oleochemicals through an epoxide route. International Journal of Sustainable Engineering. 5:280-285.

Chintareddy, V.R., Oshel, R.E., Doll, K.M., Yu, Z., Wu, W., Zhang, G., Verkade, J.G. 2012. Investigation of conjugated soybean oil as drying oils and CLA sources. Journal of the American Oil Chemists' Society. 89:1749-1762.

Sharma, B.K., Doll, K.M., Heise, G.L., Myslinska, M., Erhan, S.Z. 2012. Anti-wear additive derived from soybean oil and boron utilized in a gear oil formulation. Industrial and Engineering Chemistry Research. 51:11941-11945.

Abdekhodaie, M.J., Liu, Z., Erhan, S.Z., Wu, X.Y. 2012. Characterization of novel soybean-oil-based thermosensitive amphiphilic polymers for drug delivery applications. Polymer International. 61:1477-1484.

Last Modified: 9/29/2014
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