Alkylbenzenes, sulfonation

Linear paraffins in the C q to range are used for the production of alcohols and plasticizers and biodegradable detergents of the linear alkylbenzene sulfonate and nonionic types (see Alcohols Plasticizers Surfactants). Here the UOP Molex process is used to extract / -paraffins from a hydrotreated kerosine (6—8). 

Alkylation of benzene using alpha olefins produces linear alkylbenzenes, which are further sulfonated and neutralized to linear alkylbenzene sulfonates (LABS). These compounds constitute, with alcohol ethoxy-sulfates and ethoxylates, the basic active ingredients for household detergents. Production of LABS is discussed in Chapter 10. 

Typical properties of detergent alkylate are shown in Table 10-2. Detergent manufacturers buy linear alkylbenzene, sulfonate it with SO3, and then neutralize it with NaOH to produce linear alkylbenzene sulfonate (LABS), the active ingredient in detergents ... 

Emulsion polymerization is widely used to produce polymers in the form of emulsions, such as paints and floor polishes. It also used to polymerize many water insoluble vinyl monomers, such as styrene and vinyl chloride. In emulsion polymerization, an agent emulsifies the monomers. Emulsifying agents should have a finite solubility. They are either ionic, as in the case of alkylbenzene sulfonates, or nonionic, like polyvinyl alcohol. 

When comparing secondary alkanesulfonates (SAS) and linear alkylbenzene-sulfonates (LAS), it is obvious that SAS are more readily degraded than LAS. This is somewhat more pronounced at lower temperatures (Table 34). 

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. 

The CMC of commercial AOS and other surfactants at 40°C has been determined by Gafa and Lattanzi [6] who plotted the surface tension of aqueous surfactant solutions against concentration. The surface tensions were determined with the ring method according to du Nouy. Table 5 gives their CMC values in mmol/L and the surface tension at the CMC in mN/m. Table 5 also contains CMC values of isomerically pure sodium alkyl sulfates, sodium alkylbenzene-sulfonates, sodium hydroxyalkanesulfonate, and sodium alkenesulfonates at 40°C, taken from the literature [39 and references cited therein]. 

FIG. 8 Reduction in surface tension of 0.05% solutions of linear alkylbenzene-sulfonate-a-olefinsulfonate (LABS-AOS) mixed surfactant system. (From Ref. 3.)... 

Jimenez L, A Breen, N Thomas, TW Federle, GS Sayler (1991) Mineralization of linear alkylbenzene sulfonate by a four-member aerobic bacterial consortium. Appl Environ Microbiol 57 1566-1569. 

Huang Y, A Latorre, D Barcelo, J Garcia, P Aguirre, JM Bayona (2004) Factors affecting linear alkylbenzene sulfonates removal in subsurface flow consh ucted wetlands. Environ Sci Technol 38 2657-2663. 

The thermal degradation of alkylbenzene sulfonates in alkaline media is important because of the application at elevated temperatures. The half-lives, with respect to thermal degradation, of several commercially available sulfonates were estimated at hundreds to thousands of years at 204° C. The degradation mechanism was predominately a clipping of the alkyl chain to yield an alkylbenzene sulfonate with the phenyl group attached to the a-carbon however, desulfonation also occurred [1624]. 

R. D. Shupe and T. D. Baugh. Thermal stability and degradation mechanism of alkylbenzene sulfonates in alkaline media. J Colloid Interface Sci, 145(l) 235-254, August 1991. 

Surfactants used as lubricants are added to polymer resins to improve the flow characteristics of the plastic during processing they also stabilise the cells of polyurethane foams during the foaming process. Surfactants are either nonionic (e.g. fatty amides and alcohols), cationic, anionic (dominating class e.g. alkylbenzene sulfonates), zwitterionic, hetero-element or polymeric (e.g. EO-PO block copolymers). Fluorinated anionic surfactants or super surfactants enable a variety of surfaces normally regarded as difficult to wet. These include PE and PP any product required to wet the surface of these polymers will benefit from inclusion of fluorosurfactants. Surfactants are frequently multicomponent formulations, based on petro- or oleochemicals. 

Taking in account the results obtained by Graciaa (8) and Osborne-Lee (9) for alkylbenzene sulfonate and alkylphenols with an increasing degree of ethoxylation, we have considered that the interaction between sulfonate and associated highly ethoxylated nonylphenol (with 30, 50 or 100 E.O.) was predominant in mixed micelles of the mixtures investigated. 

PLE pressurized liquid extraction, SPE solid phase extraction, UE ultrasonic extraction, DSPE dispersive solid phase extraction, SBSE stir bar sorptive extraction, TD-GC-MS thermal desorption-gas chromatography-mass spectrometry, LAS linear alkylbenzene sulfonates, CDEAs coconut diethanol amides, NPEOs nonylphenol ethoxylates, DP degradation products, SPC sulphenyl carboxylates, PCDD dibenzo-p-dioxins (PCDD), PCDF dibenzofurans, PCBs biphenyls... 

Gonzalez S, Petrovic M, Barcelo D (2004) Simultaneous extraction and fate of linear alkylbenzene sulfonates, coconut diethanol amides, nonylphenol ethoxylates and their degradation products in wastewater treatment plants, receiving coastal waters and sediments in the Catalonian area (NE Spain). J Chromatogr A 1052(1-2) 111-120... 

Eichhom P, Lopez O, Barcelo D (2005) Application of liquid chromatography-electrospray-tandem mass spectrometry for the identification and characterisation of linear alkylbenzene sulfonates and sulfophenyl carboxylates in sludge-amended soils. J Chromatogr A 1067 171-179... 

Mackay D, Di Guardo A, Paterson S, Kicsi G, Cowan D, Kane D (1996) Assessment of chemical fate in the environment using evaluative, regional and local-scale models illustrative application to chlorobenzene and linear alkylbenzene sulfonates. Environ Toxicol Chem 15(9) 1638-1648... 

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].

Surfactants, such as linear alkylbenzene sulfonates (LAS) and alkylphenol ethoxylates, are present in whitewaters because of their use as cleaning agents or as additives in antifoamers, deinkers, dispersants, etc. The non-ionic surfactants alkylphenol ethoxylates (APEO) degrade to nonylphenol (NP) or to a... 

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