Anionic ether sulfates

Foamer. [Harcros] Anionic ether sulfate foamo- for air mist drilling, general detergents, gypsum board prod. 

Higher molecular primary unbranched or low-branched alcohols are used not only for the synthesis of nonionic but also of anionic surfactants, like fatty alcohol sulfates or ether sulfates. These alcohols are produced by catalytic high-pressure hydrogenation of the methyl esters of fatty acids, obtained by a transesterification reaction of fats or fatty oils with methanol or by different procedures, like hydroformylation or the Alfol process, starting from petroleum chemical raw materials. 

Ethylene oxide is an important intermediate chemical not only for the production of nonionic surfactants like fatty alcohol ethoxylates, alkylphenol ethoxy lates, or propylene oxide/ethylene oxide block copolymers, but also for manufacturing of anionic surfactants like alcohol ether sulfates. 

As esters of sulfuric acid, the hydrophilic group of alcohol sulfates and alcohol ether sulfates is the sulfate ion, which is linked to the hydrophobic tail through a C-O-S bond. This bond gives the molecule a relative instability as this linkage is prone to hydrolysis in acidic media. This establishes a basic difference from other key anionic surfactants such as alkyl and alkylbenzene-sulfonates, which have a C-S bond, completely stable in all normal conditions of use. The chemical structure of these sulfate molecules partially limits their conditions of use and their application areas but nevertheless they are found undoubtedly in the widest range of application types among anionic surfactants. 

Sodium dodecylbenzenesulfonate is undoubtedly the anionic surfactant used in the greatest amount because it is the basic component in almost all laundry and dishwashing detergents in powder and liquid forms. However, alcohol and alcohol ether sulfates are the more versatile anionic surfactants because their properties vary, with the alkyl chain, with the number of moles of ethylene oxide added to the base alcohol and with the cation. Consequently, alcohol and alcohol ether sulfates are used in almost all scientific, consumer, and industrial applications. 

An analysis of alcohol and alcohol ether sulfates should determine the anionic active matter, the unsulfated matter, the inorganic sulfate content, the chloride content, and water. Other more precise analysis must determine the alkyl chain distribution of the alcohol and in the case of alcohol ether sulfates the number of ethoxy groups and its distribution, as well as other more specialized determinations, such as the content of 1,4-dioxane and other impurities. 

Solutions with low content of alcohol and alcohol ether sulfates cannot be analyzed by the two-phase method and specialized procedures have been developed. ISO method 7875/1 [267] is the standard method for analyzing sulfates and other anionic surfactants at very low concentrations, such as in waste-waters. The absorbance of the chloroform layer containing the surfactant-dye complex is spectrometrically measured at 650 nm and quantified using a calibration curve. Different improvements of this method have been developed [268,269]. 

Thin-layer chromatography (TLC) is used both for characterization of alcohol sulfates and alcohol ether sulfates and for their analysis in mixtures. This technique, combined with the use of scanning densitometers, is a quantitative analytical method. TLC is preferred to HPLC in this case as anionic surfactants do not contain strong chromophores and the refractive index detector is of low sensitivity and not suitable for gradient elution. A recent development in HPLC detector technology, the evaporative light-scattering detector, will probably overcome these sensitivity problems. 

Subacute and chronic toxicity of alcohol and alcohol ether sulfates has been extensively tested in several animals and sometimes humans. The duration of the tests was in some cases as long as 2 years. When administered below the toxic amount no specific damages were observed in any of the species tested [333]. No severe side effects were observed in the study by Swisher, carried out with volunteers who ingested considerable amounts of anionic and nonionic surfactants over long periods [348]. Similarly, the effects produced by the intake of daily doses of 1 g of alcohol sulfate per person over 8 weeks [349],... 

In 1991 the use of amidether carboxylate in combination with anionics like alkanesulfonate, alkylbenzolsulfonate, and alkyl ether sulfate to improve mildness and foam properties in the presence of soil was described [72]. Later a comparison study of the use of alkyl ether carboxylate, amidether carboxylate, and cocamidopropylbetaine in concentrated dishwashing formulations showed, in addition to the above-mentioned properties, the advantage of ether carboxylates in the construction of highly active formulations [144]. 

Results described in the literature have resulted in several patents, such as one for the improvement of the transport of viscous crude oil by microemulsions based on ether carboxylates [195], or combination with ether sulfate and nonionics [196], or several anionics, amphoterics, and nonionics [197] increased oil recovery with ether carboxylates and ethersulfonates [198] increased inversion temperature of the emulsion above the reservoir temperature by ether carboxylates [199], or systems based on ether carboxylate and sulfonate [200] or polyglucosylsorbitol fatty acid ester [201] and eventually cosolvents which are not susceptible for temperature changes. Ether carboxylates also show an improvement when used in a C02 drive process [202] or at recovery by steam flooding [203]. 

One of the longest known synthetically prepared surfactants are the fatty alcohol sulfates, which were prepared on technical scale before 1940. Along with their ethoxylated counterparts, the fatty alcohol ether sulfates, which appeared on the stage shortly after, their use in toiletries is very popular but they can also be found in products for textile industry and auxiliaries in emulsion polymerization. With the exception of soaps, the mentioned anionic surfactants all have a sulfur-containing functional group. Denying the differences between these, their skin irritancy potential is remarkably high. 

Sulfosuccinates are not only less irritating to skin and mucus membranes than other surfactants, but it was also found that they reduce skin irritation of other surfactants used in skin and hair care products. In particular, the effect on sodium lauryl ether sulfate was found to be most pronounced [103]. Figure 14 shows the mollifying effect of disodium oleic acid monoethanol amide sulfo-succinate when blended with anionic surfactant at a total concentration of 15%. 

DuPont is an active player in OLED technology. Polymers used in devices as emitting materials are poly(p-phenylenevinylene), poly(arylenevinylene)s, poly(p-phenylene), poly(arylene)s, polyquinolines, and polyfluorenes. In some cases, an anionic surfactant such as lithium nonylphenoxy ether sulfate was added to the above-mentioned polymeric emitters... 

X. Domingo, In H.W. Stache (Ed.), Alcohol and Alcohol Ether Sulfates, Anionic Surfactants, Surfactant Science Series, Vol. 56, Marcel Dekker, New York, USA, 1996, p. 223. 

A wide range of anionic surfactants (Fig. 23) has been classified into groups, including alkyl benzene sulfonates (ABS), linear alkyl benzene sulfonates (LAS), alcohol sulfates (AS), alcohol ether sulfates (AES), alkyl phenol ether sulfates (APES), fatty acid amide ether sulfates (FAES), alpha-olefin sulfates (AOS), paraffin sulfonates, alpha sulfonated fatty acids and esters, sulfonated fatty acids and esters, mono- and di-ester sulfosuccinates, sulfosuccinamates, petroleum sulfonates, phosphate esters, and ligno-sulfonates. Of the anionic surfactants, ABS and LAS continue to be the major products of anionic surfactants [314, 324]. Anionic surfactants have been extensively monitored and characterized in various environmental matrices [34,35,45,325-329]. 

Alkyl ether sulfates are/after alkyl benzene sulfonates(LAS),the group of technically important anionic surfactants with the largest production voluJne and product value. They have in comparison with other anionic surfactants special properties which are based on the particular structure of the molecule. These are expressed,for example,in the general adsorption properties at different interfaces, and in the Krafft-Point. Alkyl ether sulfates may be used under conditions, at which the utilization of other surfactant classes is very limited. They possess particularly favorable interfacial and application properties in mixtures with other surfactants. The paper gives a review of all important mechanisms of action and properties of interest for application. 

Alkyl ether sulfates with chain lengths ranging from to Cw are quantitatively the most important products currently based on fatty alcohols. It is estimated, that about 20 % of all surfactant alcohols -about 40 % of all fatty alcohols in the coconut range (C,2 Ci,) - are used in the form of alkyl ether suirateg ( ). Alkyl ether sulfates are the most important group of anionic surfactants after linear alkyl-benzenesulfonate (LAS) (2). 

In 1980, the total consumption of alkyl ether sulfates in Western Europe equaled that of all other anionic surfactants with the exception of alkyIbenzene-sulfonates (Fig. 1). Since alkyl ether sulfates are the most expensive group of anionic surfactants, which are produced in larger quantities, their importance on a... 

Other Anionic Surfactants Alkyl Ether Sulfates... 

An especially effective reduction of the Krafft Point results from the insertion of ether groups into the molecule of the anionic surfactant. In table I this is examplified with Na dodecyl sulfate and Na-tetra-decyl sulfate in comparison to various n-alkyl ether sulfates of the same chain length (10). As a measure of the Krafft Point, a temperature is deTined at which a 1 7o solution dissolves clearly. By the incorporation of oxyalkylene groups into the molecule, the Krafft -Point and the melting point are greatly depressed. This depression is especially effective if there is branching in the oxyalkylene groups. 

Washing and Cleaning Action. The properties of alkyl ether sulfates, due to the good solubility and the special hydrophilic/hydrophobic properties of the molecule, are of particular practical interest. From the investigations described in sections 2 and 3, it can be concluded that, in addition to the decrease in the Krafft Point, favorable properties for practical applications can be expected as a result of the inclusion of the oxyethylene groups into the hydrophobic part of the molecule. As is true for other anionic surfactants, the electrical double layer will be compressed by the addition of multivalent cations. By this means, the adsorption at the interface is increased, the surface activity is raised, and, furthermore, the critical micelle concentration decreased. In the case of the alkyl ether sulfates, however these effects can be obtained without encountering undesirable salting out effects. 

In most products,alkyl ether sulfates are used in form of mixtures with other surfactants. Alkyl benzene sulfonate (LAS) is the most important anionic surfactant used in combination with alkyl ether sulfates. 

Uranyl ions form complexes in solutions with most anions. Uranyl sulfate and carbonate complexes are especially strong and are used in extracting uranium from its ores. Of great practical importance are the complexes of the uranyl ions with nitrate that are soluble in organic liquids such as alcohols, ethers, ketones, and esters. One of the most important of these reactions is that involving the extraction of uranyl nitrate into TBP (the Purex process) ... 

Thus these characterization results not only give the distribution of the acrylic acid between the aqueous serum, particle surface, and particle interior, but also account satisfactorily for the total number of strong-acid groups arising from the anionic emulsifier and initiator. In addition, both the sodium lauryl ether sulfate and the nonylphenol polyoxyethylene adduct used in the polymerization were recovered from the fractions obtained by serum replacement. 

Several other anionic surfactants are commercially available, such as sulfosuccinates, isethionates, and taurates, and these are sometimes used for special applications. The carboxylates and sulfates are sometimes modified by the incorporation of a few moles of ethylene oxide (referred to as ether carboxylates and ether sulfates, respectively). 

Danielsson et al. [25] have studied the synthesis of PEDOT in ionic liquids that utilize bulky organic anions, l-butyl-3-methylimidazolium diethylene glycol monomethyl ether sulfate and l-butyl-3-methylimidazolium octyl sulfate, the latter of which is a solid at room temperature and thus requires the addition of either monomer or solvent (in this case water) to form a liquid at room temperature. Polymerization in a water-free ionic liquid was only possible in the octyl sulfate species, but the polymerization of EDOT was successful in aqueous solutions of both the ionic liquids (0.1 M). The ionic liquid anions appear to be mobile within the polymer, exchangeable with chloride ions at a polymer/KCl(aq) interface, but it is interesting that when the PEDOT is in aqueous solutions of the ionic liquid, at higher concentrations (0.01-0.1 M) the imidazolium cation can suppress this anion response. The ion mobility in both the ionic liquid and in the polymer film in contact with the solution is significantly increased by addition of water. 

Alkyl and Ether Sulfates. The second largest class of anionic surfactants is sulfated alcohols and ethoxylates. Falling film reactors are also used to sulfate these materials, however, cooling water and sulfation temperature are adjusted to lower values for these materials. The digestion and hydration steps are not required in sulfation and these systems are bypassed. The acids are neutralized immediately to minimize degradation and side reactions in storage. Typical S03 sulfation reactions for alcohols and alcohol ethoxylates are shown in Fig. 36.31. 

Alkyl ether sulfates (AES) are anionic surfactants obtained by ethoxy-lation and subsequent salfation of alcohols derived from feedstock or synthetic alcohol. AES, also known as alcohol ether sulfates, have low sensitivity to water hardness (Fig. 5.3), high solubility, and good storage stability at low temperature [4, 11]. 

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