Alkylbenzenesulfonate

Fig. XII-12. Top friction traces for two calcium alkylbenzenesulfonate monolayers on mica where the monolayers are in a liquidlike state. A—in inert air atmosphere B—in saturated decane vapor. Bottom contact radius-load curves showing adhesion energy measured under the same conditions as the friction traces. (From Ref. 53.)...

Detergents are metal salts of organic acids used primarily in crankcase lubricants. Alkylbenzenesulfonic acids, alkylphenols, sulfur- and methjiene-coupled alkyl phenols, carboxyUc acids, and alkylphosphonic acids are commonly used as their calcium, sodium, and magnesium salts. Calcium sulfonates, overbased with excess calcium hydroxide or calcium carbonate to neutralize acidic combustion and oxidation products, constitute 65% of the total detergent market. These are followed by calcium phenates at 31% (22). 

Alkylation. Benzene and phenol feedstocks are readily alkylated under Friedel-Crafts conditions to prepare extensive families of alkylated aromatics. These materials generally are intermediates in the production of surfactants or detergents such as linear alkylbenzenesulfonate (LABS) and alkylphenolethoxylate (APE). Other uses include the production of antioxidants, plasticizers, and lube additives. 

Linear alkylbenzenesulfonic acid is the largest intermediate used for surfactant production in the world. In the United States it has been determined that 2.6 g/d of material is used per inhabitant (46). Owing to the large volumes of production and consumption of linear alkylbenzenesulfonate, much attention has been paid to its biodegradation and a series of evaluations have been performed to thoroughly study its behavior in the environment (47—56). Much less attention has been paid to the environmental impact of other sulfonic acid-based materials. 

Linear alkylbenzenesulfonate showed no deleterious effect on agricultural crops exposed to this material (54,55). Kinetics of biodegradation have been studied in both wastewater treatment systems and natural degradation systems (48,57,58). Studies have concluded that linear alkylbenzenesulfonate does not pose a risk to the environment (50). Linear alkylbenzenesulfonate has a half-life of approximately one day in sewage sludge and natural water sources and a half-life of one to three weeks in soils. Aquatic environmental safety assessment has also shown that the material does not pose a hazard to the aquatic environment (56). 

Surfactants and Detergents Uses. Perhaps the largest use of sulfonic acids is the manufacture of surfactants (qv) and surfactant formulations. This is primarily owing to the dominance of linear alkylbenzenesulfonic acid production for detergent manufacture. In almost all cases, the parent sulfonic acid is an intermediate which is converted to a sulfonate prior to use. The largest volume uses for sulfonic acid intermediates are the... 

Sulfur dioxide is usefiil as a solvent for sulfur trioxide in sulfonation reactions for example, in the large-scale production of alkylbenzenesulfonate surfactant (329). A newer use for sulfur dioxide is in cyanide detoxification in connection with cyanide leaching of precious metals from mine dumps. 

Acids such as fatty acids and alkylbenzenesulfonic acids are neutralized with NaOH during slurry preparation to form soap and sodium alkylbenzenesulfonate, respectively. 

Several cleaning formulations for specific uses contain unreacted polyamines. Examples include mixtures of ammonium alkylbenzenesulfonate, solvents, and PIP which give good cleaning and shine performance on mirrors and other hard surfaces without rinsing (305), and a hard-surface cleaner composed of a water-soluble vinyl acetate—vinyl alcohol copolymer, EDA, cyclohexanone [108-94-1] dimethyl sulfoxide [67-68-5] a surfactant, and water (306). TEPA, to which an average of 17 moles of ethylene oxide are added, improves the clay sod removal and sod antiredeposition properties of certain hquid laundry detergents (307). 

AH detergent proteases are destabilized by linear alkylbenzenesulfonate (LAS), the most common type of anionic surfactant in detergents. The higher the LAS concentration and wash temperature, the greater the inactivation of the enzyme. The presence of nonionic surfactants, however, counteracts the negative effect of LAS. Almost aH detergents contain some nonionic surfactant therefore, the stabHity of proteases in a washing context is not problematic. 

Chemical Designations - Synonyms Alkylbenzenesulfonic acid, sodium salt Sulfonated alkylbenzene ... 

Laundry and cleaning products (powder and liquid household cleaners), in which linear alkylbenzenesulfonate (LAS) and tetrapropylenebenzenesulfonate (TPBS) are used in combination with other surfactants, builders, and additives. Today TPBS is used only in small amounts because of its poor biodegradability. 

B. Historical Development of the Industrial Production of Alkylbenzenes and Alkylbenzenesulfonates... 

The development of alkylbenzenesulfonates (ABSs) goes back to 1923, when the British chemist Adams discovered that it was possible to obtain water-soluble products by the sulfonation and neutralization of hexadecyl- and octadecyl-benzene. Such products have also soap-like characteristics [1]. In 1926 IG-Farbenindustrie (Hoechst) and Chemische Fabrik Pott, Pirna/Sachsen simultaneously discovered that long-chain ABSs have excellent surface-active properties. 

The color of the derivative alkylbenzenesulfonic acid is clearly better. The solubility characteristics remain good. An olefin from the Pacol-Olex process (C, 0/13 olefin) is used as a starting olefin. The DeFine step is employed to reduce the diolefin content to <0.5%. With such an olefin an LAB is obtained over an aluminum chloride catalyst with a linear content of >99% and from which the sulfonation product has a biodegradability (DOC) comparable to that of other LABs[122,123].Table 25 gives typical physical-chemical data about different LAB types. 

TABLE 21 Biodegradation Data from Linear Alkylbenzenesulfonate (C1 6-LAS)... 

Physical Properties and Behavior of Linear Alkylbenzenesulfonates in Mixtures with Other Surfactants in Household Detergent Products... 

Examples comparing the secondary alkanesulfonate content of influents and effluents of various sewage treatment plants with the concentrations of linear alkylbenzenesulfonates are shown in Table 12. In sludges the specimen secondary alkanesulfonate (linear alkylbenzenesulfonate) concentration of less than 0.1... 

TABLE 12 Secondary Alkanesulfonates (SAS) and Linear Alkylbenzenesulfonates (LAS) in Sewage Treatment Plant Influents and Effluents (pg/L)... 

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