New High-Value Biobased Materials with Applications Across Industry

Goals / Objectives
Objective 1: Resolving chemical processes advancing high-value polymers from agriculturally based oils and other feedstocks. Objective 2: Enabling commercially relevant biobased materials and fuels. Sub-objective 2.A. Transforming cellulose into porous composites used for controlled release or capture of analytes. Sub-objective 2.B. Use of catalytic technology to synthesize biobased fuels with higher value.

Project Methods
Alternatives to petroleum-derived products from biobased products has been a research goal of private, university, and government researchers for many years. Although progress toward the goal of a major biobased economy is evident in several commercialized areas, such as biobased fuels, high profile business failures are unfortunately still commonplace in the private sector. The basis for biobased marketplace failures may be due to multiple factors, but enabling more high-value, cutting-edge products that expand the biobased market place is seen as a likely successful solution. This plan utilizes a balanced approach that combines mature technologies, with readily available markets, with newer and less developed areas of research. Existing markets, such as soybean oil-based structural resins and biobased aviation fuels, are targeted for improvements that will increase the biobased content of products that are already available in the marketplace. Entirely new products, such as biobased 3-dimensionally printed films and supercritical solvent-expanded ion absorbing resins, are proposed in this plan. Such an approach reaches across several industries while looking into the future at emerging technologies with market opportunities. More specifically, the first objective is the synthesis of high-value polymers. New reaction technologies and the application of polyfunctional co-reactants will lead to structures that have previously not been possible when starting from vegetable oils. The second objective will develop new materials from cellulosic feedstocks by transforming them into higher surface area polymers that can then be activated with further facile chemical modification. Additionally, newly developed decarboxylation technology will be leveraged to convert fatty acids into a high-value renewable hydrocarbon aviation fuel that mimics the composition of the corresponding petroleum-derived fuel.

Progress 10/01/23 to 09/30/24

Outputs
PROGRESS REPORT Objectives (from AD-416): Objective 1: Resolving chemical processes advancing high-value polymers from agriculturally based oils and other feedstocks. Objective 2: Enabling commercially relevant biobased materials and fuels. Sub-objective 2.A. Transforming cellulose into porous composites used for controlled release or capture of analytes. Sub-objective 2.B. Use of catalytic technology to synthesize biobased fuels with higher value. Approach (from AD-416): Alternatives to petroleum-derived products from biobased products has been a research goal of private, university, and government researchers for many years. Although progress toward the goal of a major biobased economy is evident in several commercialized areas, such as biobased fuels, high profile business failures are unfortunately still commonplace in the private sector. The basis for biobased marketplace failures may be due to multiple factors, but enabling more high-value, cutting-edge products that expand the biobased market place is seen as a likely successful solution. This plan utilizes a balanced approach that combines mature technologies, with readily available markets, with newer and less developed areas of research. Existing markets, such as soybean oil-based structural resins and biobased aviation fuels, are targeted for improvements that will increase the biobased content of products that are already available in the marketplace. Entirely new products, such as biobased 3-dimensionally printed films and supercritical solvent-expanded ion absorbing resins, are proposed in this plan. Such an approach reaches across several industries while looking into the future at emerging technologies with market opportunities. More specifically, the first objective is the synthesis of high-value polymers. New reaction technologies and the application of polyfunctional co-reactants will lead to structures that have previously not been possible when starting from vegetable oils. The second objective will develop new materials from cellulosic feedstocks by transforming them into higher surface area polymers that can then be activated with further facile chemical modification. Additionally, newly developed decarboxylation technology will be leveraged to convert fatty acids into a high-value renewable hydrocarbon aviation fuel that mimics the composition of the corresponding petroleum-derived fuel. Objective 1: Biobased epoxy resins from vegetable oils were developed. Commercial epoxy resins are widely utilized as coatings and adhesives, among other important applications. These materials are made from toxic and nonrenewable chemicals obtained from petroleum and do not biodegrade once they have reached the end of their operational lifespans. Because of this, the materials accumulate and persist in the environment as soil and water pollutants, which may cause negative human and wildlife health effects. Thus, ARS researchers in Peoria, Illinois, continued to develop renewable and biodegradable replacements based on vegetable oils and other agricultural chemicals. These biobased polymers are produced using a simple process that avoids the use of toxic materials. Characterization of the properties of the newly developed biopolymers revealed that they are potentially useful in adhesives applications. Future research will further improve properties through feedstock and structural modifications and expand industrial uses into surface coatings applications. Objective 1: Biobased chewing gum elastomers from vegetable oils were developed. Over 1.7 trillion sticks of chewing gum are produced annually, which equates to a market size of approximately $25 billion. Chewing gum base materials primarily consist of petrochemically-based elastomers. These elastomers proliferate as unsightly waste in public areas due to their nonbiodegradable nature. Therefore, biobased and biodegradable chewing gum base materials were developed by ARS researchers in Peoria, Illinois. Citric acid is commonly found in citrus fruits and is generally regarded as safe for human consumption. Characterization of the properties of the newly developed renewable materials indicated that they are soft and rubbery (as opposed to hard and/or glassy) at room temperature and at body temperature, which is essential for chewing gum. Objective 2.A: New renewable porous materials were developed. Porous materials have many advantages over nonporous polymers, such as low density, excellent heat and sound insulation, and high strength, which enables their use in structural and construction applications. However, most porous materials are nonrenewable and nonbiodegradable. For example, foam insulation is based on petrochemically-derived polyurethane, which is typically synthesized using a toxic blowing agent such as a chlorofluorocarbon. Therefore, ARS researchers in Peoria, Illinois, developed biobased replacement materials utilizing environmentally friendly materials and methods. The behavior of the reaction was studied to better understand the process and structure of the newly formed biobased materials. Objective 2.A: A new technology was developed for modification of renewable materials into more useful products. Isomerization is a desirable chemical reaction that leads to products with different properties. A novel process was developed by ARS researchers in Peoria, Illinois. This process uses a common catalyst and an environmentally friendly reaction medium. The usefulness of the new method was demonstrated by converting jojoba oil (a natural material) into a new material. Natural jojoba oil is a liquid at room temperature. Isomerized jojoba oil is a solid with a melting point around the normal human body temperature. Thus, isomerization of jojoba oil and other materials using the newly developed technology offers the following advantages: 1) the ability to transform a liquid into a solid material that may have applications in the cosmetic and food areas due to its higher melting point and 2) the possibility for further modification into other materials. Objective 2.B: Biodiesel fuels from vegetable oils were studied. The properties of biodiesel made from high oleic soybean oil, jojoba oil, and palm fatty acid distillate were investigated by ARS researchers in Peoria, Illinois. Cold flow properties, oxidative stability, kinematic viscosity (thickness), and lubricity (anti-wear) characteristics were measured. Comparisons were made to important biodiesel fuel standards and the results revealed satisfactory performance in most cases. Biodiesel resulting from palm fatty acid distillate froze at higher temperatures due to its different composition. In addition, a new and reusable catalyst was developed from waste palm leaf biomass. This new catalyst can efficiently convert low-quality, low-cost feedstocks directly into biodiesel. Normally, such feedstocks require an inefficient two-step process that utilizes nonreusable catalysts due to the presence of contaminants that deactivate conventional catalysts. Overall, this work showed that high oleic soybean oil, jojoba oil, and palm fatty acid distillate are suitable for utilization as feedstocks for production of biodiesel and that the new catalyst allows for facile conversion of low- quality feedstocks into biodiesel. ACCOMPLISHMENTS 01 New renewable porous materials were developed that will benefit both the environment and agricultural producers. Porous materials are important polymers that contain many small pores. Porous materials have several advantages over nonporous polymers, such as low density, excellent heat and sound insulation, and high strength, which enables their use in structural and construction applications. However, most porous materials are nonrenewable and nonbiodegradable and are synthesized using toxic substances. Therefore, ARS researchers in Peoria, Illinois, developed biobased porous materials from epoxidized vegetable oils using environmentally friendly methods and materials. The behavior of the reaction was studied to better understand both the process and the structure of the newly formed biobased porous materials. This result is beneficial to the agricultural and polymer industries, as well as the environment, because it represents a new source of porous materials produced from agricultural feedstocks that can replace existing materials derived from petroleum, thereby aiding American farmers by providing additional high-value outlets for soybean oil and other agricultural materials. 02 Biodiesel made from jojoba oil will benefit the environment. Biodiesel is normally produced from commodity crops that have competing food related applications. In addition, the cost of commodity oils can account for up to 80% of the cost to produce biodiesel. Therefore, non- food, low-cost feedstocks are needed to augment the supply of alternative fuels, avoid competing food applications, and lower the cost of biodiesel to levels more economically competitive with conventional diesel fuel. Thus, ARS researchers in Peoria, Illinois, investigated inedible jojoba oil as a feedstock for production of biodiesel. Jojoba oil is obtained from the seeds of the jojoba plant, which is native to parts of the United States and elsewhere. Fuel properties of the resulting jojoba oil-based biodiesel were investigated and compared to important fuel standards. The results indicated excellent low temperature performance, which is advantageous in winter months and/or in cold climates. These findings highlight the enormous potential of jojoba oil as an alternative inedible feedstock for biodiesel production, offering favorable fuel properties that can contribute to sustainable and environmentally friendly energy solutions. These results will be beneficial to the renewable fuels industry, jojoba farmers, and the public, as augmentation of alternative fuels facilitates the societal transition away from petroleum and its consequent environmental and climatic impacts.

Impacts
(N/A)

Publications

Doll, K.M., Moser, B.R. 2023. Industrial chemicals via decarboxylation of natural carboxylic acids. In: Liu, Z., Kraus, G., editors. Green Chemistry and Green Materials from Plant Oils and Natural Acids. Vol. 83. Cambridge, UK:Royal Society of Chemistry Publishing. p. 144-158. https://doi.org/10. 1039/9781837671595.
Liu, Z., Kraus, G. 2023. Green chemistry and green materials from plant oils and natural acids. Cambridge, UK: Royal Society of Chemistry Publishing. Volume 83, 280 p. https://doi.org/10.1039/9781837671595.
Shah, S.N., Liu, Z. 2023. Natural epoxy oil (Euphorbia oil) polymerization in liquid carbon dioxide-green solvents.In: Liu, Z, Kraus, G., editors. Green Chemistry and Green Materials from Plant Oils and Natural Acids. Volume 83. Cambridge, UK: Royal Society of Chemistry Publishing. p. 23-41. https://doi.org/10.1039/9781837671595.
Liu, Z., Shah, S.N., Vermillion, K., Cheng, H.N., Biswas, A. 2023. Lewis acid catalyzed cis (liquid) to trans (solid) isomerization of Jojoba oil in supercritical CO2. Biocatalysis and Agricultural Biotechnology. 54. Article 102902. https://doi.org/10.1016/j.bcab.2023.102902.
Moser, B.R., Cermak, S.C., Evangelista, R.L. 2023. Fully biobased epoxy resins from ring opening polymerization of epoxidized pennycress (Thlaspi arvense L.) oil with itaconic and citric acids. Industrial Crops and Products. 208. Article 117914. https://doi.org/10.1016/j.indcrop.2023. 117914.
Cheng, H.N., Biswas, A., Kuzniar, G., Kim, S., Liu, Z., He, Z. 2024. Blends of carboxymethyl cellulose and cottonseed protein as biodegradable films. Polymers. 16(11). Article 1554. https://doi.org/10.3390/ polym16111554.
Aliyu, M., Moser, B.R., Alharthi, F.A., Rashid, U. 2024. Efficient production of biodiesel from palm fatty acid distillate using a novel hydrochar-based solid acid catalyst derived from palm leaf waste. Process Safety and Environmental Protection. 187:1126-1139. https://doi.org/10. 1016/j.psep.2024.05.040.

Progress 10/01/22 to 09/30/23

Outputs
PROGRESS REPORT Objectives (from AD-416): Objective 1: Resolving chemical processes advancing high-value polymers from agriculturally based oils and other feedstocks. Objective 2: Enabling commercially relevant biobased materials and fuels. Sub-objective 2.A. Transforming cellulose into porous composites used for controlled release or capture of analytes. Sub-objective 2.B. Use of catalytic technology to synthesize biobased fuels with higher value. Approach (from AD-416): Alternatives to petroleum-derived products from biobased products has been a research goal of private, university, and government researchers for many years. Although progress toward the goal of a major biobased economy is evident in several commercialized areas, such as biobased fuels, high profile business failures are unfortunately still commonplace in the private sector. The basis for biobased marketplace failures may be due to multiple factors, but enabling more high-value, cutting-edge products that expand the biobased market place is seen as a likely successful solution. This plan utilizes a balanced approach that combines mature technologies, with readily available markets, with newer and less developed areas of research. Existing markets, such as soybean oil-based structural resins and biobased aviation fuels, are targeted for improvements that will increase the biobased content of products that are already available in the marketplace. Entirely new products, such as biobased 3-dimensionally printed films and supercritical solvent-expanded ion absorbing resins, are proposed in this plan. Such an approach reaches across several industries while looking into the future at emerging technologies with market opportunities. More specifically, the first objective is the synthesis of high-value polymers. New reaction technologies and the application of polyfunctional co-reactants will lead to structures that have previously not been possible when starting from vegetable oils. The second objective will develop new materials from cellulosic feedstocks by transforming them into higher surface area polymers that can then be activated with further facile chemical modification. Additionally, newly developed decarboxylation technology will be leveraged to convert fatty acids into a high-value renewable hydrocarbon aviation fuel that mimics the composition of the corresponding petroleum-derived fuel. Objective 1: Biopolymers from vegetable oils were synthesized using economical catalytic processes. New methods are required to convert vegetable oils into high-performance materials, such as paints, coatings, elastomers, and adhesives. Using fatty acids derived from vegetable oils as chemical building blocks, ARS researchers in Peoria, Illinois, advanced the knowledge and technology required to produce valuable industrial products from vegetable oils. Different chemical processes were employed to transform fatty acid derivatives into polymeric biomaterials. These processes utilized commercially available catalysts to produce renewable and biodegradable polymers with excellent thermal and chemical stability as well as solubility and melting properties needed for target applications. These polymers represent biobased alternatives to existing nonrenewable and nonbiodegradable petrochemically derived materials, which often cause water and soil pollution as well as negative human and wildlife health effects. Thus, this research fulfilled the 36-month milestone for Objective 1 by reporting polymer properties of commercial significance, such as thermal and oxidative behavior. Objective 2.A: An ion-exchange method for the recovery of lithium from used batteries was developed. To combat global climate change, numerous governments and other entities have pledged to achieve carbon neutrality in the middle to long-term future. A critical step toward reaching that goal is electrified transportation, especially electric vehicles using lithium-ion batteries. However, economical recycling of used batteries remains elusive primarily due to the low value of recovered lithium. Thus, ARS researchers in Peoria, Illinois, in collaboration with university partners, developed a simple, economical, and practical method based on commercially mature ion-exchange technology to recover lithium from spent lithium iron phosphate cathodes. The process produces a potential high- value single or multi-element fertilizer containing potassium and phosphorous in a simple and low-cost way. This research therefore fulfilled the 36-month milestone for Objective 2.A by developing a new resin-based recycling technology for binding lithium from spent battery cathodes. Objective 2.B: Biodiesel from citrus seed oil was studied. Citrus seed oil, an unutilized waste product of commercial orange juice production, was investigated as a low-cost feedstock for production of biodiesel. The oil, provided by ARS researchers in Fort Pierce, Florida, was converted to biodiesel by ARS researchers in Peoria, Illinois. The fuel properties of the resulting citrus seed oil methyl esters were measured and compared against the same data for biodiesel prepared from other plant seed oil feedstocks as well as against the American biodiesel standard. Findings indicated that the oxidative stability was below the minimum limit in the biodiesel standard, but this could be corrected with antioxidants. However, other important fuel properties were within the limits prescribed in the standard and similar to the properties of soybean oil- based biodiesel. Therefore, this research fulfilled the 36-month milestone for Objective 2.B by reporting the fuel properties of biodiesel prepared from citrus seed oil arising as waste from orange juice production. Objective 2.B: A biobased anti-mosquito compound was developed. Mosquito- borne diseases continue to pose problems throughout the world, and without effective vaccines for specific diseases, vector control is one of the only practical solutions. Current methods for mosquito control include atmospheric and chemical insecticides, but these pose problems relating to environmental safety and onset of insecticide resistance. Thus, ARS researchers in Peoria, Illinois, developed a vegetable oil- based compound that showed larvicidal activity against Aedes aegypti, a common mosquito that spreads dengue fever, chikungunya, Zika fever, yellow fever, and other diseases. The key synthetic step produced a spin- labelled derivative that allowed for the study of mechanisms of larvicidal effectiveness. Findings indicated that the median lethal concentration (LC50) values for the new compound and a reference comparison were 48 and 55 ppm, respectively, indicating that spin labelling did not negatively affect larvicidal activity. ACCOMPLISHMENTS 01 Composite polymers with enhanced mechanical strength made from renewable agricultural precursors. Because conventional polymers have excellent durability and mechanical strength for high-performance applications, they have become ubiquitous in modern society. However, these materials are nonrenewable, not biodegradable, and in some cases toxic. Sustainable and biodegradable polymers prepared from renewable resources are attractive alternatives, but often suffer from performance deficiencies relative to conventional polymers. ARS researchers in Peoria, Illinois, developed a biobased composite polymer made from a mixture of cellulose nanofibers and polymerized soybean oil to overcome these deficiencies. Composites are advantageous because they are stronger and more functional than the individual components. The new composites are suitable for packaging, textile, fiber, and rigid plastic applications that non-composites are often unsuitable for. The resulting renewable composites had mechanical strengths that were comparable to nonrenewable conventional plastics like polypropylene. This result is beneficial to the agricultural and polymer industries because it represents a new source of polymer produced from agricultural materials that can potentially replace existing materials derived from petroleum, thereby aiding American farmers by providing additional high-value outlets for soybean oil and residual crop waste (cellulose). 02 Biodiesel made from waste citrus seeds. Worldwide, the citrus industry generates around 50-60 million tons of excess biomass when producing juices, such as orange juice, for human consumption. This underutilized biomass causes environmental issues when discarded, so finding uses for this material reduces food industry waste while potentially generating new revenue streams. ARS researchers in Peoria, Illinois, converted vegetable oil from waste citrus seeds into biodiesel using a well-known process referred to as transesterification. The fuel properties of the biodiesel produced from waste citrus seed oil were within the specifications of the American biodiesel standard. Using a waste oil as a feedstock for production of biodiesel is economically advantageous because feedstock acquisition can approach 80% of the cost to produce biodiesel when refined commodity lipids are utilized as feedstocks. These results are beneficial to the citrus and renewable fuels industries as well as to the public, as an agricultural waste material was utilized to produce an alternative fuel that facilitates the societal transition away from petroleum and its consequent environmental and climatic effects.

Impacts
(N/A)

Publications

Zhang, X., Liu, Z., Qu, D. 2022. Proof-of-Concept study of ion-exchange method for the recycling of LiFePO4 cathode. Waste Management. 157:1-7. https://doi.org/10.1016/j.wasman.2022.12.003.
Doll, K.M., Muturi, E.J., Flor-Weiler, L.B. 2022. Combining TEMPO and methyl undecenoate to produce an effective anti-mosquito compound with convenient spin-labeling. Experimental Parasitology. 244. Article 108440. https://doi.org/10.1016/j.exppara.2022.108440.
Moser, B.R., Doll, K.M., Price, N.P. 2022. Comparison of aliphatic polyesters prepared by acyclic diene metathesis and thiol-ene polymerization of alpha,omega-polyenes arising from oleic acid-based 9- decen-1-ol. Journal of the American Oil Chemists' Society. 100:149-162. https://doi.org/10.1002/aocs.12668
Moser, B.R., Dorado, C., Bantchev, G.B., Winkler-Moser, J.K., Doll, K.M. 2023. Production and evaluation of biodiesel from sweet orange (Citrus sinensis) lipids extracted from waste seeds from the commercial orange juicing process. Fuel. 342. Article 127727. https://doi.org/10.1016/j.fuel. 2023.127727.
Moser, B.R., Cermak, S.C., Doll, K.M., Kenar, J.A., Sharma, B.K. 2022. A review of fatty epoxide ring opening reactions: Chemistry, recent advances, and applications. Journal of the American Oil Chemists' Society. 99(10) :801-842. https://doi.org/10.1002/aocs.12623.
Kohli, K., Chandrasekaran, S.R., Prajapati, R., Kunwar, B., Al-Salem, S., Moser, B.R., Sharma, B.K. 2022. Pyrolytic depolymerization mechanisms for post-consumer plastic wastes. Energies. 15(23). Article 8821. https://doi. org/10.3390/en15238821.
Winfield, D.D., Moser, B.R. 2023. Selective hydroxyalkoxylation of epoxidized methyl oleate by an amphiphilic ionic liquid catalyst. Journal of the American Oil Chemists' Society. 100(3):237-243. https://doi.org/10. 1002/aocs.12672.
Hanif, M., Bhatti, I., Hanif, M., Rashid, U., Moser, B.R., Hanif, A., Alharthi, F. 2023. Nano-magnetic CaO/Fe2O3/Feldspar catalysts for the production of biodiesel from waste oils. Catalysts. 13(6). Article 998. https://doi.org/10.3390/catal13060998.
Shah, S.N., Liu, Z., Sharma, B.K. 2023. Glycerol Monooleate (GMO): a valuable biobased lubricity and pour point enhancer blend component for the ULSD fuel. ACS Omega. 8(22):19503-19508. https://doi.org/10.1021/ acsomega.3c00889.

Progress 10/01/21 to 09/30/22

Outputs
PROGRESS REPORT Objectives (from AD-416): Objective 1: Resolving chemical processes advancing high-value polymers from agriculturally based oils and other feedstocks. Objective 2: Enabling commercially relevant biobased materials and fuels. Sub-objective 2.A. Transforming cellulose into porous composites used for controlled release or capture of analytes. Sub-objective 2.B. Use of catalytic technology to synthesize biobased fuels with higher value. Approach (from AD-416): Alternatives to petroleum-derived products from biobased products has been a research goal of private, university, and government researchers for many years. Although progress toward the goal of a major biobased economy is evident in several commercialized areas, such as biobased fuels, high profile business failures are unfortunately still commonplace in the private sector. The basis for biobased marketplace failures may be due to multiple factors, but enabling more high-value, cutting-edge products that expand the biobased market place is seen as a likely successful solution. This plan utilizes a balanced approach that combines mature technologies, with readily available markets, with newer and less developed areas of research. Existing markets, such as soybean oil-based structural resins and biobased aviation fuels, are targeted for improvements that will increase the biobased content of products that are already available in the marketplace. Entirely new products, such as biobased 3-dimensionally printed films and supercritical solvent-expanded ion absorbing resins, are proposed in this plan. Such an approach reaches across several industries while looking into the future at emerging technologies with market opportunities. More specifically, the first objective is the synthesis of high-value polymers. New reaction technologies and the application of polyfunctional co-reactants will lead to structures that have previously not been possible when starting from vegetable oils. The second objective will develop new materials from cellulosic feedstocks by transforming them into higher surface area polymers that can then be activated with further facile chemical modification. Additionally, newly developed decarboxylation technology will be leveraged to convert fatty acids into a high-value renewable hydrocarbon aviation fuel that mimics the composition of the corresponding petroleum-derived fuel. Under Objective 1, polymers were prepared from biobased products using economical catalytic conversions. New routes are needed to transform natural oils into high-performance materials such as paints, coatings, and adhesives. Using chemical building blocks made from fatty acids, ARS researchers in Peoria, Illinois, are making progress toward those routes. A chemical process called acyclic diene metathesis (ADMET) polymerization was employed to achieve the transformation. The system uses commercially available catalysts and can make products with a wide range of molecular weights needed for advanced materials such as biodegradable medical devices, composite fibers, and adhesives. The products from this work showed good solubility, chemical stability, and melting temperatures. Additionally, the process is such that all atoms from the starting material end up in the products, as it does not produce any unwanted side products, making it highly efficient. These renewable polymers represent biobased alternatives to existing petrochemically-based materials, which often cause water and soil pollution in addition to negative health effects. Under Objective 2, Sub-objective 2.A, a renewable polymer coating system was formulated. Durable coatings are required for many of the items that people use every day. Many of these high-performance coatings, while effective, contain volatile organic chemicals. Conventional coatings that use natural oils are currently not strong enough for applications that require high abrasion resistance such as stair railings, desktops, and other furniture. However, ARS researchers in Peoria, Illinois, are testing a new approach to make a biobased coating that is highly durable. By mixing a natural oil with a biobased additive that is found in apple juice, a new coating material was produced. The product was applied to a surface and then cured by a simple process using ultraviolet light to form a coating with excellent properties. A formulation that is up to 58% biobased was developed. This work will benefit those looking to use safe commodity oils in applications that need new versatile coatings. Additionally, a 3-dimensional print method was also improved, where cellulose was coated with a soybean oil polymer. Under Objective 2, Sub-objective 2.B, a partially biobased electrochemically active material was developed. Materials with electrochemical properties are needed for the next generation of batteries, fuel cells, and active catalysts of the future. Inclusion of biobased materials into these components is not a current practice as conventional petroleum-derived polymers are still the material of choice for these manufacturers. However, ARS researchers in Peoria, Illinois, are investigating a way to incorporate natural materials into these advanced products. Starting from a medium chain length fatty acid, a new electrochemical catalyst in which overall material is approximately 50% comprised of the plant-based fatty acid was produced. This new product was tested in an electrochemical reaction and gave conversion rates similar to the conventional material. ACCOMPLISHMENTS 01 Developed new 3-dimensional printing technology for composite materials. The synthesis of materials that are made from natural products, yet are as useful as conventional materials, is an elusive goal. The starting point toward this goal requires finding natural materials that have characteristics that allow them to be converted into durable goods. A promising candidate for this is vegetable oil. Another candidate is cellulose, the structural part of the cell walls of green plants. Considerable work has been done using each of these, but the results often fall short of the strength and other properties needed. In this research, the two commodities were combined into something that is a stronger and more functional polymer than could be made from either commodity alone. In order to get the reinforcing material where it needs to be, ARS researchers in Peoria, Illinois, developed a new 3- dimensional printing technology. The cellulose component is the core of the new product, which is then coated with a modified vegetable oil, layer by layer. The new composite is then cured with ultraviolet light to form the versatile material. The product, cellulose reinforced- soybean oil polymer, has stronger mechanical properties and performs better in thermal tests, compared to samples made from either material alone. For example, a strength test showed that the material was 37% stronger when a small amount of cellulose filler was added, and it can be twice as strong if even more filler is used. This is approaching the strength of common plastics, such as polypropylene, and with this improved strength, these polymers could be used to build household goods such as furniture. These materials are of great environmental interest not only because they consist of high amounts of agricultural resources, but also because they are mechanically strong. 02 New biodiesel catalysts and feedstocks were investigated. Biodiesel, a renewable, environmentally friendly alternative to conventional petroleum diesel fuel, is produced from vegetable oils and animal fats by a process called transesterification. However, conventional transesterification requires high quality oils to be successful. In addition, the most common catalysts are not recyclable and generate large quantities of wastewater during their removal from the biodiesel product. Thus, ARS researchers in Peoria, Illinois, in collaboration with external partners, converted lower-quality feedstocks, such as tallow, Jatropha oil, and others, to biodiesel using new catalyst technologies. The recoverable and recyclable catalysts included one made from calcium and iron oxides, and another that was from a common bacteria found in soil. In addition, their use also reduced the amount of wastewater generated during the process compared to older methods. With this new technology, a variety of low-quality oils were processed, and the fuel property results compared favorably to the fuels from more expensive sources, such as a green algal oil. The improved economic competitiveness of biodiesel with petroleum diesel may result in new possibilities for fuel from agricultural resources. These benefits, such as enhancing vegetable oil supply, reducing wastewater generation, and lowering catalyst costs, will help facilitate the societal transition away from petroleum to mitigate the impact of climate change.

Impacts
(N/A)

Publications

Ibrahim, N.A., Rashid, U., Hazmi, B., Moser, B.R., Alharthi, F.A., Lalthazuala Rokhum, S., Ngamcharussrivichai, C. 2022. Biodiesel production from waste cooking oil using magnetic bifunctional calcium and iron oxide nanocatalysts derived from empty fruit bunch. Fuel. 317. Article 123525. https://doi.org/10.1016/j.fuel.2022.123525.
Fadzilah Abdullah, R., Rashid, U., Lokman Ibrahim, M., NolHakim, M.A.H.L., Moser, B.R., Alharthi, F.A. 2021. Bifunctional biomass-based catalyst for biodiesel production via hydrothermal carbonization (HTC) pretreatment ⿿ Synthesis, characterization, and optimization. Process Safety and Environmental Protection. 156:219-230. https://doi.org/10.1016/j.psep.2021. 10.007.
Mushtaq, A., Asif Hanif, M., Zahid, M., Rashid, U., Mushtaq, Z., Zubair, M. , Moser, B.R., Alharthi, F.A. 2021. Production and evaluation of fractionated Tamarind seed oil methyl esters as a new source of biodiesel. Energies. 14(21). Article 7148. https://doi.org/10.3390/en14217148.
Saeed, A., Asif Hanif, M., Hanif, A., Rashid, U., Iqbal, J., Irfan Majeed, M., Moser, B.R., Alsalme, A. 2021. Production of biodiesel from Spirogyra elongata, a common freshwater green algae with high oil content. Sustainability. 13(22). Article 12737. https://doi.org/10.3390/su132212737.
Hanif, M., Bhatti, H.N., Asif Hanif, M., Rashid, U., Hanif, A., Moser, B.R. , Alsalme, A. 2021. A novel heterogeneous superoxide support-coated catalyst for production of biodiesel from roasted and unroasted Sinapis arvensis seed oil. Catalysts. 11(12). Article 1421. https://doi.org/10. 3390/catal11121421.
Khan, K., Ul-Haq, N., Ur Rahman, W., Ali, M., Rashid, U., Ul-Haq, A., Jamil, F., Ahmed, A., Ahmed, F., Moser, B.R., Alsalme, A. 2021. Comprehensive comparison of hetero-homogeneous catalysts for fatty acid methyl ester production from non-edible Jatropha curcas oil. Catalysts. 11(12). Article 1420. https://doi.org/10.3390/catal11121420.
Shabbir, A., Mukhtar, H., Waseem Mumtaz, M., Rashid, U., Abbas, G., Moser, B.R., Alsalme, A., Touqeer, T., Ngamcharussrivichai, C. 2022. Lewatit- immobilized lipase from Bacillus pumilus as a new catalyst for biodiesel production from tallow: Response surface optimization, fuel properties and exhaust emissions. Process Safety and Environmental Protection. 160:286- 296. https://doi.org/10.1016/j.psep.2022.02.032.
Doll, K.M., Moser, B.R., Knothe, G. 2021. Decarboxylation of oleic acid using iridium catalysis to form products of increased aromatic content compared to ruthenium systems. International Journal of Sustainable Engineering. 14(6):2018-2024. https://doi.org/10.1080/19397038.2021. 1978589.
Liu, Z., Knetzer, D.A., Wang, J., Chu, F., Lu, C., Calvert, P.D. 2021. 3D printing acrylated epoxidized soybean oil reinforced with functionalized cellulose by UV curing. Journal of Applied Polymer Science. 139(4):e51561. https://doi.org/10.1002/app.51561.
Liu, Z., Vermillion, K., Jin, C., Wang, X., Zhao, W. 2021. NMR study on the oxidation of vegetable oils for assessing the antioxidant function of trehalose. Biocatalysis and Agricultural Biotechnology. 36. Article 102134. https://doi.org/10.1016/j.bcab.2021.102134.
Perveen, S., Hanif, M.A., Nadeem, R., Rashid, U., Azeem, M.W., Zubair, M., Nisar, N., Alharthi, F.A., Moser, B.R. 2021. A novel route of mixed catalysis for production of fatty acid methyl esters from potential seed oil sources. Catalysts. 11(7). Article 811. https://doi.org/10.3390/ catal11070811.
Liu, Y., Zhou, X., Jin, C., Liu, G., Liu, Z., Kong, Z. 2022. Efficient and rapid removal of typical phenolic compounds from water with biobased porous organic polymers. Industrial Crops and Products. 184. Article 114971. https://doi.org/10.1016/j.indcrop.2022.114971.
Li, Q., Zhang, Y., Liu, Z., Liu, S., Huang, F., Zheng, M. 2022. Novel bacterial cellulose-TiO2 stabilized pickering emulsion for photocatalytic degradation. Cellulose. 29:5223-5234. https://doi.org/10.1007/s10570-022- 04604-8.
Zhang, J., Huang, J., Zhu, G., Yu, X., Cheng, J., Liu, Z., Hu, Y., Shang, Q., Liu, C., Hu, L., Zhou, Y. 2021. Self-healing, recyclable, and removable UV-curable coatings derived from tung oil and malic acid. Green Chemistry. 23(16):5875-5886. https://doi.org/10.1039/d1gc01726h.
Doll, K.M., Cermak, S.C. 2022. Selective electrochemical oxidation of alcohols catalyzed by partially biobased TEMPO analogs. ChemistrySelect. 7(29). Article e202201736. https://doi.org/10.1002/slct.202201736.
Li, W., Xiao, L., Wang, Y., Huang, J., Liu, Z., Chen, J., Nie, X. 2022. Thermal-induced self-healing bio-based vitrimers: Shape memory, recyclability, degradation, and intrinsic flame retardancy. Polymer Degradation and Stability. 202. Article 110039. https://doi.org/10.1016/j. polymdegradstab.2022.110039.
Hazmi, B., Rashid, U., Kawi, S., Mokhtar, W.N.A.W., Yaw, T.C.S., Moser, B. R., Alsalme, A. 2022. Palm fatty acid distillate esterification using synthesized heterogeneous sulfonated carbon catalyst from plastic waste: Characterization, catalytic efficacy and stability, and fuel properties. Process Safety and Environmental Protection. 162:1139-1151. https://doi. org/10.1016/j.psep.2022.05.001.
Xiao, L., Li, W., Liu, Z., Zhang, K., Li, S., Wang, Y., Chen, J., Huang, J. , Nie, X. 2022. Tung oil-derived epoxy vitrimers with high mechanical strength, toughness, and excellent recyclability. ACS Sustainable Chemistry & Engineering. 10(30):9829-9840.
Ro, K.S., Jackson, M.A., Szogi, A.A., Compton, D.L., Moser, B.R., Berge, N. D. 2022. Sub- and near-critical hydrothermal carbonization of animal manures. Sustainability. 14(9). Article 5052. https://doi.org/10.3390/ su14095052.

Progress 10/01/20 to 09/30/21

Outputs
PROGRESS REPORT Objectives (from AD-416): Objective 1: Resolving chemical processes advancing high-value polymers from agriculturally based oils and other feedstocks. Objective 2: Enabling commercially relevant biobased materials and fuels. Sub-objective 2.A. Transforming cellulose into porous composites used for controlled release or capture of analytes. Sub-objective 2.B. Use of catalytic technology to synthesize biobased fuels with higher value. Approach (from AD-416): Alternatives to petroleum-derived products from biobased products has been a research goal of private, university, and government researchers for many years. Although progress toward the goal of a major biobased economy is evident in several commercialized areas, such as biobased fuels, high profile business failures are unfortunately still commonplace in the private sector. The basis for biobased marketplace failures may be due to multiple factors, but enabling more high-value, cutting-edge products that expand the biobased market place is seen as a likely successful solution. This plan utilizes a balanced approach that combines mature technologies, with readily available markets, with newer and less developed areas of research. Existing markets, such as soybean oil-based structural resins and biobased aviation fuels, are targeted for improvements that will increase the biobased content of products that are already available in the marketplace. Entirely new products, such as biobased 3-dimensionally printed films and supercritical solvent-expanded ion absorbing resins, are proposed in this plan. Such an approach reaches across several industries while looking into the future at emerging technologies with market opportunities. More specifically, the first objective is the synthesis of high-value polymers. New reaction technologies and the application of polyfunctional co-reactants will lead to structures that have previously not been possible when starting from vegetable oils. The second objective will develop new materials from cellulosic feedstocks by transforming them into higher surface area polymers that can then be activated with further facile chemical modification. Additionally, newly developed decarboxylation technology will be leveraged to convert fatty acids into a high-value renewable hydrocarbon aviation fuel that mimics the composition of the corresponding petroleum-derived fuel. Under Objective 1, an industrially useful route to a renewable version of p-Cymene, an important industrial chemical currently derived from petroleum, was developed. p-Cymene is usually made from toluene or benzene and is used as a precursor for specialty chemicals like pharmaceuticals and pesticides. It can also be directly used as a solvent or as a component in perfumes. Our method involved catalytic dehydration and isomerization of a natural material, and the proposed mechanism of the transformation was uncovered. This transformation will be useful as a guide to the modification of many similar agricultural materials in support of the industrial utilization of agriculture. Under Objective 2, Sub-objective 2.A, new synthetic porous materials were made from biobased resources. They were characterized via the Brunauer-Emmett-Teller method and results show that they have a large surface area and excellent adsorption properties. Initial studies on absorption of lead using the new materials were done, with further investigations now underway. Because these materials involve the use of chemical catalysis to turn liquid oils into solid polymer resins, these materials are a potential industrial outlet for those agricultural oils. Under Objective 2, Sub-objective 2.B., significant improvements were made in the synthesis of fuels from biological sources. A new catalyst was uncovered that improves the product of the process, allowing a wider range of blending possibilities. This will be a key development in the replacement of petrochemically-based fuels. Record of Any Impact of Maximized Teleworking Requirement: The use of maximized telework had minimal impact on this research project. During the laboratories use of Max telework, patenting and preparation of publications have continued. Interactions with stakeholders have been conducted virtually. This is adequate, but in-person meetings are considered superior by the unit scientists and will recommence when allowed. Laboratory work has continued with a focus on obtaining mission critical data. Experiments of lower priority have been delayed until a time when more normal working policies are in place. ACCOMPLISHMENTS 01 Improved catalyst for fuel production from vegetable oils. The transformation of a vegetable oil into a material that can be directly used as a replacement for a petroleum oil is a difficult process. ARS researchers at Peoria, Illinois, have developed a new catalyst that is capable of producing a fuel from fatty acids. This new fuel has higher aromatic ring content compared to fuels made using other technologies, which is an advantage in the development of different fuel blends. These aromatic ring structures keep seals in the fuel systems pliable and elastic. They must be included in specified amounts for a fuel to meet standard specifications. The new product is a viable fuel replacement when used alone. Even more, the structures also make it compatible with petroleum fuels so blends of the biobased fuel with conventional fuel are possible. This technology will benefit those producing bio-derived fuels, as well as fuel blenders and end users. It will also enhance agricultural markets and reduce the consumption of petroleum resources.

Impacts
(N/A)

Publications

Moser, B.R., Jackson, M.A., Doll, K.M. 2021. Production of industrially useful and renewable p-cymene by catalytic dehydration and isomerization of perillyl alcohol. Journal of the American Oil Chemists' Society. 98(3) :305⿿316. https://doi.org/10.1002/aocs.12468.
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. https://doi.org/10.1093/jme/tjaa097.
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. https://doi.org/10.1016/j.indcrop.2020.112829.
Xiao, L., Liu, Z., Li, N., Li, S., Fu, P., Wang, Y., Huang, J., Chen, J., Nie, X. 2020. A hyperbranched polymer from tung oil for the modification of epoxy thermoset with simultaneous improvement in toughness and strength. New Journal of Chemistry (RSC). 44:16856-16863. https://doi.org/10.1039/ C9NJ06373K.
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. https://doi.org/10.1039/C9RA09830E.
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. https://doi.org/10.1002/aocs.12338.
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. https://doi.org/10.1371/journal.pone.0229076.

Progress 10/01/19 to 09/30/20

Outputs
Progress Report Objectives (from AD-416): 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 (from AD-416): 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. This bridging project plan 5010-41000-186-00D replaces 5010-41000-170-00D. Project plan is currently under review by 306 OSQR cycle.

Impacts
(N/A)

Publications