Research Project: Industrial Monomers and Polymers from Plant Oils

Location: Bio-oils Research

2019 Annual Report

Objectives
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).

Approach
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
Work on both objectives of this project was accomplished during this fiscal year. A previously developed synthesis of the building blocks of plastic materials from biological sources was improved by discovering a different catalyst to do this process. New plasticizers, which enable plastics to be malleable enough to mold, were also produced. The new materials are based on natural products and are as effective as commercial products. Further work studying the use of a vegetable oil to help remove metals from water was published in a popular trade journal. Finally, the chemistry involved in the oxidation and breakdown of natural oils was studied, and the use of a natural amino acid was found to limit the degradation. This is important since diesel fuel is often formulated with added cold flow enhancers. Because our tung oil based additive is effective in each oil, it will work in the mixtures as well. Our additive can be used to help fuel lubricity without disrupting the effect of the other additives in the fuel.

Accomplishments
1. New diesel fuel additive from plant oil. Due to the development of ultra-low sulfur diesel fuel, diesel fuel injection systems have had to deal with poor lubrication. Usually, an additive is required to get satisfactory performance. Traditional biodiesel is often used for this purpose; however, to be effective, 1-2% or even more additive is required. This project has developed a new additive based on the natural oil, tung oil. Its structure allows it to be chemically modified with a compound called maleic anhydride, then it is further changed by the addition of an alcohol such as methanol or butanol. These new additives were studied in diesel fuel at low additive levels, where they were found to be as effective as traditional biodiesel at 20-40 times the amount. For example, the wear scar and friction results of diesel fuel laboratory tests were found to be improved by 40% and 46% respectively, at only 500 ppm additive levels of the new additives. Other oils, such as polyalphaolefin, have also been evaluated and the additive is effective in those oils as well.

Review Publications
Lokman, I.M., Rashid, U., Moser, B.R., Taufiq-Yap, Y.H. 2018. Appraisal of biodiesel prepared via acid catalysis from palm fatty acid distillate. Iranian Journal of Science and Technology, Transactions A: Science. https://doi.org/10.1007/s40995-018-0642-5.
Luo, C., Wang, C., Tang, J., Zhang, J., Shang, Q., Hu, Y., Wang, H., Wu, Q., Zgou, Y., Lei, W., Liu, Z. 2018. High-performance biobased unsaturated polyester nanocomposites with very low loadings of graphene. Polymers. 10(11):1288. https://doi.org/10.3390/polym10111288.
Chen, J., Liu, Z., Wang, K., Huang, J., Li, K., Nie, X., Jiang, J. 2018. Epoxidized castor oil-based diglycidyl-phthalate plasticizer: Synthesis and thermal stabilizing effects on poly(vinyl chloride). Journal of Applied Polymer Science. 136(9):47142. https://doi.org/10.1002/app.47142.
Kalita, D.J., Tarnavchyk, I., Sibi, M., Moser, B.R., Webster, D.C., Chisholm, B.J. 2018. Biobased poly(vinyl ethers) derived from soybean oil, linseed oil, and camelina oil: Synthesis, characterization, and properties of crosslinked networks and surface coatings. Progress in Organic Coatings. 125:453-462.
Ge, X., Yu, L., Liu, Z., Liu, H., Chen, Y., Chen, L. 2019. Developing acrylated epoxidized soybean oil coating for improving moisture sensitivity and permeability of starch-based film. International Journal of Biological Macromolecules. 125:370-375. https://doi.org/10.1016/j.ijbiomac.2018.11.239.
Xiao, Y., Zheng, M., Liu, Z., Shi, J., Huang, F., Luo, X. 2018. Constructing a continuous flow bioreactor based on a hierarchically porous cellulose monolith for ultrafast and nonstop enzymatic esterification/transesterification. ACS Sustainable Chemistry & Engineering. 7(2):2056-2063. https://doi.org/10.1021/acssuschemeng.8b04471.
Maglinao, R.L., Resurreccion, E.P., Kumar, S., Maglinao, Jr., A.L., Capareda, S., Moser, B.R. 2019. Hydrodeoxygenation-alkylation pathway for the synthesis of a sustainable lubricant improver from plant oils and lignin-derived phenols. Industrial and Engineering Chemistry Research. 58(10):4317-4330. https://doi.org/10.1021/acs.iecr.8b05188.
Alleman, T.L., Christensen, E.D., Moser, B.R. 2018. Improving biodiesel monoglyceride determination by ASTM method D6584-17. Fuel. 241:65-70.
Moser, B.R., Doll, K.M., Peterson, S.C. 2019. Renewable poly(thioether-ester)s from fatty acid derivatives via thiol-ene photopolymerization. Journal of the American Oil Chemists' Society. 96(7):825-837. https://doi.org/10.1002/aocs.12244.
Anderson, S.T., Walker, T., Moser, B.R., Drapcho, C., Zheng, Y., Bridges, William. 2019. Evaluation of dominant parameters in lipase transesterification of cottonseed oil. Transactions of the ASABE. 62:467-474.
Liu, Z., Li, J., Knothe, G., Sharma, B.K., Jiang, J. 2019. Improvement of diesel lubricity by chemically modified tung-oil-based fatty acid esters as additives. Energy and Fuels. 33(6):5110-5115. https://doi.org/10.1021/acs.energyfuels.9b00854.
Hwang, H.-S., Winkler-Moser, J.K., Doll, K.M., Gadgil, M., Liu, S.X. 2019. Factors affecting antioxidant activity of amino acids in soybean oil at frying temperatures. European Journal of Lipid Science and Technology. https://doi.org/10.1002/ejlt.201900091.
Dong, Z., Liu, Z., Shi, J., Tang, H., Xiang, X., Huang, F., Zheng, M. 2019. Carbon nanoparticle-stabilized Pickering emulsion as a sustainable and high-performance interfacial catalysis platform for enzymatic esterification/transesterification. ACS Sustainable Chemistry & Engineering. 7(8):7619-7629.