Location: Bio-oils Research Unit
2013 Annual Report
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.
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.
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.