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ARS Home » Midwest Area » Peoria, Illinois » National Center for Agricultural Utilization Research » Bio-oils Research » Research » Research Project #427292

Research Project: Industrial Monomers and Polymers from Plant Oils

Location: Bio-oils Research

2016 Annual Report

Objective 1: Enable the commercial production of monomers from biobased acids. Sub-objective 1.A. Enable, from a technological standpoint, the commercial conversion of fatty acids into olefinic hydrocarbon monomers. Sub-objective 1.B. Enable the commercial production of oxygenated monomers from biological feedstocks. Objective 2: Enable the commercial production of polymers from acrylated and epoxidized soybean oil (ESO).

The decarboxylation of fatty acids is thermodynamically favorable at temperatures above 100 deg C. However, the barrier to decarboxylation is quite high, resulting in exceedingly slow rates at temperatures which are convenient for industrial reactions. The barrier is influenced by the functional groups on the fatty acid, especially those near the carbonyl carbon of the carboxylic acid moiety. Specifically, a fatty acid with a double bond at the beta-gamma position undergoes decarboxylation significantly faster than that of other positions. A process which takes advantage of this phenomenon has already been demonstrated, in a preliminary manner, utilizing a new ARS technology. Cross-metathesis of methyl oleate with ethene in the presence of a Grubbs catalyst yields methyl 9-decenoate (M9D) and 1-decene. M9D will serve as a platform chemical for readily polymerizable monomers, whereas 1-decene already has established commercial outlets as a monomer for industrial poly alpha olefins. Anticipated commercial applications of materials derived from M9D include as components in adhesives, coatings, latexes, and sealants. Separation of M9D from 1-decene and unreacted methyl oleate (if present) will be accomplished using methods selected for economic and practical considerations. There are currently many different 3D printing technologies available. The use of this additive technology has many advantages including efficient use of materials, versatility and ability to produce different shapes at only the touch of a button. However, the amount of available materials useful for these printing technologies has fallen behind the printing hardware itself.

Progress Report
This is the first annual report for the project 5010-41000-170-00D, which was certified in March 2015. During this year, research was performed by ARS scientists in Peoria, Illinois, which pertains to each of the objectives and sub-objectives of the plan. The process where chemicals can be produced from natural oils was studied and improved. Specifically, oleic acid, potentially from soybean oil, and cinnamic acid, also a plant oil, were subjected to chemistry where their oxygen was removed from the materials by a catalyst. Using other chemical methods, the building blocks of polyesters and polyurethanes were also made from natural oils with environmentally-friendly processes. In addition, methods to spray and cure soybean oil were improved resulting in a resin where it is now possible to use three dimensional printer technology to produce thin films.

1. Vegetable oil was changed into building blocks for making plastic. Transforming plant oil into a usable replacement for petroleum is a complicated, yet worthwhile process. One of the problems with natural materials is that they contain too many oxygen atoms in their structures to be used in plastics that Americans use every day. These oxygen atoms must be removed in order for the correct reactions to take place and to form strong, durable, and useful plastic products. To make these materials from natural oils, there are a couple of different approaches, but some only work at extreme temperatures and other methods require expensive chemicals. These reactions can also produce undesirable side products, such as the poisonous carbon monoxide, or large amounts of sulfur-containing byproducts. ARS scientists in Peoria, Illinois, have developed a new technology which uses a very small amount of catalyst, and the only by-product is carbon dioxide. A patent application covering this technology has been filed, and the result will enable major polymer industrial partners to replace their currently used petroleum.


Review Publications
Moser, B.R., Evangelista, R.L., Isbell, T.A. 2016. Preparation and fuel properties of field pennycress (Thlaspi arvense) seed oil ethyl esters and blends with ultra-low sulfur diesel fuel. Energy and Fuels. 30:473-479.
Chandrasekaran, S.R., Murali, D., Marley, K.A., Larson, R.A., Doll, K.M., Moser, B.R., Scott, J., Sharma, B.K. 2016. Antioxidants from slow pyrolysis bio-oil of birch wood: Application for biodiesel and biobased lubricants. ACS Sustainable Chemistry & Engineering. 4:1414-1421.
Chen, J., Liu, Z., Li, X., Liu, P., Jiang, J., Nie, X. 2016. Thermal behavior of epoxidized cardanol diethyl phosphate as novel renewable plasticizer for poly(vinyl chloride). Polymer Degradation and Stability. 126:58-64.
Chen, J., Liu, Z., Jiang, J., Nie, X., Zhou, Y., Murray, R.E. 2015. A novel biobased plasticizer of epoxidized cardanol glycidyl ether: Synthesis and application in soft poly(vinyl chloride) films. RSC Advances. 5:56171-56180.
Chandrasekaran, S.R., Kunwar, B., Moser, B.R., Rajagopalan, N., Sharma, B.K. 2015. Catalytic thermal cracking of post-consumer waste plastics to fuels. 1. Kinetics and optimization. Energy and Fuels. 29(9):6068-6077.
Doll, K.M., Walter, E.L., Bantchev, G.B., Jackson, M.A., Murray, R.E., Rich, J.O. 2016. Improvement of lubricant materials using ruthenium isomerization. Chemical Engineering Communications. 203(7):901-907.
Dien, B.S., Zhu, J.Y., Slininger, P.J., Kurtzman, C.P., Moser, B.R., O'Bryan, P.J., Gleisner, R., Cotta, M.A. 2016. Conversion of SPORL pretreated Douglas fir forest residues into microbial lipids with oleaginous yeasts. RSC Advances. 6(25):20695-20705. doi: 10.1039/c5ra24430g.
Knothe, G., Moser, B.R. 2015. Fatty acid profile of seashore mallow (Kosteletzkya pentacarpos) seed oil and properties of the methyl esters. European Journal of Lipid Science and Technology. 117(8):1287-1294. doi: 10.1002/ejlt.201400612.
Moser, B.R. 2016. Fuel property enhancement of biodiesel fuels from common and alternative feedstocks via complementary blending. Renewable Energy. 85:819-825.
Lindquist, M.R., Lopez-Nunez, J.C., Jones, M.A., Cox, E.J., Pinkleman, R.J., Bang, S.S., Moser, B.R., Jackson, M.A., Iten, L.B., Kurtzman, C.P., Bischoff, K.M., Liu, S., Qureshi, N., Tasaki, K., Rich, J.O., Cotta, M.A., Saha, B.C., Hughes, S.R. 2015. Irradiation of Yarrowia lipolytica NRRL YB-567 creating novel strains with enhanced ammonia and oil production on protein and carbohydrate substrates. Applied Microbiology and Biotechnology. 99(22):9723–9743.
Hughes, S.R., Cox, E.J., Bang, S.S., Pinkelman, R.J., Lopez-Nunez, J.C., Saha, B.C., Qureshi, N., Gibbons, W.R., Fry, M.R., Moser, B.R., Bischoff, K.M., Liu, S., Sterner, D.E., Butt, T.R., Reidmuller, S.B., Jones, M.A., Riano-Herrera, N.M. 2015. Process for assembly and transformation into Saccharomyces cerevisiae of a synthetic yeast artificial chromosome containing a multigene cassette to express enzymes that enhance xylose utilization designed for an automated platform. Journal of Laboratory Automation. 20(6):621-635. doi: 10.1177/2211068215573188.
Dien, B.S., Slininger, P.J., Kurtzman, C.P., Moser, B.R., O'Bryan, P.J. 2016. Identification of superior lipid producing Lipomyces and Myxozyma yeasts. AIMS Environmental Science. 3(1):1-20. doi: 10.3934/environsci.2016.1.1.
Chen, J., Liu, Z., Li, K., Huang, J., Nie, X., Zhou, Y. 2015. Synthesis and application of a natural plasticizer based on cardanol for poly(vinyl chloride). Journal of Applied Polymer Science. 132(35). doi: 10.1002/APP.42465.
Zhang, X., Fan, X., Solaiman, D., Liu, Z., Yan, R., Mukhopadhyay, S., Ashby, R.D. 2015. Inactivation of Escherichia coli O157:H7 in vitro and on the surface of spinach leaves by biobased surfactants. Food Control. doi: 10.1016/j.foodcont.2015.07.026. 60:158-165.
Liu, Z., Chen, J., Knothe, G., Nie, X., Jiang, J. 2016. Synthesis of epoxidized cardanol and its antioxidative properties for vegetable oils and biodiesel. ACS Sustainable Chemistry & Engineering. 4(3):901-906.
Moser, B.R., Seliskar, D.M., Gallagher, J.L. 2016. Fatty acid composition of fourteen seashore mallow (Kosteletzkya pentacarpos) seed oil accessions collected from the Atlantic and Gulf coasts of the United States. Industrial Crops and Products. 87:20-26.
Doll, K.M., Cermak, S.C., Kenar, J.A., Isbell, T.A., 2016. Synthesis and characterization of estolide esters containing epoxy and cyclic carbonate groups. Journal of the American Oil Chemists' Society. 93(8):1149-1155.
Doll, K.M., Moser, B.R., Liu, Z., Murray, R.E. 2016. Producing monomers and polymers from plant oils. In: Sharma, B.K., Biresaw, G., editors. Environmentally Friendly and Biobased Lubricants. Boca Raton: CRC Press. p. 79-98.