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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

2018 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
The synthesis of methacrylic acid, which is a commodity monomer used in the production of acrylic glass, was improved. The process can use either itaconic acid or the less expensive citric acid. A table comparing the new technology to the old technology was part of the main publication on this technology. In this research, conducted by ARS scientists in Peoria, Illinois, it was determined that the technology used to create heptadecene can also create useful alkylaromatic molecules. Finally, the natural product, cardanol, was used as the starting material to make two different plasticizers for poly (vinyl chloride), the plastic used in toys, furniture, electronics, and many other household items. The new plasticizers were demonstrated to be as effective as commercially available counterparts giving potential customers a biobased option to replace petroleum based plasticizers.

1. Production of organogel using biobased materials. Gel materials are very useful in many applications, such as soaking up spills, altering the texture of other products, and slowly releasing moisture or other substances in a controlled manner. Gels formed from water are more common than the type that form with oil based solutions. These less common gels are called organogels, and they have been less studied than their water based analogs. However, they are especially useful, specifically in the removal of toxic solvents from aqueous environments. In this research, ARS scientists in Peoria, Illinois, produced a new organogel from an agriculturally based material, and a cheap ingredient which is often used in chewing gum. This new approach avoids a difficult chemical reaction, and increases the chance that this material could be made at an affordable price. The new product has been shown to form stable gels with several different oil based solutions. The organogel was also tested in a timed release application, where satisfactory results were also obtained. These controlled release properties are of specific interest in many applications. Some are in agriculture, such as in the use of a controlled delivery of compounds used in plant growth or pest control, while others are in the medical field, where accurate delivery of organic compounds is often needed.

Review Publications
Doll, K.M., Walter, E.L., Murray, R.E. 2018. Decarboxylation of cinnamic acids using a ruthenium sawhorse. International Journal of Sustainable Engineering. 11(1):26-31.
Moser, B.R. 2018. Biodiesel. In: Konur, O., editor. Bioenergy and Biofuels. Boca Raton, FL: CRC Press. p. 121-144.
Liu, Z., Tisserat, B.H. 2018. Coating applications to natural fiber composites to improve their physical, surface and water absorption characters. Industrial Crops and Products. 112:196-199.
Evangelista, R.L., Cermak, S.C., Hojilla-Evangelista, M.P., Moser, B.R., Isbell, T.A. 2017. Field pennycress: A new oilseed crop for the production of biofuels, lubricants, and high-quality proteins. In: Biresaw, G., Mittal, K.L., editors. Surfactants in Tribology. Volume 5. Boca Raton, FL: CRC Press. p. 369-400.
Kenar, J.A., Moser, B., List, G.R. 2017. Naturally occurring fatty acids: Source, chemistry, and uses. In: Ahmad, M.U., editor. Fatty Acids: Chemistry, Synthesis, and Applications. Amsterdam, The Netherlands: Elsevier. p. 23-82.
List, G.R., Kenar, J.A., Moser, B. 2017. History of fatty acids. In: Ahmad, M.U., editor. Fatty Acids: Chemistry, Synthesis, and Applications. Amsterdam, The Netherlands: Elsevier. p. 1-22.
Knothe, G., Steidley, K.R., Moser, B.R., Doll, K.M. 2017. Decarboxylation of fatty acids with triruthenium dodecacarbonyl: Influence of the compound structure and analysis of the product mixtures. ACS Omega. 2:6473-6480.
Li, R., Liu, Z., Tomasula, P.M., Sousa, A.M., Liou, S., Tunick, M.H., Liu, L.S. 2017. Electrospinning pullulan fibers from salt solutions. Polymers. doi: 10.3390/polym9010032.
Tisserat, B., Liu, Z., Haverhals, L.M. 2018. Lignocellulosic composites prepared utilizing aqueous alkaline/urea solutions with cold temperatures. International Journal of Polymer Science.
Muturi, E.J., Ramirez, J.L., Doll, K.M., Bowman, M.J. 2017. Combined toxicity of three essential oils against Aedes aegypti (Diptera: Culicidae) larvae. Journal of Medical Entomology. 54:1684-1691. doi: 10.1093/jme/tjx168.
Biswas, A., Alves, C.R., Trevisan, M.T.S., Berfield, J., Furtado, R.F., Liu, Z., Cheng, H.N. 2016. Derivatives of cardanol through the ene reaction with diethyl azodicarboxylate. Journal of Brazilian Chemical Society. 27(6):1078-1082.
Li, R., Jin, Z.T., Liu, Z., Liu, L.S. 2018. Antimicrobial double-layer coating prepared from pure or doped-titanium dioxide and binders. Coatings. 8(1):41-51.
Chen, J., Liu, Z., Nie, X., Zhou, Y., Jiang, J., Murray, R.E. 2018. Plasticizers derived from cardanol: Synthesis and plasticization properties for poly(vinyl chloride). Journal of Polymer Research. 25:128.
Liu, Z., Biresaw, G., Biswas, A., Cheng, H.N. 2018. Effect of polysoap on the physical and tribological properties of soybean oil-based grease. Journal of the American Oil Chemists' Society. 95(5):629-634.
Chen, J., Liu, Z., Nie, X., Jiang, J. 2018. Synthesis and application of a novel environmental C26 diglycidyl ester plasticizer based on castor oil for poly(vinyl chloride). Journal of Materials Science. 53(12):8909-8920.
Doll, K.M., Walter, E.L., Murray, R.E., Hwang, H.-S. 2018. Organogel polymers from 10-undecenoic acid and poly(vinyl acetate). Journal of Polymers and the Environment. 26:3670-3676.
Dunn, R.O., Bantchev, G.B., Doll, K.M., Ascherl, K.L., Lansing, J.C., Murray, R.E. 2018. Thioether-functionalized corn oil biosorbents for the removal of mercury and silver ions from aqueous solutions. Journal of the American Oil Chemists' Society. 95:1189-1200.