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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

2017 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
Styrene and decanoate were synthesized from renewable materials for use in plastics and motor oils. Using a combination of computer modeling and laboratory reactions, factors that affect the energy of this reaction were uncovered by ARS scientists in Peoria, Illinois. In addition, a biobased route to methacylic acid from natural sugars was developed. This new technology is more environmentally friendly than the commercial petrochemical method. Relating to the final objective of this project, soybean oil based materials were chemically modified and cast into thin films. These thin films were then cured with ultraviolet light and their properties, such as tensile strength and flexibility, were studied. This development will enable production of resins that will be useful in three-dimensional (3D) printing technology.

1. Renewable synthesis of methacrylate. Methacrylic acid is an important commodity monomer used for the production of many commercially significant polymers, most notably acrylic glass. The annual world-wide market of methacrylic acid is in excess of nine billion dollars. The traditional route to methacrylic acid is petrochemically-based and involves the reaction of acetone with concentrated sulfuric acid and hydrogen cyanide. By using simple sugars from natural sources to yield a sustainable and renewable product, this new technology is more environmentally friendly than the commercial petrochemical method. This research will ultimately provide a renewable alternative to an otherwise nonrenewable commercial material, thus further reducing the environmental impact of and demand for petroleum and its various products.

Review Publications
Doll, K.M., Bantchev, G.B., Walter, E.L., Murray, R.E., Appell, M., Lansing, J.C., Moser, B.R. 2017. Parameters governing ruthenium sawhorse-based decarboxylation of oleic acid. Industrial and Engineering Chemistry Research. 56(4):864-871.
Liu, C., Shang, Q., Jia, P., Dai, Y., Zhou, Y., Liu, Z. 2016. Tung oil-based unsaturated co-ester macromonomer for thermosetting polymers: Synergetic synthesis and copolymerization with styrene. ACS Sustainable Chemistry & Engineering. 4(6):3437-3449.
Doll, K.M., Cermak, S.C., Kenar, J.A., Walter, E.L., Isbell, T.A. 2017. Derivatization of castor oil based estolide esters: Preparation of epoxides and cyclic carbonates. Industrial Crops and Products. 104:269-277.
Moser, B.R., Knothe, G., Walter, E.L., Murray, R.E., Dunn, R.O., Doll, K.M. 2016. Analysis and properties of the decarboxylation products of oleic acid by catalytic triruthenium dodecacarbonyl. Energy and Fuels. 30(9):7443-7451.
Slininger, P.J., Dien, B.S., Kurtzman, C.P., Moser, B.R., Bakota, E.L., Thompson, S.R., O'Bryan, P.J., Cotta, M.A., Balan, V., Jin, M., da Costa Sousa, L., Dale, B.E. 2016. Comparative lipid production by oleaginous yeasts in hydrolyzates of lignocellulosic biomass and process strategy for high titers. Biotechnology and Bioengineering. 113(8):1676-1690. doi: 10.1002/bit.25928.
Kunwar, B., Moser, B.R., Chandrasakaran, S.R., Rajagopalan, N., Sharma, B.K. 2016. Catalytic and thermal depolymerization of low value post-consumer high density polyethylene plastic. Energy. 111:884-892.
Bantchev, G.B., Moser, B.R., Murray, R.E., Biresaw, G., Hughes, S.R. 2016. Synthesis and characterization of phosphonates from methyl linoleate and vegetable oils. Journal of the American Oil Chemists' Society. 93(12):1671-1682.
Lepak, G.S., Moser, B.R., Bakota, E.L., Sharp, J., Thornton, C.D., Walker, T. 2016. Improved oxidative stability of biodiesel via alternative processing methods using cottonseed oil. International Journal of Sustainable Engineering. 10(2):105-114.
Kunwar, B., Chandrasekaran, S.R., Moser, B.R., Deluhery, J., Kim, P., Rajagopalan, N., Sharma, B.K. 2017. Catalytic thermal cracking of postconsumer waste plastics to fuels. 2. Pilot-scale thermochemical conversion. Energy and Fuels. 31(3):2705-2715.
Lansing, J.C., Murray, R.E., Moser, B.R. 2017. Biobased methacrylic acid via selective catalytic decarboxylation of itaconic acid. ACS Sustainable Chemistry & Engineering. 5(4):3132-3140.
Cheng, W.W., Liu, G.Q., Wang, L.Q., Liu, Z. 2017. Glycidyl fatty acid esters in refined edible oils: A review on formation, occurrence, analysis, and elimination methods. Comprehensive Reviews in Food Science and Food Safety. 16:263-281.