Surface properties of linear alkyl benzene sulfonates in hard river water

Surface properties of a series of highly purified linear alkyl benzene sulfonates were extensively studied in hard river water. The effects of water hardness, alkyl chain length and position of the phenyl sulfonate group in the molecule on such surface properties as pC₂₀, critical micelle concentration (CMC), γ_CMC, CMC/C₂₀ ratio, and minimum area per molecule at the interface are discussed in detail. The position of phenyl sulfonate group in the molecule was found to have a pronounced effect on the CMC, γ_CMC value, CMC/C₂₀ ratio, and, to the contrary, a relatively small effect on the pC₂₀ value. The linear relationship between pC₂₀ or-log CMC, and m, the number of carbon atoms in the alkyl chain, was found for surfactants with the phenyl sulfonate group either at the terminal position or at the more central position in the molecule. γ_CMC decreases but the CMC value increases, when the position of phenyl sulfonate group moves from the terminal toward a more central position of the molecule, reflecting the “Hartley Effect” resulting from the branched alkyl chain.     

High pressure liquid chromatography of alpha olefin sulfonates

Alpha olefin sulfonates (AOS) are a complex mixture of the posi-tional isomers of hydroxyalkane sulfonates, alkene sulfonates, and disulfonates. This paper describes a qualitative method for separat-ing these various components by reverse-phase high pressure liquid chromatography. The column utilized was a DuPont Zorbax TMS (4.6 mm × 25 cm) with a water/methanol (25:75, v/v) mobile phase containing sodium nitrate at a concentration of 0.4M. The hydroxyalkane sulfonate and alkene sulfonate peaks were identified using laboratory prepared standards. The disulfonate peaks were located using controlled sulfonation conditions. More work needs to be done to separate an overlap of C₁₆ 3-hydroxyalkane sulfonate and C₁₄ 2-alkene sulfonate in 1416 AOS. However, if studies are based on single carbon number AOS samples, the overlap of these peaks can be avoided. This method can be utilized as a qualitative tool for the comparison of sulfonation runs, the identification of AOS within a detergent, or the identfication of the olefin type used for sulfonation.     

Ultimate biodegradation studies of α-olefin sulfonates

Single carbon cut α-olefin sulfonates (AOS) having 12, 14, 16 and 18 carbon chain lengths and several of their blends were prepared from high-quality α-olefins by continuous SO₃ sulfonation in a laboratory falling film reactor. The ultimate biodegradability of these products was studied using a modified shake flask procedure with CO₂ evolution as the major biodegradability criterion. For comparison, commercial samples of a modified Ziegler-based AOS, linear alkylbenzene sulfonates (LAS), and an alcohol ethoxysulfate (AEOS) were included. The results showed the AOS products bio-degraded to CO₂ more completely than LAS and slightly less extensively than AEOS. CO₂ evolution decreased slightly in amount and rate as AOS carbon chain length increased in the C₁₄ to C₁₈ range. Presented at the AOCS meeting, May 1977, New York City.     

Trace constituents in milk fat: Isolation and identification of oxofatty acids

Ca. 1% of the glycerides of milk fat contain oxofatty acids. The isolation, fractionation, and characterization of oxofatty acids were accomplished using the following sequence of steps: (A) transmethylation, (B) conversion into 2,4-dinitrophenylhydrazones, (C) adsorption of the 2,4-dinitrophenylhydrazones on magnesium oxide to eliminate the colorless lipid, (D) fractionation of the 2,4-dinitrophenylhydrazones into non-oxofatty acid and oxofatty acid fractions on alumina, (E) separation of the oxofatty acid 2,4-dinitrophenylhydrazones into saturated and unsaturated classes by argentation column chromatography, (F) separation of these classes by chain length using liquid-liquid column and thin layer partition chromatography, (G) resolution of positional isomers by thin layer chromatography, (H) regeneration of the positional isomer 2,4-dinitrophenylhydrazones, and (I) analysis of the parent oxofatty acids by gas liquid chromatographymass spectrometry. In this manner, 36 saturated and 11 unsaturated oxofatty acids were identified tentatively or positively. The saturated oxofatty acids ranged in chain length from C₁₀–C₂₄, predominantly C₁₈ and C₁₆, and generally contained an even number of carbon atoms. The unsaturated oxofatty acids ranged from C₁₄–C₁₈, with C₁₈ predominating.     

A Novel Alkyl Sulphobetaine Gemini Surfactant Based on S‐triazine: Synthesis and Properties

A series of alkyl sulphobetaine Gemini surfactants C_n‐GSBS (n = 8, 10, 12, 14, 16) was synthesized, using aliphatic amine, cyanuric chloride, ethylenediamine, N,N′‐dimethyl‐1,3‐propyldiamine and sodium 2‐chloroethane sulfonate as main raw materials. The chemical structures were confirmed by FT‐IR, ¹H NMR and elemental analysis. The Krafft points differ markedly with different carbon chain length, for C₈‐GSBS, C₁₀‐GSBS and C₁₂‐GSBS are considered to be below 0 °C and C₁₄‐GSBS, C₁₆‐GSBS are higher than 0 °C but lower than room temperature. Surface‐active properties were studied by surface tension and electrical conductivity. Critical micelle concentrations were much lower than dodecyl sulphobetaine (BS‐12) and decreased with increasing length of the carbon chain from 8 to 16, and can reach a minimum as low as 5 × 10^?5 mol L^?1 for C₁₆‐GSBS. Effects of carbon chain length and concentration of C_n‐GSBS on crude oil emulsion stability were also investigated and discussed.     

Performance of sulfoxylated fatty acid methyl esters

Sulfoxidation of fatty acid methyl esters with SO₂, O₂, and ultraviolet light of appropriate wavelength has led to the synthesis of methyl esters sulfonates or sulfoxylates known as Φ-MES because of the possible random position of SO₃ group in the alkyl chain. This work describes experimental measurements of physical properties such as solubility and viscosity of sodium Φ-MES water solutions. Amphipathic properties such as surface tension, critical micelle concentration, wetting and foaming powers were measured as well and compared to linear alkylbenzene sodium sulfonate (LAS). Finally, stability to water hardness, dishwashing test, and detergency performance were evaluated. Expectedly, these products may be used as LAS partners either in heavy-duty powders or in hand dishwashing liquids. Experimental results on Φ-MES of varying carbon number indicate that C₁₆ is the optimal carbon chain length.     

Molecular species of wax esters in jaw fat of atlantic bottlenose dolphin,Tursiops truncatus

The jaw fat of the Atlantic bottlenose dolphin (Tursiops truncatus) contains unusual wax esters which can be separated into short chain (<C₂₄) and long chain (>C₂₄) fractions by thin layer chromatography. The short chain wax esters (28 wt. %) have been characterized as a 72∶24∶4 mixture of isovaleroyl, isobutoryl, and 2-methylbutyrol, esters of C₁₄–C₁₈ n- and iso-alcohols. The intact <C₂₄ esters have been resolved into individual molecular species by gas liquid chromatography on open-tubular polyester columns. The long chain wax esters (12 wt. %) contain C₁₀–C₂₂ n- and iso-acids esterified to the same C₁₄–C₁₈ n- and iso-alcohols. Gas liquid chromatography of the intact, hydrogenated >C₂₄ esters on a short JXR column has characterized them according to carbon number and the number of methyl branches they contain.     

稳态荧光探针研究支链烷基苯磺酸钠的聚集行为

以芘为荧光探针、二苯酮为猝灭剂，用稳态荧光探针法测定了合成的4种带干扰基(磺酸基邻位的短链烷基)的支链烷基苯磺酸钠的临界胶团浓度、合适猝灭剂浓度下的胶团聚集数以及在不同浓度氯化钠水溶液中的胶团聚集数．结果表明，支链烷基苯磺酸钠分子中长链烷基碳数增加，临界胶团浓度大幅度降低，胶团聚集数减小；分子中短链烷基碳数增加，临界胶团浓度降低幅度小，胶团聚集数增大；胶团聚集数随氯化钠浓度增大而增大．     

Preparation and properties of some poly(alpha-olefin sulfones)

The properties of alpha-olefin–sulfur dioxide copolymer prepared from the series C₈–C₁₈ (even-numbered) alpha-olefins and sulfur dioxide are described. These polymers undergo clean thermal degradation and have high permeabilities to oxygen and carbon dioxide. Maximum permeabilities, maximum per cent elongation at the yield point, and minimum density are obtained with the C₁₆-based polymer. An explanation is proposed involving a competitive plasticizing/side chain crystallization effect.     

Effect of carbon chain and phenyl isomer distribution on use properties of linear alkylbenzene sulfonate: A comparison of ‘high’ and ‘low’ 2-phenyl LAS homologs

Phenyl isomer distributions, within current commercial limits of HF and A1C13 linear alkylbenzene sulfonates (LAS), have little effect on dishwashing performance in light-duty liquids (LDL), detergency performance in heavy-duty powders (HDP), and interfacial tension value. The most important factor in determining performance differences among commercial LAS samples is carbon chain homolog distribution. Both HF and A1C1₃ LAS perform equally well and can be used interchangeably in high-performance products. The optimum for foam stability in light-duty liquids shifts towards shorter alkyl chain length as water hardness increases. At 0 ppm water hardness the optimum occurs at C₁₃: at 50–150 ppm the optimum moves to C₁₁ and C₁₂; and above 150 ppm the optimum shifts to include C₁₀, C₁₁ and C,₁₂. The detergency performance optimum range in a phosphate built heavy-duty powder at 50 and 150 ppm water hardness includes the C₁₂, C₁₃ and C₁₄ alkyl chain lengths. In a nonphosphate built powder the optimum is similar at 50 ppm hardness to that of a phosphate built powder, but shifts at 150 ppm hardness to include C₁₁, C₁₂ and C₁₃.     

Gas chromatographic analysis for long chain sultones in olefin sulfonates

A gas Chromatographic method is described for the analysis of tetradecane-l,4-sultone (C₁₄ delta sultone) and the combination of 2-chlorotetradecane-1,3-sultone (C₁₄ 2-chloro gamma sultone), and 1-tetradecene-l,3-sultone (C₁₄ unsaturated gamma sultone) in neutral oils isolated from olefin sulfonate. Samples of the neutral oil are diluted in hexane and injected directly into the gas Chromatograph. Quantitative data are obtained by comparison to known amounts of the respective sultones. Through the use of silica gel column chromatography followed by gas chromatography of collected fractions, separation and individual quantitation of the 2-chlorotetradecane-1,3 sultone and l-tetradecene-l,3-sultone can be obtained. Routine use for control purposes has shown the method to be reliable and interlaboratory agreement of data has been good.     

Liquid chromatography-mass spectrometry of nonionic surfactants using electrospray ionization

The analysis of nonionic surfactants was investigated by reversed-phase liquid chromatography with mass spectrometry detection. On a C₁₈ column, separation was achieved on the basis of chain lengths of both alkyl and ethoxy groups in a CH₃CN/CH₃OH/H₂O/HAc solvent system. Peaks were identified by electrospray mass spectrometry.     

Identification of Polyketides in the Cuticular Waxes of Triticum aestivum cv. Bethlehem

Cuticular waxes are complex mixtures consisting mostly of very‐long‐chain aliphatics with single, primary functional groups. However, the waxes of many plant species also include aliphatics with one or more functional groups residing on subterminal or mid‐chain carbons. In the present work, the cuticular wax mixtures from flag leaf blades and peduncles of Triticum aestivum cv. Bethlehem were analyzed in a search for novel wax constituents with in‐chain functionalities, potentially of polyketide origin. The structures of compounds belonging to six different compound classes were elucidated using gas chromatography–mass spectrometry of various derivatives. Among them, a series of 2,4‐ketols was identified, with odd carbon numbers ranging from C₂₅ to C₃₇ and peaking at C₃₃. The analogous C₃₃ 2,4‐diketone was identified as well, together with a pair of co‐eluting C₃₁ mid‐chain β‐ketol isomers (16‐hydroxyhentriacontan‐14‐one and 14‐hydroxyhentriacontan‐16‐one), a pair of co‐eluting C₃₀ mid‐chain α‐ketol isomers (15‐hydroxytriacontan‐14‐one and 14‐hydroxytriacontan‐15‐one), the corresponding C₃₀ 14,15‐diketone, and a pair of co‐eluting C₃₁ ketones (hentriacontan‐14‐one and hentriacontan‐16‐one). All newly discovered structures contain ketone functional groups, with similar C₁₃H₂₇ and C₁₅H₃₁ alkyl chains on either side of the functionalities, thus resembling the previously reported very‐long‐chain β‐diketones dominating the wheat wax mixtures. Based on these structural characteristics, possible biosynthetic pathways leading to the newly identified polyketide‐like compounds are proposed.     

Synthesis, Characterization and Surface Activity of Alkyl m-Xylene Sulfonate Isomers

This paper deals with the synthesis of a series of alkyl m-xylene sulfonate isomers (with the m-xylene located at the eighth carbon atom along the long alkyl chain) by the Friedel?CCrafts reaction, and the Grignard reaction followed by hydrogenation. The structures were confirmed by ¹H NMR. All analytical methods indicated high levels of purity of the isomers with the eighth carbon atom at the long alkyl chain. The critical micelle concentration (CMC), surface tension and maximum surface excess concentration at the CMC and area per molecule at the interface were determined. As the long alkyl chains increased the surfactant molecule tends to pack closely at the gas?Cliquid interface. Accordingly, the CMC decreased, the adsorption density increased, and the surface tension reduction was strengthened.     

Molecular species of glycerophospholipids and sphingomyelins of human erythrocytes: Improved method of analysis

This study reports the application of modern methods of molecular species analysis in determination of the structure of both major and minor glycerophospholipids and sphingomyelins of human erythrocytes. Individual phospholipid classes were resolved from total lipid extracts by thin-layer chromatography. Diradylglycerols were released by phospholipase C and converted into trimethylsilyl ethers, which were resolved into the alkenylacyl, alkylacyl and diacylglycerol subclasses by normal phase high performance liquid chromatography. Molecular species of diradylglycerols and ceramides were quantitated according to carbon and double bond number by gas liquid chromatography using a fused silica capillary column wall-coated with bonded RTx-2330. The molecular species of ceramides were determined by GC/MS. The diradyl glycerophosphocholines contained 93.0% diacyl, 4.6% alkylacyl and 2.5% alkenylacyl, white the diradyl glycerophosphoethanolamines were made up of 48.8% diacyl, 47.8% alkenylacyl and 3.4% alkylacyl subclasses. Analysis of the molecular species showed that the long chain polyunsaturated acids were mainly combined with C₁₆ in all diradyl GPC subclasses and in diacyl GPE, while in the alkylacyl and alkenylacyl GPE and in diacyl glycerophosphoinositol and diacyl glycerophosphoserine they were combined mainly with C₁₈ saturated fatty chains. In addition to the C₁₆ and C₁₈ alkyl and alkenyl, the ether fractions also contained significant proportions of C₂₀, C₂₂ and C₂₄ chains. The molecular species of the ceramide moieties of the SPH were made up largely of mono- and diunsaturated species. Over 200 molecular species were identified and quantitated in a representative sample of human red blood cells.     

Alpha olefin sulfonates from a commercial SO3-Air reactor

Alpha olefin sulfonate (AOS) can be made by SO₃-air sulfonation of straight chain alpha olefins followed by saponification of the neutralized product. The sulfonation step forms unsaturated sulfonic acids, sultones and sultone sulfonic acids. Hydrolysis of the various sultones yields a mixture of unsaturated and hydroxy sulfonates. Sulfonation of commercial mixtures of straight chain alpha olefins in a large-scale SO₃ falling film unit has given AOS of 1.5–3.0% oil based on active content and tristimulus color of about 40% saturation (2% solution) which is readily bleachable with 1–3% NaOCl to about 10–15% saturation. Performance of AOS made from C₁₅−C₁₈ alpha olefin is comparable to that of the high-foaming C₁₁−C₁₄ LAS in both detergency and dishwashing foam. It is superior to similar products made from internal straight chain olefins. The product shows a low order of toxicity and biodegrad-ability slightly better than that of LAS. A C₁₅−C₁₆ AOS blend is especially attractive in liquid detergent formulations. Presented at the AOCS Meeting, Los Angeles, April 1966.     

Comparison of commercially available quaternary ammonium structures for phase transfer catalysis

A variety of commercially available tetralkyl (R₁R₂R₃R₄N⁺) ammonium chlorides and methyl sulfate salts were examined under phase transfer conditions. For conversion of benzyl chloride to benzyl acetate with aqueous potassium acetate, tri C_8–10 methyl ammonium chloride was the most efficient, with tri C_16–18 methyl ammonium chloride was next. The alkyl trimethyl ammonium chlorides (particularly C_12–14 trimethyl) performed well for the oxidation of benzyl alcohol to benzaldehyde with sodium hypochlorite. Trimethyl tallow, C_16–18 partially unsaturated, ammonium chloride was the catalyst of choice for the dichlorocarbene addition to cyclohexene.     

Effect of substituents in the aromatic nucleus on the biodegradation behavior of alkylaryl sulfonates

Taking the results of methylene blue analysis as a yardstick for biodegradability, substituents in the benzene ring of linear alkylaryl sulfonates (CH₃, C₂H₅, OH) greatly deteriorate the aerobic biodegradation characteristics of these products: adaptation time, amount of hard residue, and, to a lesser extent, rate of biodegradation. Replacement of one long alkyl chain by two short ones of the same total length also retards biodegradation. When the benzene ring is replaced by a thiophene ring, adaptation is improved.     

Surface Properties of Glucose-Based Surfactants and Their Application in Textile Dyeing with Natural Dyes

In this study, propylene glycol-based glycosides were obtained using an acetalization reaction in which glucose was first reacted with propylene glycol. Subsequently, the propylene glycol glycoside was reacted with alkyl glycidyl ether of varying carbon chain lengths (i.e., 08-G, 10-G, 12-G, 14-G, and 16-G) to synthesize a series of glucose-based biodegradable surfactants. The experimental results show that the surface activity of the C₈–C₁₂ glucose-based surfactants increases with the carbon chain length. However, the surface activity of the C₁₄–C₁₆ glucose-based surfactants decreased as the carbon chain length increased. Among all the surfactants, the C₁₂ glucose-based surfactant exhibited the most efficient emulsification ability, lowest surface tension, lowest fluorescence intensity, highest zeta potential, and good emulsification stability. The glucose-based surfactants were used as additives in natural plant dyes made from turmeric or henna to dye wool fabrics. Higher color strengths were observed in the C₁₄ glucose-based surfactant.     

Control of ionic interactions in sulfonated polystyrene ionomers by the use of alkyl-substituted ammonium counterions

Polystyrenes containing up to about 20 mol % sulfonic acid are reproducibly and readily prepared by the sulfonation of polystyrene at 50°C with acetyl sulfate in 1,2-dichloroethane solution. The metal salts of sulfonated polystyrene possess extremely high melt viscosities and are soluble in single solvents such as toluene and THF only at very low sulfonate levels. Such properties are the result of the very strong ion-dipole interactions among the metal sulfonate groups. Such strong interactions can be substantially reduced through the neutralization of the sulfonic acid with ammonia and, most especially, relatively simple low molecular weight amines. Sulfonated polystyrenes varying in sulfonic acid content from about 1 mol % to about 20 mol % were neutralized with various mono-, di-, and tri-substituted alkyl amines ranging in alkyl chain length from H (ammonia) to C₂₀, and their rheological and thermal properties were measured. As the number of substituents on the nitrogen increased, the glass transition temperature and the melt viscosity decreased. The tributylamine sulfonates possessed viscosities almost as low as unsulfonated polystyrene and the longer chain amines behaved as if internally plasticized. The properties of amine neutralized sulfonated polystyrenes are concluded to be primarily a function of amine size. Increasing the size of the amine reduces the strength of the ion-dipole interaction by preventing close approach of the amine sulfonate groups.