Alkylphenol sulfation

Surfactants. Ethylene oxide-containing surfactants are generally of nonionic or anionic classes. The nonionic materials are made by base-catalyzed addition of ethylene oxide to either fatty alcohols or alkylphenols. Sulfation can be used to convert these compounds to the sulfated anionic surfactants. The products contain from a few to many ethylene oxide molecules per alcohol. The chain of polyethylene oxide) in a nonionic product acts as the hydrophile, and the alkyl or alkaryl residue is the hydrophobe. A sulfate salt group adds to the hydrophilicity of an anionic surfactant. 

Surfactants. Ethylene oxide-containing surfactants are generally of nonionic or anionic classes. The nonionic materials are made by base-catalyzed addition of ethylene oxide to either fatty alcohols or alkylphenols. Sulfation... 

Due to the kinetics of ethoxylation, low-mole ethoxylates such as these normally contain high levels of unethoxylated material, in this case alcohol sulfate or alkylphenol sulfate. 

ISO 6842 defines total active matter as ethanol solubles, which includes not only the ether sulfate but also alkyl or alkylphenol sulfate, PEG sulfate, and unsulfated nonionic material including PEG (70). ISO 6843 describes wet chemistry methods for separately determining PEG, sulfonated PEG, and inorganic salts in order to arrive at a value for the ether sulfate itself, but this value will still include alkylsulfate or alkylphenolsulfate (71). 

ISO 6843 specifies a variation of the extraction method for determination of PEG in nonionic surfactants. In this case, an aqueous salt solution of the surfactant is extracted with 9 1 ethyl acetate/l-butanol. Almost all of the ether sulfate goes into the organic phase, leaving behind PEG, PEG sulfate, and sulfate ion, as well as a small amount of the ether sulfate. Alkyl- or alkylphenol ethoxylate and alkyl- or alkylphenol sulfate are expected to partition primarily in the organic phase. The amount of anionic surfactant remaining in the aqueous phase is determined by two-phase titration, as is the equivalent weight of the extracted material (71). 

Ethoxylated andSulfatedAlkylphenols. Because these aLkylphenols degrade less readily than the sulfated alcohol ethoxylates, their anticipated expansion failed to materialize, although by 1965 they were widely used in retail detergent products. Sulfated alkylphenol ethoxylates are used in hospital cleaning products, textile processing, and emulsion polymerization. Sulfated alkyphenol ethoxylates are sold as colorless, odorless aqueous solutions at concentrations of >30%. The presence of ethylene oxide in the molecule increases resistance to hardness ions and reduces skin irritation. Representative commercial sulfated alkylphenol ethoxylates are given in Table 12. 

Table 12. Alkylphenols, Ethoxylated and Sulfated, RCgH4(0C2H4) 0S02M...

Snia Viscosa. Catalytic air oxidation of toluene gives benzoic acid (qv) in ca 90% yield. The benzoic acid is hydrogenated over a palladium catalyst to cyclohexanecarboxyhc acid [98-89-5]. This is converted directiy to cmde caprolactam by nitrosation with nitrosylsulfuric acid, which is produced by conventional absorption of NO in oleum. Normally, the reaction mass is neutralized with ammonia to form 4 kg ammonium sulfate per kilogram of caprolactam (16). In a no-sulfate version of the process, the reaction mass is diluted with water and is extracted with an alkylphenol solvent. The aqueous phase is decomposed by thermal means for recovery of sulfur dioxide, which is recycled (17). The basic process chemistry is as follows ... 

Other polyamine derivatives are used to break the oil/water emulsions produced at times by petroleum wells. Materials such as polyether polyols prepared by reaction of EDA with propylene and ethylene oxides (309) the products derived from various ethyleneamines reacting with isocyanate-capped polyols and quaternized with dimethyl sulfate (310) and mixtures of PEHA with oxyalkylated alkylphenol—formaldehyde resins (311) have been used. 

Ethylene oxide is an important intermediate chemical not only for the production of nonionic surfactants like fatty alcohol ethoxylates, alkylphenol ethoxy lates, or propylene oxide/ethylene oxide block copolymers, but also for manufacturing of anionic surfactants like alcohol ether sulfates. 

Synthetic fibers washing (Alkylphenol ethoxylates,) fatty alcohol ethoxylates, alkane (olefine)-sulfonates, fatty alcohol (ether) sulfates, end-group-blocked fatty alcohol ethoxylates... 

TABLE 18 CMC (mM) of different sodium alkylphenol propoxy sulfates... 

The complete analysis of alcohol sulfates is described in the Standard Methods of the International Organization of Standards (ISO) [200] and of the American Society for Testing and Materials (ASTM) [201]. These methods describe the analysis of inorganic sulfate content, chloride content, unsulfated matter, and water as well as other analytical values. Other ISO standards describe the analysis of sodium secondary alkyl sulfates [202], determination of pH [203], determination of water content [204,205], chlorides [206], total active matter in sul fated ethoxylated alcohols and alkylphenols [207], mean relative molecular mass in sulfated ethoxylated alcohols and alkylphenols [208], sulfate content... 

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. 

Alkylphenol ether sulfates are slightly more resistant to biodegradation than alkylbenzenesulfonates. Similarly to alcohol ether sulfates, this resistance increases with the degree of ethoxylation. Again there are some differences in favor of primary alkylphenol ether sulfates with respect to secondary alkylphenol ether sulfates [426]. 

HARRIS R M, WARING R H, KIRK c J, HUGHES p J (2000) Sulfation of oestrogenic alkylphenols and 17beta-oestradiol by human platelet phenol sulfotransferases. J Biol Chem. 275 159-66. 

Applications Various surfactant types (ABS, AES, secondary alkane sulfonates, and alkylphenol ethoxy-sulfates) have been analysed by means of a QQQ using a thermospray source [89]. Other applications of hyphenated thermospray ionisation mass-spectrometric techniques (LC-TSP-MS) are described elsewhere (Section 73.3.2). 

Capillary gel electrophoresis (CGE) is a specialised form of CE that employs a fused silica capillary filled with an immobilised and cross-linked polyacrylamide gel. This gel contains a network of pores, which allows separation of ions based on differences in molecular size. CGE was applied to the separation of ionic alkylphenol ethoxy sulfates and... 

In the negative FIA-MS spectra, the sulfate, phosphate and carboxylate of these anionic alkylphenol ether derivatives in parallel to the aliphatic ethoxy surfactants show equally spaced signals with Am/z 44. However, according to the ionisation method applied—APCI or ESI in the negative or positive mode—and also that observed in the ionisation process of AES, equally spaced signals came either from the anionic compounds themselves or from the alkylphenol ethers... 

A broad range of information pertaining to the toxicity of several classes of surfactants including anionic (linear alkylbenzene sulfonates (LAS), alkylether sulfates (AES), alkyl sulfates (AS), non-ionic (alkylphenol ethoxylates (APEO)), cationic (ditallow dimethyl ammonium chloride (DTDMAC)—a group of quaternary ammonium salts of distearyl ammonium chloride (DSDMAC)) and amphoteric surfactants (alkyl-betaines) is available. Several reviews of the scientific literature have been published [3-5,20]. 

ABS AE AE/P AES AG AOS APEO APG AS BiAS BM c6(EO)3 CNPEC CTAS D DATS DCPEG DEEDMAC branched alkylbenzene sulfonate alcohol ethoxylate alcohol ethoxylate/propoxylate alkylether sulfate alkyl glucamide a-olefin sulfonate alkylphenol ethoxylate alkyl polyglucoside alkyl sulfate bismuth active substances alkyldimethylbenzyl ammonium triethylene glycol monohexyl ether carboxylated nonylphenoxy carboxylates cobalt thiocyanate active substances R2S10(o.5)2 dialkyl tetralinsulfonate dicarboxylated PEG ditallow ester of di(hydroxyethyl)dimethyl ammonium chloride... 

SDS was an exception. Among the traditional surfactant work-horses, including anionics (such as alkylbenzene sulfonates and alkyl sulfates), nonionics (such as alcohol ethoxylates and alkylphenol ethoxylates), and cationics (such as alkyl quats and dialkyl quats), only alkyl sulfates are not chemically stable under normal conditions. 

---