Mixtures of Nonionic Surfactants made from Renewable Resources with Alkyl Sulfates and Sodium n-Alkanecarboxylates: Comparison of Mixing Behavior using Rubingh’s Treatment

Binary aqueous mixtures of (1) alkyl glucopyranosides (glycosides), (2) alkyl maltopyranosides (maltosides), or (3) alkyl N-methyl glucamines with (1′) sodium alkyl sulfates or (2′) sodium n-alkyl carboxylates were investigated in an effort to evaluate physiochemical properties for mixtures of surfactants from renewable resources. Solutions at various concentrations and mixture ratios were tested and evaluated to determine critical micelle concentrations (CMCs). The greatest reduction in CMC was found for surfactants with long and intermediate hydrophobe lengths. In agreement with other studies, an increase in hydrophilic group size and flexibility decreased the electrostatic repulsion of ionic-nonionic mixed micelles as evidenced by a more negative Rubingh’s β parameter. However, at low hydrophobe length, carboxylate and glycoside headgroup mixtures produced mixed micelle interactions displaying synergism at low nonionic surfactant mole fractions and slight antagonism at high nonionic mole fractions. The asymmetry in interaction produces an S-shaped CMC curve and demonstrates that the one-parameter Rubingh model is insufficient in describing both synergism and antagonism for this binary mixture.     

Effect of alkyl carbon chain length and ethylene oxide content on the performance of linear alcohol ether sulfates

A series of linear alcohol ether sulfates varying in alkyl carbon chain length and ethylene oxide content was evaluated with respect to surface activity, viscosity, foaming, and detergency. Performance data agree well with surface property data. A low level of EO is best in terms of effectiveness and efficiency in lowering surface tension, which is why a low-mole ether sulfate salt-thickens better, produces foam which is more tolerant of soil, and gives good detergency performance. A lauryl-range alkyl carbon chain length is best for foaming and salt-thickening, but a higher carbon chain length appears to be better for detergency performance.     

Surfactants from glucamines and ω‐epoxy fatty acid esters

The ring‐opening reaction of ω‐epoxy fatty acid methyl esters (9,10‐epoxy decanoic acid methyl ester, 10,11‐epoxy undecanoic acid methyl ester and 13,14‐epoxy tetradecanoic acid methyl ester) with N‐methyl glucamine or glucamine was studied. A new method (in methanol under reflux) leads to products, which are surfactants of linear‐ or γ‐type‐structure, in fair yields and purities. In a following step the ring‐opening products were saponificated by enzymatic catalysis or by conversion with sodium hydroxide leading to amphoteric surfactants. The surface‐active properties of the methyl esters and their corresponding acids or salts were studied at various pH‐values by measurement of surface tension of aqueous solutions and by examination of foaming properties. Depending on the chain length of the used epoxides, the structure of the obtained sugar‐based surfactant and the pH‐values, different surface‐active properties were observed. Several of the achieved products reduce the surface tension of aqueous solution down to 26—40 mN/m. Examination of foaming properties of the latter show rather poor or good foamers, depending on the surfactant used or the pH‐value of the solution.     

Surface activities,biodegradability and antimicrobial properties of glucosamine derivatives containing alkyl chains

Three series of D-glucosamine derivatives containing an alkyl chain with 8 to 14 atoms, methyl 2-acylamino-2-deoxy-D-glucopyranosides,n-alkyl 2-acetylamino-2-deoxy-D-glucopyranosides andn-alkyl 2-amino-2-deoxy-D-glucopyranoside hydrochlorides, were synthesized, and their surface properties (such as surface tension, critical micelle concentration (CMC), dynamic surface tension and foaming properties), biodegradability and antimicrobial activities were evaluated.n-Alkyl 2-amino-2-deoxy-D-glucopyranoside hydrochlorides containing C8 to C12 carbon chains showed surface activities, a CMC and excellent foaming properties. The α-anomers showed a slightly lower CMC than the β-anomers, indicating less hydrophilicity of the α-anomers. On the other hand, glucosamine derivatives containing amide groups showed poor surface activities in water due to their lower solubilities in water. All glucosamine derivatives containing alkyl chains were biodegraded as well as conventional ethoxylated nonionics by activated sludge from the municipal sewage treatment plant. Methyl 2-acylamino-2-deoxy-D-glucopyranosides andn-alkyl 2-amino-2-deoxy-D-glucopyranoside hydrochlorides showed a broader spectrum of antimicrobial activity than the correspondingn-alkyl glucopyranosides. Among them the C12 derivatives showed the best results.     

均质脂肪醇聚氧乙烯醚硫酸盐的合成与性能研究

以十八醇、十二醇为原料 ,通过Williamson合成法合成了聚氧乙烯醚加成数n =2、3、4的均质十八醇聚氧乙烯醚硫酸盐和加成数n =2 ,3的十二醇聚氧乙烯醚硫酸盐。经减压蒸馏提纯 ,薄层色谱显示为单一斑点。综合表面活性测试结果可以看出 ,随着聚氧乙烯醚加成数的增加 ,均质十八醇和十二醇聚氧乙烯醚硫酸盐表面活性增加 ,当聚氧乙烯醚加成数相同时 ,均质十八醇聚氧乙烯醚硫酸盐表面活性高于均质十二醇聚氧乙烯醚硫酸盐     

Synthesis and Properties of Dissymmetric Gemini Surfactants

A series of novel dissymmetric gemini cationics surfactants was synthesized by three-step reactions. The dissymmetric gemini surfactants contain a dodecanoic acid dimethylethylamine ester as the constant cationic part on one side of the hydroxypropyl center and a similar other cationic part, but with a different acid length (from octanoic to palmitic), on the other side. The critical micelle concentration (CMC) and the effectiveness of surface tension reduction (γ _CMC) were determined. The surface tension measurements of dissymmetric gemini surfactants showed good water solubility, and low CMC had great efficiency in lowering the surface tension and a strong adsorption at the air/water interface. The CMC was observed to increase initially with the increase of the ester bond alkyl group. They also showed good foaming properties and wetting capabilites.     

温度及无机盐对LMEE和SDS混合溶液表面张力的影响

通过表面张力的测定,研究了温度和不同无机盐对月桂酸甲酯乙氧基化物(laurylmethylesterethoxylate,简称LMEE)与十二烷基硫酸钠(SDS)复配物表面张力及临界胶束浓度(CMC)的影响。研究表明:混合体系的CMC在很宽的复配比例内出现最低值,25℃、未加无机盐时可使CMC最低降至3 8×10-5mol/L;温度对复配体系表面张力的影响较小,温度上升复配物的CMC略有降低。3种价态无机盐的加入均可使复配物的CMC有所降低,但与单一表面活性剂相比,温度和无机盐对复配物的CMC影响均不大,说明复配体系的抗温变及抗盐能力均有增强。     

Mixed micelles of some metal dodecyl sulfates and triton X-100 in aqueous media

Tensiometric studies on several binary surfactant mixtures containing anionic surfactants, viz., metal (lithium, sodium, potassium, copper, cobalt, and magnesium) dodecyl sulfates and a nonionic surfactant (Triton X-100) in water at different mole fractions (0–1) provide critical micelle concentration (CMC) values. The composition of mixed micelles and the interaction parameter, β, evaluated from the CMC data for different systems using Rubingh's theory, are discussed. Marked interaction is observed with monovalent dodecyl sulfates. The influence of counter-ion valence on the formation of mixed micelles was investigated for anionic-nonionic systems, and results indicated that mixed systems with bivalent counter-ions in metal dodecyl sulfate resembled nonionic-nonionic systems where weak/negligible interaction has been reported. Salt addition revealed the weakening of interaction in the mixed systems, which is attributed to the head group charge neutralization and the dehydration of the ethylene oxide units of the nonionic surfactants. A few cloud point and viscosity data are also reported.     

Chemical structure/property relationships in surfactants. 17. N-substituted-N-acyl glycinates in pure and synthetic hard river water

The surface properties [effectiveness of surface tension reduction (γ_CMC), critical micelle concentration (CMC), efficiency of surface tension reduction (pC ₂₀), maximum surface excess concentration (Γ_CMC), minimum area/molecule at the interface (A _min), and the CMC/C ₂₀) ratio] of well-purified N-substituted glycine derivatives, having the structural formula RC(O)N(R′)CH₂COONa, where RC(O)=lauroyl, myristoyl, or oleoyl, and R′=Et, Pr, Bu, CH₂CH₂OH or CH₂CH₂CH₂OCH₃, were investigated at 25°C in hard river water and distilled water. These surfactants show greater surface activity in hard river water than in distilled water. The effect of both the main alkyl chain R and the N-substituent R′ on surface properties was elucidated, the oleoyl group showing properties equivalent to that of a C₁₆ saturated acyl group. A linear relationship was observed between the pC ₂₀ or CMC values and the number of carbon atoms in the alkyl chain R or in R′ when it was alkyl. With increase in the number of carbon atoms in either R or the N-substituent R′ when it is alkyl, both pC ₂₀ and micelle-forming ability increase, although the effect of R′ on the foregoing two surface properties is lower than that of R. When R′ is (CH₂)₃OCH₃, however, the results suggest that R′ is only partly removed from contact with the aqueous phase either upon adsorption at the water/air interface or upon micellization. It increases A _min, is equivalent only to an ethyl group in its effect on pC ₂₀ and to a methyl group in its effect on CMC, and, in contrast to the effect of R′ when it is alkyl, produces no increase in the CMC/C ₂₀ ratio. As a result, γ_CMC increases with R when R′ is alkyl and decreases with R when R′ is (CH₂)₃OCH₃.     

Synthesis,Surface Activity and Aggregation Behavior of Novel Gemini Pyridinium Amphiphiles

A series of novel pyridinium cationic gemini amphiphiles, 3,3′-(carbonyldiimino)bis (1-n-alkylpyridinium) dibromides, having octyl, decyl, dodecyl, tetradecyl alkyl chains were synthesized. The surface properties and aggregation behavior in aqueous solution were evaluated by surface tension, dynamic light scattering (DLS), and transmission electron microscopy (TEM) measurement. The adsorption at the air/solution interface of all the compounds were quantitative described using the Frumkin model, and the effect of alkyl chain length on surface activity and aggregate behavior was analyzed. It was found that all the gemini amphiphiles possess surface activity and low critical micellization concentration (CMC) values. The values of log CMC depended linearly on the carbon number of the alkyl chains, but the surface tension at the CMC (γ_cmc) showed a minimum for the compound with dodecyl chains. Combinations of DLS and TEM observations showed the existence of vesicles with a broad size distribution in aqueous solution. Meanwhile, vesicles formed below the CMC could be a possible reason for the observed deviation of surface tension curves from the Frumkin model.     

Glucamine-based gemini surfactants I: Gemini surfactants from long-chain <Emphasis Type="Italic">N</Emphasis>-alkyl glucamines and α,ω-diepoxides

N-Alkyl glucamines can be reacted with α,ω-diepoxides to yield gemini (dimeric) surfactants similarly to the reaction of glucamine with terminal epoxides. Under the conditions chosen for this work, epoxides were quantitatively converted in the presence of an equimolar amount of amine to gemini surfactants. Reactions could be carried out under mild conditions (70°C) in methanol, and products were obtained quantitatively by removing the solvent. The combination of N-octyl glucamine, N-decyl glucamine, or N-dodecyl glucamine with diepoxides of α,ω-diolefins having chain lengths of C₈, C₉, C₁₀, or C₁₄ resulted in gemini surfactants differing in spacer length and length of hydrophobic alkyl chains. Surface-active properties were studied by measuring surface tension and evaluating foaming properties. Tensiometric studies showed the reduction of surface tension down to 29–33 mN/m and critical micelle concentrations often in the range of 3–150 mg/L. Comparison of a selected gemini surfactant [1,8-bis(N-dodecyl glucamino-2,7-octane diol] with its corresponding “single surfactant” demonstrated the enhancement of surface-active properties afforded by the gemini structure.     

Effect of aromatic ring in the alkyl chain on surface properties of arylalkyl surfactant solutions

Surface properties of two series of anionic arylalkyl surfactants, containing different aromatic rings in the straight aliphatic chain, sodium N-aryloleyl-N-methyl-2-aminoethanesulfonates and sodium N-aryloleyl p-methoxyanili-nesulfonates, were investigated. An increase of the aromatic ring size in the alkyl chain increases the critical micelle concentration (CMC) and surface tension at CMC. However, this also decreases the efficiency and effectiveness in reducing water surface tension. The dominant factor of the decrease of efficiency and effectiveness is attributed to the function of the hydrophilic segment and hydrophobic segment for arylalkyl surfactants, respectively. The same results are found in the standard free energy of adsorption (ΔG ^o _ads) and the standard free energy of micellization (ΔG ^o _mic) values. Moreover, with the increase of the aromatic ring size, the adsorption and micellization of arylalkyl surfactants begin to weaken. The data indicate that some parts of surface properties for arylalkyl surfactants are affected by the bulkiness of the arylalkyl chain. The results provide opportunities for further detailed examination of surface properties of arylalkyl surfactants with other branched alkyl chains.     

Synthesis of alkyl glycoside fatty acid esters in non-aqueous media byCandida sp. lipase

Alkyl glycoside fatty acid esters were successfully synthesized by lipase-catalyzed transesterification of methyl glucoside, methyl glucoside, methyl galactoside and octyl glucoside with methyl oleate. The experiments were carried out in organic media with lipase enzymes fromCandida sp. as biocatalysts. Time course and the effects of temperature, solvent type, substrate concentration, added water and of immobilizedvs. nonimmobilized enzyme were studied. The optimal conditions for the enzymatic synthesis of alkyl glycoside fatty acid esters were: a molar ratio of alkyl glycoside and methyl oleate of 1:4, an immobilized lipase, SP382 fromCandida sp.; benzene/pyridine (2:1, vol/vol) with no added water; temperature, 55°C; reaction time, 48 h; and shaking at 200 rpm. Acceptable levels of oleic acid incorporation (58.6–100 mol%) onto the alkyl glycosides were achieved.     

Synthesis,characterization, and surface properties of phenylalanine-glycerol ether surfactants

A novel homologous series of 1-N-l-phenylalanine-glycerol ether surfactants was synthesized in satisfactory yields via reaction of epichlorohydrin with aliphatic alcohols with alkyl chains of 10–15 carbon atoms. Structural assignment of the new compounds was made on the basis of elemental analysis and spectroscopic data. Critical micelle concentration (CMC), surface tension at the CMC (γ_CMC), surfactant concentration required to reduce the surface tension of the solvent by 20 mN/m (pC₂₀), and the interfacial area occupied by the surfactant molecules (A_min) were determined from aqueous surface tension measurements using the Wilhelmy plate technique.     

Micellar and Interfacial Behavior of Mixed Systems Containing Glycoside‐Based Surfactant and Cationic Didecyldimethylammonium Chloride

The behavior of binary mixtures of glycoside‐based surfactants in combination with didecyldimethylammonium chloride (DDAC) has been studied using surface tension measurements. The three glycoside‐based surfactants are nonionic decyl glycoside (APG), nonionic dodecyl ethoxy glycoside (AEG) and anionic disodium dodecyl ethoxy glycoside citrate (AEG‐EC). Lower critical micelle concentrations (CMC) and minimum molecular area (A_min) values were obtained for all the mixed systems. The pC₂₀ values of APG/DDAC and AEG‐EC/DDAC mixtures are larger than pure surfactants, while the values of AEG/DDAC are between those of AEG and DDAC. Interactions between the monomers have also been investigated by determining the interaction parameters. Negative β_m and β_s values indicate synergistic effects in both the mixed micelle and monolayer formation. For different mixed systems, interaction in the mixed micelle formation becomes stronger in the order: AEG/DDAC < AEG‐EC/DDAC < APG/DDAC. The degree of synergism in the mixed monolayer formation follows the order: AEG/DDAC < APG/DDAC < AEG‐EC/DDAC.     

Polymeric surfactants for enhanced oil recovery. Part V: Prediction models for the effect of temperature and length of polyoxyethylene chain or hlb on surface and thermodynamic properties of some ethoxylated polymeric nonionics

Several equation models were investigated to find the relationship between temperature (T). number of ethylene oxide (EO) units (n) or the hydrophile-lipophile balance (HLB) and the surface and thermodynamic properties of some ethoxylated alkylphenol-formaldehyde polymeric nonionic surfactants. These properties include critical micelle concentration (CMC), free energy of micellization (ΔG_mic), surface tension at CMC (7_CMC), effectiveness (γ_CMC) and efficiency (pC₂₀) of surfactant to reduce the surface tension of water. The values of the ratio CMC/C_{2(π = 20)} were also considered. The linear multiple regression technique was employed to determine the parameters of the equations and to choose the best forms with the highest values of R² and F-ratio which reflect the goodness and the reliability of the fit.     

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.     

Lipase-mediated synthesis of alkyl ricinoleates and 12-hydroxy stearates and evaluation of the surfactant properties of their sulfated sodium salts

An efficient and simple lipase-mediated synthesis of alkyl ricinoleates and 12-hydroxy stearates was performed by transesterification of methyl ricinoleate/12-hydroxy stearate and various alcohols in a solvent-free system without estolide formation. The reaction conditions were optimized by varying the temperature, pressure, and dosage of lipase. Sulfates of alkyl ricinoleates/12-hydroxy stearates were evaluated for surfactant properties such as surface tension, critical micelle concentration, emulsifying properties, foaming power, and calcium tolerance. The surfactant properties of sulfated alkyl ricinoleates were found to be superior to the sulfated alkyl 12-hydroxy series. The surfactant properties of the above two series of compounds were then compared with sodium dodecyl sulfate, and the properties of sulfated dodecyl ricinoleate and sulfated dodecyl 12-hydroxy stearate were found to be comparable with sodium dodecyl sulfate.     

Selection of surfactant pairs for optimization of interfacial properties

Guidelines are provided for the selection of surfactant pairs when synergism in various interfacial properties in aqueous media is desired. To maximize the reduction of the critical micelle concentration, the two surfactants should show strong attractive interaction in the mixed micelle; in order to maximize efficiency in surface tension reduction, strong interaction in the mixed monolayer at the aqueous solution/air interface (large negativeβ values is needed). The more surface-active material should predominate in the mixture. When interaction is not strong, the two surface-active materials used should have approximately equal surface activities and should be used at equimolar concentration in the aqueous phase. To minimize the surface tension (γ) of the solution, the surfactant-surfactant attractive interaction in the mixed monolayer at the aqueous solution/air interface must exceed that in the mixed micelle. Optimization can be achieved by using two surfactants with approximately equal γ values at their respective critical micelle concentrations (CMC’s). When these γ values are not equal, the surfactant with the higher γ value at its CMC should have the smaller area/molecule at the surface. The greater the difference between attractive interaction at the interface and in the micelle, the lower the value of the surface tension.     

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.