Higher alcohols alcohol ether sulfates

Monohydrochloride, CWhite solid uv max (HjQ) 282 nm (Ej 46), Soly in water >100mg/m]. Moderately sol in di] methanol. In sol in the higher alcohols, acetone, ether. Low conens of urea increase the soly in neutral aq solns. Ammonium sulfate and sodium chloride ppt the antibintic from acidic solns. LIX, in mice (mg/kg) 489 i.v. 1734 i.p. 5000 s.c. and oral -ly (Anderson). 

While alcohol sulfates, like sodium lauryl sulfate, are seldom used in household cleaning formulations, ethoxylated alcohol sulfates or alcohol ether sulfates are used more often. The ethoxyl-ated alcohol sulfates like sodium alkyl ethoxylated sulfate have become extensively used in many types of cleaners, often in mixtures with LAS for heavy-duty cleaners, or as the main surfactants themselves in the lighter-duty spray cleaners. They are generally somewhat milder than LAS and paraffin sulfonates, and higher foaming but somewhat less effective at grease removal. 

Higher n-olefins of Cs-Ci4 are used as intermediates in the manufacture of several types of surfactant materials. Linear internal olefins are used in the production of linear alkylbenzene alkylphenol detergent alcohols, which in turn is used to produce alcohol sulfates, alcohol ethoxylates, and alcohol ether sulfates and synthetic lubricants. a-Olefins are used in the production of detergent alcohols, linear alkylbenzene, synthetic lubricants, and a-olefin sulfonates (another ionic surfactant). 

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. 

The major derivatives of normal primary higher alcohols used in the detergent industry were discussed. These included alcohol ethoxylates, alcohol ether sulfates, and alkyl sulfates. The chemical reactions for preparation of each were also given. 

The more complex the olefin, the lower the temperature and pressure at which reaction (1) will take place. Furthermore, ethylene requires a more concentrated sulfuric acid for efficient absorption than its homologues. Both mopo- and dialkyl sulfates are formed simultaneously when ethylene or propylene is absorbed in sulfuric acid., An appreciable amount of diethyl sulfate is formed when the acid has reacted with about inole of ethylene. In addition, appreciable amounts of the corresponding ethers are produced. Ethyl ether, for example, is formed to a considerable extent by the reaction of alcohol with diethyl sulfate. Polymer formation, particularly for higher olefins, is also an undesirable side reaction. 

Preparation of Ethanol from Ethylene. Via Ethyl Hydrogen Sulfate Ethylene is scrubbed, purified, and piped in gaseous form direct to processing in the alcohol plant (Fig. 13-6). On entering an absorber, ethylene comes into contact with sulfuric acid of 95 per cent concentration or higher. The resulting liquid is a mixture of monoethyl and diethyl sulfate. The esters leave the bottom of the absorber and are pumped into the bottom of a hydrolyzer column along with a measured volume of water. Here the esters formed in the absorber are converted to alcohol, ethyl ether, weak sulfuric acid, and small volumes of other materials. 

Besides the ether sulfates derived from coconut oil fatty alcohols, it is possible to produce other compounds with a higher degree of ethoxylation by using, other alcohols as starting materials. In this way, the hydrophilic/lipophilic balance (HLB) value can be widely varied. Thus, additives can be produced for oil-in-water (OAV) or water-in-oil (W/O) emulsions, for use in saline water, for detergents, and for dispersants of lime soap. 

Hydration of Olefins. The earliest and still the largest production of chemicals from petroleum hydrocarbons was based on the hydration of olefins to produce alcohols by the employment of sulfuric acid. The addition of olefins to sulfuric acid to form alkyl sulfates and dialkyl sulfates takes place on simple contact of the hydrocarbons with the acid. To keep down polymerization and isomerization of the hydrocarbons, the temperature is kept relatively low, usually below 40° C. and commonly considerably lower than that (18). The strength of the sulfuric acid used depends on the olefin to be absorbed. Absorption of ethylene requires an acid concentration higher than 90%, whereas propylene and butylenes are readily absorbed in 85% acid or less. The alkyl and dialkyl sulfate solutions, on dilution and heating, are hydrolyzed to the alcohols plus small amounts of by-product ethers. After distilling off the organic products, the dilute sulfuric acid is reconcentrated and re-used. 

Mixed aliphatic ethers containing methyl or ethyl radicals can be synthesized from the corresponding alkyl sulfate and magnesium alcoholates, e.g., methyl n-butyl, methyl cyclohexyl, and methyl isoamyl ethers (70-78%). A higher yield of ethyl isobutyl ether is obtained by substituting sodium for magnesium (70% vs. 30%). ... 

The a-position of an ether is susceptible to attack by free radicals and, in certain circumstances, by halogens. Ethers are slowly oxidized by the oxygen from air to form peroxides- This can be a hazard in stored bottles of ethers, particularly with the higher ethers such as di-isopropyl ether. These peroxides may be destroyed by treatment with iron(IT) sulfate. Chlorine reacts with ethers, particularly in sunlight. These a-halo ethers then decompose to the aldehyde and an alcohol. 

Sulfate esters may be analyzed by GC and GC/MS techniques. Individual substances may be separated on a suitable column (capillary column such as DB-5 or equivalent) and determined by an FID, FPD or a mass selective detector. Alternatively, the aqueous solutions of lower esters may be distilled. The hydrolysis products alcohols are separated on distillation and determined by derivatization and/or chromatography. Aqueous solution of unhydrolyzed higher esters at trace levels may be directly injected onto the GC column for FID determination, or serially extracted with petroleum ether, the extract concentrated and analyzed by chromatographic technique. 

The chlorosulfonic acid-ether complex is a milder reagent than free chlorosulfonic acid for the sulfation of alcohols and is outstanding in respect of yield and purity of the alkyl hydrogen sulfates 45 produced. The use of chlorosulfonic acid in diethyl ether at low temperature (-50 °C) is a standard method for sulfation of higher (Cg-C28) primary and secondary alcohols. The latter have also been successfully sulfated using a mixture of chlorosulfonic acid in acetic acid the active entity here is probably acetyl sulfate. This method has been adapted for the synthesis of very pure sodium alkyl sulfates for use as detergents thus chlorosulfonic acid and 1-dodecanol were successively added to acetic acid at low temperature (—10 to -15 °C), the solid product was neutralized with sodium carbonate and unreacted alcohols extracted with solvents to give 98.6% pure dodecanyl sodium sulfate. ... 

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