Production of fatty alcohols from fatty acids

Detergent-range alcohols from natural feedstock can be produced by high pressure hydrogenation of either methyl esters or fatty acids. The increasing quantities of fats and oils on the world market secure a reliable and economically priced material. Although fatty acid is an abundant worldwide commodity, most alcohol producers hydrogenate methyl esters, because direct hydrogenation of fatty acids is difficult as the catalyst is sensitive to acid attack. The process described here makes it possible to hydrogenate fatty acids directly to alcohols of high quality without prior esterification. The reaction takes place in the liquid phase over a fine-grained copper chromite slurry in a single reactor vessel. A special reactor design with an optimum arragement of the feeding nozzles causing an appropriate circulation of the reacting components inside the reactor facilitates the rapid “in situ” esterification reaction. This minimizes the free fatty acid concentration in the reactor to nearly zero. This results in a low consumption of catalyst. The most important advantages of the process are: direct feed of fatty acids of various origins, use of reasonably priced raw materials such as soapstock fatty acids and lower grade tallow acids, no process steps with methanol, and excellent economics. The process is industrially proven.     

Reduction of unsaturated fatty acids and fatty alcohols with diimide from hydroxylamine-ethyl acetate

Hydroxylamine has been recently found to react with ethyl acetate to generate diimide in situ. This reaction was used to reduce 10-undecenoic, oleic, linoleic, stearolic, concentrates of ricinoleic, cyclopentene and cyclopropene fatty acids (FA), dehydrated castor oil FA, 10-undecen-1-ol, oleyl alcohol and castor fatty alcohols. Unsaturated FA and their corresponding alcohols reacted in a similar manner. Terminally unsaturated, cyclopropene and cyclopentene FA were more reactive than oleic acid, which, in turn, was more reactive than hydroxymonoenoic acids. Conjugated dienoic FA reduced faster than nonconjugated dienoic acids. Partial hydrogenation using this reagent is particularly advantageous in determining geometry and the position of double bonds in the polyunsaturated FA, as it can be carried out in the absence of oxygen or oxidizing agents unlike hydrazine reductions.     

Chlorinated alcohols: I. Preparation from chlorinated acids

Rhenium, ruthenium and rhodium oxides, hydrogenolysis catalysts for stearic acid at 150 C, were tried for the conversion of 9,10-dichloro-stearic acid to the dichloro alcohol but only ReO₃ was effective in some degree (yield 14%). Dehydrochlorination or hydrogenolysis at the carbon-chlorine bond was the principal reaction. Reductions with diborane or with lithium aluminum hydride, however, were found to be excellent methods for preparing 9,10-dichloro-stearyl alcohol.     

Preparation and properties of esters of monohydric alcohols and fatty acids of tall oils

Esters of pure tall oil fatty acids and commercially available monohydric alcohols were prepared, distilled, and analyzed for pertinent values. The tall oil fatty acid fraction used in the esterification contained approximately 0.6% rosin acids with essentially equal distribution of fatty acids into oleic and linoleic acids. The use of various techniques, such as fast cooling by the addition of cold water to ester solutien, vacuum topping before water washing, and/or use of carbon dioxide as a blanketing gas resulted in the production of light-colored ester products. These esters, low in acidic impurities and light in color, are another source of chemical intermediates for the preparation of plasticizers, cutting oils, hydraulic fluids, and lubricants. Presented at the 51st annual meeting, American Oil Chemists' Society, Dallas, Tex., April 4–6, 1960.     

Continuous production of cyclic fatty acids

Kinetic studies of a batch treatment of linseed oil to produce cyclic acids indicated that of a continuous process conducted in a flow-through reactor and involving rapid heat-up of reactants, followed by a short reaction time, might be feasible. Tests were conducted in a continuous system to examine the effects of flow rate (retention time), reaction temp, reaction system pressure and reagents on product yields. The reactant solution (linseed oil-ethylene glycol-sodium hydroxide) was pumped through an externally heated tube and discharged through a back-pressure valve. Maximum cyclic acid yields based on wt of oil were 37% by the continuous method and 40.4% by the batch process when the feed was saturated with nitrogen, and 39.5% and 46.1% for the respective methods when the feed was saturated with ethylene. These differences may be offset by the advantages inherent in a continuous process. Presented in part at the AOCS Meeting, New Orleans, 1962. A laboratory of the No. Utiliz. Res. & Dev. Div., ARS, USDA.     

Nitrogenous derivatives of cyclic fatty acids

A number of nitrogenous derivatives of cyclized acids derived from C-18, triene-containing fatty acid sources, were prepared. Mixed amides (mp 33C), nitriles (fp −25C), and amines (fp −34C), prepared from the hydrogenated cyclic acids, have uniquely low mp for fat-derived substances of their mol wt. Compatibility with synthetic resins and solubility in organic solvents of the mixed amides are high compared to common fatty-amide mixtures. The nitriles and morpholides are compatible with polyvinyl chloride and may have potential as plasticizers for it. The hydrogenated cyclic fatty acid amines have an approximate fp of −34C. The diethanolamides, ethenoxylated amides, and quaternary amines were prepared and their surface-active properties compared with similar fat-derived substances. Presented at AOCS meeting in St. Louis, Mo., 1961. A laboratory of the Northern Utilization Research and Development Division, Agricultural Research Service, U.S.D.A.     

Straight-chain fatty acids from alcohols,olefins, and ziegler intermediates

Six synthetic routes to straight-chain saturated fatty acids other than from saturated hydrocarbons currently in research and development within the petrochemical industry are discussed and evaluated and the prospects for each reviewed in the light of advantages and disadvantages for each.     

Homogeneously catalysed hydrogenation of unsaturated fatty acids to unsaturated fatty alcohols

The use of copper and cadmium oxides or soaps as catalysts for the hydrogenation of unsaturated fatty acids to unsaturated fatty alcohols has been investigated. It is shown that copper soaps homogeneously activate hydrogen. When copper and cadmium oxides are used as catalysts, they react with the acid under formation of a homogeneous soap solution. A continuous reaction system for the preparation of unsaturated fatty alcohols by hydrogenation under the influence of copper and cadmium soaps is described.     

Useful direct conversion of tetrahydropyranyl ethers of fatty alcohols into fatty acids

Tetrahydro-2-pyranyl ethers from fatty primary alcohols can be converted in a one-step procedure into the corresponding carboxylic acids in high yields. This process avoids the synthesis of symmetrical esters, particularly for long-chain compounds. This reaction proved to be useful, for instance, to produce polyunsaturated fatty acids immediately before their biological testing.     

Characterization of esters of fatty acids and dicarboxylic acids with Guerbet alcohols

Esters of some common fatty acids and diacids with Guerbet alcohols were prepared by p-toluenesulfonic acid-catalyzed esterification. Such materials are of interest in applications such as additives in various industrial products. Gas chromatography-mass spectrometry with chemical ionization using methane as ionization gas is an efficient characterization method for these Guerbet esters and diesters. Under these conditions, structural features such as molecular weight and site of branching are easily determined. The spectra of the present compounds were compared to those of di-Guerbet esters reported earlier and differences noted. The compounds were also characterized by ¹³C nuclear magnetic resonance spectroscopy.     

Microbial production of rare unsaturated fatty acids and alcohols

Aeromonas hydrophila N‐6, isolated from a soil sample, converted vegetable oils to several rare unsaturated fatty acids and alcohols accumulated inside the cells as a wax ester form. A. hydrophila N‐6 effectively decreased fatty acid chain lengths, and converted rapeseed, safflower and linseed oils into 7‐16:1 and 5‐14:1 fatty acids, 7,10‐16:2 and 5,8‐14:2 fatty acids, and 7,10,13‐16:3 fatty acids, respectively. Furthermore, A. hydrophila N‐6 reduced the resulting fatty acids to rare unsaturated fatty alcohols, such as 7‐16:1, 5‐14:1, 9,12‐18:2, 7,10‐16:2, 9,12,15‐18:3 and 7,10,13‐16:3. Such unsaturated fatty acids and alcohols are rarely found in natural oils. Because decreasing fatty acid carbon chain lengths from the carboxyl end and reducing unsaturated fatty acids to unsaturated fatty alcohols in industrially applicable scale are both difficult reactions to accomplish by chemical means, we suggest that A. hydrophila N‐6 may facilitate the introduction of new bioprocesses for producing rare unsaturated fatty acids and alcohols, especially fatty alcohols with more than two double bonds.     

Determination of cyclic fatty acids by gas-liquid chromatography

A method is described to determine cyclic fatty acids in cyclic monomers by gas-liquid chromatography (GLC), which separates saturated straight-chain esters from cyclic esters. The content of cyclic esters can be determined by integration of the area on the chromatograph under the cyclic peaks. GLC was applied to cyclic monomers made from linseed oil and from linolenic acid. Samples of both hydrogenated and nonhydrogenated cyclic monomers were analyzed; however, more reliable results were obtained on the hydrogenated samples. The results show a standard deviation of 0.25 for linseed oil and 0.36 for linolenic acid. Accuracy of the analysis was established by comparing data with that obtained by crystallization. The GLC method is approximately three times faster. Presented at the AOCS meeting, New Orleans, La., 1962. A laboratory of the No. Utiliz. Res. & Dev. Div., ARS, U.S.D.A.     

Synthetic detergents from animal fats. VIII. The ethenoxylation of fatty acids and alcohols

Summary A laboratory survey of the properties of a series of ethenoxylated fatty acids and alcohols containing about 10, 15, 20, 30, and 40 ethenoxy groups per molecule has brought together information on solubility, cloud point, surface and interfacial tension, detergency, and wetting, foaming and emulsifying properties. Ethenoxylated alcohols were generally more soluble and had better wetting and foaming properties than the acids. Ethenoxylated acids had generally lower surface and interfacial tension values. Both types of nonionics appeared to be excellent emulsifying agents. Most of the ethenoxylated acids and alcohols were equally effective as built detergents. Built ethenoxylated oleic acid (n=10) and built hydroxy-, dihydroxy-, phenyl-, and xylylstearic acids (n=20) were the best detergents. Nonionic surface-active agents derivable from animal fats appeared to have an optimum range in the average number of ethenoxy groups per molecule, with respect to certain properties. The optimum was in the range of about 14 to 18 for wetting properties, the foaming properties of ethenoxylated alcohols, and the interfacial tension of ethenoxylated acids. This range is about equal to the value suggested for adequate solubility [3 less than the number of carbon atoms in the parent alcohol (3)] but somewhat higher than the general rule for maximum detergency [2/3 the number of carbon atoms in the parent acid or alcohol (1,5)]. The rate of the reaction of octadecanol and stearic acid with ethylene oxide was compared. The alcohol reacted faster, in a non-specific manner. The acidity of the carboxyl group of stearic acid promoted conversion to ethylene glycol monostearate before further ethenoxylation occurred. After disappearance of the carboxylic acid the rate of the reaction of the ethenoxylated acid approached that for octadecanol. A reaction mechanism consistent with these results is proposed. Presented at the meeting of the American Oil Chemists' Society, Chicago, September 24–26, 1956. For number VII in this series see reference 14. A laboratory of the Eastern Utilization Research Branch, Agricultural Research Service, U. S. Department of Agriculture.     

Gas chromatographic identification of fatty acids,fatty alcohols,and hydrocarbons ofHibiscus rosa-sinensis leaves

Hibiscus rosa-sinensis leaves (family Malvaceae) were analyzed for their fatty acid, fatty alcohol, and hydrocarbon contents. Wax hydrocarbons ranging from C₁₆ to C₃₂ with C₂₃, C₂₅, C₂₇, and C₃₁ as major components and wax alcohols between C₂₁ and C₃₀ with C₂₆, iso-C₂₈, and iso-C₃₀ as major components were found to be present in the petroleum ether fraction of the leaves. Fatty acids ranging from C₈ to C₂₈ with C₈, C₁₂, C₁₄, C₁₆, and C_18:2 as major components were found in the combined form. Two cyclic acids, sterculic and malvalic, have also been identified.     

Esterification kinetics of long-chain fatty acids and fatty alcohols with a surfactant-coated lipase in n-hexane

The esterification reaction kinetics of long-chain fatty acids and fatty alcohols catalyzed with a surfactant-coated lipase in a microaqueous n-hexane system were studied. The biocatalytic complex, surfactant-lipase adduct, showed 40 times the activity after a reaction time of 5 h compared to the unmodified lipase in the same reaction system. Various factors that may affect the activity of the modified lipase were studied, such as the influence of substrate fatty acid chainlength, water content, and temperature. By varying the concentration of each of the two substrates while keeping that of the other substrate constant, it was found that the esterification reaction follows Michaelis-Menten kinetics. The surfactant-enzyme complex kinetic parameters were determined with respect to both substrates. It was suggested that the kinetics of the lipase-catalyzed esterification reaction model follow a Ping-Pong Bi Bi mechanism with no substrate or product inhibition.     

Identification of novel octadecadienoic fatty acids in the seaweedCladophora rupestris through oxidative ozonolysis of the alcohols prepared from the acids

The BF₃−MeOH reagent for ozonolysis of ethylenic unsaturation does not oxidize alcohols. It is therefore feasible to determine the position of ethylenic unsaturation in long chain fatty alcohols of synthetic or natural origin by recovering the methyl ester products intact and silylating the alcohol function of half-ester, half-alcohol, products prior to gas liquid chromatographic analysis. The C₃ fragment from methylene-interrupted alkyl chains is not recovered, but, by first reducing carboxyl ester groups to alcohols, the terminal difunctional products can be identified in nonmethylene-interrupted dienoic fatty acids. The seaweedCladophora rupestris is shown to contain Δ5,Δ11-,Δ8,Δ11-, and Δ11, Δ14- as well as Δ9,Δ12-octadecadienoic acid.     

Thermomechanical and cyclic behavior of biocomposites based on renewable thermoplastics from dimer fatty acids

Microbiocomposites based on renewable thermoplastic matrices such as thermoplastic polyurethane (TPU) and polyamide (DAPA), synthesized from dimer fatty acids, and high aspect ratio talc were prepared. TPU/DAPA blends and their corresponding biocomposites exhibited mechanical behavior, which is linked to those of the matrices and their relative contents, i.e., going from a typical semicrystalline behavior (DAPA) to an elastomeric one (TPU). The understanding of the thermomechanical and cyclic behavior of these advanced materials, particularly for TPU/DAPA with high TPU content, is detailed. Addition of particles of high aspect ratio natural talc (HAR) improved the storage modulus over the whole temperature range (almost five times with 5 wt % HAR). Under cyclic manipulation, the biocomposites displayed a stress softening related to the Mullins' effect. An increase of the hysteresis and the residual deformation with the HAR content has been shown. The hyperelastic models of Mooney–Rivlin and Ogden–Dorfmann, used to predict the loading and unloading behavior, fitted with experimental data. The present work also reports the experimental characterization of the deformation mechanisms of these renewable biocomposites through different microscopic techniques at different scales, such as atomic force, scanning electron and transmission electron microscopies. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44610.     

Reactions of unsaturated fatty alcohols. XIII. copolymers of unsaturated fatty vinyl ethers and cyclic monomers

Conjugated linseed, conjugated soybean, and nonconjugated linseed vinyl ethers were copolymerized with various cyclic comonomers. The comonomers used were dihydroabietyl, cyclohexyl, 5-norbornene-2-methyl, di- and tetra-hydrodicyclopentadienyl vinyl ethers, and cyclo-and methylcyclo-pentadiene. All copolymers containing a cyclic comonomer gave baked films that are distinctly superior to unmodified drying oils or vinyl ether homopolymers in hardness and alkali resistance. Several of these copolymers air-dried overnight to moderately hard, wrinkle-free films. The improvement in hardness and alkali resistance may be caused by the steric effects of the cyclic comonomers. These hold the fatty side chains apart thus increasing the proportion of intermolecular to intramolecular crosslinking. Presented in part at the spring meeting, American Oil Chemists' Society, St. Louis, Mo., May 1–3, 1961. A laboratory of the Northern Utilization Research and Development Division, Agricultural Research Service, U.S.D.A.     

Plasticizing properties of esters of monohydric alcohols and tall oil fatty acids

Tall oil fatty acid esters prepared as intermediates in an epoxy ester plasticizer program were similarly evaluated as low-temp plasticizers in polyvinyl chloride resins. Performance characteristics as primary and secondary plasticizers in polyvinyl sheeting and extruded tapes were determined on esters from methyl to heptadecyl tallate. Results indicate that these materials impart low-temp properties which would make them of value as low-cost plasticizers in extruded and molded products where light and heat stability are not primary factors.     

Identification of minor cyclic fatty acids in fractionated tall oil

The structure of several minor cyclic fatty acids present in Finnish tall oil fatty acids are elucidated by gas chromatography-mass spectrometry. The origin and mechanism of formation of these cyclic fatty acids are discussed. The cyclic fatty acids identified in tall oil fatty acids are: 4-(5-pentyl-3a,4,7,7a-tetrahydro-4-indanyl)butanoic acid,ω-(o-alkylphenyl)alkanoic acid, 2,6-dimethyl-9-(3-isopropylphenyl)-6-nonenoic acid, 4-(5-pentyl-4-indanyl)butanoic acid, and 4-(2-hexyl-1,2,4a,5,6,7,8,8a-octahydro-1-naphthyl)butanoic acid. In addition, three different branched or cyclic unsaturated C₁₉ fatty acids are reported to be present in tall oil.