Characteristic properties of cutting fluid additives derived from fatty alcohols

Many 3-aminopropyl alkyl ethers were prepared and their characteristics as water-based cutting fluids were examined. 3-Aminopropyl octyl-, decyl- and dodecyl ethers showed good lubricities and antimicrobial properties for a water-based cutting fluid.     

Characteristic properties of cutting fluid additives derived from half esters of dimer acids

A number of half esters were prepared from the reaction of alcohols with dimer acids and screened for anti-rust properties and antimicrobial activity in spent coolants of water-based cutting fluids. Aqueous solutions of triethanolamine salts with lower-alcohol half esters of dimer acid showed good anti-rust properties for water-based cutting fluids.     

Characteristic properties of cutting fluid additives made from the derivatives of some polymeric nonionic surface-active agents

A series of esters was prepared from the reaction of acid chlorides with polymeric nonionic surface-active agents (copolymer of propylene oxide and ethylene oxide), and they were screened for antirust and other properties associated with water-based cutting fluids. An aqueous emulsion of an adduct of triethanolamine and the oleic acid ester of polymeric nonionic surface-active agent showed excellent antirust properties when used as a water-based cutting fluid. The emulsion of triethanolamine and the mono nonyl ether of the surface-active agent also showed antirust properties.     

Characteristic properties of cutting fluid additives derived from the derivatives of ricinoleic acid polymers

A number of esters were prepared from the reaction of acid chlorides with ricinoleic acid polymers and screened for anti-rust properties and antimicrobial activity in spent coolants of water-based cutting fluids. Aqueous solutions of triethanolamine salts with decanoic acid, undecanoic acid and oleic acid esters of ricinoleic acid dimer, trimer, tetramer and hexamer showed good anti-rust properties for water-based cutting fluids. Dehydrates of ricinoleic acid polymers also showed good anti-rust properties for water-based cutting fluids.     

Characteristic properties of cutting fluid additives derived from the adducts of diamines and acid chlorides

A number of N,N′-diacylalkyldiamines were prepared from the reaction of acid chlorides with 1,8-diaminooctane and 1,12-diaminododecane and screened for anti-rust properties and antimicrobial activity in spent coolants of water-based cutting fluids. Aqueous solutions of N,N′-dihexanoyl-1,8-diaminooctane and N,N′-isobutyroyl-1,12-diaminododecane showed good anti-rust properties for water-based cutting fluids. Aqueous emulsions of N,N′-dibutyroyl-, dipentanoyl-, dihexanoyl- and dioctanoyl-1,12-diaminododecane showed good lubricities and antimicrobial activity for water-based cutting fluids.     

Adducts of cyclic acid anhydrides and fatty amines as anti-rust additives in water-based cutting fluids

A variety ofN-alkyl carboxylic acid amides was prepared from the reaction of cyclic dicarboxylic acid anhydrides and various amines, and screened for anti-rust properties and antimicrobial activity in spent coolants of water-based cutting fluids. The triethanol amine salts of the adducts of maleic anhydride with octylamine, decylamine, dodecylamine and oleylamine, and the one of phthalic anhydride with octylamine showed both good anti-rust and antimicrobial activity.     

Water-soluble metalworking fluid additives derived from the derivatives of 3-mercaptopropionic acid

A number of derivatives of thiocarboxylic acid were prepared from the reaction of 3-mercaptopropionic acid and alkyl halides, and screened for anti-rust properties in water-soluble metalworking fluids. Aqueous metalworking fluids containing octylthiopropionic acid or hexylthioacetic acid showed excellent anti-rust properties for water-soluble metalworking fluids.     

Products from the reaction of fatty acids with ketones and their characteristic properties as cutting fluids additives

Hydroxy acids were synthesized in good yields from ketones and fatty acids by the use of lithium naphthalene in the presence of diethylamine. For example, from cyclohexanone and undecylenic acid (I), 2-(1-hydroxy-1-cyclohexyl)-10-undecenoic acid (III) was obtained in 92% yield. Hydroxy acids were treated withp-toluenesulphonic acid to give corresponding unsaturated fatty acids. From the reaction of (III), 2-(1-cyclohexenyl)-10-undecenoic acid (IV), a 3,4-unsaturated acid was obtained (yield 59%). Corrosion and lubricity tests for these products as water-based cutting fluid additives were carried out. We have found that triethanolamine salts of 2-cyclohexenyl and 2-hydroxycyclohexyl fatty acids showed effective rust-inhibiting and antiwear properties for water-based cutting fluids.     

Purification of polyunsaturated fatty acid esters from tuna oil with supercritical fluid chromatography

The technical and economic feasibility of producing docosahexaenoic acid (DHA)- and eicosapentaenoic acid (EPA)-ethyl ester concentrates from transesterified tuna oil using supercritical fluid chromatography (SFC) was studied. A systematic experimental procedure was used to find the optimal values for process parameters and the maximal production rate. DHA ester concentrates up to 95 wt% purity were obtained in one chromatographic step with SFC, using CO₂ as the mobile phase at 65°C and 145 bar and octadecyl silane-type reversed-phase silica as the stationary phase. DHA ester, 0.85 g/(kg stationary phase · h) and 0.23 g EPA ester/(kg stationary phase · h) can be simutaneously produced at the respective purities of 90 and 50 wt%. The process for producing 1,000 kg DHA concentrate and 410 kg EPA concentrate per year requires 160 kg stationary phase and 2.6 tons/h carbon dioxide eluant recycle. The SFC operating cost is U.S. $550/kg DHA and EPA ethyl ester concentrate.     

Kinetics and mechanism of the reaction between maleic anhydride and fatty acid esters and the structure of the products

Alkenyl succinic anhydrides (ASA) were obtained by reaction between maleic anhydride and high‐oleic sunflower oil (HOSO) esters. A kinetics study of the maleinization of alkyl esters indicated that the maleinization reaction was second order overall and first order with respect to the individual reactants, and the activation energy was 77.2 ± 3.3 kJ/mol in the investigated temperature range (185–225 °C). These results showed that the cis configuration and the central position of the double bond in HOSO esters facilitate the maleinization of the latter. On the contrary, the length of the linear ester moiety had no influence on the course of the maleinization reaction. Moreover, new evidence demonstrates that there are two different reaction mechanisms: ene‐reaction and addition in allylic position with a 2 : 1 ratio, respectively. This ratio was constant throughout the reaction, thus indicating that these mechanisms are independent.     

Oxidation stability of biodiesel derived from free fatty acids associated with kinetics of antioxidants

Biodiesel derived from free fatty acids (FFAs), which has the advantage of not competing with the edible-oil market, exhibited poor oxidation stability. The induction period (IP) of the FFA-based biodiesel determined by the Rancimat method at 110 °C was 0.20 h. This study investigates the effectiveness of one natural and ten synthetic antioxidants, including α-tocopherol (α-T); butylated hydroxyanisole (BHA); butylated hydroxytoluene (BHT); 2, 5-di-tert-butylhydroquinone (DTBHQ); Ethanox 4740; Ethanox 4760E; 2,2′-methylene-bis-(4-methyl-6-tert-butylphenol) (MBMTBP); N,N′-di-sec-butyl-p-phenylenediamine (PDA); propyl gallate (PG); pyrogallol (PY); and tert-butylhydroquinone (TBHQ), at concentrations between 100 and 1000 ppm to improve the oxidation stability of the FFA-based biodiesel. The order of antioxidant effectiveness with respect to the oxidation stability of the FFA-based biodiesel was PY > Ethanox 4760E > PG > Ethanox 4740 > PDA ~ BHA > BHT > MBMTBP ~ TBHQ > DTBHQ > α-T. The IP of the FFA-based biodiesel increased as the antioxidant concentration was increased and decreased at high test temperatures. Furthermore, the relationship between the IP values associated with the consumption of antioxidants in the FFA-based biodiesel was described by first-order reaction rate kinetics. However, the natural logarithm of IP (ln IP) at various concentrations of Ethanox 4760E showed a linear relation with the test temperature. The IP at ambient temperature was predicted based on the extrapolation method of the temperature dependence relation. After long-term storage at room temperature, the IP and acid value of the original FFA-based biodiesel significantly decreased and increased, respectively, with storage time, while the addition of antioxidants ensured the oxidation stability of the FFA-based biodiesel over 6 months of storage.     

Sulfonated polystyrene: A catalyst with acid and superabsorbent properties for the esterification of fatty acids

In this work, catalysts with acid and superabsorbent properties were obtained by sulfonation of expanded polystyrene and used to promote the esterification of oleic acid with ethanol. The prepared superabsorbent polymers (SAP) showed high concentration of active sulfonic acid sites (0.7-5.9 mmol acid sites g⁻¹) and high water absorption capacity (445-900 g_water g⁻¹). It was observed that the catalytic activity increased with the number of acid site and water absorption capacity. Turnover frequencies suggested that the catalytic activity depends on the accessibility/diffusion processes determined by the crosslinks in the polymer. Commercial sulfonic acid resins and polyacrylate based superabsorbent polymers showed very low activities compared with the SAP produced. The SAP also showed higher activity compared to the homogeneous catalyst p-toluenesulfonic acid. The higher activity of the prepared SAP is discussed in terms of the acidity of sulfonic groups combined with the water absorption which shifts the esterification equilibrium.     

Influence of monomeric and polymeric structure on the physical properties of thermoplastic polyesters derived from hydroxy fatty acids

The physical properties of three vegetable oil derived medium and long chain poly(ω‐hydroxy fatty ester)s (P(Me‐ω‐OHFA)s), namely poly(ω‐hydroxynonanoate) [P(Me‐ω‐OHC9)], poly(ω‐hydroxytridecanoate) [P(Me‐ω‐OHC13)] and poly(ω‐hydroxyoctadecanoate) [P(Me‐ω‐OHC18)] (n = 8, 12 and 17, respectively), of the [?(CH₂)_n?COO–]_x polyester homologous series are presented. The effect of M_n (M_n 10–40 kg mol^?1) and n on the crystal structure and thermal and mechanical properties of the P(Me‐ω‐OHFA)s were investigated by wide‐angle X‐ray diffraction (WAXD), TGA, DSC, dynamic mechanical analysis (DMA) and tensile analysis and are discussed in the context of the [?(CH₂)_n?COO–]_x polyester homologous series, contrasted with linear polyethylene (PE). For all P(Me‐ω‐OHFA)s the WAXD data indicated an orthorhombic crystal phase reminiscent of linear PE with crystallinity (X_c = 50%?80%) depending strongly on M_n. The glass transition temperature and Young's modulus for P(Me‐ω‐OHFA)s increased with X_c. The DSC, DMA and TGA studies for P(Me‐ω‐OHFA)s (n = 8, 12 and 17) indicated strong correlations between the melting, glass transition and thermal degradation behavior and n. The established predictive structure relationships can be used for the custom engineering of polyester materials suitable for specialty and commodity applications. © 2014 Society of Chemical Industry     

Fatty acid composition of meat from ruminants, with special emphasis on trans fatty acids

The fatty acid composition was determined in 39 samples of beef, 20 samples of veal, and 34 samples of lamb, representative of the supply of ruminant meat in Denmark. Five cuts of beef and veal and three cuts of lamb with increasing fat content were selected, and analysis of the fatty acid methyl esters was performed by gas-liquid chromatography (GLC) on a polar 50-m capillary column CP Sil 88 with flame-ionization detection. Lamb had the highest content of saturated fatty acids (52.8±1.8 g/100 g fatty acids), higher than beef and veal (45.3±3.1 and 45.4±0.8 g/100 g fatty acids, respectively). Cis monounsaturated fatty acids were 49.2±3.1, 44.9±1.8, and 37.7±1.7, and polyunsaturated fatty acids were 3.3±0.7, 5.8±2.0, and 5.0±0.1 g/100 g fatty acids in beef, veal, and lamb, respectively. Beef contained 2.1±0.8 g trans C_18:1 per 100 g fatty acids, about half that found in veal (4.0±1.2 g/100 g fatty acids) and lamb (4.5±0.6 g/100 g fatty acids). Trans C_16:1 was 0.24±0.01, 0.14±0.02, and 0.79±0.02 g/100 g fatty acids in beef, veal, and lamb, respectively. Only small variations in trans and other fatty acids could be demonstrated between cuts. The overlap between cis and trans C_18:1 by capillary GLC was verified by argentation-thin-layer chromatography followed by GLC, on three samples of veal and three samples of lamb. In veal 1.0 g, and in lamb 1.4 g trans C_18:1 per 100 g fatty acids were hidden under the cis C_18:1 peak. The mean intake of trans fatty acids from ruminant meat is estimated at 0.2 g/d.     

Description of the mutual solubilities of fatty acids and water with the CPA EoS

Data for the mutual solubilities of fatty acid + water mixtures are scarce and so measurements for seven fatty acid (C₅‐C₁₀, C₁₂) + water systems were carried out. This new experimental data was successfully modelled with the cubic plus association EoS. Using data from C₆ to C₁₀ and the Elliot's cross‐associating combining rule a correlation for the k_ij binary interaction parameter, as a function of the acid chain length, is proposed. The mutual solubilities of water and fatty acids can be adequately described with average deviations inferior to 6% for the water rich phase and 30% for the acid rich phase. Furthermore, satisfactory predictions of solid‐liquid equilibria of seven fatty acids (C₁₂‐C₁₈) + water systems were achieved based only on the k_ij correlation obtained from liquid–liquid equilibria data. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

小桐子油脂肪酸聚酯多元醇及聚氨酯泡沫的制备和性能

研究了脂肪酸环氧-开环-酯化三步反应制备聚酯多元醇,比较了3种不同碘值的脂肪酸原料制备的聚酯多元醇及其聚氨酯泡沫（PUF）性能。脂肪酸碘值越高多元醇的羟值也越高：1#、2#和3#聚酯多元醇羟值分别为：261.47 mgKOH/g、370.28 mgKOH/g和434.49 mgKOH/g。3种多元醇的相对分子量为600～2000。3种泡沫的压缩和弯曲性能与泡沫密度成正比。泡沫SEM分析显示：羟值较高的多元醇泡沫2#和3#泡沫孔结构较规则,以正五边形和正六边形居多;1#泡沫泡孔不规则,易变形。对3种泡沫的TG-DSC、DTG分析结果表明：3种泡沫的热分解温度都约为300 ℃,具有较好热稳定性。     

Controlled heterogeneous modification of cellulose fibers with fatty acids: Effect of reaction conditions on the extent of esterification and fiber properties

The controlled heterogeneous partial modification of cellulose fibers with fatty acids, partially preserving the fiber structure, was investigated. The effect of reaction conditions, such as reaction time, fatty acid chain length, and solvent types (swelling and non swelling), on the extent of esterification and fiber properties was evaluated by elemental analysis, IR‐ATR, X‐ray diffraction, ¹³C CPMAS NMR, contact angle measurement, thermogravimetry, and scanning electron microscopy. The degree of substitution (DS) increased with reaction time and with the swelling effect of the reaction medium and decreased with the fatty acids chain length. Higher the DS, higher is the decrystallization of cellulose as a result of the heterogeneous esterification reaction. The esterification with fatty acids enhanced the hydrophobic character of the fibers, but decreased their thermal stability. These properties are not strongly affected by the DS in the range investigated, viz. up to 1.4. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1093–1102, 2006     

Fatty acid composition of French infant formulas with emphasis on the content and detailed profile oftrans fatty acids

The aim of the present study was to identify and quantitatetrans isomers of C18 fatty acids in some French infant formulas. Twenty powdered infant formulas were purchased in pharmacies and supermarkets in order to assess theirtrans mono- and poly-unsaturated fatty acids content. The fatty acid profiles were examined using methyl and isopropyl ester derivatives. The combination of gas-liquid chromatography, high-performance liquid chromatography, and silver nitrate thin-layer chromatography was needed to describe the detailed fatty acid compositions of the samples, includingtrans isomers of unsaturated C18 fatty acids. All the samples containedtrans isomers of C18∶1 acid (mean level 1.97±0.28% of total fatty acids), with vaccenic acid being generally the major isomer (15 out of 20 samples), thus indicating the origin from bovine milk. All the formulas also contained various isomers of linoleic and α-linolenic acids, but at lower levels.Trans PUFA isomers are the same as those present in deodorized oils. In conclusion, all the infant formulas analyzed in this study contained sometrans fatty acids, including isomers of essential fatty acids. This should be taken into account in the dietary intake of the newborn.     

Gas chromatographic separation of the fatty acid methyl esters prepared from dairy products,partially hydrogenated oils,and refined vegetable oils applying a negative temperature gradient

To date no single gas chromatographic method can simultaneously measure all fatty acids (FA), including trans-FA (TFA), that are contained in dairy products, partially hydrogenated oils (PHO), and refined vegetable oils. Using 100% poly(biscyanopropyl siloxane) capillary columns, ruminant and dairy fats are preferentially analyzed by applying temperature programs that separate short chain FA, but not trans-18:3 from 20:1. Refined vegetable oils and PHO are preferentially analyzed by applying isothermal elutions that provide quantification of all 18 carbon TFA including trans-18:3 FA, but not of all short chain FA. In this short communication, we propose a temperature program method capable of simultaneously measuring short chain FA and all 18 carbon TFA including trans-18:3 by applying a negative temperature gradient after the elution of trans-18:1. A simplified version of the method is also described for equipment not able to perform negative temperature gradients.