Darstellung und Eigenschaften von Fettsäurepolyglykolestersulfaten

Production and Properties of Fatty Acid Polyglycol Ester Sulfates Fatty alcohol oxethylates, produced by reaction of fatty alcohols from hydrogenated fatty acid methyl esters with ethylene oxide, are the basic material for an important class of anionic tensides, the fatty alcohol ether sulfates. The fatty acid polyglycol ester sulfates are a very interesting alternative to the fatty alcohol ether sulfates. The former are available by saving hydrogenation, in principle directly by fatty acid oxethylation or interesterification of fatty acids with polyglycols, followed by sulfatation. We report about the production of fatty acid ester sulfates by sulfatation of the fatty acid polyglycol monoesters by sulfurtrioxide or chlorosulfonic acid. By means of the results of physicochemical measurements and process trials it is discussed how far fatty acid polyglycol monoester sulfates are suited as alternative tenside raw material fatty alcohol ether sulfates.     

Efflorescence Resulting from Sulfates in Clay Raw Materials

An attempt has been made to isolate the effects of sulfates in clay raw materials on efflorescence from the effects of sulfides and sulfurous fuels. A low-sulfur shale was used and sulfates were added in different amounts and particle sizes. It was found that sulfates react with clays between 1800° and 1900°F. with the result that efflorescence is reduced. Sulfates were not considered as a serious source of soluble salts causing efflorescence. Recommendations are given for minimizing efflorescence when sulfates occur in the raw material.     

Analysis of surfactant mixtures. I

Summary Some data on the use of 93% phosphoric acid as a reagent for recovering the hydrophobic portion of surfactants are presented, and their application to the analysis of surfactant mixtures is discussed. Aromatic sulfonates, straight-chain alkyl sulfates, fatty acid amides, and fatty acid esters decomposed to give good yields of the starting hydrophobic materials. Dioctylsulfosuccinate gave a mixture of octyl alcohols and olefins while the ethylene oxide condensates of lauryl alcohol, tridecyl alcohol, and tertiary dodecyl mercaptan gave olefins derived from the starting hydrophobic materials. Diisobutylene phenol-ethylene oxide condensate decomposed to olefins, conjugated olefins, and alcohols formed by rupture of the aromatic ring. The products are characteristic of the hydrophobic oils, and in most cases products from mixtures of surfactants can be separated by known analytical methods.Alpha-sulfo fatty acids or alkane sulfonates do not give recoverable oils by this treatment.     

Ether alcohol sulfates. The effect of oxypropylation and oxybutylation on surface active properties

The reaction of 1,2-butylene oxide with fatty alcohols of 12 to 18 carbon atoms was investigated and products were compared with those from the propylene oxide reaction. A 60% yield of the first derivative was obtained for the butylene oxide reaction compared with a maximum yield of 50% for the propylene oxide reaction. First and second derivatives were fractionally distilled from the reaction mixtures and characterized as pure ether alcohols and their acetates. Sulfation of the pure ether alcohols permitted some interesting comparisons of the effect of structural change on surface active properties. Oxybutylation gave slightly greater solubility increases than oxypropylation and both reactions were more effective than oxyethylation. Dioxyalkylated products had lower Krafft points than monooxyalkylated products. A low degree of oxyalkylation had only minor effects on the detergency of alcohol sulfates but polyoxybutylation caused significant reductions in foam height for the 16 and 18 carbon alcohol sulfates. Critical micelle concentration was reduced both by increasing degree of oxyalkylation and molecular weight of epoxide. All of the ether alcohol sulfates were effective lime soap dispersing agents. Presented at the AOCS Meeting in Philadelphia, October 1966. E. Utiliz. Res. Dev. Div., ARS, USDA.     

Highly Enantioselective Synthesis of Secondary Alcohols using Triphenylborane

Asymmetric phenyl transfer reactions with triphenylborane as aryl source and a ferrocene‐based catalyst give secondary alcohols in high yields and excellent enantioselectivities.     

Synthesis of Chloroalkoxy eicosanoic and docosanoic acids from meadowfoam fatty acids by oxidation with aqueous sodium hypochlorite

Chloroalkoxy substituted C₂₀ and C₂₂ fatty acids can be synthesized from the unsaturated fatty acids in meadow-foam oil by reaction of the fatty acids with primary or secondary alcohols and an aqueous sodium hypochlorite solution (commercial bleach). The reactions are conducted at room temperature for 3 h. Chlorohydroxy fatty acid derivatives are formed as by-products owing to the presence of water in the reaction mixture. Chlorinated δ-lactones are also produced by direct reaction of sodium hypochlorite with the Δ5 unsaturated fatty acids present in meadowfoam or by ring closure of the 6-chloro-5-hydroxy fatty acids. The product yield of chloroalkoxy fatty acids is dependent on the nature and volume of the alcohol used in the reaction, as well as the concentration and pH of the sodium hypochlorite solution. Primary alcohols such as methanol and butanol produce maximal yields (50–60%) of chloroalkoxy fatty acids whereas the secondary alcohol 2-propanol gives a 30% yield. Chloroalkoxy fatty acid yields can be increased to 75–80% by elimination of water from the reaction mixture through a procedure that partitions sodium hypochlorite from water into hexane/ethyl acetate mixtures. All of the reaction products were fully characterized using nuclear magnetic resonance and gas chromatography-mass spectrometry.     

A convenient preparation of 10-hydroxydecanoic acid

The alkaline cleavage of ricinoleates may be carried out in ethanol at temperatures of 190–200 C using two to three equivalents of NaOH to give yields up to 69% of pure 10-hydroxydecanoic acid. This method avoids the use of large excesses of alkali as well as the use of high boiling alcohols as reaction media.     

Fettalkoholsulfate – Die ökologische Absicherung einer wichtigen Gruppe von Waschmitteltensiden

Fatty Alcohol Sulfates – The Ecological Evaluation of a Group of Important Detergent Surfactants The biodegradability and ecotoxicological properties of natural raw materials based fatty alcohol sulfates were extensively investigated. These surfactants displayed very fast and virtually complete biodegradation with respect to primary (MBAS) loss) as well as ultimate degradability (mineralization abd assimilation). This pertains also to the partially poorly soluble tallow alcohol sulfate as was shown by radiolabelling. In addition, complete anaerobic biodegradability was proved in a simulation test for sludge digestion. The effect concentrations determined in acute, subacute and chronic toxicity tests with bacteria, algae, daphniae and fish prove fatty alcohol sulfates to be surfactants of relatively low ecotoxicity, i. e. they are innocuous in the realistic environmental concentration range. This conclusion was supported by results obtained in models of aquatic biocenoses (microcosm, ecological system “sewage treatment plant – receiving water”). Thus, fatty alcohol sulfates can be unequivocally classified as “environmentally compatible” on the basis of the presented ecological data.     

Vinyl esters of some aldehydic acid acetals

Vinylation of azelaaldehydic and brassylaldehydic acid cyclic acetals from ethylene glycol gave excellent yields of the vinyl esters. Under conditions of the vinyl exchange reaction used, acyclic acetals from monohydric alcohols cleaved to give enol-ethers as major, inseparable impurities. Radical-initiated polymerization of the pure vinyl esters of the aldehydic-acid cyclic acetals resulted in crosslinking when initiation was by either peroxide or azobis (isobutyronitrile). Presented at the AOCS Meeting, Toronto, October 1962. A laboratory of the No. Utiliz. Res. Dev. Div., ARS, USDA.     

Herstellung verzweigter Fettsäuren durch katalytische Oxidation von Alkoholen

Synthesis of Branched Fatty Acids by Catalytic Oxidation of Alcohols Transition metals fixed on solid supports are able to catalyze the oxidation of branched alcohols with air yielding branched fatty acids. As typical example 2-hexyldecanol was chosen which is well available via the guerbet reaction. Catalyst screening and reaction optimization will be described. Highest activities were obtained with palladium-, platinum- and ruthenium-catalysts. 2-hexyldecanoic acid (“isopalmitic acid”) was synthesized in yields of 65%; important by-products are wax esters and 7-pentadecanone.     

A study of the surface activity of tertiary alcohol sulfates

A number of tertiary alcohols were prepared by the action of a series of Grignard reagents on ethyl oleate. The tertiary alcohols were converted to alkyl sulfates by reaction with sodium chlorosulfonate. The surface active properties of the prepared sodium alkyl sulfates were studied in relation to the length of the branched chain and the bulkiness of the charged head of the surfactants.     

Bi (NO3)3·5H2O and cellulose mediated Cu-NPs — A highly efficient and novel catalytic system for aerobic oxidation of alcohols to carbonyls and synthesis of DFF from HMF

A highly efficient and versatile catalytic system for oxidation of primary and secondary aromatic alcohols to carbonyls has been developed. High efficiency, general synthetic applicability, broader functional group tolerance and versatility towards oxidation of both primary and secondary aromatic alcohols are the key features of this green and sustainable protocol. Selective oxidation of 5-hydroxymethyl furfural (HMF) to biofuel 2,5-diformylfuran (DFF) has been observed in excellent yields. Use of sustainable bio-polymer cellulose as a Cu-nanoparticle support makes the catalytic system environmentally benign.     

Chemical reactions of fatty acids with special reference to the carboxyl group

Unsaturated fatty acids contain unsaturated centres and the carboxyl group both of which can be modified to give a range of interesting and useful compounds. The former have been discussed in detail in two recent references [8, 9] and therefore this paper will be concerned with the reactions of the carboxyl group and its derivatives. Attention is directed to the lactones, alcohols and their ethoxylates and sulfates, to the preparation of cleavable surfactants (acetals, ketals, ortho esters and ester quats), Guerbet alcohols and acids, alkyl polyglycosides and to amines and other nitrogencontaining compounds.     

Oxypropylation of fatty alcohols,and the sulfation products

Reaction of propylene oxide, rather than ethylene oxide, with fatty alcohols, gives a higher yield (50%) of mono-oxyalkylation product because the secondary alcohol formed is less reactive than the primary alcohol formed with ethylene oxide. Rate of further reaction is about half the rate of the parent primary alcohol. Distributuon of propylene oxide reaction products follows the Weibull-Nycander equation. Analysis of reaction products was accomplished by gas-liquid chromatography of the acetylated ether alcohol mixtures. Pure mono-oxypropylated alcohols ROCH₂CHOHCH₃ and in some cases dioxypropylated alcohols R[OCH₂CH(CH₃)]₂OH were separated by fractional distillation. Individual ether alcohols and products with a known average number of oxypropyl groups were sulfated and evaluated in terms of Krafft point, critical micelle concentration, detergency, foam height and lime soap dispersing properties. Incorporation of one oxypropyl group was more effective than the same degree of oxyethylation, and improved solubility with no significant loss in foaming and detergency. Ether alcohol sulfates from propylene oxide are stable to alkaline hydrolysis and nearly equal to the sulfates from ethylene oxide in their stability to acid hydrolysis. Presented at the AOCS Meeting in Cincinnati, 1965. E. Utiliz. Res. Dev. Div., ARS. USDA.     

Palladium(II)‐Catalyzed Oxidation of Alcohols with Air as Reoxidant

Oxidation of primary and secondary aliphatic and secondary benzylic alcohols into their corresponding aldehydes and ketones was achieved in good yields with palladium catalysts using air as the reoxidant of palladium. The use of palladacycle 1 resulted in higher yields and a faster reaction than the use of Pd(OAc)₂ as the palladium source.     

Properties and uses of some unsaturated fatty alcohols and their derivatives

A number of unsaturated fatty alcohols are known, but only those of the C₁₆ and C₁₈ chain lengths are of much importance. In particular, oleyl alcohol., 9,10-octadecenol-1, is by far the most important. A variety of grades of oleyl alcohols is produced and used in the USA ranging from high purity material having iodine values (IV) of 90–95 to those having IV of 45–55, with the other components being primarily cetyl (hexadecanol-1) and stearyl (octadecanol-1) alcohols. This paper takes a brief look at the various grades of unsaturated alcohols used in the USA, methods of preparation, and the change in physical and chemical properties as the octadecanol-1 content and IV decline. Uses of these alcohols industrially and in cosmetic and pharmaceutical preparations are also discussed. Unsaturated alcohols are useful chemical intermediates since they have two reactive sites, the hydroxyl group and the carbon-carbon double bond. Particular attention is paid to the properties, uses and potential uses of some of their sulfates, ether sulfates, ethylene oxide adducts and ethylene/propylene oxide adducts as detergents and emulsifiers for ultimate use in cosmetics and light-duty and heavy-duty systems. Current estimated consumption of unsaturated alcohols in the USA is discussed.     

3,4-二氨基苯甲腈的合成新方法

以3-硝基-4-氯苯甲酸为起始原料,经酰胺化、脱水、氨解、还原等4步反应,制得3,4-二氨基苯甲腈,总收率达86%。     

Hydrogen-bond networks in linear, branched and tertiary alcohols

Molecular dynamics simulations are used to determine the hydrogen-bond networks formed by 54 linear and branched alcohols containing 5-20 carbon atoms, and the results show systematic differences in their hydrogen-bonded structures, depending both on hydroxyl group position and the alcohol's molecular weight. The hydrogen-bonded networks within these pure solvents correspond with experimentally determined water capacities for solvents in four main structural classes. These categories are: primary alcohols, secondary alcohols, tertiary alcohols, and alcohols with the branching point removed from the hydroxyl group. Each of these structural classes exhibits unique behavior in the correlation between the extended hydrogen-bond networks and observed capacities for water.     

Torque‐rheometry investigation of model transreactions involving condensation polymers. I. Polyesters

The chemical transformations taking place when poly(ethylene terephthalate) (PET) or poly(ethylene naphthalate) (PEN) are blended in the melt with different low molar mass substances containing hydroxyl, carboxyl, or amine functional groups have been investigated as models of the transreactions, undergone by the polyesters in reactive blending operations. The polyester molecular weight changes caused by the alcoholysis, acidolysis, aminolysis, and esterolysis reactions have been monitored by torque‐rheometry, using a Brabender Plasticorder static mixer. The degradation of the polyesters by hydrolysis was also studied, under similar conditions, by the addition of a water‐releasing substance (wet polyamide‐6), and was shown to occur quite rapidly, although most of the added water was lost by flash vaporization caused by the high temperature of the polyester melt. It has been shown that the rate constants of the reactions leading to breakage of the inner ester bonds of the polyester macromolecules decrease in the following order: aminolysis (with aliphatic amines, either primary and secondary) > alcoholysis (with aliphatic alcohols) ≈ hydrolysis > acidolysis (with aromatic acids) ≥ acidolysis (with aliphatic acids) ? aminolysis (with aromatic amines) > alcoholysis (with phenols) ? esterolysis. POLYM. ENG. SCI. 46:139–152, 2006. © 2005 Society of Plastics Engineers     

Products of the Fischer-Tropsch synthesis (A Review)

The composition of the products of hydrocarbon synthesis from carbon monoxide and hydrogen and also the composition and properties of individual fractions (commercial products) obtained by this method are considered. The reaction paths of the formation of different carbon-containing compounds (gaseous, liquid, and solid hydrocarbons) under the Fischer-Tropsch synthesis conditions and synthesis by-products (alcohols and CO₂) and the possible directions of their secondary conversions are demonstrated.