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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

2012 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. A strong acid polymerization catalyst used at relatively high temperatures will cause intermolecular polymerization of the double bonds of soybean oil. Catalysts 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 nuclear magnetic resonance (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 that 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. This project is biosafety exempt.


3.Progress Report:
This is the second year of this project which was certified by the Office of Scientific and Quality Review (OSQR) in September, 2010. Progress has been made by scientists in the Bio-Oils Research Unit, at the USDA-ARS National Center for Agricultural Utilization Research (NCAUR), Peoria, IL, in all objective areas of this project during the year. In the lubricant area, three patents have been filed and another has finally worked its way through the system and been granted. The new materials will find their way to formulators who are working on bio-based oils. Manuscripts on the performance of these materials have been produced and are either submitted, or are already published, which will also help this growing market. New lipid materials have also been made through chemistry, where a benign bismuth catalyst can be used in place of the dangerous potassium permanganate. In the area of polymer science, we have used a sophisticated method to determine how fast water can diffuse through a gel. This is important in the development of a drug released material. Additional methods for making soy polymers are ongoing, and we have also made solid materials from nonfood oils as well.


4.Accomplishments
1. Patent filed on a boron-containing lubricant additive. Many lubricant additives require the use of undesirable phosphorous, zinc, and sulfur in order to be effective. Additionally, they are often incompatible with bio-based lubricants. ARS scientists in the Bio-Oils Research Unit at the USDA-ARS National Center for Agricultural Utilization Research (NCAUR), Peoria, IL, in collaboration with an industrial partner, have synthesized and filed for a patent on a new family of lubricant additives. These additives are made primarily from organoboron compounds prepared by utilizing epoxidized soybean oil. From this research, an antiwear and an antioxidation additive have been made, and they show high effectiveness even in soybean oil-based lubricant formulations. This work will help in the creation of new bio-based lubricants which will perform in a wide variety of industrial applications.


Review Publications
Arca, M., Sharma, B.K., Price, N.P.J., Perez, J.M., Doll, K.M. 2012. Evidence contrary to the accepted Diels-Alder mechanism in the thermal modification of vegetable oil. Journal of the American Oil Chemists' Society. 89:987-994.

Arca, M., Sharma, B.K., Perez, J.M., Doll, K.M. 2012. Isothermal thermogravimetric analysis of soybean oil oxidation correlated to thin film micro-oxidation test methods. Industrial and Engineering Chemistry Research. 51:3550-3555.

Selling, G.W., Hojillaevangelist, M.P., Evangelista, R.L., Isbell, T., Price, N.P., Doll, K.M. 2013. Extraction of proteins from pennycress seeds and press cake. Industrial Crops and Products. 41(1):113-119.

Doll, K.M., Sharma, B.K. 2012. Physical properties study on partially bio-based lubricant blends: Thermally modified soybean oil with popular commercial esters. International Journal of Sustainable Engineering. 5(1):33-37.

Tisserat, B., Harry O Kuru, R.E., Cermak, S.C., Evangelista, R.L., Doll, K.M. 2012. Potential uses for cuphea oil processing byproducts and processed oils. Industrial Crops and Products. 35:111-120.

Doll, K.M., Vermillion, K., Fanta, G.F., Liu, Z. 2012. Diffusion coefficients of water in biobased hydrogel polymer matrices by NMR imaging. Journal of Applied Polymer Science. 125:E580-E585.

Last Modified: 4/23/2014
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