The preparation and purification of monoglycerides

Mono- and diglycerides were produced by reacting the following oils with glycerol: coconut, peanut, sesame, linseed, and sardine. It was shown that the yield of monoglyceride was not dependent upon the fatty acid composition of the oil but on the solubility of glycerol in oil, which is dependent in part on the temperature. An excess of glycerol above that which is soluble does not change the composition of the reaction product. At 180°C, no more than 45% monoglycerides can be formed by glycerolysis. Presented at the 51st annual spring meeting, Dallas, Texas, April 4–6, 1960.     

Studies on the alcoholysis of some seed oils

The effects of time and temperature on the alcoholysis of rubber seed, melon seed, linseed, and soyabean oils have been studied. The following temperatures were investigated: 200, 220, 245, and 260°C. Litharge (PbO) was used as the alcoholysis catalyst. The optimum alcoholysis temperature was found to be 245 ± 2 °C for each of the oils. At lower alcoholysis temperatures (<245°C), there is the preferential alcoholysis of seed oils derived from unsaturated acid; and the general alcoholysis rates were found to be in the following order: linseed oil ≈ rubber seed oil ≥ soyabean oil ≈ melon seed oil. The alcohol‐solubility of the oils is generally observed to begin at 42–45% conversion of oils to monoglycerides. The α‐monoglyceride contents of the alcoholysis mixtures of rubber seed and linseed oils were generally similar at methanol tolerance, and higher than those of melon seed and soyabean oils. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1826–1832, 2000     

Correlating chemical structure and physical properties of vegetable oil esters

The influence of FA ester chemical structures on the rheology and crystallization temperature of those compounds was evaluated using methyl, n-butyl, n-octyl, and 2-ethyl-1-hexyl FA esters with different chain lengths and different degrees of unsaturation. The rheological properties were analyzed in a high-precision rheometer at various temperatures, and the crystallization temperatures were determined by DSC. Esters produced from the esterification of pure FA and from the transesterification of vegetable oils (i.e., soybean, corn, linseed, and babassu coconut oils) were evaluated. The length of the FA chain was shown to have a marked influence on the viscosity and crystallization temperature of the systems, whereas branching affected only the crystallization temperature to a significant extent. The viscosity and crystallization temperature of the systems were also influenced by the degree of unsaturation. One double bond was shown to increase viscosity, whereas two or three double bonds caused a decrease in the viscosity of the systems. Unsaturation lowered the crystallization temperature in all cases, regardless of the number of double bonds. From all the oils studied, methyl esters from babassu coconut oil presented the lowest crystallization temperatures.     

Performance of higher poly(alkyl lactate acrylate)s as viscosity modifiers in vegetable oils

Recently, bio-derived materials such as vegetable oils are significantly employed in lubricating oil formulations due to its high flash point, high lubricity, low evaporation loss, renewability, biodegradability, and eco-friendliness when compared to mineral oil. We investigated the performance of seven poly(alkyl lactate acrylate)s as viscosity modifiers in two vegetable oils, namely, coconut oil and sunflower oil, which differ in the percentage of polar compounds and degree of unsaturation. Poly(alkyl lactate acrylate)s having alkyl as hexyl to dodecyl group in different concentrations between 1 and 2 wt% were added to coconut and sunflower oil and parameters such as thickening power or Q factor, kinematic viscosity (μ), and viscosity index (VI) were calculated. The μ values at 40°C and 100°C of vegetable oils studied were lower than commercially available SAE20W40 engine oil, but the VI of coconut and sunflower oil was higher by about 22%. Value of Q factor higher than 1, indicated that these poly(alkyl lactate acrylate)s were VI improvers. VI increased with increase in the polymer concentration in both the vegetable oils. The length of the alkyl side chain of these polymers and the polarity of vegetable oil had predominant effect in determining the values of VI of vegetable oils. By using these polymer additives, VI was improved by 85.5% in coconut oil and by 61.7% in sunflower oil. Varying the concentration and alkyl group of these additives, one can largely modify the viscosity ranges enabling them to be used in different lubricating applications.     

Synthesis and properties of cross‐linked polymers from epoxidized rubber seed oil and triethylenetetramine

A series of epoxidized oils were prepared from rubber seed, soybean, jatropha, palm, and coconut oils. The epoxy content varied from 0.03 to 7.4 wt %, in accordance with the degree of unsaturation of the oils (lowest for coconut, highest for rubber seed oil). Bulk polymerization/curing of the epoxidized oils with triethylenetetramine (in the absence of a catalyst) was carried out in a batch setup (1 : 1 molar ratio of epoxide to primary amine groups, 100°C, 100 rpm, 30 min) followed by casting of the mixture in a steel mold (180°C, 200 bar, 21 h) and this resulted in cross‐linked resins. The effect of relevant pressing conditions such as time, temperature, pressure, and molar ratio of the epoxide and primary amine groups was investigated and modeled using multivariable nonlinear regression. Good agreement between experimental data and model were obtained. The rubber seed oil‐derived polymer has a T_g of 11.1°C, a tensile strength of 1.72 MPa, and strain at break of 182%. These values are slightly higher than for commercial epoxidized soybean oil (T_g of 6.9°C, tensile strength of 1.11 MPa, and strain at break of 145.7%). However, the comparison highlights the potential for these novel resins to be used at industrial/commercial level. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42591.     

Styrenation of castor oil and linseed oil by macromer method

In this study a novel macromer technique has been described for the styrenation of triglyceride oils. Macromers were prepared through the interesterification of castor oil with linseed oil followed by esterification with acrylic acid. In this preparation various castor oil/linseed oil ratios were applied to obtain a macromer which gave a copolymer with good film properties after copolymerization with styrene. Macromers were styrenated at 100°C using benzoyl peroxide as an initiator. The styrenation leads to improved film properties with the related interesterification product although castor oil is a non‐drying oil.     

Effect of oil unsaturation and wax composition on stability,properties and food applicability of oleogels

Oleogelation is emerging as one of the most exigent oil structuring technique. The main objective of this study was to formulate and characterize rice bran/sunflower wax-based oleogels using eight refined food grade oils such as sunflower oil, mustard oil, soybean oil, sesame oil, groundnut oil, rice bran oil, palm oil, and coconut oil. Stability and properties of these oleogels with respect to oil unsaturation and wax composition were explored. Sunflower wax exhibited excellent gelation ability even at 1%–1.5% (w/v) concentration compared to rice bran wax (8%–10% w/v). As the oleogelator concentration increased, peak melting temperature also increased with increase in strength of oleogels as per rheological studies. X-ray diffraction and morphological studies revealed that oleogel microstructure has major influence of wax composition only. Sunflower wax oleogels unveiled rapid crystal formation with maximum oil binding capacity of 99.46% in highly unsaturated sunflower oil with maximum polyunsaturated fatty acid content. Further, the applicability of this wax based oleogels as solid fat substitute in marketed butter products was also scrutinized. The lowest value of solid fat content (SFC) in oleogel was 0.20% at 25°C, resembling closely with the marketed butter products. With increase in oil unsaturation, oleogels displayed remarkable reduction in SFC. Depending upon prerequisite, oleogel properties can be modulated by tuning wax type and oil unsaturation. In conclusion, this wax-based oleogel can be used as solid fat substitute in food products with extensive applications in other fields too.     

Fat splitting by the twitchell process at low temperature

Summary A study was made of the degree of splitting of coconut and soybean oils by the Twitchell process at 35±0.1°C. with no shaking or stirring, using an agent consisting mainly of tetrabutyl naphthalene sulfonic acid with water or dilute sulfuric acid. The degree of splitting was greater with sulfuric acid than with water. In general, the degree of splitting of soybean oil was greater when the sulfonic acid was dissolved in the oil layer than when it was in water. The reverse was true with coconut oil. Although addition of glycerol had no effect on the degree of splitting, addition of glacial acetic acid to the coconut oil system decreased fat splitting to a considerable extent. Addition of coconut fatty acids to the coconut oil system had little effect, but soybean fatty acids added to the soybean oil system markedly increased the degree of splitting. For the first time it has been demonstrated that, at 35±0.1°C., splitting of a fat by the Twitchell process occurs in a stepwise way. Coconut oil in contact with 1N sulfuric acid containing the sulfonic acid, corresponding to 1% by the weight of the oil, was about 90% split in 15 to 30 days, depending on the area of contact of the two layers. The diglyceride concentration reached a maximum during the early days of the reaction and then decreased somewhat. Monoglyceride concentration appeared to reach a maximum more slowly and then continued at that level as the concentrations of free fatty acids and glycerol steadily increased. Presented at the symposia on fat of the Chemical Society of Japan, Nov. 10, 1954, and Nov. 8, 1955, Nagoya, Japan; and the 8th annual meeting of the Chemical Society of Japan, Apr. 2, 1955, Tokyo, Japan.     

Polymerization of linseed oil in an electric discharge

Summary The treatment of linseed oil by the action of electric discharges (voltolization) in a hydrogen atmosphere (80 mm. Hg, 70°C.) is described. It has been known for a long time that voltolization of linseed oil brings about a polymerization of the oil. Now it has been proven that the nature of the polymerization product thus obtained is absolutely different from that of thermally or catalytically polymerized linseed oils. In contrast to the latter, voltolized linseed oils contain only small amounts of cyclic compounds. Their viscosity is relatively low, even at a high polymerization degree, and considerably less than that of thermally polymerized oils of a corresponding degree of polymerization. Atomic hydrogen seems to play an important part in the voltolization process. Coupling of fatty acid chains is made possible by combining radicals, formed primarily by the action of hydrogen atoms. Coupling reaction occurs almost exclusively intermolecularly. The possibility of transforming linseed oil and other drying oils into polymerization products of a completely different chemical structure, depending on the applied polymerization process, opens new possibilities for their manufacture. Compare T. Hoekstra, Thesis, Delft 1958 (in Dutch).     

Melting behavior of blends of milk fat with hydrogenated coconut and cottonseed oils

The melting behavior of milk fat, hydrogenated coconut and cottonseed oils, and blends of these oils was examined by nuclear magnetic resonance (NMR) and differential scanning calorimetry (DSC). Solid fat profiles showed that the solid fat contents (SFC) of all blends were close to the weighted averages of the oil components at temperatures below 15°C. However, from 15 to 25°C, blends of milk fat with hydrogenated coconut oils exhibited SFC lower than those of the weighted averages of the oil components by up to 10% less solid fat. Also from 25 to 35°C, in blends of milk fat with hydrogenated cottonseed oils, the SFC were lower than the weighted averages of the original fats. DSC measurements gave higher SFC values than those by NMR. DSC analysis showed that the temperatures of crystallization peaks were lower than those of melting peaks for milk fat, hydrogenated coconut oil, and their blends, indicating that there was considerable hysteresis between the melting and cooling curves. The absence of strong eutectic effects in these blends suggested that blends of milk fat with these hydrogenated vegetable oils had compatible polymorphs in their solid phases. This allowed prediction of melting behavior of milk-fat blends with the above oils by simple arithmetic when the SFC of the individual oils and their interaction effects were considered.     

Cationically cured natural oil‐based green composites: Effect of the natural oil and the agricultural fiber

Green composites were produced from various cationically cured natural oil‐based resins and agricultural fibers. The natural oils and agricultural fibers of interest included corn, soybean, fish, and linseed oils and corn stover, wheat straw (WS), and switchgrass fibers. The effects of the types of natural oil and agricultural fiber on the structure and thermal and mechanical properties of the composites were studied using Soxhlet extraction, thermogravimetric and dynamic mechanical analysis, and tensile testing. The green composites, with agricultural fiber loadings of 75 wt %, have thermal stabilities up to 275°C. The Young's moduli and tensile strengths of the composites ranged from 1590 to 2300 and 5.5 to 11.3 MPa, respectively. In general, an increase in the degree of unsaturation of the natural oil resulted in improvements in the thermal and mechanical properties of the composites. The WS fibers tended to give composites with the best thermal and mechanical properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Endogenous antioxidants and stability of sesame oil as affected by processing and storage

The effect of processing of coated and dehulled sesame seeds on the content of endogenous antioxidants, namely sesamin, sesamolin, and γ-tocopherol in hexane-extracted oils, was studied over 35 d of storage under Schaal oven test conditions at 65°C. Seeds examined were Egyptian coated (EC) and dehulled (ED) and Sudanese coated (SC) varieties. Processing conditions of raw (RW) seeds included roasting at 200°C for 20 min (R), steaming at 100°C for 20 min (S), roasting at 200°C for 15 min plus steaming for 7 min (RS) and microwaving at 2450 MHz for 15 min (M). The sesamin content in fresh oils from EC, ED, and SC raw seeds was 649, 610, and 580 mg/100 g oil, respectively. Corresponding values for the content of sesamolin in oils tested were 183, 168 and 349 mg/100 g oil, respectively. Meanwhile, the content of γ-tocopherol, the only tocopherol present in the oils, ranged from 330 to 387 mg/kg sample. The effect of processing on changes in the sesamin content in oils from coated seeds was low and generally did not exceed 20% of the original values. On the other hand, oils from dehulled seeds underwent a more pronounced decrease in their sesamin content than the oil from coated seeds after 35 d of storage at 65°C. The corresponding changes in sesamolin and γ-tocopherol contents were more drastic. The RS treatment, which would be the optimal to prepare sesame oil with better quality, was found to retain 86, 80 and 60% of the sesamin, sesamolin and γ-tocopherol, respectively, originally present in the seeds after the storage period. The loss in the content of endogenous antioxidants present in the oils paralleled an increase in their hexanal content.     

Synthesis of triglyceride estolides from lesquerella and castor oils

Triglyceride (TG) estolides were synthesized from the hydroxy moieties of lesquerella and castor oils with oleic acid. Complete esterification of the hydroxy oils was possible when a slight excess of oleic acid was employed (1 to 1.5 mole equivalents). The estolides could be formed in the absence of catalyst at 175 to 250°C under vacuum or a nitrogen atmosphere. The optimal reaction conditions were found to be under vacuum at 200°C for 12 h for lesquerella and 24 h for castor oil. The lesquerella esterification reaction was completed in half the time of the for castor and with lower equivalents of oleic acid due to the difunctional hydroxy nature of lesquerella TG compared to the trifunctional nature of castor TG. Interesterification or dehydration of the resulting estolides to conjugated FA was not a significant side reaction, with only a slight amount of dehydration occurring at the highest temperature studied, 250°C. Use of a mineral-or Lewis-acid catalyst increased the rate of TG-estolide formation at 75°C but resulted in the formation of a dark oil, and the reaction did not go to completion in 24 h. Estolide numbers (i.e., degree of estolide formation) for the reaction and characterization of the products were made by ¹H NMR and ¹³C NMR. The decrease in the hydroxy methine signal at 3.55 ppm was used to quantify the degree of esterification by comparing this integral to the integral of the alpha methylene protons on the glycerine at 4.28 and 4.13 ppm.     

Recovery of sterols as fatty acid steryl esters from waste material after purification of tocopherols

Tocopherols are purified industrially from soybean oil deodorizer distillate by a process comprising distillation and ethanol fractionation. The waste material after ethanol fractionation (TC waste) contains 75% sterols, but a purification process has not yet been developed. We thus attempted to purify sterols by a process including a lipase-catalyzed reaction. Candida rugosa lipase efficiently esterified sterols in TC waste with oleic acid (OA). After studying several factors affecting esterification, the reaction conditions were determined as follows: ratio of TC waste/OA, 1∶2 (wt/wt); water content, 30%; amount of lipase, 120 U/g-reaction mixture; temperature, 40°C. Under these conditions, the degree of esterification reached 82.7% after 24 h. FA steryl esters (steryl esters) in the oil layer were purified successfully by short-path distillation (purity, 94.9%; recovery, 73.1%). When sterols in TC waste were esterified with FFA originating from olive, soybean, rapeseed, safflower, sunflower, and linseed oils, the FA compositions of the steryl esters differed somewhat from those of the original oils: The content of saturated FA was lower and that of unsaturated FA was higher. The m.p. of the steryl esters synthesized (21.7–36.5°C) were remarkably low compared with those of the steryl esters purified from high-b.p. soybean oil deodorizer distillate substances (56.5°C; JAOCS 80, 341–346, 2003). The low-m.p. steryl esters were soluble in rapeseed oil even at a final concentration of 10%.     

Interaction Between Polar Components and the Degree of Unsaturation of Fatty Acids on the Oxidative Stability of Emulsions

Minor components (polar components) and the degree of unsaturation of the fatty acids are the main factors responsible for the oxidative stability of bulk oils and emulsions. The isolated effects of these two factors and their interaction were evaluated in oil–in-water emulsions stored at 32 °C. Samples of coconut, olive, soybean, linseed and fish oils, both full and stripped of their polar components, were used to prepare the emulsions (1% w/w). The maximum concentration of hydroperoxide (LOOH_max) and the rate of formation of hydroperoxides (μmol L⁻¹ h⁻¹) were used to measure the primary products. Hexanal, propanal and malondialdehyde were used to determine the secondary products of the oxidized emulsions containing polyunsaturated fatty acids. LOOH_max varied from 0.16 to 12.75 mmol/kg among the samples. The interaction between the polar components and the degree of unsaturation of the fatty acids was significant (p < 0.001) when the hydroperoxides were evaluated. In general, the degree of unsaturation (β₁) and the absence of polar components (β₂), respectively, represented 30 and 20% of the contribution to increase the mean oxidation, with the interaction (β₁₂) contribution being more sensitive to the rate of formation of hydroperoxides (16%) than to the LOOH_max (5%). The significance of this interaction suggests that both strategies present synergism and should be applied to improve the oxidative stability of food emulsions.     

The decomposition of secondary esters of castor oil with fatty acids

In this study, thermal splitting of secondary fatty acid esters of castor oil was investigated to determine the reaction kinetics under various conditions. Zinc oxide,p toluenesulfonic acid and sulfuric acid were used as catalysts. Reactions were carried out at 260, 270, and 280°C. Experimental data fitted the first-order rate equation for the catalyzed and noncatalyzed reactions. In addition to the kinetic investigation, the splitting (pyrolysis) mixture was evaluated in the preparation of a synthetic drying oil. For this purpose, the mixed fatty acids of linseed, sunflower andEcballium elaterium seed oils were used in the esterification stage of the process. Pyrolysis mixtures were converted to drying oils by combining the liberated acids with equivalent amounts of glycerol. The oils thus obtained show good drying oil properties.     

Formation of 4‐Hydroxy‐2‐Trans‐Nonenal,a Toxic Aldehyde,in Thermally Treated Olive and Sunflower Oils

4‐Hydroxy‐2‐trans‐nonenal (HNE) is a toxic aldehyde produced mostly in oils containing polyunsaturated fatty acid due to heat‐induced lipid peroxidation. The present study examined the effects of the heating time, the degree of unsaturation, and the antioxidant potential on the formation of HNE in two light olive oils (LOO) and two sunflower oils (one high oleic and one regular) at frying temperature. HNE concentrations in these oil samples heated for 0, 1, 3, and 5 hours at 185 °C were measured using high‐performance liquid chromatography. The fatty‐acid distribution and the antioxidant capacity of these four oils were also analyzed. The results showed that all oils had very low HNE concentrations (<0.5 μg g^?1 oil) before heating. After 5 hours of heating at 185 °C, HNE concentrations were increased to 17.98, 25.00, 12.51, and 40.00 μg g^?1 in the two LOO, high‐oleic sunflower oil (HOSO), and regular sunflower oil (RSO), respectively. Extending the heating time increased HNE formation in all oils tested. It is related to their fatty‐acid distributions and antioxidant capacities. RSO, which contained high levels of linoleic acid (59.60%), a precursor for HNE, was more susceptible to degradation and HNE formation than HOSO and LOO, which contained only 6–8% linoleic acid.     

Effect of hydrogenation on density and viscosity of sunflowerseed oil

The densities and viscosities of unhydrogenated and hydrogenated sunflowerseed oils have been determined at temperatures ranging from 25 to 50°C at 5°C intervals. The densities of these oils vary linearly with temperature. The values of the parameters for the density equation have been calculated. Smooth curves were obtained when the changes in viscosity with temperature were plotted in the form of ln η vs. 1/T. The energy of activation, the free energy of activation, and the entropy of activation have been calculated at 25°C, and they decreased with the degree of unsaturation in the fatty acid chains of the sunflowerseed oil.     

Sperm oil replacements: Synthetic wax esters from selectively hydrogenated soybean and linseed oils

Synthetic wax esters with properties similar to those of sperm whale oil have been prepared entirely from soybean and linseed oils. the synthesis required: (a) selective hydrogenation of the oils with copper-on-silica gel catalyst, (b) hydrogenolysis of fatty acids to fatty alcohols with copper-cadmiumchromium catalyst, and (c) esterification of hydrogenolysis products to yield predominantly long chain fatty esters which contained unsaturation in both the alcohol and acid moieties. Similarity of physical and chemical properties indicate that these wax esters are possible replacements for sperm oil. After sulfurization, the wax esters also have potential as extreme pressure lubricant additives.     

Production of vinylic unsaturation by partial dehydrobromination of vicinal dibromo fatty derivatives

The reaction of methyl dibromostearate with metal cyanates in dimethyl formamide or dimethyl sulfoxide results in the disappearance of the peak at 548 cm⁻¹ in the IR spectrum due to the -C-Br group. Chemical analysis of the products reveals the presence of residual bromine. Gas liquid chromatography and nuclear magnetic resonance examination of the products shows the presence of olefinic unsaturation and this indicates that partial dehydrobromination has occurred. The result is a double bond with one carbon atom attached to a bromine atom. This structure has some vinylic characteristics. The application of this process to partially brominated linseed oil yields a dehydrobrominated linseed oil, with residual bromine. This oil has drying properties very similar to raw linseed and safflower oils. Presented at the AOCS-AACC Joint Meeting, Washington, D.C., April, 1968.