Linear alcohol sulfates

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 foaming properties of sodium symmetrical secondary alcohol sulfates, sodium secondary alcohol sulfates, isomeric sodium secondary pentanol sulfates, and sodium linear alcohol sulfates were studied by Dreger et al. [72] via the Ross-Miles test [150] at 46°C. Within the linear series sodium tetradecyl sulfate produces the largest amount of foam. The influence of several electrolytes was also studied. 

TABLE 32 Primary Biodegradation of Linear Alcohol Sulfates... 

Steinle et al. [426] studied the primary biodegradation of different surfactants containing ethylene oxide, such as sulfates of linear primary alcohols, primary oxoalcohols, secondary alcohols, and primary and secondary alkyl-phenols, as well as sulfates of all these alcohols and alkylphenols with different degrees of ethoxylation. Their results confirm that primary linear alcohol sulfates are slightly more readily biodegradable than primary oxoalcohol sulfates and that secondary alcohol sulfates are also somewhat worse than the corresponding linear primary. 

Surfactants can be divided into four general areas cationic surfactants, anionic surfactants, nonionic surfactants, and amphoteric surfactants. Major anionic surfactants are soaps, linear alcohol sulfates, linear alcohol ethoxy-sulfates, and linear alkylbenzenesulfonates. 

Chem. Descrip. Linear alcohol sulfates Ionic Nature Anionic... 

Anhydrous sulfonic acids, particularly linear alkylben2enesulfonic acids, are typically stored ia stainless steel containers, preferably type 304 or 316 stainless steel. Use of other metals, such as mild steel, contaminates the acid with iron (qv), causiag a darkening of the acid over time (27). The materials are usually viscous oils which may be stored and handled at 30—35°C for up to two months (27). AH other detergent-grade sulfonic acids, eg, alcohol sulfates, alcohol ether sulfates, alpha-olefin sulfonates, and alpha-sulfomethyl esters, are not stored owiag to iastabiUty. These are neutrali2ed to the desired salt. 

APG, alkyl polyglucoside FAA, fatty acid alkanolamide FAEO, fatty alcohol ethoxylate FAES, fatty alcohol ether sulfate FAGA, fatty acid glucamide FAS, fatty alcohol sulfate LAS, linear alkylbenzenesulfonate SAS, secondary alkanesulfonate. 

Alcohols obtained from fats and oils contain an even number of carbon atoms and they are completely linear. Alcohols obtained from petrochemical sources can be linear or branched, depending on the manufacturing process, and can also have even or odd numbers of carbon atoms. In many practical applications the small differences observed in the behavior of sulfated alcohols or indeed sulfated alcohol ethoxylates from either source is of no significance and the choice is made on economic grounds. 

Shedlovsky et al. studied mixtures of sodium decyl, dodecyl, and tetradecyl sulfates by electromotive force measurements and determined the extent of the dissociation of the sodium counterions by the micelles. From the data obtained strong interaction below the CMC was found for all of the mixtures except those containing more than 25 mol % of sodium decyl sulfate [122]. Commercial alcohol sulfates are mixtures of homologs with different hydrocarbon chains. It has been demonstrated [123] that the CMC of such products is lower than that expected by calculation from the linear relationship between log CMC and the number of carbon atoms of the alcohol as stated in Eq. (11). These results are shown in Fig. 9. 

Alcohol and alcohol ether sulfates are commonly considered as extremely rapid in primary biodegradation. The ester linkage in the molecule of these substances, prone to chemical hydrolysis in acid media, was considered the main reason for the rapid degradation. The hydrolysis of linear primary alcohol sulfates by bacterial enzymes is very easy and has been demonstrated in vitro. Since the direct consequence of this hydrolysis is the loss of surfactant properties, the primary biodegradation, determined by the methylene blue active substance analysis (MBAS), appears to be very rapid. However, the biodegradation of alcohol sulfates cannot be explained by this theory alone as it was proven by Hammerton in 1955 that other alcohol sulfates were highly resistant [386,387]. 

Linear primary alcohol sulfates can also be biodegraded under anaerobic conditions but the process seems to be limited to the hydrolysis of the sulfate [407]. 

Linear primary alcohol sulfates often need only one day for 95 % primary biodegradation and degrade faster than other anionic surfactants, which usually need several days. This difference has been confirmed by Ruschenberg [412, 413]. 

However, they behave similarly to alcohol sulfates since linear alcohol ether sulfates are more easily biodegradable than branched alcohol ether sulfates. Also linear secondary alcohol ether sulfates are poorer than linear primary alcohol ether sulfates [425]. 

Figure 7. Dependence of the fluorescence quamum yield of BMPC on solvent viscosity ( ) in linear alcohols, from methanol to dccanol, at 25°C, (o) in absolute ethanol between 200 and 298 K. The quantum yields were measured on optically thin samples (Am <0.2). The value in ethanol, 5.7x10, was determined relative to quinine sulfate in 0.5 mol 1" HjSO ((j)p=0.55 [62]) and 9,10-diphenylanthracene in cyclohexane (4ip=0.90 [63]). It was then used as a reference for the determinations in the other alcohols.

Fig. 4.3 Interfacial tension between a solution of C,2/i4-fatty alcohol sulfate (FAS) and linear alkylbenzene sulfonate (LAS) and two different oils as a function of time [43].

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]. 

The shift to oleochemicals has been supported by increasing environmental concerns and a preference by some consumers, especially in Europe, for materials based on natural or renewable resources. Although linear alkylbenzenesulfonates (LASs) are petrochemically based, alcohol ethoxylates, alcohol ethoxysulfates, and primary alcohol sulfates are derived from long-chain alcohols that can be either petrochemically or oleochemically sourced. There has been debate over the relative advantages of natural (oleochemical) vs synthetic (petrochemical) based surfactants. However, detailed analyses have shown there is litde objective benefit for one over the other. 

Matthis, E., M. S. Holt, A. Kiewiet, and G. B. J. Rijs, Environmental monitoring for linear alkylbenzene sulfonate, alcohol ethoxylate, alcohol ethoxy sulfate, alcohol sulfate, and soap , Environ Toxicol. Chem., 18,2634-2644 (1999). 

Amnionic surfactants used in shampoos, cosmetics, toothpaste, and laundry products include linear alkylbenzenesulfonates (LAS), alcohol sulfates (AS), alcohol ethoxysulfates (AES), alcohol glycerol ether sulfonates, and alpha-olefin sulfates. Household end use of anionic surfactants in the United States was 7.3 X 105 metric tons in 1987 LAS, AS, and AES accounted for 98% of the total (I). 

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