ABSTRACTS 2018 AOCS ANNUAL MEETING and EXPO May 6–9, 2018

ABSTRACTS 2018 AOCS ANNUAL MEETING AND EXPO May 6–9, 2018

BIO 1.1/IOP 1: Biorenewable Polymers Chairs: Richard D. Ashby, USDA, ARS, ERRC, USA; and Baki Hazer, Kapadokya University and Bülent Ecevit University, Turkey

Synthesis of Resinic Acid and Lignin Derivative in large quantity and high yield via enzymatic Dimers for Copolymerization with Vegetable Oil- catalysis using a laccase. After chemical based Monomers Audrey Llevot*, LCPO, France modifications, the obtained dimers were tested The awareness of environmental in copolymerization with different fatty acid deterioration and our dependency on depleting derivatives. The thermomechanical properties of fossil feedstocks force research to find innovative the polymers will be discussed, as well as the solutions in order to design a more sustainable sustainability of their synthesis. future. With a worldwide plastic production of over 300 million metric tons per year, polymer Dual Cure Alkyds Mark D. Soucek*, University of science represents a very active field in the use of Akron, USA renewable feedstocks. Among the available A number of different approaches have bioresources, vegetable oils lead to a large been used to speed the curing/drying process: platform of aliphatic molecules and to a wide 1) reactive diluents, allyl ether; 2) change catalyst range of thermoplastic and thermoset polymers Fe based; 3) change curing mechanism, moisture, after modifications. In order to broaden the UV or Visible light. Light curable alkyds were palette of renewable polymers, other molecules synthesized by functionalizing hydroxyl need to be investigated and used to tune the terminated medium and long linseed oil alkyds thermomechanical properties of the vegetable with methacryloyl chloride or acryloyl chloride. oil-based aliphatic polymers. Cycloaliphatic and Two glycerol based reactive diluents were aromatic compounds are two categories of prepared by reacting glycerol with methacryloyl molecules which enable the synthesis of chloride or acryloyl chloride. Real time FTIR, polymers with high thermal stability and rigidity. photo-DSC and UV-Rheometer were used to In our work, a polycyclic biobased molecule, i.e., study the curing kinetics of UV curable alkyd with resinic acids, and phenolic compounds potentially 0–30 wt% of reactive diluent. The conversion of derived from lignin were studied as comonomers methacrylic and acrylic double bonds are above for vegetable oil-based polymers. Both classes of 80% within 10s of radiation at wavelength substrates were dimerized in order to get ranging from 320nm to 500nm. The difunctional symmetric synthons. On the one polymerization rate increases with the addition hand, abietic acid dimers synthesized via a of reactive diluent, however the final conversion cationic mechanism were esterified with slightly decreases with increasing percentage of undecenol and copolymerized with undecenyl reactive diluent due to the formation of undecenoate by ADMET methodology. On the crosslinking between UV curable alkyd and other hand, we developed a “green” process to reactive diluent limiting the mobility of the dimerize phenolic compounds derived from lignin reactive double bonds. DMA was utilized to

– 1 – ABSTRACTS 2018 AOCS ANNUAL MEETING AND EXPO May 6–9, 2018 determine the Tg and crosslink density of each Stereolithography (SLA), Selective Laser Melting system. With the increase of reactive diluent (SLM), Selective Laser Sintering (SLS), etc. The percentage, initial elastic modulus and crosslink progress in production systems and machinery is density will also increase. followed by strong demand for new materials that can meet the specific requirements of Reflection of Structural features of oils on new technology. Plastics produced from properties of polymeric materials Zoran petrochemicals are common materials in this Petrovic*, Pittsburg State University, USA area. Due to the depleting natural resources and Oils are present in all living organisms as an negative effect of carbon dioxide on the important energy source. They are triglycerides environment, there is a strong demand for of widely varying composition. Natural oils as a replacement of petrochemicals with bio-based platform for new oleochemicals have several renewable resources. Bio-based plastics can be features which make them attractive for a made from a variety of natural resources, range of new products. They are generally very including oils. Bio-oils are emerging and are heterogeneous in structure, length of fatty acids, promising raw materials for synthesis of a variety number of double bonds, with or without of polymers and plastics, including those that can functional groups and varying their positions be used in additive manufacturing. Natural oil in the fatty acid chains. Generally, oil-based based non-isocyanate polyurethanes (NIPUs) materials are softer than corresponding products synthesized from cyclic carbonates and amines from petrochemical sources but structural are promising new materials for this application. peculiarities can be beneficial or detrimental There are some structural specifics of NIPUs depending on application. Effects of specific which give them excellent adhesive properties. features of oils on properties will be discussed. We used soybean oil based NIPUs for improvement of interlayer adhesion of polylactic Bio-based Oil Potential in Additive acid filaments used in AM. The effect of natural Manufacturing. Ivan Javni1, Olivera Bilic2, Jian oil-based NIPUs on physical and mechanical Hong2, Vivek Sharma1, Xianmei Wan1, and Jamie M. Messman4, 1Pittsburg State University, USA; properties of filaments was evaluated. The 2Kansas Polymer Research Center, Pittsburg State experimental results corroborated the presumed University, USA; 3Dept. of Energy's National NIPUs structure and their effect on filament Security Campus, managed by Honeywell FMT, preparation and 3D printing. LLC, USA Additive Manufacturing (AM), or 3D printing Multifunctional Fatty Acid Macroperoxide is a rising technology that is breaking existing Initiators Obtained by the Autoxidization. product design and manufacturing methods. Synthesis of Block/Graft Copolymers via Free This technology is advancing very strongly in Radical and Ring Opening Polymerization Baki 1,2 1 2 capability of making complex elements in low Hazer , Melike Eren , Elif Ayyıldız , Faruk Bahadır1 , 1Bülent Ecevit University Faculty of Arts volumes in a rapid and cost-effective way. This and Sciences, Dept. of Chemistry; Faculty of technology involves very different processes, Engineering, Departments of Metallurgical and such as Fused Deposition Modeling (FDM), Materials Engineering,Turkey; 2 Bülent Ecevit

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University Faculty of Arts and Sciences, Nano amount of trisaturated triacylglycerols from Technology Engineering, Turkey about 4.2% to about 28.5%, 6.8 times higher than Unsaturated plant oils/fatty acids (UPOFA) the initial amount found in the mother oil. The can undergo autoxidation under atmospheric high melting fraction which concentrated with conditions to produce macroperoxide initiators. the trisaturated triacylglycerols is well separated Pure unsaturated fatty acids such as linolenic, from the low melting fraction (shown by the linoleic and oleic acid were exposed to air oxygen differential scanning calorimetry melting profile), under daylight at room temperature which is indicating easy of fractionation. Fractionation of called “ecofriendly autoxidation”. Eco-friendly the EDIE PO produced palm stearin (POs) with an autoxidation process creates peroxide linkages iodine value of less than 10. The POs crystallized in order to obtain fatty acid oligomer that is rapidly and stabilized in mixtures of β and β’ called macroperoxide initiator. Oleic acid crystals. The POs as it is, blended or restructured macroperoxide initiator was used in the free with vegetable oil via interesterification, and radical polymerization of styrene in order to texturized, produced a trans-free hardstock with evaluate the polymerization kinetics. Because of excellent oil binding capacity, and able to different functional groups, the macroperoxide perform effectively as structural fat in the initiators were used in the synthesis of formulation of trans free reduced saturated solid block/graft copolymers. Polystyrene-poly oleic fat products. acid-polycaprolactone, polystyrene-poly oleic acid-polyethylene glycol, poly N-isopropyl acryl Unexpected Selectivity in the Functionalization amide-poly oleic acid-polyethylene glycol of Neat Castor Oil Under Benign Catalyst-free 1 block/graft copolymers were obtained. Structural Conditions Latchmi Raghunanan* , and José M. 2 1 and physicochemical characterization of the Franco , Trent Centre for Biomaterials Research, Departments of Physics & Astronomy and products was done. Lower critical solution Chemistry, Trent University, Canada; 2Pro2TecS- temperature of the thermo responsive double Chemical Product and Process Technology hydrophilic copolymer, poly N-isopropyl acryl Research Centre. Departamento de Ingeniería amide-poly oleic acid-polyethylene glycol was Química, Facultad de Ciencias Experimentales, found to be 36 oC. Universidad, Spain

Super Palm Stearin from Enzymatic Directed Abstract Pending Interesterification of Palm Oil Noor Lida Habi Mat Dian*1, Miskandar Mat Sahri1, Tan Chin Ping2, and Lai Oi Ming2, 1Malaysian Palm Oil Board, Malaysia; 2Universiti Putra Malaysia, Malaysia Enzymatic directed interesterification (EDIE) of palm oil (PO) resulted in an increase in the

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IOP 2: Biofuels Chairs: Lieve Laurens, National Renewable Energy Laboratory, USA; and Steve Howell, M4 Consulting, Inc., USA

Technical Needs for Biodiesel Blends Over B20 interferences from diesel fuel hydrocarbons Steve Howell*, M4 Consulting, Inc., USA while using standard analysis methodology, such Over the past 20 years, most technical efforts as ASTM D6584 or EN14105 without suitable in the United States have focused on use of procedural and methodology adjustments, or blends of up to 20% biodiesel with conventional GCMS. Similar interferences thwart routine petroleum-based diesel fuel (petrodiesel). The checks of FG in biodiesel blends by such choice of B20 and lower was primarily based on a methods, and can destroy the validity of an combination of factors which include cold flow analysis of fuel, such as B99. We reported at various earlier AOCS meetings (1) that the properties, emissions benefits, compatibility with solubility of glycerol in polished biodiesel is much existing engines and infrastructure, and other lower than previously thought, and can cause a societal benefits. Recent natural disasters have variety of unexpected effects due to its density, spurred on renewed interest in climate change, high viscosity and biodegradability (2). In addition especially on the East and West Coasts. Goals to to temperature, several compositional entities reduce carbon emissions by 80% by 2050 are can potentially influence the solubility of glycerol. being seriously considered and use of biodiesel in Data from more recent studies of blend strength higher blends up to B100 is one potential option. and the aromatic content of hydrocarbon diesels This presentation will review the technical needs at different temperatures using model solutions and challenges for use of blends over B20 and is presented along with comparisons to our provide an update of current and planned earlier solubility data for saturated industry technical efforts in targeted markets to monoglycerides. Results show that in addition to temperature and interacting impurities, such as address them. moisture (2), blend composition looms as an important modulator of solubility. However, the The Equilibrium Solubility Behavior of Glycerol anticipated gradual increases in solubility due to in Biodiesel Fuels at Reduced Temperatures increasing FAME%, are surprisingly small in Richard W. Heiden*1, and Martin Mittelbach2, blends below about 50%, and are further 1R.W. Heiden Associates, LLC, USA; 2Institute of attenuated by declining temperatures. This Chemistry, University of Graz, Austria indicates formation of heterophases can be Low level free glycerin (FG) residuals in B100 induced by blending. are limited to 200ppm by internationally (1) Heiden and Mittelbach, 105th AOCS National recognized specifications dating back to the mid Meeting, 2014. (2) Heiden, Schober, Mittelbach, 1990’s. FG easily escapes detection because of JAOCS, 2017.

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Green Diesel by Hydrotreatment of Vegetable they had different degree of participation in the Oils: Effect of Oil Quality on Hydrocarbon Yield global process. and Composition Elisa Volonterio, Juan Bussi, Jorge Castiglioni, Ignacio Vieitez, and Iván Extractability and Quality of Lipids in Algae, a Jachmanián*, Facultad de Química, Universidad Study of Species-specific Lipase Activation Ryan de la República, Uruguay A. Herold and Lieve Laurens*, National The effect of the degree of oxidation of a Renewable Energy Laboratory, USA vegetable oil on the efficiency of its conversion Algae form an excellent basis to develop raw to green diesel by an hydrotreating process was biofuel feedstocks, thanks to the abundance of studied. Refined rice bran oil (RBO) was used, lipids and carbohydrates in the biomass. One of which was oxidized for different periods by the main challenges associated with algal biofuels heating at 180 °C inside an open vessel provided production is improving the lipid extraction and with a magnetic stirrer. Hydrotreatment was conversion efficiency. Process yields are highly performed using 100 g of oil in a high dependent on the efficiency of extraction and pressure/high temperature Parr reactor ultimately conversion of the individual lipid (4570 HP/HT, 250 mL) at 350°C and 100 bar of components. This study utilized different storage H2. Samples from the reaction mixture were conditions of mid-stage harvested microalgal collected at different reaction periods and biomass from at least six different species to analyzed by gas chromatography. When a sample affect lipid extractability and quality and of RBO oxidized after 4.5 h (containing 19.5% of selectively induce lipase activity. All six species total polar compounds and 4.3% of polymers) that were tested showed a significant increase in was hydrotreated using 0.5% PtO2 (Sigma lipid extractability, some more than two-fold Aldrich) as catalyst, a product containing 73.4% compared to control samples, following storage hydrocarbons was obtained after 4hs reaction. As for 24 hours at 37°C as a wet paste. It was also TAG disappeared after 30 min of reaction, FFA shown that storage of C. vulgaris as a wet paste were rapidly generated and their concentration for 24 hours at 37°C can induce the upregulation raised to 88%. From then on, FFA concentration of free fatty acids (FFA), whereas other species gradually diminished and hydrocarbons started appear to exhibit a more constitutive high lipase to be accumulated in the system. After 4h activity or much more rapid initiation of lipolysis reaction FFA concentration was 10,2% and to FFA, since high levels of FFA were detected at hydrocarbons concentration was 73.4%. all time points and storage conditions. Since Although a similar behaviour of the system was many industrial-scale models for algal biofuel observed when the process was performed at production include short term storage of wet identical conditions using the refined oil, a algal biomass, it is important to understand any product with 4.3% FFA and 93.4% hydrocarbons physiological changes induced by storage was achieved. Products showed different ratios conditions that might affect fuel quality and/or heptadecane/ octadecane, suggesting that lipid extractability. Furthermore, if algal lipids can although always hydrodeoxygentation and be extracted more easily simply by manipulating decarbonylation + decarboxylation occurred, short term storage conditions, this may be a

– 5 – ABSTRACTS 2018 AOCS ANNUAL MEETING AND EXPO May 6–9, 2018 viable way to reduce chemical and energy performed nearly as well as the SLE model consumption during lipid extraction, while despite the presence of small concentrations of maintaining yields. other saturated-FAME in the admixtures.

Correlating the Cold Flow and Melting Hydroprocessing Algal Lipids to Renewable Properties of Fatty Acid Methyl Ester (FAME) Diesel Blend Stock. Jake Kruger, Earl Christensen, Mixtures Robert O. Dunn*, USDA, ARS, Tao Dong, Gina Fioroni, Robert McCormick, and NCAUR, USA Philip Pienkos, National Renewable Energy Fatty acid methyl ester (FAME) mixtures Laboratory, USA derived from plant oils or animal fats are used to Objective There has been increasing interest in make biodiesel, lubricants, surfactants, converting algal lipid feedstocks to a drop-in plasticizers, ink solvents, paint strippers and hydrocarbon diesel fuel via deoxygenation many other products. Processing requires a (DO) and hydroisomerization (HI) reactions. A precise knowledge of the physico-chemical significant body of work exists on the DO step, properties of mixtures with diverse and changing but the HI step has been less explored. In fatty acid concentration profiles. FAME mixtures particular we were motivated to investigate the may become problematic if ambient effect of impurities in the lipid feed on the temperatures cause them to gel or solidify during upgrading catalysts both in two-step DO-HI, and processing. This work examines mathematical combined, single-step DO-HI. correlation models for calculating the cloud point Methods Used We have performed continuous- (CP) and cold filter plugging point (CFPP) of flow reactions for DO of crude, hexane-extracted multicomponent FAME mixtures (biodiesel) algal lipds and two bleached samples over a based on composition and the melting properties commercial Pd/C catalyst, followed by HI of the of the FAME species present. To obtain a diverse resulting n-alkane stream over a custom Pt/SAPO-11 catalyst. We have also performed set of measured property data, binary one-step DO-HI of crude, hexane-extracted algal admixtures were prepared made with biodiesel lipids over a Pt/SAPO-11 catalyst. fuels made from canola, palm and soybean oils Results Both two-step and one-step DO-HI are and yellow grease. Two models were developed effective for converting algal lipids into green in the present study. The solid-liquid equilibrium diesel fuel through 10 h time-on-stream, yielding (SLE) model correlated CP and CFPP to the a liquid alkane product with cloud point < 0 °C. SLEtemperatures of admixtures calculated from The Pt-SAPO-11 catalyst is susceptible to freezing point depression theory. This model deactivation in one-step DO-HI, however, with yielded close to a 1:1 correlation between cloud points increasing to ~10 °C after 24 h time- calculated and measured cold flow properties for on-stream. the admixtures. The MODified Empirical Conclusions Crude algal lipids can be Correlation (MODEC) model was developed by hydrotreated to green diesel fuel in either two- correlating the inverse of CP or CFPP (1/T) to the step or one-step DO-HI reactions, though further natural log of the total methyl palmitate process development is necessary, especially for concentration in the FAME mixtures. This model one-step DO-HI.

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IOP 3: Green Chemistry Chairs: Nurhan T. Dunford, Oklahoma State University, USA; Dharma Kodali, University of Minnesota, USA; and Jerry W. King, Critical Fluid Symposia, USA

Oil and Oilseed Processing with Sustainability in mechanical extraction and enzyme aided oil and Mind Nurhan T. Dunford*, Oklahoma State oilseed processing will be reviewed. Application University, USA of biorefinery approach to specialty oil The focus of this presentation will on production will also be highlighted in this specialty oils that are used as ingredients in presentation. foods, cosmetics and pharmaceuticals. These types of oils are available in relatively small Biobased Surfactants: A Useful Biorefinery quantities because of the limited feedstock Product That Can be Prepared Using Green Manufacturing Douglas G. Hayes*, University of supply and/or challenges involved in feedstock Tennessee, USA handling and storage. Commonly specialty oils Biobased surfactants, readily prepared from are processed to retain the distinctive qualities common biorefinery process streams and naturally associated with the oil. Color, flavor, commonly employed as emulsifiers, wetting nutrient content and functionality are some of agents, plasticizers, and agents for lowering the important attributes that distinguish specialty surface and interfacial tension, are becoming oils from commodity product such as cooking increasingly popular for use in foods, cosmetics, oils. Although specialty oils receive a premium pharmaceuticals, and other industries. This trend price, economic feasibility of producing high is driven the enhanced environmental quality specialty oils might not be easy to sustainability provided through use of renewable achieve. Typically consumers of the specialty oils resources, increased abundance of biobased tend to be “natural minded” and environment feedstocks resulting from development of and health conscious individuals who favor biorefineries, and concerns for the increase of products that do not contain chemical residues cost for petroleum in the future. Although most and are produced by environmentally benign biobased surfactants are manufactured by processing techniques and following sustainable chemical means, their preparation via practices. The presentation will emphasize bioprocessing is very attractive for future sustainable approaches to wheat germ, rice bran, employment due to further enhancement of corn fiber and Daphne (Laurus nobilis L.) seed oil sustainability and potential savings in energy, processing. Challenges involved in feedstock downstream purification, and disposal costs. This supply and quality, selection of oil extraction and presentation provides an overview of current refining processes and the ways to meet research and development to prepare biobased consumer expectations while achieving economic surfactants via conventional and green feasibility will be discussed. Pros and cons of manufacturing approaches, including enzymatic supercritical fluid technology, aqueous and processes.

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Eastern Red Cedar: Critical Fluid Extraction and Synthesis of Biobased Building Blocks from Bioactivity of Extracts Fred J. Eller*, USDA, ARS, Cashew Nutshell Liquid: A Chemical Platform NCAUR, USA Approach for Polymer Synthesis Sylvain Caillol*, Eastern red cedar is an abundant natural Institut Charles Gerhardt, France resource in the United States. It is valuable for its We propose a platform approach for the lumber and cedarwood oil derived from the synthesis of various building blocks from cardanol wood. Cedarwood is generally obtained by steam in one or two-steps syntheses. Cardanol, which is distillation; however, this process has several a natural phenolic oil, is issued from Cashew disadvantages, including relatively low yields and Nutshell Liquid (CNSL), a non-edible renewable altered oil characteristics. Our laboratory has resource, co-produced from cashew industry in been investigating several alternative methods large commercial volumes (1Mt p.a.). Cardanol is for extracting cedarwood oil from Eastern red non-toxic and particularly suitable for the cedar, including liquid and supercritical fluid addition of aromatic renewable resources in carbon dioxide and pressurized solvent polymers and materials. Various routes were extraction. Carbon dioxide extractions have been used for the synthesis of di- and poly-functional demonstrated to give high yields of high quality building blocks used thereafter in polymer oil. Pressurized hexane also gave high yields of syntheses. Phenolation was used to cedarwood oil and pressurized polar solvents like dimerize/oligomerize cardanol to propose ethanol and methanol gave high yields of polar increase functionality of cardanol. Thio-ene was compounds not extracted by CO2 or hexane as used to synthesize new reactive amines. well high yields of flavonoids. The CO2-derived Epoxidation and (meth)acrylation were also used extracts have been tested for a variety of to insert oxirane or (meth)acrylate groups in bioactivities. The extracts have been found to order to synthesize polymers and materials. impart resistance to wood-decay and termites Finally, we also synthesized a new radically when they are impregnated into otherwise polymerizable monomer from cardanol. Hence susceptible wood. The cedarwood oil has also we synthesized cardanol-based aromatic latex by been shown to be repellent to several species of water emulsion radical polymerization for ants, including red imported fire ants and little styrene-free coating applications. fire ants. The cedarwood oil is toxic to black- legged ticks, brown dog ticks, lone star ticks, Feruloylated Soy Glycerides: UV Absorbance 1 houseflies and several species of mosquitoes. Capacity and Photostability David L. Compton* , 2 1 1 Interestingly, polar solvent extracts contain John R. Goodell , and Kervin O. Evans , USDA, ARS, NCAUR, USA; 2iActive Naturals, USA compounds that induce egg-laying by ladybird Feruloylated soy glycerides (FSG) are plant- beetles. Cedarwood oil is a very safe material based, naturally derived compounds with towards humans but has great potential for antioxidant and ultraviolet (UV) absorbing managing a wide range of economically properties. FSG is synthesized by the important pests transesterification of soybean oil with ethyl ferulate in a continuous, enzymatic, packed-bed bioreactor. A small, limited, independent

– 8 – ABSTRACTS 2018 AOCS ANNUAL MEETING AND EXPO May 6–9, 2018 laboratory clinical trial determined that FSG has degassed water and hemp seed oil through a an empirical benefit as an emulsifier and stainless-steel tubing maintained at the desired moisturizer in anti-wrinkling applications, thus temperatures inside a temperature-controlled FSG is beginning to be used in formulations in the oven and kept pressurized with a backpressure personal care and health and beauty industries. regulator. An ice bath was used to cool the The antioxidant capacity of FSG has been well oil/water effluent from the reactor. Collected documented in the literature; however, the UV hydrolysates were centrifuged and the oil absorbing efficacy of FSG has not been samples were used for analytical tests. Hydrolysis investigated. The total absorbance capcity, yield was measured by the ASTM-D5555 method, photostability, and broad UV spectrum and fatty acid identification was done by gas absorbance capcity of FSG (λmax of 328 nm) chromatography with FID detection and mass were determined and compared to commercially spectrometry. Process conditions were defined used, non-naturally derived UV absorbing by a central composite rotatable experimental ingredients Octinoxate (ONX, λmax 310 nm) and design with three factors and five levels. Factors Avobenzone (AVO, λmax 356 nm). FSG was and levels were temperature (150–275°C), tested as a fungible replacement for ONX in reaction time (40–120 min), and oil/water ratio equimolar mixtures with AVO and was found to (0.125–0.250). The free fatty acid yield ranged provide the same or superior UV absorbance between 20 and 91% (w/w). The highest degree capacity, photostability, and broad spectrum of hydrolysis took place at temperatures above coverage. 200°C and retention times over 60 minutes. Similar fatty acid profiles were observed in the Subcritical Water Hydrolysis of Hemp Seed Oil unhydrolyzed and hydrolyzed oils, which in a Continuous Flow Coil Reactor Andres F. indicates minimal or no fatty acid degradation. 1 2 Aldana Rico* , Ruben O. Morawicki , Jerry W. Linoleic acid (C18:2) was the predominant 3 4 King , Marco E. Sanjuan Mejia , and Antonio J. fatty acid. Bula Silvera1, 1Universidad del Norte, Colombia; 2University of Arkansas, USA; 3Critical Fluid 4 Green Chemistry in Cannabis “Oils” Extraction, Symposia, USA; [email protected], Processing and Derived Products Jerry W. King*, Colombia Critical Fluid Symposia, USA When water is heated to the subcritical The dynamic growth of the cannabis industry region, changes in the dielectric constant and —both for traditional Cannabis as well Cannabis ionic product, make water capable of intervening sativa L. (hemp)—is well documented and for in acid- or base-like catalytic reactions, such as hemp-derived-CBD (cannabidiol is projected to hydrolysis. The objective of this research was to be $1.65 billion by 2021. Production of cannabis- study the hydrolysis of hemp seed oil using derived “oils” differs chemically from traditional- subcritical water in a continuous flow reactor. derived lipophilic oils, although the presence of The reaction was followed by analyzing the the latter in cannabis extracts requires both their evolution of free fatty acids and the composition inclusion and/or removal depending on the of their mixtures. The experimental equipment desired end product. Although the use of “green” consisted of two syringe pumps that delivered

– 9 – ABSTRACTS 2018 AOCS ANNUAL MEETING AND EXPO May 6–9, 2018 processing technology is inherent in commercial as well as the inclusion-exclusion of lipophilic co- practice and imperative for consumer safety, extractives, i.e., triglycerides, waxes and plant quantitative evaluation of such chemical choices pigments. Particular note will be paid to the use and procedures is lacking and will be reported of CO2 in its dry ice, subcritical, and supercritical here. “Cannabis derived-oils” are used states for comminution, terpene isolation, and particularly in infused products and inhalable- the extraction of specific rations of cannabinoids. delivery systems and can be obtained by An assessment of low temperature (<–60oC) and hydrocarbon extraction, varying formats of CO2 pressure (~300 psi) ethanol for extraction and extraction, the use of ethanol for extraction and refining will be provided. Finally, the reduced purification, and other processing agents. Here solubility parameter concept will be shown to be the relative “greenness” of such processes and applicable to final product content including derived products is accessed with the aid of the desired and unwanted contaminants such as ”reduced” solubility parameter concept for the pesticides, solvent residuals, and lipophilic co- major cannabinoid constituents found in extracts, extractives. their inclusive “entourage” terpene components,

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IOP 4: Oleochemicals Chairs: Xiaofei P. Ye, University of Tennessee, USA; and Franck Dumeignil, Université de Lille, France

The Global Challenges in Chemicals and Energy efficiently impregnated with the magnesium Mischa Schneider*, Chemspeed Technologies AG, nitrate salt and used in the isomerization of oleic Switzerland acid to produce iso-oleic acid (precursor of Standardization and acceleration of R+D isostearic acid). The catalyst surface areas, acid within the oil and gas industries are vital for sites, crystallinity, thermal property, morphology coping with all the dynamically increasing and elemental compositions were investigated challenges in their broadest sense. Many industry before and after modifications. When the leaders have recognized the need to act and catalysts were used in the isomerization successfully boosted their R+D outputs. The reactions, various factors were studied including global challenges in chemicals and energy magnesium nitrate loading amounts, zeolite comprise: types, reaction times and temperatures, and amounts of catalyst loadings. For instance, when • Increasing constraints in energy supply from comparing the non-salt H+-ZSM5 to the salt fossils and recently nuclear power version of 5wt%MgO-H+-ZSM5 catalyst, with • Increasing constraints by regulations (CO2 the salt version the amount of undesirable emission, global warming, …) • Increasing energy demand e.g. spurred by the byproduct (i.e., dimer acid) was reduced by 50%, dynamic growths in the BRIC countries accompanied by a high yield of iso-oleic acid • e.g., by 2020 China is projected to consume (79%) and a high reaction conversion of oleic acid more than 50% of the global energy. (98%). Most significantly, these magnesium salts are similar to the zeolite solids since both are not Effective Magnesium Oxide-Zeolite Catalysts soluble in the oil products and therefore could to Produce Iso-Oleic Acid, Precursor of potentially be a new environmentally friendly Isostearic Acid Helen Ngo Lew, Jianwei Zhang, catalyst system for producing commercial and Robert A. Moreau, USDA, ARS, Eastern isostearic acid. Regional Research Center, USA A family of magnesium oxide (MgO)-zeolite A Soybean Oil-based Adhesive and its catalysts has been thoroughly investigated to Application for Birdseed Binding Tao Fei*, produce iso-oleic acid followed by hydrogenation Melissa Slagle, Darren H. Jarboe, and Tong Wang, to give the isostearic acid. Isostearic acid, a type Iowa State University, USA of methyl branched-chain fatty acid, is a unique A soybean oil-based adhesive was commercial product that is an important synthesized and tested for birdseed binding. The component in the formulation of bio-lubricants effects of the quantity of saturated fatty including cosmetics and personal care products. acylglycerols (i.e., fully hydrogenated soybean oil, In this investigation, three types of zeolites (i.e., FHSO) introduced into epoxidized soybean oil H+-ZSM5, H+-BETA and H+-Ferrierite) were (ESO) and a phosphoric acid (H3PO4) crosslinker

– 11 – ABSTRACTS 2018 AOCS ANNUAL MEETING AND EXPO May 6–9, 2018 on product characteristics were investigated. excellent plasticizer functional properties. Two Increasing the quantity of FHSO improved classes of compounds, alkyl and diacetyl glyceryl hardness and adhesiveness while further fatty acid esters from these two oils were increasing the quantity led to various degrees of synthesized by transesterification with alkanol or phase separation in the binder. Increasing the triacetin respectively. The unsaturation on the quantity of H3PO4 also improved hardness and fatty acid backbone was converted to epoxy adhesiveness of the binder. A binder-MDAG (a function by reacting with hydrogen peroxide and mixture of mono and diacylglycerols at about a acetic acid. The final plasticizer compounds, 1:1 ratio) mixture (BMD) having an average epoxy estolide fatty acid esters, were synthesized hardness and adhesiveness of 4,024 and 1, 197 g, by partial ring opening of epoxide and respectively, was selected for seed binding. acetylation. These two classes of compounds Curing of BMD in open air led to increased derived from two different oils were evaluated hardness, adhesiveness, and melting point. Seed for their plasticizer functionality by compounding cakes bound with 15 wt% BMD were about twice with PVC. The plasticizers derived from these two as hard as gelatin-bound seed cakes. Curing seed structurally different oils showed excellent cakes in open air significantly increased their compatibility, gelation temperatures, cold hardness and temperature tolerance. Seed cakes flexibility, and efficiency. The plasticizers derived bound with BMD also presented much better from HSBO had greater structural homogeneity water resistance. It is possible and feasible to use resulting in better functional properties. The a minimally modified soybean oil as bird seed chemical modifications of the fatty acid esters binder. and the detailed structural differences of the resulting plasticizers and their functionality based Bioplasticizers Derived from Regular and High Oleic on the starting oil composition will be presented. Soybean Oil Lucas J. Stolp* and Dharma R. Kodali, University of Minnesota, USA Innovations in Biodiesel Production Value Chain Plasticizers are organic liquids added to Toward Circular Economy Xiaofei P. Ye*, University of polymeric materials to improve their flexibility. Tennessee, USA The majority of plasticizers are used to enhance Current biodiesel production fits into a linear the polyvinylchloride (PVC) functionality in economy, which is a take-make-dispose model. applications such as flooring, wire and cable For a sustainable future of biofuels, it is coatings, and medical tubing. Currently used imperative to move away from a linear economy petroleum derived phthalate esters have come toward a circular economy with key elements of under scrutiny due to health and safety concerns. prioritizing regenerative resources, using waste Fatty acid esters derived from regular soybean oil as a resource, designing for the future, preserving (RSBO) and high oleic soybean oil (HSBO) can be and extending what is already made, and further chemically modified to produce collaborating to create joint value. In the plasticizers that can replace phthalates in PVC biodiesel production, considerable amount of applications. The ideal plasticizers should possess methanol remains with crude glycerol and low volatility, color and viscosity with a moderate catalyst after separating the produced biodiesel. molecular weight of about 350 Daltons and The separation of methanol and catalyst, and the

– 12 – ABSTRACTS 2018 AOCS ANNUAL MEETING AND EXPO May 6–9, 2018 purification of crude glycerol are costly. We Laser-assisted Catalytic Oxidation of Glycerol demonstrated that it is feasible to directly use over Gold Supported Catalysts Zeinab Chehadi1, the mixture of crude glycerol, methanol, and Jean-Sébastien Girardon2, Mickaël Capron3, 4 1 1 catalyst from biodiesel production for chemical Franck Dumeignil* , and Safi Jradi , Laboratoire production. This presentation showcases our de Nanotechnologie et d’Instrumentation efforts integrating the production of value-added Optique, Institut Charles Delaunay, UMR 6281 CNRS, Université de Technologie de Troyes, oleochemcials in the biodiesel production value France; 2Univ. Lille, CNRS, Centrale Lille, ENSCL, chain considering the above key elements toward Univ. Artois, UMR 8181 - UCCS - Unité de Catalyse a circular economy. et Chimie du Solide; 3Univ. Lille, CNRS, Centrale Lille, ENSCL, Univ. Artois, UMR 8181 - UCCS - Improved Synthesis and Cost Estimates for Unité de Catalyse et Chimie du Solide, France; the Production of Saturated Branched-Chain 4Université de Lille, France Fatty Acids from Vegetable Oils Jianwei Zhang, We studied the feasibility of new efficient Winnie Yee, Robert A. Moreau, and Helen Ngo catalytic process by laser excitation in the Lew, USDA, ARS, Eastern Regional Research reaction of oxidation of glycerol over catalysts Center, USA based on supported gold nanoparticles. We Saturated branched-chain fatty acids, such as showed that this catalytic oxidation reaction can isostearic acids, are one of the most important efficiently proceed via laser excitation of surface oleochemical ingredients used in bio-lubricants plasmon resonance of gold nanoparticles including cosmetics and personal care products. inducing local thermal heating. While the They are produced as coproducts during the reaction did not occur in the absence of any dimerization of tall oil fatty acids with clays as external heat source, with this original approach, catalysts. More recently, research has shown that 88% of glycerol was converted after 2 h, leading they can also be produced in high yields from to the formation of glyceric acid and tartronic refined fatty acids with zeolite solid catalysts. acid as primary main products. The photonic Both technologies however have their drawbacks activation led to a 2.5 times more efficient in terms of costs and yields. In this poster, conversion than an equivalent thermal activation discussions on our research efforts to efficiently using a conventional heating source. improve the production of isostearic acids will be Investigations of the laser power and the nature presented. Topics will be specifically focused on of support catalyst revealed a significant various types of modified solid catalysts contribution of electron transfer from plasmonic investigated for the synthesis of saturated nanoparticles to TiO2 in the oxidation reaction. branched-chain fatty acids from mixed fatty acids This work paves the way to a rethinking of the derived from vegetable oils. Reaction conditions design of industrial processes for glycerol and detailed characterizations on both solid oxidation in the liquid phase, using laser catalysts and oil products will be presented. activation. Finally, the practicality of the overall processing cost for converting mixed fatty acids to isostearic acids will be discussed.

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The Effect of Plant Oil-Based Monomer monomer feed unsaturation, it can be concluded Structure on Properties of Latex Synthesized in that the latex network formation and Miniemulsion Polymerization Zoriana thermomechanical properties can be adjusted by 1 2 1 Demchuk* , Ananiy Kohut , Ihor Tarnavchyk , simply combining various plant oil-based 2 1 1 Stanislav Voronov , and Andriy Voronov , North monomers at certain ratios in the reaction feed. 2 Dakota State University, USA; Lviv Polytechnic The incorporation of POM’s fragments into National University, Ukraine copolymer have a plasticization effect, increases Recently, library of plant oil-based acrylic the toughness of latex films and converts brittle monomers (POM’s) was synthesized in one-step polymers into flexible film-forming materials. direct transesterification of vegetable oils (olive, sunflower, soybean, and linseed) with N- Preparation of Mango Kernel Fat Stearin using hydroxyethyl acrylamide. Based on kinetic study, 2-methylpentane and its Application in Heat- POM’s behave as conventional vinyl monomers in resistant Chocolate Fats Jun Jin*, Qingzhe Jin, free radical polymerization and copolymerization. and Xingguo Wang, Jiangnan University, China In this study, stable latexes from olive, soybean Objective Mango kernel fat (MKF) is an and linseed oil-based monomers copolymerized untapped resource and contains more than 30% with styrene were synthesized using of 1,3-distearoyl-2-oleoyl-glycerol (StOSt). The miniemulsion which provides an opportunity to StOSt-rich fat in natural form is difficult to obtain polymerize highly hydrophobic monomers. Using and enjoyed in producing heat-resistant 1H NMR spectroscopy it was determined that chocolate fats. The present study is focused on double bonds of fatty acid fragments remain preparing StOSt-rich fat from MKF and further mostly unaffected during the polymerization and making hard chocolate fats. Methods Used StOSt- can be further used for post-polymerization rich fat (mango kernel fat stearin, MKFS) was reactions (e.g., crosslinking). The latex free films produced by three-stage selective fractionation were formed by curing at elevated temperature using 2-methylpentane (a new processing and tested using DMA, DSC and tensile solvent). Heat-resistant chocolate fats were then techniques. It was observed that the amount of prepared by mixing MKFS, cocoa butter (CB) and unsaturation in POM’s impacts mechanical palm mid-fraction (PMF, if necessary). Fat and properties of the resulting latex films. To triacylglycerol (including isomers) compositions, investigate the effect of POM unsaturation compatibilities, solid fat contents, melting and amount in monomer feed on the mechanical crystallization behaviors, polymorphic forms properties of latex films, new mostly saturated and hardness were analyzed to select the monomer from hydrogenated soybean oil (H- ideal mixing ratios. Results The new solvent, SBM) was synthesized. As a result, crosslink 2-methylpentane, showed lower toxicity than density of the polymer network, measured by acetone and higher polarity than hexane, and DMA, can be varied by integration of successfully enriched StOSt into MKFS hydrogenated soybean oil-based monomer (H- (44.0%→69.2%) by removing other SBM) into the polymer backbone. Based on the undesired compounds (e.g., diacylglycerol and linear dependence of the crosslink density on di-unsaturated triacylglycerols). However, for

– 14 – ABSTRACTS 2018 AOCS ANNUAL MEETING AND EXPO May 6–9, 2018 binary blends of MKFS and CB, eutectic effects through a hydrothermal liquefaction (HTL), and were observed at 18–32°C. Therefore, PMF (1,3- the presence of mcl-PHA can also improve the dipalmitoy‐2‐oleoyl-glycerol (POP), 70.2%) was yield and quality of bio-oil. In this study, involved to improve the miscibility. Accepted Pseudomonas putida biomass rich in mcl-PHA compatibilities were found in the ternary blends was used in HTL at 300°C for 30 min. It was found consisting 10% PMF, 10%-45% MKFS and 45%- that up to 65mol% of the mcl-LAO was produced 80% CB. The POP-rich fat is help to make the from mcl-PHA via the HTL. The yield and quality mixtures transfer into β structure and three-pack of obtained HTL bio-oil was remarkably improved layer, and contribute to improving their thermal with the presence of mcl-PHA in the biomass. properties and hardness. Conclusions Addition of Experiments with extracted mcl-PHA revealed 10% PMF could improve the miscibility of MKFS the fates of mcl-PHA in HTL. Overall, this work and CB mixtures, and further make the fat blends demonstrates a sustainable process to produce more suitable to be as heat-resistant chocolate mcl-LAO and bio-oil from renewable biomass via fats. an integrated green chemical approach.

Producing Fully Renewable Medium Chain Alpha High Linoleic Soybean Oil a New Feedstock Olefins via an Integrated Biorefinery Process for Industry: Alkyd Resin and Paint Example Tao Dong*, Wei Xiong, Jianping Yu, and Rick Heggs*, Oilseed Innovation Partners, Canada Philip Pienkos, National Renewable Energy Oilseed Innovation Partners (formerly Soy Laboratory, USA 2020) in conjunction with the University of Medium chain-length linear alpha-olefins Guelph in Canada has developed a new non-GMO (mcl-LAO) are versatile precursors to produce soybean variety that has a unique fatty acid many commodity chemicals, such as synthetic profile with about 70% linoleic acid. The lubricants and biodegradable detergents. mcl- additional unsaturation of this oil has been found LAO have been traditionally produced from to be very useful in producing alkyd resins that ethylene oligomerization and Fischer-Tropsch are faster drying than conventional soybean oil synthesis. Recently it has been reported that alkyds and result in paints with surprisingly good polyhydroxybutyric acid (PHB) can be converted corrosion resistance. Other industrial applications into propylene via an intramolecular β- that may benefit from this oil include plasticizers, elimination and decarboxylation. Our hypothesis polyols and inks. is that mcl-polyhydroxyalkanoic acid (mcl-PHA) might be used as a feedstock to produce mcl-LAO

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EAT 5/IOP 5: Waxes and Phase Change Materials Chairs: Nuria Acevedo, Iowa State University, USA; and Chelsey Castrodale, Clasen Quality Chocolate, USA

Multiple β Forms of Tripalmitin in Different PPP have four different polymorphs, β4 and β3, Crystallization Pathway Seiya Takeguchi*1, which were transformed from α form, and β2 Hironori Hondoh2, Hidetaka Uehara3, and Satoru and β1, which were transformed from β' form. Ueno2, 1The Nisshin OilliO Group, Ltd./Hiroshima University, JAPAN; 2Graduate School of Biosphere The Effect of Processing on Hybrid Shortenings Science, Hiroshima University, Japan; 3The Nisshin Containing Diacylglycerols Iris Tavernier1, Tom OilliO Group, Ltd., Japan Rimaux2, Koen Dewettinck3, and Ian T. Norton4, Polymorphic transformation of fat crystals, 1Ghent University, Belgium; 2Vandemoortele such as fat bloom in chocolate, will be a cause of R&D Centre, Belgium; 3University of Gent, deterioration of foods. Therefore, it is important Belgium; 4Chemical Engineering, University of to understand polymorphic behavior of fat Birmingham, UK crystals. Tri-saturated triacylglycerol is known to Oleogelation has attracted a lot of attention have three polymorphs, α, β’ and β. In addition, as possible alternative for saturated and trans-fat some researchers suggested the existence of structuring of food products. Despite the extra structures. However, the details remain development of numerous food-grade oleogels, unidentified. Here we report that tripalmitin they are still under-appreciated in the food (PPP) shows different β forms depending on their industry. This reluctance to move from crystallization history. PPP was crystallized in α or fundamental research to actual product β' forms from melt, and then they were development is related to the unknown effect of transformed into β forms (β4 from α, and β2 actual processing conditions on these newly from β’) by solid-solid phase transition by developed products. Oil structuring using solely gradually increasing temperature. Additional diacylglycerols (DAGs) have received little heat treatment was applied for further phase attention so far. However, they are known to transformation to β3 and β1. The following form crystallite networks in a relatively similar results were obtained. 1) From the polarized way as TAGs. Furthermore, at concentrations of microscopy, the β2 changed its morphology over 40%, 1,3-DAGs possess nutritional benefits during transformation from β’, while β4 kept the compared to TAGs. In the current research, palm same morphology as α form. 2) From the X-ray oil DAGs were combined with palm oil TAGs in diffraction measurement, we confirmed the various ratios, forming hybrid systems. Samples β4 transformed into β3 (α route) and β2 were prepared both statically, without shear or transformed into β1 (β’ route) because β4 (β2) rapid cooling, and dynamically, in a bench-top and β3 (β1) had different short spacing. scraped surface heat exchanger. Results 3) From the differential scanning calorimetry demonstrate the drastic effect of processing on measurements, the order of melting points were the texture of the final products, which could be β4 < β3 < β2 < β1. These results indicated that related to the different amount of crystalline

– 16 – ABSTRACTS 2018 AOCS ANNUAL MEETING AND EXPO May 6–9, 2018 matter (DSC) and the different crystalline oils, caused by the presence of partial glycerols. microstructure (PLM). The functionality of the The onset of crystallization for peanut oil statically crystallized samples could not predict increased from 2°C to 21°C. For cottonseed oil, the behavior of dynamically crystallized samples. this temperature increased from –3°C to 21°C, Furthermore, post-crystallization effects were and for soybean oil the onset was raised from more pronounced for the samples with a high –6°C to 10°C. Furthermore, pulsed nuclear concentration of DAGs, which is relevant in magnetic resonance was used to investigate the terms of further product development. This melting profile of these modified oils. Solid fat research clearly demonstrates that a thorough content measurements demonstrated understanding of the processing parameters is differences in the melting profiles of these essential for efficient product and process modified oils, confirming the earlier onset of development. Furthermore, it is also shown that crystallization and delay in melting observed only realistic processing conditions allow the through DSC. This research will help to provide a assessment of the true potential of alternative better understanding of how partial glycerols can structuring techniques. be used to tailor the physical properties of oils for their use in food applications. Engineering Lipid Properties Through Glycerolysis Reed A. Nicholson* and Alejandro G. Developing Vegetable Oil Based Wax Coating Marangoni, University of Guelph, Canada Alternatives Tong Wang* and Tao Fei, Iowa State Partial glycerols are commonly used as food University, USA ingredients because of their emulsification The demand from industry for “green” properties. Additionally, monoacylglycerols coating materials has been increasing in recent (MAGs) and diacylglycerols (DAGs) can be found years due to the environmental concerns as well at varying concentrations in some types of edible as the availability and supply fluctuation of oils, the most famous being palm oil, which is imported specialty natural waxes. We have known to contain DAGs at concentrations of explored minimal and feasible modification 5–8%. The presence of these molecules alters the methods to make vegetable hardstock have the crystallization behaviour of palm oil and is performance of paraffin and carnauba waxes. thought to contribute to its unique Structure-function relationships are studied and characteristics. The purpose of this research is to established to provide direction for desirable and investigate the effect that partial glycerols have tunable properties. The effect of hydrocarbon on the crystallization and melting properties of chain length, pendent and terminal hydroxyl various edible oils. Glycerolysis reactions were group, and type of linkage of the liner chain on performed at 65°C for various lengths of time in physical properties of the bulk materials are the presence of an excess of glycerol using demonstrated. These properties and laboratory- Candida antarctica lipase B as the catalyst. scale coating performance are compared to the Differential scanning calorimetry (DSC) benchmark commercial products. Hardness, demonstrated changes in crystallization cohesiveness, melting profile and water behaviour of peanut, cottonseed, and soybean resistance of the alternative coating compare

– 17 – ABSTRACTS 2018 AOCS ANNUAL MEETING AND EXPO May 6–9, 2018 well to paraffin wax (hardness of 1.40 mm Role of Rice Bran Wax on Crystallization and vs. 1.85 mm penetration, cohesiveness of Rheological Properties of Oleogels from Rice 1300 g.mm vs. 1500 g.mm, melting point of Bran Oil Khakhanang Wijarnprecha*1, Pravit 2 3 67°C vs. 65°C, and water repellency of 90° vs. Santiwattana , Sopark Sonwai , and Dérick 4 1 100° surface contact angle). Our carnauba-like Rousseau , Department of Food Technology, 2 material has similar hardness (0.10 mm vs. Silpakorn University, Thailand; Thai Edible Oil Co., Ltd., Thailand; 3Silpakorn University, 0.10 mm), much higher melting point (145°C vs. Thailand; 4Ryerson University, Canada 82°C) and better water repellency (65° vs. 45°) The crystallization and rheological properties compared to carnauba wax. Working with of oleogels consisting of 0.5–25 wt% rice bran commercial partners, we expect to have these wax (RBX) in rice bran oil (RBO) were explored. technologies adopted by the various industries RBX was an efficient, thermoreversible that use waxes in their product formulations. oleogelator capable of structuring RBO at concentrations as low as 0.5 wt% RBX. A An Emerging Natural Wax: Sorghum qualitative temperature-composition phase Wax from Bioethanol Production Jeffrey T. Cafmeyer*, Battelle, USA diagram showed that oleogels containing higher Wax from grain sorghum has long been concentrations of RBX were the most resistant to suggested as a potential alternative to high- melting. Polarized light microscopy revealed the melting, high-hardness natural waxes such as presence of a network of interlinked, long aspect carnauba. However, the uses and potential of ratio wax crystal needles up to 50 µm in length in sorghum wax have remained largely unexplored oleogels at higher RBX concentrations. Upon due to the lack of a readily available source and heating, RBX crystals did not undergo any process. Recently the bioethanol industry has polymorphic transition, based on the short begun to diversify its feedstocks and in turn has spacings at ~ 4.16 and ~ 3.73 Å, indicative of an increased its use of grain sorghum. This has orthorhombic subcell, and d001 long spacing at created opportunities to collect the sorghum wax 74–76 Å that persisted until RBX fusion. This long resulting from bioethanol production resulting in spacing was ascribed to the presence of wax several millions of pounds potentially available esters consisting of long chain saturated fatty for use. Efficient wax isolation methods that can acids (C24 and C22) esterified to C28–C34 be performed without affecting ethanol saturated fatty alcohols. During cooling from 90 production are under development. Significant to 20°C, the increase in oleogel viscosity resulting sorghum wax quantities are now accessible for from the RBX liquid-solid phase transition was sampling to industrial evaluators with the goal of corroborated by the DSC-based crystallization identifying uses for a domestic natural wax onset and enthalpy data. Similarly, elastic moduli product that increases the value of grain and hardness both rose with increasing RBX sorghum for both the bioethanol producers and concentration. This study, which demonstrated sorghum farmers. that RBX can structure RBO with distinct concentration-dependent properties, serves as the foundation for the development of oleogel-

– 18 – ABSTRACTS 2018 AOCS ANNUAL MEETING AND EXPO May 6–9, 2018 based approaches to saturated and trans fats of these mixtures. Here, we propose using Multi- replacement in processed foods. Speckle Diffusing Wave Spectroscopy (MS-DWS) as a method to monitor the phase change Phase Change Analysis of Waxes and Wax profiles of these mixtures during heating and Blends by Thermal Microstructure Evolution cooling ramps. This technology utilizes a light 1 Analysis Matt Vanden Eynden* , Roland scattering method on bulk samples in order to 2 2 2 Ramsch , Giovanni Brambilla , Pascal Bru , and monitor the microstructure evolution of the Gerard Meunier2, 1Formulaction, Inc., USA; crystal structures within the wax formulations. 2Formulaction, France This is accomplished by correlating Brownian Different raw wax materials clearly have motion of particles during a phase change event different melting and crystallization profiles to crystal structure evolution. Specifically, varying which can make the formulation of wax blends cooling profiles of select Beeswax and Candelilla difficult in regards to achieving a homogeneous blends will be shown as they are monitored for crystal structure. In addition to the raw content, variances in crystallization structure profiles. This heating and cooling types and rates will also have will allow for facile analysis of wax blending an influence of the resulting mixture. To analyze formulations as well as to assess the raw material this, an accurate, reproducible method must be quality of the waxes. employed to effectively measure the T50 profiles

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IOP-P: Industrial Oil Products Poster Session Chair: Jerry W. King, Critical Fluid Symposia, USA

1. Polyol and Polyurethane Prepared from 2. An Emerging Natural Wax: Sorghum Rubber Seed Oil by Hydroformylation. Wax from Bioethanol Production. Jian Hong1, Xiao-Qin Yang2, Xianmei Wan3, Jeffrey T. Cafmeyer, Battelle, USA Zhifeng Zheng2, and Zoran Petrovic3, 1Kansas Wax from grain sorghum has long been Polymer Research Center, Pittsburg State suggested as a potential alternative to high- University, USA; 2Southwest Forestry University, melting, high-hardness natural waxes such as 3 China; Pittsburg State University, USA carnauba. However, the uses and potential of Renewable raw materials are being sorghum wax have remained largely unexplored increasingly used to satisfy the quest for due to the lack of a readily available source and sustainability and environmental concerns. In the process. Recently the bioethanol industry has search for new vegetable oils as platform for new begun to diversify its feedstocks and in turn has polymers, rubber seed oil (RSO) was relatively increased its use of grain sorghum. This has little investigated. High free fatty acid content of created opportunities to collect the sorghum wax 13% in crude RSO is impediment for many resulting from bioethanol production resulting in applications including biodiesel, but can be several millions of pounds potentially available beneficial when strong bonding with substrate for use. Efficient wax isolation methods that can is desired. RSO was used to prepare a polyol via be performed without affecting ethanol hydroformylation/hydrogenation. The polyol production are under development. Significant had hydroxyl number 244 mg KOH/g and acid sorghum wax quantities are now accessible for number of 21 mg KOH/g. The polyurethane sampling to industrial evaluators with the goal of prepared from this polyol and diphenylmethane identifying uses for a domestic natural wax diisocyanate was highly crosslinked with gel product that increases the value of grain content of 98.1% and 50% swelling degree of sorghum for both the bioethanol producers and toluene. It was a tough plastics at room sorghum farmers. temperature (Tg: 44°C) with tensile strength of 25.4 MPa, and elongation 16.7%. When 3. Soy-based Polyester Polyols for Flexible used as wood adhesive, it displayed Polyurethane Foams and Elastomers. Dragana extraordinary shear strength characterized Radojcic and Mihail Ionescu, Pittsburg State by substrate wood failure at 7.3 MPa rather than University, USA the adhesive bond. The objective of this work was synthesis of new polyols with high renewable content suitable for preparation of elastic polyurethanes (flexible foams and cast elastomers). Most

– 20 – ABSTRACTS 2018 AOCS ANNUAL MEETING AND EXPO May 6–9, 2018 commonly, polyester polyols for flexible development of polyols derived from renewable polyurethanes are prepared by polyesterification resources. These intermediates can then be used of diacids with diols using trimethylopropane for the production of a broad range of polymers. as starter. A new family of polyester polyols Polyurethanes are of particular interest because from soybean oil is described, synthesized by of their wide use and excellent physical and polyesterification of hydroxyacids, or of diacids mechanical properties. One potential drawback with glycols, initiated by soy polyols; or by ring for vegetable oil-based polyols, when substituted opening addition of cyclic esters to the hydroxyl for petroleum-based polyols, is their naturally groups of soybean polyols. Two different heterogeneous composition which greatly soy based polyols were used as starters: impacts the properties of the resulting hydroformylated soybean oil, having all primary polyurethanes. Algae, as a promising renewable hydroxyl groups and hydroxyl number of source, can be manipulated by both classical and around 220 mg KOH/g; and soybean oil polyol genetic means to provide oleochemicals with synthesized from epoxidized soybean oil by ring narrowly defined compositions and, hence, opening of epoxy groups with methanol, having facilitate the production of polymers with highly all secondary hydroxyl groups and hydroxyl predictable structures and performance. The number of around 170 mg KOH/g. Polyesteri- primary objective of this work is to develop algal fication was performed with petrochemical oil-based polyurethane foams with compression monomers: adipic acid and diethylene glycol, as strengths comparable to current petroleum- well as with ricinoleic acid, a bio-based hydroxy based materials. For the work reported here, acid. ε-Caprolacton was used as ring opening our efforts have focused on exploring the polymerization monomer. Final polyester polyols preparation of both low and high density having hydroxyl numbers from 45 to 75 mg polyurethane foams from algal oil-based polyols. KOH/g, by reaction with commercial diphenyl- methane diisocyanate, were transformed to 5. Study of Physical and Tribology Properties of cast polyurethane elastomers and flexible Soybean Oil-based Grease Formulated with polyurethane foams with physical-mechanical Polysoap. Zengshe Liu1, Girma Biresaw1, Atanu properties comparable to the petroleum-based Biswas1, and H.N. Cheng2, 1Food and Industrial Oil reference. Research, NCAUR, ARS/USDA, USA; 2SRRC/ARS/USDA, USA 4. Algal Oil Derived Polyurethane Foams. Soybean oil‐based grease formulated with Olivera Bilic1, Zoran Petrovic2, Ivan Javni2, Milica polysoaps, which was synthesized from polymeric Lovric2, and Scott Franklin3, 1Kansas Polymer epoxdized soybean oil, were investigated. 2 Research Center/PSU, USA; Pittsburg State Greases were prepared using a mixture of lithium 3 University, USA; Checkerspot, Inc., USA soap and triethanolammonium polysoap. Grease As pressure continues to mount for materials properties investigated were: hardness, using that reduce environmental impact, while cone penetration procedure (ASTM D217); retaining performance properties, intensive oxidation stability, using the pressurized research efforts have focused on the

– 21 – ABSTRACTS 2018 AOCS ANNUAL MEETING AND EXPO May 6–9, 2018 differential scanning calorimetry (PDSC) method and thermal stability were measured. Number (ASTM D-5483); friction and wear, using 4-ball average molecular weights ranged from 11–45 tribometer (ASTM D-2266). Penetration data kDa, melting points were 25 Celsius or greater, showed that grease formulated in the presence crystallization onset temperatures ranged from of polysoap was harder than that without –15 to 55 Celsius, glass transitions varied from polysoap, and this was attributed to the cross- –26 to 17 Celsius, and thermal stabilities were linking in the polysoap structure which was greater than 330 Celsius (temperature expected to provide higher resistance to corresponding to 10% mass loss by DSC). deformation. PDSC results indicated that the onset temperature of grease formulated with Determination of mechanical properties such 3.8 wt% and 7.3 wt% polysoap increased by as tensile strength and Young’s modulus are 8°C and 12°C, respectively, compared to grease planned for future studies. In summary, thiol-ene without polysoap. The coefficient of friction chemistry is a useful tool for rapid production of of grease formulated with polysoap was renewable polymers utilizing mild, solventless much lower (0.015) than grease without reaction conditions. polysoap (0.034). 7. Chemometric Comparison of Neutral Lipids 6. Copolymers from Photochemical Thiol-ene in Camellia Oil with Other Cooking oils. Ling Polycondensation of Fatty Dienes with Alkyl Peng, Chi Chen, and Yiwei Ma, University of Dithiols. Bryan R. Moser, USDA Agricultural Minnesota, USA Research Service, USA Camellia oil, or tea seed oil, is widely used in Photochemical thiol-ene polycondensation Asian countries as a cooking oil due to its high of unsaturated monomers based on renewable flash point and its favorable properties in color, 9-decenoic acid with various alkyl dithiols readily odor, and flavor. It has also been used in dietary afforded copolymers in high yield. Monomers supplement and skin care products for its diverse were prepared by acid-catalyzed condensation of bioactive components. The fatty acid profile of 9-decenoic acid with diols such as ethylene hydrolyzed Camellia oil has been examined in glycol, 1,2-propylene glycol, 1,3-propanediol, previous studies, but the composition of intact 1,4-butanediol, neopentyl glycol, 1,4- lipids in Camellia oil has not been reported. In cyclohexanedimethanol, 9-decenol, and this study, the profile of triacylglycerols (TAG) in 2-allyloxyethanol to give fatty dienoic esters. Camellia oil was compared with other common These dienes were then polymerized with cooking oils, including olive, safflower, peanut, 1,2-ethanedithiol, 1,3-propanedithiol and canola, soybean, corn, grapeseed, palm and 1,4-butanedithiol in the presence of catalytic coconut oils, through the liquid chromatography- 2,2-dimethoxy-2-phenylacetophenone as mass spectrometry (LC-MS) analysis and photoinitiator to afford a family twelve novel multivariate modeling. The distribution of all linear copolymers. Physical properties such as examined oils in the principal components molecular weight, polydispersity index, degree of analysis (PCA) model suggested that the polymerization, glass transition temperature, composition of neutral lipids in Camellia oil is melting point, crystallization onset temperature, much more similar to olive oil than other cooking

– 22 – ABSTRACTS 2018 AOCS ANNUAL MEETING AND EXPO May 6–9, 2018 oils. However, subtle differences in TAG profile fresh bran) compared to those of hexane (~11%) exist between Camellia oil and olive oil. Camellia because additional materials were extracted. For oil has more TAG(18:1/18:1/18:1) (triolein), while both solvents, the traditional single-step olive oil has more saturated fatty acid-containing extraction resulted in a mixture of ~80% oil and TAG species, including TAG(16:0/18:1/18:1), ~14% waxes. The two-step, dual-temperature TAG(16:0/18:0/18:1), and TAG(18:0/18:1/18:1). fractionation resulted in predominantly oils in the The ratio between these two groups of TAG first pass (~95%) for both solvents. For hexane, species could be used as an indicator to primarily waxes (~67%) were extracted in the distinguish Camellia oil and olive oil. second pass. For ethanol, the second pass resulted in a mixture of oils (46%), waxes (37%), 8. Two-Step Temperature Extraction for the and other unidentified materials (17%). Separation of Waxes and Oil in Sorghum Bran. Robert A. Moreau and Megan E. Hums*, USDA, 9. Free Fatty Acid Generation during Dry-grind ARS, ERRC, USA Corn Ethanol Fermentation. Brett Brothers, Tong Grain sorghum is primarily used for animal Wang, and Hui Wang, Iowa State University, USA feed and ethanol production but has the The fermentation of corn into ethanol is a potential of providing value-added co-products major usage of the American-grown corn crop. such as waxes and oil. The surface of sorghum During the process of corn to ethanol, corn lipid contains 0.1–0.4% w/w wax; however, extraction class composition changes. The formation of free of wax prior to fermentation may not be fatty acid (FFA) from triacylglycerol is commonly economical. An alternative method for wax and observed. Increased free fatty acid fermentation oil extraction could occur through decortication, byproducts results in troublesome processing to abrasion of the surface to remove bran (pericarp remove excess FFA. The objective of this work and germ). Decortication can increase the starch was to determine where in the process of corn to content of decorticated sorghum, thereby ethanol FFA is generated using both industrial improving ethanol yields, while concentrating and laboratory-scale approaches. Specific wax and oil to the separated bran. Typically oil commercial and conditions steps in the process and waxes are extracted from bran in a single of corn to ethanol were tested to determine their extraction and then waxes are separated from oil role in the generation of FFA. Thin-layer via winterization. The aim of this research was to chromatography (TLC) and gas chromatography compare the traditional fractionation to a two- was used to quantify FFA in extracted total lipids. step, dual-temperature extraction for the FFA assay by titration was also used for fractionation of oil (triacylglycerols) and waxes by quantification to compare to TLC-based methods. first extracting oil at room temperature and then Results indicate generation may be due to waxes with a second higher temperature incremental increases at each step in the process, extraction. Extractions were performed using an not due to one specific processing step. accelerated solvent extractor at 1000 psi using Furthermore, laboratory-based fermentations hexane or ethanol as a solvent. Ethanol indicate the possible oxidation of linoleic acid, extraction resulted in higher yields (~15% w/w particularly in the FFA fraction, in corn may

– 23 – ABSTRACTS 2018 AOCS ANNUAL MEETING AND EXPO May 6–9, 2018 increase% FFA determined using titration based distance between the molecules stretches methods. Overall FFA generation is seen beyond the critical molecular distance, which is throughout the entire process of corn to ethanol, necessary to hold the liquid intact, the liquid will and this trend also agrees with the increased FFA be broken down and voids (cavities) will be levels in industrial samples observed in multiple created, which is known as cavitation bubbles. ethanol plants and studies. It shows that the initial conversion rate is about 50 times higher under ultrasounds than in the 10. Extraction and Characterization of Passion purely catalytic system whether or not solvent Fruit and Guava Oils from Industrial Residual was added. Performing this reaction under Seeds and Their Application as Biofuels. Paulo ultrasounds will therefore have important A.Z. Suarez, University of Brazil, Brazil consequences for future developments of this A great diversity of fruits is used in the food industrial process. industry to obtain different products such as juices, sauces, and foods. However, the food industry produces high amounts of residues. Passion fruit and guava are worldwide known fruits and very used by the food industry and generate tons of seed as residue. This work aims to study the extraction of oils from passion fruit and guava juice industries residues, their characterization and potential application as raw materials to obtain biodiesel and bio-oil. The passion fruit and guava seed oils content were 25% and 9%, respectively. In both oils, polyunsaturated fatty acids are predominant. Biodiesel obtained by esterification/ transesterification of both seed oils match most of the parameters specified for biodiesel in Brazil. Bio-oils obtained by thermal cracking of the seed oils were mainly composed by hydrocarbons similar to those observed in petroleum diesel.

11. Glycerolysis Reaction Under Ultrasound. Kiran Shinde and Atul Deshmane, Whole Energy Fuels Corp., USA Triglyceride transesterification reaction by small alcohol such as glycerol is used to illustrate the significance of cavitation in ultrasound assisted reactions. When a large negative pressure gradient is applied to the liquid, the

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