Higher alcohols alcohol sulfates

Sulfation by sulfamic acid has been used ia the preparation of detergents from dodecyl, oleyl, and other higher alcohols. It is also used ia sulfating phenols and phenol—ethylene oxide condensation products. Secondary alcohols react ia the presence of an amide catalyst, eg, acetamide or urea (24). Pyridine has also been used. Tertiary alcohols do not react. Reactions with phenols yield phenyl ammonium sulfates. These reactions iaclude those of naphthols, cresol, anisole, anethole, pyrocatechol, and hydroquinone. Ammonium aryl sulfates are formed as iatermediates and sulfonates are formed by subsequent rearrangement (25,26). 

Ethoxylated alcohol sulfates have several advantages over alcohol sulfates including lower sensitivity to hardness with respect to foaming and detersive effectiveness, less irritation to skin and eyes, and higher water solubiUty. 

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 rheology and phase behavior of sodium linear C16-C18 alcohol sulfate and sodium oxo C14-Cl5 (80% linear) alcohol sulfate was studied by van Zon et al. [75]. The oxoalcohol sulfate can be prepared as a handleable 65-70% concentrate. The linear C16-C18 alcohol sulfate only allows 55-60% as maximum concentration. The hexagonal phase of the oxoalcohol sulfate extends from 38% to 55% active matter whereas the hexagonal band of the linear alcohol sulfate is very narrow, only extending from 35% to 40% and its crystallization line is situated at a higher level than for the oxo derivative. 

The aggregation numbers of alcohol sulfates can be as low as 20 for sodium octyl sulfate in water solution but usually range from 60 to 150 for higher alcohol sulfates. 

A similar process allows reacting triethyl phosphate and phosphorous pentoxide to form a polyphosphate in an organic solvent [871]. An excess of 1.3 moles of triethyl phosphate with respect to phosphorous pentoxide is the most preferred ratio. In the second stage, a mixture of higher aliphatic alcohols from hexanol to decanol is added in an amount of 3 moles per 1 mole phosphorous pentoxide. Aluminum sulfate is used as a crosslinker. Hexanol results in a high-temperature viscosity of the gel, while maintaining at a pumpable viscosity at ambient temperatures [870]. 

Sulfate-resisting cement, 5 498 Sulfate surfactants, 24 145 Sulfate titanium dioxide production process, 29 388-391 Sulfathiazole, 28 684 Sulfation, 23 513, 514, 536-538 higher aliphatic alcohols, 2 4 in higher olefins, 27 713 Sulfation operations, industrial changes affecting, 23 515-516 Sulfation processes, general overviews of, 23 555... 

In step four the bottoms are mixed with water and a trace of sulfuric acid. The chains separate from the aluminum in favor of a hydrogen atom, creating the higher alcohols and aluminum hydroxide, Al (OH)3, which drops out of solution as a precipitate. The aluminum product can be readily dehydrated to alumina, AI2O3, and sold. Some processes use sulfuric acid, H2SO4, to do the hydrolyzing instead of water. That results in by-product aluminum sulfate, A1(S04)3, a marketable but less valuable product than alumina. 

Alcohol sulfates (AS) are usually manufactured by the reaction of a primary alcohol with sulfur trioxide or chlorosulfonic acid followed by neutralization with a base. These are high foam surfactants but they are sensitive to water hardness and higher levels of phosphates are required. This latter requirement has harmed the market for this type of detergent, but they are 2% of production for the major household surfactant market. Sodium lauryl sulfate (R = Cn) is a constituent of shampoos to take advantage of its high-foaming properties. 

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. 

Linear internal monoolefins can be oxidized to linear secondary alcohols. The alpha (terminal) olefins from ethylene oligomerization, described earlier in this chapter, can be converted by oxo chemistry to alcohols having one more carbon atom. The higher alcohols from each of these sources are used for preparation of biodegradable, synthetic detergents. The alcohols provide the hydrophobic hydrocarbon group and are linked to a polar, hydrophilic group by ethoxylation, sulfation, phosphorylation, and so forth. 

The higher alcohols are used as plasticizers and solvents in the polymer industry. They also have several other important industrial uses. They can be sulfated using H2S04 to give a long-chain sulfate ... 

These long-chain sulfates are used as anionic detergents [109]. Higher alcohols can react with ammonia and methyl amines ... 

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