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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

2020 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 final report for this project which terminated in May 2020. See the report for the replacement project, 5010-41000-186-00D, “New High-Value Biobased Materials with Applications Across Industry” for additional information. Accomplishments for this year included: A new reaction technology was used to make hard plastic materials from plant derived fatty acids. In other work, the technology which can help turn these same fatty acids into a useable fuel was further developed. It was tested, not only on high purity fatty acids, but also on a mixture that was made without separating the individual components. On the final objective, lignocellulose, an agricultural byproduct of little value was used to reinforce a plastic material with promising results. Over the life of this project, significant breakthrough science has been accomplished in many areas. It has resulted in well over 70 peer reviewed journal publications, as well as six granted U.S. patents and two additional U.S. patent applications. Some of the work was performed in the fuels area, where a lubricating additive for low sulfur diesel fuel was invented and fuels were made by removing oxygen atoms from natural oil materials. Other work was done in the polymer area, where methacrylic acid, a building block for Plexiglass, was made from a simple sugar, and a gel material capable of taking oil out of water was developed. In a final area of this product, a couple of different antioxidation compounds were synthesized. These discoveries will help enable soybean oil-based materials function in a variety of industrial environments.

1. A new method to make coating materials. Using chemical building blocks made from fatty acids derived from vegetable oils, ARS researchers in Peoria, Illinois, used a process called acyclic diene metathesis (ADMET) in order to achieve a sustainable route to a new set of renewable polymers from vegetable oils. Renewable polymers are important because they represent biobased alternatives to existing petrochemically-based materials, which often cause water and soil pollution in addition to negative health effects. Using this ADMET technology, vegetable oil-based materials with useful melting points were made in high yield and many of their physical properties were measured. Additionally, the technology used in this process is simple, rapid and proceeds under mild conditions. Polymers like these are found in paints where they impart proper thickness for achieving a smooth finish and easy application. They are also good for forming the gel used in glues and other similar materials. This research may ultimately expand markets for biobased polymers, thus reducing the environmental impact of and demand for petroleum-derived products while simultaneously enhancing rural economies by increasing the use of agricultural materials.

2. Understanding why frying oils do not last. Frying oils are an important part of the foods that most of us eat every day. However, they do not last forever, and their short life makes those foods more expensive. ARS researchers in Peoria, Illinois, have studied this degradation (breakdown), by taking a closer look at the larger molecules formed during the process, called polymers, and tracking their formation, information about the overall process was uncovered. It was determined that the amount of a specific type of chemical bond, called an ester, is a previously overlooked player in the destruction of the valuable oil. This fundamental new idea will be instrumental in developing new additives to give long oil life. This is one step that will ultimately impact the useful life of frying oil with positive impacts throughout the food systems that we all depend on every day.

Review Publications
Moser, B.R., Vermillion, K.E., Banks, B.N., Doll, K.M. 2020. Renewable aliphatic polyesters from fatty dienes by acyclic diene metathesis polycondensation. Journal of the American Oil Chemists' Society. 97(5):517-530.
Sun, T., Zhang, H., Dong, Z., Liu, Z., Zheng, M. 2020. Ultrasonic-promoted enzymatic preparation, identification and multi-active studies of nature-identical phenolic acid glycerol derivatives. RSC Advances. 10:11139-11147.
Zanetti, F., Isbell, T.A., Gesch, R.W., Evangelista, R.L., Alexopoulou, E., Moser, B.R., Monti, A. 2019. Turning a burden into an opportunity: Pennycress (Thlaspi arvense L.) a new oilseed crop for biofuel production. Biomass and Bioenergy. 130:105354.
Muturi, E.J., Selling, G.W., Doll, K.M., Hay, W.T., Ramirez, J.L. 2020. Leptospermum scoparium essential oil is a promising source of mosquito larvicide and its toxicity is enhanced by a biobased emulsifier. PLoS One. 15(2):e0229076.
Muturi, E.J., Doll, K.M., Berhow, M.A., Weiler, L., Rooney, A.P. 2019. Honeysuckle essential oil as a potential source of ecofriendly larvicides for mosquito control. Pest Management Science. 75(7):2043-2048.
Hwang, H.-S., Ball, J.C., Doll, K.M., Anderson, J.E., Vermillion, K. 2020. Investigation of polymers and alcohols produced in oxidized soybean oil at frying temperatures. Food Chemistry. 317:126379.
Gonzalez, J.M., Boddu, V.M., Jackson, M.A., Moser, B.R., Ray, P. 2020. Pyrolysis of creosote-treated railroad ties to recover creosote and produce biochar. Journal of Analytical and Applied Pyrolysis. 149. Article 104826.
Muturi, E.J., Hay, W.T., Doll, K.M., Ramirez, J.L., Selling, G.W. 2020. Insecticidal activity of Commiphora erythraea essential oil and its emulsions against larvae of three mosquito species. Journal of Medical Entomology. 57(6):1835-1842.
Jin, C., Liu, G., Wu, G., Huo, S., Liu, Z., Kong, Z. 2020. Facile fabrication of crown ether functionalized lignin-based biosorbent for the selective removal of Pb(II). Industrial Crops and Products. 155. Article 112829.