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United States Department of Agriculture

Agricultural Research Service

Research Project: CHEMICAL SYSTEMS FOR SOYBEAN OIL CONVERSION TO INDUSTRIAL PRODUCTS
2005 Annual Report


1.What major problem or issue is being resolved and how are you resolving it (summarize project aims and objectives)? How serious is the problem? What does it matter?
The major use of vegetable oils (such as soybean oil) is directed to food products, salad and cooking oils, shortenings, and margarines in particular. Less than 3% is utilized in non-food applications, since a number of former vegetable oil markets are lost to petroleum products. In the years following World War II, petroleum derived products rapidly displaced vegetable oil-based materials. Certain performance and technical properties can be easily achieved using seed oil derivatives. Such products based on agro raw materials are at par with available petroleum based products in the market. The importance of natural products for industrial applications becomes very clear with increasing social emphasis on the issues of environment, waste disposal, and depleting non-renewable resources.

Seed oils and products based on seed oil derivatives suffer from some technical drawbacks such as oxidation, cold flow behavior and extended stability. For applications such as composites, lubricants, plastics, fuel, and chemical intermediates; soybean oil and other vegetable oils are too viscous and too reactive toward atmospheric oxygen to establish significant markets. Limitations in molecular weight and crystallization properties restrict the uses of vegetable oils in solvents, plastics, fuels, and industrial fluids. In addition to above problems, this research project will address low Volatile Organic Chemicals (VOC), high biodegradability in ink formulations, and low or no VOC, improved oxidative stability/low temperature properties in biodegradable lubricants.

U.S. Environmental Protection Agency (EPA), Clean Air Act Amendment, and U.S. Department of Labor, Occupational Safety & Health Administration, (OSHA) regulations exert ever growing pressure on the graphic arts (inks, paints, coatings), lubricants and hydraulic oils, detergents, emulsifiers, and the polymer industries on limiting the use of organic solvents, creating less toxic waste, using a renewable resource, and producing more biodegradable products. Parties affected by these regulations and parties interested in enhanced marketability of soybean (American Soybean Association, United Soybean Board) and other oilseed crops will use the results and/or products of this research project to expand the market for these commodities.


2.List the milestones (indicators of progress) from your Project Plan.
First Year FY2005: 1. Seed oil-based metalworking fluid for aluminum hot rolling will be formulated. 2. Complete initial preparation of grease samples with Li metal, fatty acids and check for consistency and smooth paste like texture conforming to National Lubricant Grease Index (NLGI) specifications. 3. Complete preparation of synthetic lubricant base stocks using epoxidized vegetable oils, long chain/branched alcohols and catalyst; and further reaction on above product using acid anhydrides. 4. Complete the reaction optimization of vegetable oils with different sulfur compounds (which may or may not contain an amine functionality) using a catalyst (perchloric acid) to obtain biobased additives in higher yields and characterization using Nuclear Magnetic Resonance (NMR), Fourier Transform Infrared (FTIR) and Pressurized Differential Scanner Calorimetry (PDSC). 5. Complete initial preparation of composites samples with non-coated flax fibers using compression molding method and study their mechanical and water absorption properties. 6. Complete the samples preparations of nano-clay reinforced soybased composites. Thermo and mechanical properties will be studied. 7. Soybased Hydrogels prepared from ring-opening polymerization and hydrolysis of obtained polymers will be studied for their temperature sensitive and pH sensitive properties. 8. Epoxidized Soybean Oil (ESO) will be cured with polyamine compounds to form energy absorbing materials sheets for mechanical, thermophysical properties tests. 9. Ring opening polymerization will be carried out using Lewis catalysts for preparing soybean oil based polymeric surfactants.

Second Year FY2006: 1. Seed oil-based metalworking fluid for aluminum hot rolling will be tested for various performance and tribochemical properties in-house. 2. Characterization of grease samples for their penetration, oxidation and thermal stability using PDSC, micro-oxidation, oven test, Rotary Bound Oxidation Test (RBOT). 3. Complete ring-opening reaction of epoxidized seed oil followed by esterification of resulting hydroxyl group to give lubricant base fluid. Characterize the chemically modified vegetable oil fluids for their oxidative stability and pour point and check to see if the process significantly improved the low temperature fluidity and thermal stability of the oil. 4. Complete the reactions of vegetable oils with different amines using same catalyst to synthesize bio-based anti-wear, anti-oxidants additives and characterization using NMR, FTIR and PDSC. 5. Prepare composites samples reinforced with coated flax fibers and to characterize their binding properties using a Transmission Electron Microscope (TEM). Three point bend and tensile tests will be performed on samples fabricated under task 1 (first year) using noncoated fibers and coated fibers. Compare their mechanical and water absorption properties. Evaluate polyamine curing agents. 6. Optimum clay loading, curing conditions and study the structures of clay dispersion in the host polymers for nano-clay reinforced soybased composites. 7. Study drug loading and release rate of soybased hydrogels. Effect of dissolution media such as temperature, pH on the release rate will be investigated. 8. Complete material selection and formulation of energy absorbing materials. Glass transition temperatures (Tgs) will be determined using DSC. 9. Initiator evaluation for ring opening polymerization will be performed. Optimization of polymerization conditions necessary to obtained soybean oil based polymeric surfactants in high yield will also be investigated. Synthesis of other derivatives of epoxidized methyl esters such as epoxidized methyl oleate, epoxidized methyl linoleate, and epoxidized linolenate.

Third Year FY2007: 1. Tribochemical evaluation and physical property determination of metal working fluids will continue based on feedback from Cooperative Research and Development Agreement (CRADA) partner. 2. Develop methods to study wear-friction properties of grease samples. Try to establish structure-property relationship using above data. 3. Complete the formulation and blending of chemically modified vegetable oil fluids with other seed oils and suitable Pour Point Depressant (PPD), Anti-Oxidant (AO) and Anti-Wear (AW) additives. Evaluate the final products for pour point, viscosity, viscosity index, oxidative stability using PDSC, friction and wear characteristics using Falex to study the effect of structural variation in the oil molecules. 4. Complete the reactions of vegetable oils with different alcohol-amines using same catalyst to synthesize bio-based anti-wear, anti-oxidants additives and characterization using NMR, FTIR and PDSC. Synthesis of vegetable oil analogs using carboxylic acids using base catalysis. 5. Optimization of curing agents for epoxidized soybean oil and curing conditions such as pressure, temperature, and reaction time; study of fiber loading influence on the mechanical properties of composites; and analysis of water swelling data of composites. 6. Work will continue on the characterization of nano-clay reinforced soybased composites using X-ray and TEM. 7. Study drug release kinetics followed Fickian law or nonFickian law for Soybased Hydrogels. 8. Damping and falling weight properties of soybased energy absorbing materials will be evaluated. 9. Hydrolysis of obtained soybean oil based polymers using sodium hydroxide to remove glycerin small molecule, purification of the samples for Gel Permeation Chromatography (GPC) analysis. Surface tension and contact angle measurements of soybean oil based polymeric surfactants are performed. The Critical Micelle Concentration (CMC) will be determined. Synthesis of small molecule surfactants derived from vegetable oil and the carboxylic acids and esters of vegetable oil.

Fourth Year FY2008: 1. Using established structure - property relationship and optimized conditions such as metal, fatty acid content, baseoil amount to complete preparation/formulation of NLGI grade 2 grease with AO, AW, Extreme Pressure (EP) additives. Formulation will be tested by industrial CRADA partners. 2. Complete scale up in 20L reactor to prepare 6 lbs of synthetic lubricant base fluids and optimization of reaction variables for economically producing the environmentally friendly ester-based lubricants from epoxidized vegetable oil; following test by industrial CRADA partners. 3. Complete development of PDSC and Falex methods to test effectiveness (anti-oxidant and anti-wear behavior) of synthesized bio-based additive compounds, comparison with industrially available additives and screening for potential bio-based anti-oxidant and anti-wear additives. 4. Complete development of composites which are reinforced by natural fiber and nano clay. Industrial CRADA partner finishes their site tests. 5. A soybased drug controlled release system will be developed. Industrial partners will test this system. 6. New energy absorbing materials with good damping and energy absorbing properties will be developed from soybean oil. 7. Finish studies on soybean oil based polymeric surfactants. Further evaluation and comparison of vegetable oil based small molecule surfactants with available products. Synthesis of bio-based surfactants using vegetable oil based esters and other biological small molecules such as sugars and glycerides. Evaluation of the surfactants for CMC and surface tension reduction.

Fifth Year FY2009: 1. Complete bio-based grease studies, patent/transfer technology. 2. Complete final evaluation of synthetic lubricants/metal working fluids/gear oils/under-carriage oils after analyzing data obtained from industrial CRADA partners, offer recommendations for changes in final formulation and patent/transfer technology. 3. Finish studies on bio-based speciality additives, complete patents/paper writing. 4. Technical paper will be written for publication for studies on soybased composites reinforced with flax fibers and nano-clay reinforced soybased composites. 5. Complete patent/paper writings and patent filing on the soybased hydrogels for controlled release systems. 7. Related scientific papers will be written on energy absorbing material developed from soybean oil. 8. Complete patent/paper writing on polymeric surfactants derived from soybean oil.


4a.What was the single most significant accomplishment this past year?
The collaborators (CRADA Partners) in Alcoa Technology were provided with 150 gallons of USDA's soy oil based base oil for metalworking fluid, which they used in their formulation and tried in one of their pilot plants at Reno, NV. The plant trial was a huge success and USDA's bio-based lubricant outperformed the equivalent control lubes. In quality of metal, USDA bio-based lube without scratch-brushes outperformed control with scratch-brush (use of scratch-brush improves rolled metal quality). In productivity, USDA's bio-based lube allowed increased reduction that was unattainable with existing dispersion lubes. As far as operator exposure are concerned, EHS conducted tests and found that USDA bio-based lube outperformed control lubes, i.e., exposure was minimum with bio-based lubes. They also did a price evaluation of the cost to make a hot rolling lubricant using USDA's base oil. They conclude that USDA's base oil makes this formulation very attractive even though its cost is much higher than mineral oil. The reason for this is that the cost of the overall package is actually slightly less than many of their commercial hot mill lubricants because boundary additives are not needed for USDA formulation. They will conduct a trial or two for their large rolling mills in coming months (one in Europe and one in USA).


4b.List other significant accomplishments, if any.
1. Invention report. Erhan, S. Z., Liu, Z. and McKeon, T. "Soybased Thermosensitive Hydrogels for Controlled Release Systems." 2. Invention Report. Erhan, S. Z., Sharma, B. K. and Adhvaryu, A. "Process Development of Bio-based Grease for Industrial Applications." 3. Patent Pending. Erhan, S. Z. Adhvaryu, A. and Sharma, B. K. "Poly(hydroxylthioether) Vegetable Oil Derivatives Useful as Lubricant Additives." 4. CRADA with Advanced Ceramics Research, Tucson, AZ, (soybased composition) continuing. 5. CRADA with Alcoa Technology, PA, (hot and cold rolling fluid for metal processes) continuing. 6. CRADA with Caterpillar Inc. (Under carriage lubricants) is in final stage of development. 7. CRADA with Caterpillar Inc., IL (Antisticking coating) is in final stage of development. 8. CRADA with Anderson Development Co., MI (Boron based lubricants) is in final stage of development 9. MTA with University of Toronto, CA; Sullair Corp, IN, Cephalon Inc., UT, The Valvoline Company, KY, is in place. 10. Confidentiality Agreement with Anesta Corp., UT.


4c.List any significant activities that support special target populations.
None


4d.Progress report.
We are developing the synthesis of carbonated methyl esters and carbonated soybean oil from their corresponding epoxides and supercritical carbon dioxide. These carbonates will be useful as starting materials for ester based surfactants and polymers. We have synthesized one previously unreported compound and our synthesis of carbonated soybean oil is ~3x faster than a reported literature synthesis.


5.Describe the major accomplishments over the life of the project, including their predicted or actual impact.
Accomplishments through September 2004 related to industrial uses of vegetable oils can be found in the last progress report of the terminated project 3620-41000-101-00D. The collaborators (CRADA Partners) in Alcoa Technology were provided with 150 gallons of USDA's soy oil based base oil for metalworking fluid, which they used in their formulation and tried in one of their pilot plants at Reno, NV. The plant trial was a huge success and USDA's bio-based lubricant outperformed the equivalent control lubes. In quality of metal, USDA bio-based lube without scratch-brushes outperformed control with scratch-brush (use of scratch-brush improves rolled metal quality). In productivity, USDA's bio-based lube allowed increased reduction that was unattainable with existing dispersion lubes. As far as operator exposure are concerned, EHS conducted tests and found that USDA bio-based lube outperformed control lubes, i.e., exposure was minimum with bio-based lubes. They also did a price evaluation of the cost to make a hot rolling lubricant using USDA's base oil. They conclude that USDA's base oil makes this formulation very attractive even though its cost is much higher than mineral oil. The reason for this is that the cost of the overall package is actually slightly less than many of their commercial hot mill lubricants because boundary additives are not needed for USDA formulation. They will conduct a trial or two for their large rolling mills in coming months (one in Europe and one in USA).


6.What science and/or technologies have been transferred and to whom? When is the science and/or technology likely to become available to the end-user (industry, farmer, other scientists)? What are the constraints, if known, to the adoption and durability of the technology products?
Ink and Hydraulic Elevator Fluid Technology licensing procedure is in final stage (Bunge/AgriLube Inc. is in process of licensing). One patent is pending and two patent applications are in process. In two to three years products through CRADA partners should be available to the public.


7.List your most important publications in the popular press and presentations to organizations and articles written about your work. (NOTE: List your peer reviewed publications below).
a. Statue of Liberty Goes Green with Soy-Based Elevator Fluid http://www.agclassroom.org/teen/ars_pdf/tech/2004/10soy.pdf Agricultural Research, October 2004, pg. 22.

b. ARS's Soy-Based Hydraulic Fluid Powers Lady Liberty's Elevator Federal Technology Transfer, 2005, pg. 12.

c. Statue of Liberty to use Biolubricants Lubricants World, September/October, 2004, pg. 10.


Review Publications
Xu, J., Liu, Z., Erhan, S.Z., Carriere, C.J. 2004. Cross-linkers control the viscoelastic properties of soybean oil based biomaterials. Journal of the American Oil Chemists' Society. 81(8):813-816.

Sharma, B.K., Adhvaryu, A., Erhan, S.Z. 2005. Vegetable oil-based lubricants: improvement in oxidation and low temperature stability. Annual Meeting and Expo of the American Oil Chemists' Society. p. 66.

Doll, K.M., Erhan, S.Z. 2005. The improved synthesis of carbonated soybean oil in supercritical carbon dioxide. American Chemical Society Abstracts. p.74.

Erhan, S.Z., Sharma, B.K., Adhvaryu, A. 2005. Biobased lubricants for industrial applications. World Oleochemical Conference. p. 89.

Adhvaryu, A., Erhan, S.Z. 2005. Fatty acids and antioxidant effects on grease microstructures. Industrial Crops and Products. 21:285-291.

Erhan, S.Z. 2005. Vegetable oils as lubricants, hydraulic fluids, and inks. In: Shahidi, F., editor. Bailey's Industrial Oil and Fat Products: Industrial and Nonedible Products from Oils and Fats. Chapter 7, 6th edition. Indianapolis, IN: John Wiley & Sons, Inc. p. 259-278.

Liu, Z., Erhan, S.Z., Calvert, P.D. 2004. Solid freeform fabrication of soybean oil based composites reinforced with clay and fibers. Journal of the American Oil Chemists' Society. 81(6):605-610.

Adhvaryu, A., Liu, Z., Erhan, S.Z. 2005. Synthesis of novel triacylglycerol molecule with improved high and low temperature behavior. Industrial Crops and Products. 21:113-119.

Panizzi, M., Kwanyuen, P., Erhan, S.Z. 2005. Environmental and genetic variation of beta-conglycinin and glycinin content in brazilian soybean cultivars. Annual Meeting and Expo of the American Oil Chemists' Society. p. 100.

Liu, Z., Erhan, S.Z., Akin, D.E., Barton Ii, F.E. 2005. Development of soybean oil/flax fiber based composites by compression molding method. Annual Meeting and Expo of the American Oil Chemists' Society. pg. 106

Doll, K.M., Erhan, S.Z. 2006. Synthesis of carbonated methyl oleate from methyl oleate epoxide (EMO) in supercritical carbon dioxide [abstract]. 97th American Oil Chemists' Society Annual Meeting and Expo. p. 89.

Erhan, S.Z., Sharma, B.K., Adhvaryu, A. 2005. Additive-additive interactions in vegetable oil: the search for synergistic antioxidant using pdsc. Society of Tribologists and Lubrication Engineers. p. 189.

Liu, Z., Erhan, S.Z. 2005. Preparation of epoxidized soybean oil/clay nanocomposites. World Oleochemical Conference. p. 145.

Doll, K.M., Erhan, S.Z. 2005. Improved synthesis of carbonated soybean oil in supercritical carbon dioxide. American Chemical Society National Meeting. p. 191.

Liu, Z., Akin, D.E., Barton Ii, F.E., Onwulata, C.I., Erhan, S.Z. 2004. Preparation of soy-based composites reinforced with protein coated flax fiber. UJNR Food & Agricultural Panel Proceedings. p. 134.

Erhan, S.Z., Sharma, B.K., Adhvaryu, A. 2005. Biobased lubricants: improvement in oxidation and low temperature stability. Association for the Advancement of Industrial Crops Conference. p. 204.

Erhan, S.Z. 2005. Printing inks. In: Erhan, S.Z., editor. Industrial Uses of Vegetable Oils. Champaign, IL: AOCS Press. Chapter 9. p. 163-169.

Liu, Z., Erhan, S.Z. 2005. Development of soy composites by direct deposition. In: Erhan, S.Z., editor. Industrial Uses of Vegetable Oils. Champaign, IL: AOCS Press. Chapter 7. p. 131-142.

Last Modified: 4/18/2014
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