Dependence of oil stability index of fatty compounds on their structure and concentration and presence of metals

During storage and use, vegetable oil-derived industrial products such as biodiesel and biodegradable lubricants can be subjected to conditions that promote oxidation of their unsaturated components. The materials arising during oxidation and subsequent degradation can seriously impair the quality and performance of such products. Therefore, oxidative stability is a significant issue facing these vegetable oil-derived products, and enhanced understanding of the influence of various components of vegetable oils and storage parameters is necessary. In this work, the oil stability index (OSI) was used for assessing oxidation of monoalkyl esters of FA by varying several parameters. Neat fatty compounds and prepared mixtures thereof were studied for assessing the influence of compound structure and concentration. Small amounts of more highly unsaturated compounds had a disproportionately strong effect on oxidative stability. The recently developed concept of bis-allylic equivalents correlated more closely than the iodine value with the OSI times of mixtures of fatty esters. The OSI times of free acids were shorter than those of the corresponding alkyl esters. The presence of copper, iron, and nickel also reduced oxidative stability, but their effect was less than the presence of more highly unsaturated fatty compounds. Of these metals, copper had the strongest catalytic effect on OSI time. OSI may be an alternative to long-term storage tests for determining the influence of extraneous materials such as metals on oxidative stability.     

三氧化二钕催化制备尼泊金乙酯

研究了以三氧化二钕为固体催化剂，由对羟基苯甲酸和乙醇合成尼泊金乙酯。讨论了影响酯化反应的因素，与大孔阳离子交换树脂和Ｆｅ２（ＳＯ４）３·ＸＨ２Ｏ相比，三氧化二钕用量少，是对酸的６％，反应时间短，只需４ｈ，反应温度低，不超过９０℃，可循环使用，产率较高，对环境和产品无污染等。     

πSynthesis and evaluation of a series of α-hydroxy ethers derived from isopropyl oleate

Several fatty derivatives with bulky moieties were prepared by treatment of epoxidized isopropyl oleate with a number of alcohols in the presence of sulfuric acid catalyst to provide a series of α-hydroxy ethers in good yield. The materials were analyzed for cold flow performance through cloud point and pour point determinations. The most promising α-hydroxy ether produced in this study, with respect to both low temperature behavior and economic criteria, was isopropyl 9(10)-(2-ethylhexoxy) 10(9)-hydroxystearate, which has a cloud point of −23°C and pour point of −24°C.     

Selectivity of Supercritical CO<Subscript>2 </Subscript>in the Fractionation of Hake Liver Oil Ethyl Esters

The solubility of different ethyl esters derivatized from hake liver oil in supercritical carbon dioxide was studied. A selectivity factor was used to determine optimal conditions to fractionate the ethyl ester mixture. A strong influence of solvent pressure and temperature was observed within 8.63–18.04 MPa and 40–70 °C. The lowest total solubility of the ethyl ester mixture was obtained when using supercritical carbon dioxide at the lowest density (the lowest pressure and the highest temperatures value tested). The highest discrimination against long-chain polyunsaturated fatty acids (e.g. EPA and DHA) was also obtained at these above conditions. Conversely, higher solubility and lower selectivity were obtained when solvent density increased. Considering this inverse correlation between selectivity and solubility, a single-step batch-fractionation process was designed to increase the 22:6 ethyl ester content from an initial value of 17.5% in the starting material to 55% in the final extract.     

酯对钼系Ziegler-Natta催化剂引发丁二烯聚合的影响

以MoCl_4(Mo)为主催化剂,甲苯氧基二异丁基铝(Al)为助催化剂,在加氢汽油溶剂中,研究了8种酯对丁二烯(Bd)聚合的影响。结果表明,凡是能够溶解在酯中的Mo与Al所组成的二元催化体系,大多能很好地引发Bd聚合,并有较高的催化活性。酯的主要作用是增加Mo在加氢汽油中的溶解性,对聚合物的分子量影响不大,对微观结构几乎无影响。     

Kinematic viscosity of biodiesel components (fatty acid alkyl esters) and related compounds at low temperatures

Biodiesel, defined as the mono-alkyl esters of vegetable oils and animal fats is, has undergone rapid development and acceptance as an alternative diesel fuel. Kinematic viscosity is one of the fuel properties specified in biodiesel standards, with 40 °C being the temperature at which this property is to be determined and ranges of acceptable kinematic viscosity given. While data on kinematic viscosity of biodiesel and related materials at higher temperatures are available in the literature, this work reports on the kinematic viscosity of biodiesel and a variety of fatty acid alkyl esters at temperatures from 40 °C down to −10 °C in increments of 5 °C using the appropriately modified standard reference method ASTM D445. Investigating the low-temperature properties of biodiesel, including viscosity, of biodiesel and its components is important because of the problems associated with the use of biodiesel under these conditions. Such data may aid in developing biodiesel fuels optimized for fatty ester composition. An index termed here the low-temperature viscosity ratio (LTVR) using data at 0 °C and 40 °C (divide viscosity value at 0 °C by viscosity value at 40 °C) was used to evaluate individual compounds but also mixtures by their low-temperature viscosity behavior. Compounds tested included a variety of saturated, monounsaturated, diunsaturated and triunsaturated fatty esters, methyl ricinoleate, in which the OH group leads to a significant increase in viscosity as well as triolein, as well as some fatty alcohols and alkanes. Esters of oleic acid have the highest viscosity of all biodiesel components that are liquids at low temperatures. The behavior of blends of biodiesel and some fatty esters with a low-sulfur diesel fuel was also investigated.     

Fatty acid esters with short‐chain alcohols in two‐phase olive pomace oils

Two‐phase decanter olive pomace (TPOP) is the by‐product of a centrifugation system, used to produce olive oil, that separates olive oil and moist pomace. The water content in these olive pomaces is about 70%, while it was 45‐50% in the olive pomace stemming from three‐phase systems (oil, water, and pomace) and 30% in the old press system. The aim of this work is focused on quantification and changes undergone during olive pomace storage in ponds of esters of fatty acids with short‐chain linear alcohols, which can be considered as a refining loss. The results indicate that oil deterioration increases very rapidly, in particular when oil is extracted from the TPOP surface. Special attention should be paid to the storage of TPOP, establishing a maximum of 2 months in all cases.     

Toughening of cycloaliphatic epoxy resins by poly(ethylene phthalate) and related copolyesters

Poly(ethylene phthalate) (PEP) and poly(ethylene phthalate–co‐ethylene terephthalate) were used to improve the brittleness of the cycloaliphatic epoxy resin 3,4‐epoxycyclohexylmethyl 3,4‐epoxycyclohexane carboxylate (Celoxide 2021?), cured with methyl hexahydrophthalic anhydride. The aromatic polyesters used were soluble in the epoxy resin without solvents and effective as modifiers for toughening the cured epoxy resin. For example, the inclusion of 20 wt % PEP (MW, 7400) led to a 130% increase in the fracture toughness (K_IC) of the cured resin with no loss of mechanical and thermal properties. The toughening mechanism is discussed in terms of the morphological and dynamic viscoelastic behaviors of the modified epoxy resin system. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 388–399, 2002; DOI 10.1002/app.10363     

Properties of alkyl esters base on castor oil

Castor oil is a non‐traditional raw material for the preparation of methyl and ethyl esters of higher fatty acids as alternative fuels for diesel engines. Castor oil contains ricinoleic acid (12‐hydroxy octadecene acid) with a major share of about 90%. The article presents the parameters of castor oil‐based methyl esters (COME) and ethyl esters (COEE) defined by the standard EN 14 214. The densities of COME and COEE are higher than the limit defined by the standard EN 14 214. The viscosities are more than twice as high as the limit value. The cetane numbers are lower than defined by the standard EN 14 214. For the remaining parameters, COME and COEE meet, in principle, the standard EN 14 214. The presence of the free hydroxyl group has virtually no effect on the values of such parameters as carbon residue, filterability at low temperatures and oxidation stability, for which some influence was expected. The physicochemical parameters of the castor oil esters are discussed in comparison to the analogous esters of high‐oleic sunflower oil, which contain about 80% of oleic acid. Both the methyl and ethyl esters of high‐oleic sunflower oil meet the standard EN 14 214 in all prescribed parameters.     

Chemistry of mandibular and Dufour's gland secretions of ants in genusMyrmecocystus

Males of several species ofMyrmecocystus produce mandibular gland secretions that contain 2,4-dimethyl-2-hexenoic acid and a variety of monoterpenes that include neral, geranial, citronellol, limonene, and 2,6-dimethyl-5-hepten-1-ol. Other components identified include methyl anthranilate, octanal, octanol, octyl octanoate, and 2-hexyl-2-decenal. Methyl salicylate has been identified as a mandibular gland constituent of workers of several species in addition to mellein and monoterpenes such as cymene, limonene, and the isomers of citral. The Dufour's gland secretions of workers and females of 14 species contain typical formicine alkanes (e.g., undecane), 2-alkanols (e.g., 2-tridecanol), and 2-alkanones (e.g., 2-tridecanone). Two species in the subgenusEremnocystus produce secretions that are distinguished by the presence of significant quantities of tridecyl esters. The functions of these compounds as well as their possible chemosystematic significance in the genusMyrmecocystus are discussed.