SOLVENT EXTRACTION OF PHENOL WITH MINERAL ACID SALTS OF HIGH-MOLECULAR-WEIGHT AMINES

Distribution equilibria in the solvent extractions of phenol with various mineral acid salts of high-molecular-amines were measured at 30°C to examine the effects of types of amines and mineral acids on the distribution equilibria.

It was found that the extraction is greatly enhanced by converting the free base amines into their hydrochloric acid salts in the cases of secondary and tertiary amines while it is decreased in the case of a primary amine. On the effect of types of mineral acids, sulfuric acid and hydrochloric acid salts of trioctylamine can much more effectively extract phenol than the free base amine and the order of the efficiency for phenol extraction was found to be as follows: Aliquat 336 > sulfuric acid salt of trioctylamine i its hydrochloric acid salt ≥ its nitric acid salt > its perchloric acid salt ? free base amine.     

Study of the properties of a multi-component inhibitor used for water treatment in cooling circuits

This work is devoted to the corrosion inhibition of a carbon steel in a 200 mg l^–1 NaCl solution by an original multicomponent inhibitor: fatty amines in association with phosphonocarboxylic acid salts and a biocide at low dosage. Its principal advantage is the absence of toxicity and its biodegradability. Steady-state current–voltage curves were combined with electrochemical impedance measurements to characterize the inhibitive properties of each compound and to optimize the concentration of the compounds in the mixture. Phosphonocarboxylic acid salts were observed to act as an anodic inhibitor whereas mixed action was shown for fatty amines. The inhibitive efficiency was increased when the phosphonocarboxylic acid salt concentration was increased whereas for fatty amines an increase of the concentration did not improve corrosion inhibition. Optimal concentrations of fatty amines and phosphonocarboxylic acid salts were determined. X-ray photoelectron spectroscopy (XPS) was used to analyse the layer formed on the metal surface by the inhibitive mixture. The film was composed of an iron oxide/hydroxide mixture incorporating the organic compounds. The inhibitive molecules interact with the iron oxides.     

Preparation of pure palmitic acid and a by-product plasticizer from cottonseed oil

Summary A laboratory process has been developed which permits the isolation of a highly purified palmitic acid from cottonseed acids through the recrystallization of its cyclohexylamine salt from acetone and subsequent regeneration of the acid. The by-product, predominantly cyclohexylamine salts of the unsaturated fatty acids, can be modified and converted to morpholides which have shown promise as vinyl plasticizers. The morpholine salts can be obtained as a direct byproduct by the use of an appropriate mixture of cyclohexylamine and morpholine with the composite acid. By using an amount of cyclohexylamine closely equivalent to the saturated fatty acid content and sufficient morpholine to make up the residual neutralization equivalent of the composite cottonseed acids, the saturated acids can be isolated as cyclohexylamine salts. The stripped mother liquor will consist essentially of the morpholine salts of the unsaturated acids. Pure palmitic acid is obtained by recrystallization of the cyclohexylamine salts. The complete process is applicable to fatty acids from other natural glyceridic oils in which the dominant saturated acid bears a ratio to the other saturated acids closely paralleling that in cottonseed oil. The process is not operable with partially hydrogenated oils. Presented at the 49th Annual Meeting of the American Oil Chemists’ Society, Memphis, Tenn., April 21–23, 1958. One of the laboratories of the Southern Utilization Research and Development Division, Agricultural Research Service, U. S. Department of Agriculture.     

Traditional analytical chemistry of fatty acids and their derivatives

Industrial fatty acids and their derivatives are generally manufactured under strict quality control and sold under rigid specifications. The purchase specifications are normally prescribed by a series of traditional “wet” analytical methods. These methods include acid value, saponification value, iodine value, hydroxyl value, water content, and others. Occasionally, other information is specified; this may include for tall oil fatty acids, rosin content, and free glycerol in monoglycerides, diene value for drying fatty acids, and conjugated fatty acids for specialized fatty acids. The most common fatty acid derivatives of the industrial fatty acids are anionic and nonionic surfactants and the nitrogen derivatives such as amines and quaternary ammonium salts. Rigid quality control is also applied to these compounds. The amine value and the determination of primary, secondary, and tertiary amines are the key analytical methods applied to amine derivatives. Quaternary ammonium compounds present unique problems; these are in a present state of methods improvement. Physical property test methods are often used to characterize fatty acids. Though simple in concept, they are often the most difficult to meet in purchase specifications. Examples of these tests are viscosity, titer, color, color stability, flash and fire point.     

Purification of long-chain saturated fatty acids by recrystallization of their molecular compounds with acetamide

Summary A method is described for the purification of lauric, myristic, palmitic, and stearic acid, based upon the recrystallization of the fatty acid-acetamide molecular compounds and subsequent regeneration of the acid by extraction of the acetamide with water. The choice of the crystallization solvent is rather critical because of the marked difference in the solubility characteristics of the acetamide and the fatty acids. For the purification of lauric and myristic acids acetone or a one-to-one benzene-acetone mixture by volume proved to be the best solvents, and for palmitic and stearic acids the most satisfactory results were obtained with either benzene or a two-to-one mixture by volume of benzene and acetone. Since the molecular compounds must be crystallized from concentrated solutions, the separation of the crystals from the mother liquor must be made by centrifugation. The recrystallized fatty acid-acetamide compounds provide a convenient intermediate for the preparation of pure acid amides free from homologs. One of the laboratories of the Southern Utilization Research Branch, Agricultural Research Service, U. S. Department of Agriculture.     

GOLD EXTRACTION FROM THIOSULFATE SOLUTIONS USING MIXED AMINES

ABSTRACT

The extraction of gold from thiosulfate solutions with amine oxide and its mixture with amines has been studied, the results show that the amine oxide (TRAO) has a higher extraction ability for gold compared with tertiary amine. It can extract gold from neutral and weakly alkaline thiosulfate solutions, similar to the primary amine as extractant. The addition of TRAO enhances the extent of gold extraction with primary, secondary, and tertiary alkyl amines, respectively. The stoichiometry for the extraction of gold from thiosulfate solutions using the mixed solvent containing the primary amine N₁₉₂₃ and the amine oxide TRAO was investigated using slope analysis. The compositions of the gold extraction species with mixed organic solvents are proposed.     

Industrial uses of palm,palm kernel and coconut oils: Nitrogen derivatives

Palm, palm kernel and coconut oils are sources of fatty acids that can be converted to other oleochemicals that have many applications. This paper describes manufacturing procedures, product characteristics and uses for many fatty acids, alcohols, primary amides, monosubstituted amides, diamides, disubstituted amides, nitrites, primary amines, secondary amines, tertiary amines, diamines, quaternary ammonium compounds, amphoterics, amine oxides and polyoxyalkylene alkylamines.     

Synthesis and characterization of polyimides by use of metal salts and phosphorous compounds in the presence of solvent

Polyimide precursors and polyamic acid were synthesized by direct polycondensation reaction of the 1,2,3,4-butanetetracarboxylic acid (BTCA) and diamines in the presence of metal salts and phosphorous compounds. The BTCA was reacted with an initiating species, which is the phosphonium salt of metal salts and phosphorous compounds, to form acyloxy phosphonium salt building up at moderated temperatures. The salt reacts with diamine to form polyamic acid. The reaction was markedly affected by several factors: reaction temperature and time, solvent, metal salts phosphorous compounds, and tertiary amine. The polyamic acid was converted into polyimide by chemico-thermal or thermal methods. The polyimide with a high molecular weight can be prepared from BTCA and diamines and was soluble in polar aprotic solvent. © 1996 John Wiley & Sons, Inc.     

Contact angle of surfactant solutions on precipitated surfactant surfaces

In this study, the contact angle of a saturated aqueous surfactant solution onto the surface of a precipitate of that surfactant is investigated. Those precipitates include fatty acids (C₁₀, C₁₂, C₁₄, C₁₆, and C₁₈), sodium salts of fatty acids (C₁₄, C₁₆, and C₁₈), calcium salts of fatty acids (C₈, C₁₀, C₁₂, C₁₄, C₁₆, and C₁₈). On virgin surfaces, free fatty acids and calcium salts of fatty acids have advancing contact angles (θ_A) between 77 and 92°, with little dependence on alkyl chain length for C₁₂ and higher alkyl chains. The sodium salt of a fatty acid has a lower θ_A than the free fatty or the calcium salt of the soap. The calcium salt of dodecyl sulfate has a lower θ_A than the calcium salt of dodecanoic acid (θ_A = 46 vs. 82°), but the calcium salt of the 18-carbon hydrophobes showed nearly the same contact angle for the soap and the alkyl sulfate. Greasiness, or slipperyness, or a scummy feel of a precipitated surfactant does not necessarily correspond to a hydrophobic surface.     

聚甘油的国内外研究进展

聚甘油是两个或多个甘油分子间的羟基经脱水后生成醚键的多元醇,既可直接用作于化妆品原料,也可与环氧化合物、脂肪酸和脂肪胺反应生成其环氧加成物、聚甘油脂肪酸酯和脂肪胺聚甘油醚等衍生物。文章概述了近十年来国内外在聚甘油的催化合成工艺、精制提纯技术和分析方法的研究进展,展望了其今后的发展方向。     

On the role of fatty acid in adsorption and corrosion inhibition of iron by amine—fatty acid salts in acidic solution

A study has been made of the adsorption and corrosion inhibition of iron by triethanolamine salts of 18C unsaturated fatty acids in 0.5 M deaerated H₂SO₄ solution. The adsorption was considered in terms of the competitive coadsorption of acid molecules and amine cations, being the main species in this solution. From measurements of differential double layer capacitance and dissolution kinetic of iron, the preferential adsorption of fatty acids over amine has been found. The orientation of acids appeared decisive for the formation of inhibitory effective adsorbates. Such adsorbates were originated by vertically oriented oleic acid molecules. Less effective were the layers based on salts of acids possessing a greater number of Π bonds. The double, horizontal and vertical orientation was found for these acids. The main role of amine was the cross-linkage of acid chains adsorbed on the iron surface.     

五氯化铌/离子液体[BMIm]Br共催化合成酰胺化合物

以脂肪族或芳香羧酸和脂肪胺为原料,制备了一系列酰胺类化合物.建立了一种温和条件下五氯化铌和离子液体共同参与的催化脂肪族或芳香羧酸和脂肪胺直接酰胺化的方法,用于高效制备酰胺类化合物.对催化剂用量、反应溶剂、反应时间以及反应温度进行了优化.结果表明,在最佳反应条件(有机酸2.0 mmol,有机胺2.0 mmol,五氯化铌0.16 mmol,1-甲基-3-丁基咪唑溴化物0.3 mmol,4A分子筛200 mg,甲苯4 mL,反应温度110℃,反应时间24 h)下,酰胺收率为77％～96％.     

Ein Verfahren zur Bestimmung der Kohlenstoffketten-Verteilung in Gemischen oxäthylierter aliphatischer Amine

A Procedure for Determination of the Distribution of Carbon Chains in Mixtures of Alkoxylated Aliphatic Amines Technological properties of alkoxylated products depend on the total content of alkoxy groups, distribution of their homologues and on the nature of hydrophobic part of their molecules. A method was developed, which helps to ascertain as to which fatty amines or mixtures of fatty amines constitute the hydrophobic base of alkoxylated amines. In this test, N-alkyl morpholine in an amount which is equivalent to the basic amine is formed from alkoxylated fatty amine by digestion of the latter with 20% hydrochloric acid at 180°C in a sealed tube. Subsequently, the N-alkyl morpholine or the mixture of N-alkyl morpholines are separated as free bases according to the length of N-alkyl chain by gas chromatography. The method can be applied directly for saturated alkoxylated amines; the corresponding unsaturated compounds must, however, be hydrogenated prior to analysis.     

Solution properties of polyamic acids and their amine salts

Solution properties such as viscosity, critical concentration, radius of gyration, and activation energy in aqueous solutions are described for [BPDA/PDA]polyamic acid (PAA) and their salts with various amines (PAS). Although PAA and their salts with Bu₃N, Hex₃N, Oct₃N, and pyridine, were insoluble in H₂O, only the salt with Et₃N (PAS(Et₃N)) was soluble in H₂O. The different solubility of PAS suggests that higher base strength as well as shorter alkyl length of amines enhance water solubility of PAS. PAS(Et₃N) showed critical concentrations at 18, 14, and 7.8 wt% in NMP, NMP/H₂O (1/1), and H₂O, respectively. The radius of gyration, which is calculated from the critical concentration, in H₂O is 1.3 times larger than that in NMP; that is, the polymer chain expands in H₂O rather than in NMP. PAS(Et₃N) in H₂O showed larger activation energy of viscosity than that in NMP. However, PAA and PAS(Et₃N) showed similar activation energies in the NMP solution. Therefore, it is concluded that the amine salts of the polyamic acids are hydrated by several water molecules in H₂O, resulting in the larger radius of gyration and lager activation energies.     

Flow Behavior of Oleic Acid Liposomes in Sucrose Ester Glycolipid Oil-in-Water Emulsions

Liposomes have been used widely as carriers for active ingredients in cosmetics because of their ability to encapsulate both hydrophilic and hydrophobic compounds. In this work, fatty acid liposomes were prepared and introduced into olive oil-in-water emulsions stabilized by C₁₄–C₁₈ sucrose ester mixtures at pH 8.5. Light microscopy images of the emulsions showed evidence of the coexistence of oleic acid liposomes with the emulsions. As the alkyl chain length of the sucrose ester increased, the average droplet size decreased, while the zeta potential became more negative. Further decrease in droplet size was observed when borate buffer was added to the aqueous phase. The free fatty acids in the sucrose esters and olive oil are neutralized in borate buffer; consequently, fatty acid salts were produced and served as co-surfactants. The synergistic stabilization of emulsions by the mixture of sucrose esters and fatty acid salt resulted in higher stability, smaller droplet size, and lower polydispersity. The drastic increase in negative zeta potential was possibly due to the presence of free fatty acid salts in the emulsion systems. The flow curves at steady rate displayed five distinctive regions. The polydispersity of droplets enhanced the shear thickening effect at low shear rates and shear-banding effect at middle shear rates. Formation of fatty acid salts as co-surfactants caused the viscosities of the emulsions to increase by an order of magnitude. The presence of oleic acid liposome significantly reduced the viscosities of the emulsion by half an order of magnitude; this decreased viscosity helped enhance better spreadability.     

Synthesis of alkyl‐branched fatty acids

Alkyl‐branched fatty compounds are of interest for industrial products in the cosmetics and lubricant areas. In this review, clay‐ and zeolite‐catalyzed isomerizations of unsaturated fatty compounds, especially of oleic acid, are discussed. While clay‐catalyzed reactions give most complex mixtures of dimeric fatty acids and of monomeric so‐called “isostearic acid”, the zeolite‐catalyzed process yields preferentially an isomeric mixture of isostearic acids having the methyl branch on the 8–14 positions of the alkyl chain. Synthetically useful additions of alkyl radicals can only be performed on ω‐unsaturated fatty compounds, whereas perfluoroalkyl iodides were added to fatty compounds with terminal as well as internal double bonds using electron transfer‐initiated radical addition reactions. Electrophilic additions of alkyl carbenium ions generated by decomposition of alkyl chloroformates by ethylaluminum sesquichloride give well‐defined alkyl‐branched oleochemicals with good yields.     

两性表面活性剂的合成路线概述

重点介绍了国内新型两性表面活性剂的合成研究概况。咪唑啉型表面活性剂的合成主要是利用了咪唑啉中间体羟基的反应活性,通过酯化或磺化合成出了硼酸酯、硫酸酯和磺酸盐型咪唑啉两性表面活性剂;以二乙醇胺为原料合成两性表面活性剂时,先与脂肪酸或卤代烷反应合成出叔胺,叔胺再与各种季铵化剂反应制备各种两性表面活性剂;甜菜碱型两性表面活性剂的原料可以是脂肪酸、脂肪醇或脂肪伯胺。氨基酸型两性表面活性剂以伯胺为原料,合成出分子中引入了其他原子或基团。对这些两性表面活性剂的性能测定表明,它们的性能优良。     

New methods of analyzing industrial aliphatic lipids

Methods are described for the rapid fractionation of classes of lipids containing the hetero elements N, P, and S such as primary amines, secondary amines, tertiary amines, and quaternary ammonium salts containing one, two, or three long-chain moieties; amides, nitriles, and other nitrogenous lipids; alkyl sulfates and sulfonates; alkyl phosphates and phosphonates. Thin-layer chromatography on silicic acid separates lipids according to classes of compounds. After isolation by thin-layer chromatography, each lipid class is amenable to further fractionation, according to chain length and degree of unsaturation, by complementary methods, such as paper chromatography and/or gas-liquid chromatography. These procedures permit rapid analyses of complex mixtures of industrial lipids, such as surface-active agents, and identification of industrial compounds synthesized from fatty raw materials. Supported by the Bureau of Commercial Fisheries, Fish and Wildlife Service, U.S. Department of the Interior (Contract No. 14-17-008-127). by the National Science Foundation, and by The Hormel Foundation.     

Amides ofa-sulfonated palmitic and stearic acids

Summary Carboxylic acid amides of α-sulfopalmitic and α-sulfostearic acids were prepared from ammonia, ethylamine, ethanolamine, isopropylalcoholamine, diethanolamine, and N-methyltaurine, and were isolated as the sodium, ammonium, or ethanolammonium salt. A satisfactory method was found to be the reaction of the sulfocarboxylic acid with an excess of thionyl chloride, and further reaction of the acid chloride with an amine in a chlorinated solvent. More work is needed on the application of direct amidation methods to the preparation of these compounds. The solubility of the α-sulfonated amides increased with substitution of alkyl, hydroxyalkyl, and sulfoalkyl groups at the nitrogen atom. Ethanolammonium N-hydroxyethyl-α-sulfopalmitamide, ethanolammonium N-hydroxyethyl-α-sulfostearamide, sodium N-(2-hydroxypropyl)-α-sulfostearamide, sodium di-(N-hydroxyethyl)-α-sulfostearamide, and disodium N-methyl,N-(2-sulfoethyl)-α-sulfostearamide have aqueous solubility in excess of 10% at room temperature. Most of the sodium salts of the α-sulfonated amides have good or excellent stability to calcium and other divalent ions and are excellent lime soap dispersing agents. Presented at the fall meeting, American Oil Chemists' Society, Los Angeles, Calif., September 28–30, 1959. Enstern Utilization Research and Development Division, Agricultural Research Service, U. S. Department of Agriculture.     

Solvent-Assisted Crystallization of Fatty Acid Alkyl Esters from Animal Fat

An easy and efficient method for the separation of saturated and unsaturated fatty acid mono alkyl esters, prepared from animal fat, was developed. The most efficient separation was achieved by the use of solvents such as methanol and acetone at low temperatures. The dilution of the alkyl esters with 10 times the amount of solvent (10:1 v/w) and storage of the mixture for 4 h at ?22 °C could be defined as optimum conditions. After filtration of the saturated fraction at the corresponding temperature very pure fractions were obtained. For fatty acid methyl esters deriving from tallow, with an initial content of saturated fatty acids of almost 50 %, a saturated ester fraction with only 5 % unsaturated fatty acids and an unsaturated ester fraction with about 9 % of saturated fatty acids could be obtained. The solvent easily could be recovered by distillation. In addition fatty acid ethyl, 1‐propyl, 2‐propyl, 1‐butyl, tert‐butyl and 3‐methyl‐1‐butyl esters were prepared and separated into saturated and unsaturated fractions. All fractions were analyzed according to the fatty acid compositions and showed similar or slightly worse results compared to the methyl esters. The cold filter plugging points of the unsaturated fractions were measured, showing the lowest value for the unsaturated methyl ester fraction at ?26 °C. The fractionation with the use of solvents is an easy tool in order to obtain fatty acid alkyl esters with excellent cold temperature behavior out of animal fat.