Modified Soybean Oil Research Articles

Biodegradation of polyurethane acrylate with acrylated epoxidized soybean oil blend elastomers by Chaetomium globosum

This paper studies the biodegradation features of a novel blend of polyurethane acrylate–acrylated epoxidized soybean oil-based cross-linked polyurethane elastomers in the presence of the soft-rot fungus Chaetomium globosum. After the specimens were incubated at 28 °C for 90 and 130 days, the degree of fungal damage was measured by analysis of weight loss and mechanical properties. The biodegradation of the films was also evidenced by SEM and FTIR spectroscopic studies. After fungal attack, the FTIR spectra indicate a degradation of urethane and ester groups of the polyurethane and especially of the ester groups from the modified soybean oil part. The polyurethane blend films exposed to fungal attack suffered a loss in strength of up to 55% and a loss in elongation of up to 80%, depending on the content of acrylated epoxidized soybean oil. The biodegradation of the blends was also confirmed by SEM analyses. The biodegradation results show that samples with a high content of acrylated epoxidized soybean oil are more biodegradable than mere polyurethane acrylate. These biodegradable polymer blends present an optimum balance of physical properties and biodegradable properties with the potential for application as eco-friendly biomaterials.

Purification of Stearidonic Acid from Modified Soybean Oil by Argentation Silica Gel Column Chromatography

AbstractThe objective of this study was to purify stearidonic acid (SDA, 18:4 ω‐3) from modified soybean oil containing a mixture of over 20 fatty acids (23% SDA). Interest in obtaining purified fractions of SDA arises from reported health benefits associated with polyunsaturated fatty acids (PUFA), such as cardiovascular disease prevention. In addition, SDA may also provide improved stability characteristics since its unsaturation index is less than longer PUFA, such as eicosapentaenoic acid (EPA, 20:5 ω‐3). First, a chemical ethanolysis of modified soybean oil was performed to transform the triacylglycerols into fatty acid ethyl esters (FAEE). Then, the FAEE were fractionated and SDA‐EE was purified by argentation silica gel (10% AgNO3) open column chromatography, which allows selectivity based on degree of unsaturation. Different FAEE sample loads and mobile phases were explored until the best purification of SDA‐EE was achieved. The solvents used were hexane and hexane:acetone mixtures (99 and 95%). Under the optimal conditions, a fraction with high SDA‐EE purity (96%) was obtained with 77% yield. Besides, it was possible to obtain another fraction enriched in α‐linolenic acid‐EE (37% purity and 68% yield) and γ‐linolenic acid‐EE (22% purity and 61% yield). A scaled‐up process resulted in 840 mg of final product composed of 97% SDA‐EE with 71% yield.

Biobased composites prepared by compression molding with a novel thermoset resin from soybean oil and a natural‐fiber reinforcement

AbstractBiobased composites were manufactured with a compression‐molding technique. Novel thermoset resins from soybean oil were used as a matrix, and flax fibers were used as reinforcements. The air‐laid fibers were stacked randomly, the woven fabrics were stacked crosswise (0/90°), and impregnation was performed manually. The fiber/resin ratio was 60 : 40. The prepared biobased composites were characterized by impact and flexural testing. Scanning electron microscopy of knife‐cut cross sections of the specimens was also done to investigate the fiber–matrix interface. Thermogravimetric analysis of the composites was carried out to provide indications of thermal stability. Three resins from soybean oil [methacrylated soybean oil, methacrylic anhydride modified soybean oil (MMSO), and acetic anhydride modified soybean oil] were used as matrices. The impact strength of the composites with MMSO resin reinforced with air‐laid flax fibers was 24 kJ/m2, whereas that of the MMSO resin reinforced with woven flax fabric was between 24 and 29 kJ/m2. The flexural strength of the MMSO resin reinforced with air‐laid flax fibers was between 83 and 118 MPa, and the flexural modulus was between 4 and 6 GPa, whereas the flexural strength of the MMSO resin reinforced with woven fabric was between 90 and 110 MPa, and the flexural modulus was between 4.87 and 6.1 GPa. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010

Synthesis and application of modified vegetable oils in water-repellent finishing of cotton fabrics

Abstract Fluorine containing water-repellent agents—fatty acid trifluoroethyl esters were prepared by modification of different vegetable oils—castor oil, palm oil, and soybean oil via a reaction of hydrolysate of vegetable oil with 2,2,2-trifluoro ethanol. The structures of the modified vegetable oils were characterized by FT-IR. With contact angle, time for water to disappear, whiteness, and breaking strength as indicators, the optimum finishing processes of cotton fabrics with each modified vegetable oil were studied. The results showed that the cotton fabrics treated with the modified vegetable oils demonstrated excellent water repellency, while the whiteness and breaking strength of the fabrics reduced a little. The fabrics treated with modified palm oil exhibited the highest water repellency among all treated fabrics. All the treated fabrics showed good durability of water repellency after 5 cycles of washing, the contact angle remained about 90° or even higher, among which the durability of fabric treated with modified soybean oil was the best.

Synthesis of reactive soybean oils for use as a biobased thermoset resins in structural natural fiber composites

AbstractBiobased thermosets resins were synthesized by functionalizing the triglycerides of epoxidized soybean oil with methacrylic acid, acetyl anhydride, and methacrylic anhydride. The obtained resins were characterized with FTIR, 1H‐NMR, and 13C‐NMR spectroscopy to confirm the functionalization reactions and the extent of epoxy conversion. The viscosities of the methacrylated soybean oil resins were also measured for the purpose of being used as a matrix in composite applications. The cross‐linking capability was estimated by UV and thermally initiated curing experiments, and by DSC analysis regarding the degree of crosslinking. The modifications were successful because up to 97% conversion of epoxy group were achieved leaving only 2.2% of unreacted epoxy groups, which was confirmed by 1H‐NMR. The 13C‐NMR confirms the ratio of acetate to methacrylate methyl group to be 1 : 1. The viscosities of the methacrylated soybean oil (MSO) and methacrylic anhydride modified soybean oil (MMSO) were 0.2 and 0.48 Pas, respectively, which indicates that they can be used in resin transfer molding process. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010

Preparation of thermoset composites from natural fibres and acrylate modified soybean oil resins

AbstractStructural composites with a high content of renewable material were produced from natural fibres and an acrylated epoxidized soybean oil resin. Composites were prepared by spray impregnation followed by compression moulding at elevated temperature. The resulting composites had good mechanical properties in terms of tensile strength and flexural strength. Tensile testing as well as dynamical mechanical thermal analysis showed that increasing the fibre content, increased the mechanical properties. The resin can be reinforced with up to 70 wt % fibre without sacrifice in processability. The tensile modulus ranged between 5.8 and 9.7 GPa depending on the type of fibre mat. The study of the adhesion by low vacuum scanning electron microscopy shows that the fibres are well impregnated in the matrix. The aging properties were finally evaluated. This study shows that composites with a very high content of renewable constituents can be produced from soy bean oil resins and natural fibres. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Lubricant Base Stock Potential of Chemically Modified Vegetable Oils

The environment must be protected against pollution caused by lubricants based on petroleum oils. The pollution problem is so severe that approximately 50% of all lubricants sold worldwide end up in the environment via volatility, spills, or total loss applications. This threat to the environment can be avoided by either preventing undesirable losses, reclaiming and recycling mineral oil lubricants, or using environmentally friendly lubricants. Vegetable oils are recognized as rapidly biodegradable and are thus promising candidates as base fluids in environment friendly lubricants. Lubricants based on vegetable oils display excellent tribological properties, high viscosity indices, and flash points. To compete with mineral-oil-based lubricants, some of their inherent disadvantages, such as poor oxidation and low-temperature stability, must be corrected. One way to address these problems is chemical modification of vegetable oils at the sites of unsaturation. After a one-step chemical modification, the chemically modified soybean oil derivatives were studied for thermo-oxidative stability using pressurized differential scanning calorimetry and a thin-film micro-oxidation test, low-temperature fluid properties using pour-point measurements, and friction-wear properties using four-ball and ball-on-disk configurations. The lubricants formulated with chemically modified soybean oil derivatives exhibit superior low-temperature flow properties, improved thermo-oxidative stability, and better friction and wear properties. The chemically modified soybean oil derivatives having diester substitution at the sites of unsaturation have potential in the formulation of industrial lubricants.

Novel modified soybean oil containing hydrazino-ester: synthesis and characterization

A novel synthetic approach for chemical modification of vegetable oils is presented. The structural modification is carried out using diethyl azodicarboxylate (DEAD) in the absence of catalyst and solvent. In a microwave oven the reaction can be achieved in 5–15 minutes. The reaction can also proceed using conventional heat, albeit for a longer time. The products are characterized by 1H, 13C, and two-dimensional NMR.

Novel soybean oils with different fatty acid profiles alter cardiovascular disease risk factors in moderately hyperlipidemic subjects

A variety of soybean oils were developed with improved oxidative stability and functional characteristics for use as alternatives to partially hydrogenated fat. The objective was to assess the effect of selectively bred and genetically modified soybean oils with altered fatty acid profiles, relative to common soybean and partially hydrogenated soybean oils, on cardiovascular disease risk factors. Thirty subjects (16 women and 14 men) aged >50 y with LDL-cholesterol concentrations >130 mg/dL at screening consumed 5 experimental diets in random order for 35 d each. Diets contained the same foods and provided 30% of energy as fat, of which two-thirds was either soybean oil (SO), low-saturated fatty acid soybean oil (LoSFA-SO), high-oleic acid soybean oil (HiOleic-SO), low-alpha-linolenic acid soybean oil (LoALA-SO), or partially hydrogenated soybean oil (Hydrog-SO). Plasma phospholipid patterns reflected the predominant fat in the diet. LDL-cholesterol concentrations were 3.66 +/- 0.67(b), 3.53 +/- 0.77(b), 3.70 +/- 0.66(b), 3.71 +/- 0.64(a,b), and 3.92 +/- 0.70(a) mol/L; HDL-cholesterol concentrations were 1.32 +/- 0.32(a,b), 1.32 +/- 0.35(b), 1.36 +/- 0.33(a), 1.32 +/- 0.33(b), and 1.32 +/- 0.32(a,b) mol/L for the SO, LoSFA-SO, HiOleic-SO, LoALA-SO, and Hydrog-SO diets, respectively (values with different superscript letters are significantly different, P < 0.05). No significant effects were observed on VLDL-cholesterol, triacylglycerol, lipoprotein(a), and C-reactive protein concentrations or on ratios of LDL cholesterol to apolipoprotein B (apo B) and HDL cholesterol to apo A-I. Total cholesterol:HDL cholesterol was lower after subjects consumed the unhydrogenated soybean oils than after they consumed the Hydrog-SO diet. All varieties of soybean oils resulted in more favorable lipoprotein profiles than did the partially hydrogenated form. These soybean oils may provide a viable option for reformulation of products to reduce the content of trans fatty acids.

Temperature‐dependent kinematic viscosity of selected biodiesel fuels and blends with diesel fuel

AbstractThe kinematic viscosities of four biodiesel fuels—two natural soybean oil methyl esters, one genetically modified soybean oil methyl ester, and one yellow grease methyl ester—and their 75, 50, and 25% blends with No. 2 diesel fuel were measured in the temperature range from 20 to 100°C in steps of 20°C. The measurements indicated that all these fuels had viscosity‐temperature relationships similar to No. 2 diesel fuel, which followed the Vogel equation as expected. A weighted semilog blending equation was developed in which the mass‐based kinematic viscosity of the individual components was used to compute the mixture viscosity. A weight factor of 1.08 was applied to biodiesel fuel to account for its effect on the mixture viscosity. The average absolute deviation achieved with this method was 2.1%, which was better than the uncorrected mass average blending equation that had an average absolute deviation of 4.5%. The relationship between the viscosity and the specific gravity of biodiesel fuels was studied. A method that could estimate the viscosity from the specific gravity of biodiesel fuel was developed. The average absolute deviation for all the samples using this method was 2.7%. The accuracy of this method was comparable to the weighted mass‐based semilog blending equation.

Mechanical properties of glass/flax hybrid composites based on a novel modified soybean oil matrix material

In the Affordable Composites from Renewable Resources (ACRES) program at the University of Delaware, soybean oil and other plant triglycerides have been made amenable to polymerization using a broad range of chemical routes. The resultant polymers range in properties from soft rubbers to hard thermosets for composite applications. In this paper we present an investigation of the mechanical properties of glass/flax hybrid composites based on these thermoset matrix materials. Composites with different glass/flax ratios and different fiber arrangements were made using a modified soybean oil matrix material. The fiber arrangement was varied to make symmetric and unsymmetric composites. The latter were tested in different modes in flexural tests and drop weight impact tests. The mechanical properties of the composites were found to depend upon the glass/flax ratio and the arrangement of fibers in the composite. On proper selection of the arrangement of fibers in the composite, the glass fibers and flax fibers were found to act synergistically resulting in an improved flexural and impact performance. POLYM. COMPOS., 26:407–416, 2005. © 2005 Society of Plastics Engineers

Low Dielectric Constant Material from Hollow Fibers and Plant Oil

A new low dielectric constant (k) material suited to electronic materials applications was developed using hollow keratin fibers (HF) and chemically modified soybean oil. High-speed microelectronics is facilitated by preventing the “rubber necking,” or slow-down of electrons on the printed wires through the use of low-k dielectrics. The unusual low-k value of the HF composite material derives both from the air (k = 1) in the hollow microcrystalline keratin fibers (k = 1.7), and the triglyceride molecules (k = 2.7), and is in the range of 1.7 to 2.7, depending on the HF fraction. These values are lower than that of the conventional silicon dioxide (k = 3.8 to 4.2) or epoxy dielectric insulators. Also, the HF dielectric is lightweight (SG < 1) and rigid (Modulus > 2 GPa), with fracture toughness (1.0 MPa m1/2) and approximates the shape and feel of a silicon dioxide insulator. The coefficient of thermal expansion (CTE) of the new material (67.4 ppm/°C) is low enough for electronic materials applications. Multi-Chip-Module circuit printing results suggest that the low-cost composite made with HF (from avian sources) and plant oil (from soybean) has the potential to replace the dielectrics in microchips and circuits boards in the ever-growing electronic materials field, in addition to many applications as new lightweight composite material.

Tribological studies of thermally and chemically modified vegetable oils for use as environmentally friendly lubricants

Boundary lubrication in a dynamic mechanical system is primarily governed by the formation of a stable tribochemical film. Polar functional groups in the triacylglycerol molecule of vegetable oil in conjunction with oil–additive–metal interaction during the metal rubbing process can significantly improve the wear resistance and extreme-pressure lubrication. Increasing the polar functionality of vegetable oil structure has a positive impact on wear protection resulting from stronger adsorption on metal surface as well as greater lateral interaction between the ester chains. The results reveal that ester groups of triacylglycerol molecule react with phosphate groups to form a protective fatty-phosphite layer. Antimony impregnation into the metal surface following strong complexation reaction with metal sulfide results in significant improvement in extreme-pressure characteristics due to alteration in surface metallurgy. In this case, seizure is averted even when the fluid adsorbed layer and phosphite coating is removed because of antimony induced surface hardness. The difference can be observed by analyzing the metal surface using scanning electron microscope (SEM). Selected bio fluids viz. soybean oil (SBO), thermally modified soybean oil (TMSBO) and chemically modified soybean oil (CMSBO) were investigated for potential application as industrial fluids.

Emulsions containing vegetable oils for cutting fluid application

Emulsions of vegetable oils were prepared using ionic and non-ionic surfactants for use as metal working fluids. The conditions for an enhanced mutual miscibility for soybean oil or modified soybean oil and water were investigated to prepare emulsions for vegetable oil-based components. Oil modification was achieved using ozonation and sulfurization reactions. The products were characterized using Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR). The viscosities of the modified oil were considerably higher than the starting oil. The emulsions were obtained with the aid of three different surface-active agents at room temperature. The stability and efficiency of these emulsions were evaluated. These emulsions also showed good stability and anticorrosion properties. The phase behavior was evaluated using phase diagrams. Cryo-scanning electron microscopy (cryo-SEM) was used in describing the oil–water interaction during the emulsion formation. It was found that the phase behavior was dependent on the nature and the concentration of surfactant used. Modified soybean oil required comparatively increased amounts of surfactant than the regular oil to obtain a stable emulsion.

Effect of genetic modification on the distribution of minor constituents in canola oil

AbstractOil derived from different lines of genetically modified canola varieties was analyzed for phospholipids, tocopherols, and phytosterols by various chromatographic techniques. As observed previously in genetically modified soybean oils, there was a decrease in the content and composition of phosphatidic acid in three of the modified canola oils derived from the 12 varieties investigated. Normal‐phase high‐performance liquid chromatographic (HPLC) analyses showed small variations in the phospholipid content of major classes, despite few differences in their composition. Reversed‐phase HPLC data indicated that the molecular species distribution of phosphatidylethanolamine was significantly altered by genetic modification when compared to phosphatidylcholine. Impact of oilseed modification on the tocopherol content was variable, with greater variation in the concentration of α‐ and γ‐tocopherols than δ‐tocopherol. Phytosterol composition was markedly affected by genetic modification. Brassicasterol, campesterol, and β‐sitosterol levels were consistently lowered in one genotype, whereas increased brassicasterol content was observed in the other variety. In general, genetic modification of canola seeds led to changes in the distribution of phospholipids, tocopherols, and phytosterols.

Effect of interesterification on the structure and physical properties of high‐stearic acid soybean oils

AbstractTriglyceride structures of genetically modified soybean oils high in stearic acid were determined by high‐pressure liquid chromatography, and their physical properties were assessed by dilatometry and dropping point. In their natural state, these oils lack sufficient solids at 10–33°C to qualify as margarine oils. However, after random interesterification, soybean oil containing 17% stearic acid shows a solid fat index (SFI) profile and dropping point closely matching those of a liquid margarine oil. Other oils, with stearic acid contents in the range of 20–33%, showed appreciable SFI values at 10°C but lacked sufficient solids at 21.1–33.3°C. After random interesterification, these oils also exhibited SFI profiles suitable for soft tub margarine, and their drop points increased from 18–19°C to 36–38°C.

Correlation of reversed-phase high-performance liquid chromatography and gas—liquid chromatography for fatty acid compositions of some vegetable oils

The triacylglycerol compositions of six genetically modified soybean oils, and commercial soybean, corn, safflower and sunflower oils were determined by reversed-phase high-performance liquid chromatography with flame ionization detection. Triacylgylcerol molecular species were identified based on theoretical carbon numbers. Fatty acid compositions of the above soybean oils were estimated from concentrations of the triacylglycerol molecular species. Fatty acid composition was calculated by multiplying the concentration of each triacylglycerol by the percent of each fatty acid species in the triacylglycerol molecule. The fatty acid composition calculated from triacylglycerol analysis was compared with the composition determined by gas—liquid chromatography. There was good agreement between the fatty acid composition as calculated from the high-performance liquid chromatographic data and as determined by gas—liquid chromatography. These results support the findings that triacylglycerol molecular species could be identified based on theoretical carbon numbers and that fatty acid composition of soybean oil can be obtained from the data of reversed-phase high-performance liquid chromatography with flame ionization detection. The triacylglycerol composition for soybean oil obtained by this procedure required no response factors for quantitation.