Review on Anionic/Cationic Surfactant Mixtures

It is commonly known that cationic and anionic surfactants cannot be mixed without the risk of precipitation or instability. However, many studies have shown that not only is it possible to combine cationic and anionic surfactants, but also that this combination can present synergic properties. Mixtures of anionic and cationic surfactants have many unique properties that can be very useful when used properly. The aim of this report is to present relevant information concerning the interaction between anionic and cationic surfactants. A bibliographic review on anionic/cationic mixtures is presented here in order to better understand their properties and possible synergic effects, as this is of practical importance for the chemical industry.

Synergism and Performance for Systems Containing Binary Mixtures of Anionic/Cationic Surfactants for Enhanced Oil Recovery

The surfactant structure–performance relationship and application properties in enhanced oil recovery (EOR) for binary mixtures of anionic and cationic surfactants are presented and discussed. A polyoxyethylene ether carboxylate anionic surfactant was blended with a quaternary ammonium chloride cationic surfactant and tested for a high-temperature, low-salinity, and high-hardness condition as found in an oil reservoir. These mixtures were tailored by phase behavior tests to form optimal microemulsions with normal octane (n-C8) and crude oil having an API gravity of 48.05°. The ethoxy number of the polyoxyethylene carboxylate anionic surfactant and the chain length of the cationic surfactant were tuned to find an optimal surfactant blend. Interfacial tensions with n-C8 and with crude oil were measured. Synergism between anionic and cationic surfactants was indicated by surface tension measurement, CMC determination, calculation of surface excess concentrations and area per molecule of individual surfactants and their mixtures. Molecular interactions of anionic and cationic surfactants in mixed monolayers and aggregates were calculated by using regular solution theory to find molecular interaction parameters β ^σ and β ^M . Morphologies of surfactant solutions were studied by cryogenic TEM. The use of binary mixtures of anionic/cationic surfactants significantly broadens the scope of application for conventional chemical EOR methods.     

Interaction Between an Anionic and an Amphoteric Surfactant. Part II: Precipitation

Use of amphoteric and anionic surfactants is very common in practical formulations such as shampoos and hand dishwashing products. Precipitation of mixtures of dimethyldodecylamine oxide (DDAO) as an amphoteric surfactant and sodium dodecyl sulfate (SDS) as an anionic surfactant were studied at different pH levels. The DDAO is a pH-sensitive surfactant and its protonation can be expressed in terms of a pK _a similar to an acid dissociation constant. The protonated form of DDAO carries a positive charge and precipitates with the oppositely charged SDS. Therefore, precipitation phase boundaries are pH dependent due to the varying degree of DDAO protonation. By combining the use of regular solution theory and the pseudophase separation model to describe micellar mixing nonidealities with the precipitate solubility product constant and the protonation dissociation constant, a model to predict the precipitation phase boundary is presented here. The model agrees well with experimental phase boundaries at different pH levels.

Surfactant Enhanced Oil Recovery in a High Temperature and High Salinity Carbonate Reservoir

The goal of this work was to find an effective surfactant system for enhanced oil recovery after water injection substituting for oil at a vuggy fractured reservoir with a high temperature and high salinity (220,000 mg/L). Four types of surfactants with concentrations (less than 0.2 %) were screened. Washing oil experiments were conducted in Amott cells. A surfactant system was established by mixing a surfactant with best ultimate recovery and one with best recovery rate. The optimized surfactant system could recover 50 % of remaining oil. To study the mechanism of enhanced oil recovery after water injection substituting oil, interfacial tension (IFT) and contact angle were measured. Experimental results showed that surfactants with good washing ability had low IFT, but surfactants with low IFT may not have a good washing ability. IFT had no obvious relationship with the increased oil recovery or washing ability. The optimized system could not alter carbonate to decrease the oil‐wetting capability. Though octadecyl trimethyl ammonium chloride had a good ability wet the carbonate with water, it could not recover much oil. Therefore, except for interfacial tension and wettability alteration, there must be other parameters dominating oil recovery after water injection substituting for oil.     

一些阴离子／阳离子二元混合体系的增溶行为

研究了十二烷基聚氧乙烯（约含3个EO基团）硫酸三乙醇铵（TADPS）分别与十六烷基三甲基溴化铵（CTABr）、氯化十六烷基毗院（CPCI）以及氯化十二烷基吡啶（DPCI）的二元混合体系对正庚烷、正辛醇以及甲苯的饱和增溶行为。结果表明,混合体系在增溶方面的协同效应取决于增港物的极性或增港物在胶团中的位置．对增溶于胶团内核的非极性正庚烷,TAPDS／CTABr体系显示出较强的实际正协同效应,最大添加浓度（MAC）可用Nishikido的阴离子-阳离子复合物理想增港模型来预测;对既可增溶于胶团的内核,又可增溶于胶团栅栏中的微极性的甲苯,三个混合体系皆表现出实际的正协同效应;但对增溶于胶团栅栏,与表面活性剂形成混合胶团的两亲物质正辛醇,TAD－PA／CTABr体系显示出负协同效应,并且增溶物在胶团相和水相中的分布系数符合Treiner的非理想增溶模型。这些结果表明,阴离子／阳离子混合体系在胶团强化超滤（MEUF）技术中具有潜在的应用前景。     

Surface Properties of an Alcohol Alkoxylate in the Presence of a Cationic Surfactant

Alcohol alkoxylate was prepared via propoxylation of an industrial alcohol ethoxylate. The chemical structure of the prepared compound was confirmed using FT-IR and the physical properties were evaluated by the usual methods according to ASTM. The surface properties of the aqueous solution of alcohol alkoxylate were determined with or without addition of a cationic surfactant in comparison to the corresponding alcohol ethoxylate. The measured parameters were surface tension, CMC, maximum surface excess, minimum surface area and the interaction parameter (β). These data indicate that surface properties changed due to the attractive complex formation in the mixed system.     

Effect of Electrolyte and Temperature on Volatile Organic Compounds Removal from Wastewater Using Aqueous Surfactant Two-Phase System of Cationic and Anionic Surfactant Mixtures

Abstract

Benzene, toluene, ethylbenzene, and xylene are frequently observed contaminants in industrial wastewaters causing concerns about environmental and health effects. An aqueous surfactant two-phase (ASTP) extraction system using mixtures of cationic and anionic surfactants have been shown to be a promising surfactant-based separation technique to concentrate solutes such as proteins and dyes from aqueous solution. A phase separation of a surfactant solution occurs at certain surfactant compositions and concentrations, forming two isotropic phases. One is rich in surfactant aggregates (surfactant-rich phase) and the other is lean in surfactant aggregates (surfactant-dilute phase). Most of the organic contaminants tend to solubilize and concentrate in the surfactant-rich phase, leaving the surfactant-dilute phase containing only small amounts of contaminants as remediated water. The effect of NaCl addition on the critical micelle concentration (CMC) and the extraction ability of ASTP formed by mixtures of cationic surfactant (dodecyltrimethylammonium bromide; DTAB) and anionic surfactant (alkyl diphenyloxide disulfonate; DPDS) at 50 mM total surfactant concentration with a 2:1 molar ratio of DTAB:DPDS was investigated; the CMC of the mixture slightly decreases with increasing NaCl concentration. The extraction and preconcentration of benzene are greatly enhanced by added NaCl. The higher the degree of hydrophobicity of contaminants, the greater the extraction into the surfactant-rich phases. At 1.0 M NaCl addition, about 95% of xylene, 92% of ethylbenzene, 90% of toluene, and 79% of benzene are extracted into the surfactant-rich phase within a single stage extraction and the contaminant partition ratios can be as high as 395 for xylene, 273 for ethylbenzene, 206 for toluene, and 84 for benzene, which are greater than those obtained from the conventional ASTP extraction system using nonionic surfactants.     

Polymer‐Cationic Surfactant Interaction: 1. Surface and Physicochemical Properties of Polyvinyl Alcohol (PVA)‐S‐Alkyl Isothiouronium Bromide Surfactant Mixed Systems

Surface properties of polyvinyl alcohol (nonionic polymer) and three synthesized cationic surfactants, namely, S‐alkyl isothiouronium bromide at different mole fractions of 1:9, 3:7, 5:5, 7:3, and 9:1, were investigated. The values of the surface parameters were discussed according to the type of interaction between the cationic surfactant and type of polymer studied. The S‐alkyl isothiouronium bromide surfactant molecules are positively charged molecules, and the PVA chains contain hydroxyl groups that are partially negatively charged centers. The comparison between the surface properties of the individual cationic surfactants and their mixture with PVA polymer showed that the mixed systems have some advantages over the individual cationic surfactants.     

Surfactants as Antimicrobials: A Brief Overview of Microbial Interfacial Chemistry and Surfactant Antimicrobial Activity

In this brief overview of a large and complex subject, as presented at the 2018 Surfactants in Solution conference, the need for, and impact of, hard surface antimicrobial products is demonstrated. The composition of the interfaces of three common classes of pathological microbes, bacteria, viruses, and fungi, is discussed so that surfactant and cleaning product development scientists better understand their interfacial characteristics. Studies of antimicrobial efficacy from the four major classes of surfactants (cationic, anionic, amphoteric, and nonionic) are shown. The need for preservatives in surfactants is elucidated. The regulatory aspects of antimicrobials in cleaning products to make antimicrobial claims are stressed.     

Surface Active Properties and Biological Activities of Novel Anionic Surfactant Based on Oxapyridazinone Derivatives

A series of novel oxapyridazinone derivatives has been synthesized via cyclization of the corresponding sodium salt of α‐sulfonated fatty acid hydrazide with chloroacetic acid in the presence of sodium acetate and acetic anhydride. The structures of the prepared compounds were elucidated using different spectroscopic and elemental analysis. The surface properties (surface tension, CMC value and area per molecule), the thermodynamic stability and antimicrobial activities of the prepared compounds were determined and compared to standard trade material Texapone^® N‐70. The prepared compounds exhibit surface activity comparable to the standard and thus can be used as anionic surfactants.     

A 1D- and 2D-NMR Study of an Anionic Surfactant/Neutral Polymer Complex

NMR chemical shifts and linewidth measurements were examined for mixtures of sodium 10-phenyldecanoate (Na ω-PhDec) in deuterated aqueous solutions in the presence of varying compositions of poly(ethylene oxide) (PEO) polymers of 2000 and 4000 molecular weight. In addition, variable temperature NMR spectra and NMR spin lattice relaxation times (T ₁) were obtained for the PEO-4000/Na ω-PhDec system as a function of varying polymer concentrations. As expected, the polymer/surfactant systems exhibit the behaviour typical of that of an anionic surfactant/neutral polymer system with well defined critical aggregation concentrations (CMC) corresponding to the formation of polymer/surfactant complexes below the CMC of the free surfactant. The ¹H-NMR linewidths acquired for the Na ω-PhDec/PEO-4000 system before and after the CMC region of the surfactant indicate that the maximum in the linewidth of the PEO proton peak is reached at approximately twice the CMC of the free surfactant. 2D-NMR NOESY measurements on this system exhibit cross peaks between the PEO protons and the protons on the surfactant backbone, consistent with the location of the phenyl group in the micellar interior. All these NMR experiments are interpreted in terms of the structure of the polymer/surfactant complexes as a function of the system composition.

阴阳离子表面活性剂自发形成囊泡的影响因素

在阴阳离子表面活性剂(SDS/CTAB)复配体系中自发形成囊泡。通过TEM、Zeta粒径分析和表面张力测定等手段进行表征,结果表明浓度、温度、溶剂、pH值等因素对囊泡稳定性有影响,在T=40℃,40%的乙醇为溶剂,调控pH=5,复配浓度在2×10-3mol/L条件下形成的囊泡稳定性最佳。     

2—十一烷基—N—羟甲基—N—羟乙基咪唑啉与阴离子表面活性剂的协同效应

用最大气泡法测定咪唑啉的表面张力和临界胶束浓度,并与N-月桂酸-N-甲基牛磺酸钠（AMT）复配后测其表面张力及其分子间的相互作用参数。利用正规溶液理论对它们的协同效应进行了讨论,表明实验值与计算结果相符。     

Synergistic Behavior and Microstructure Transition in Mixture of Zwitterionic Surfactant,Anionic Surfactant,and Salts in Sorbitol/H<Subscript>2</Subscript>O Solvent: 1. Effect of Surfactant Compositions

The phase behavior and rheological properties of a multi-component system, made of a zwitterionic surfactant cocoamidopropyl betaine (CAPB), an anionic surfactant sodium lauryl sulfate (SLSS), and mixed salts (tetrasodium pyrophosphate, sodium acid pyrophosphate, sacharrin, and sodium fluoride) in sorbitol/H₂O mixed solvent at different mass fraction of SLSS (X _SLSS) were systematically investigated by steady and dynamic rheology, dynamic light scattering, and diffusion ordered spectroscopy (DOSY). When fixing the salt concentration and the mass ratio of sorbitol in mixed solvent (R), the zero-shear viscosity increases first and then decreases showing a maximum with increasing X _SLSS, resulting from the formation and entanglement of wormlike micelles. Especially when X _SLSS is between 0.33 and 0.80, the mixture is dominated by entangled wormlike micelles coexisting with small micelles and separated wormlike micelles, and shows high viscoelasticity. The maximum of the zero-shear viscosity is ca. 5 orders of magnitude larger than that of sorbitol/H₂O mixed solvent or the CAPB/SLSS aqueous solution. The characteristic structural parameters for the micellar solutions at different X _SLSS are also estimated from further analysis of the rheological results, and indicate the stronger network structures of the wormlike micelles are formed in our systems compared with the wormlike micelles formed by a traditional zwitterionic/anionic surfactant aqueous solutions. The great improvements of rheological properties are attributed to the strong screening effects of the mixed salts and the strong solvophobic effect of sorbitol on the electrostatic and hydrophobic interaction between the CAPB and SLSS molecules. The present work has improved our understanding about the aggregation behavior of zwitterionic/anionic mixed surfactants with salts in less polar solvent/H₂O mixture, which would be of widely practical importance to optimize the formulation of products for personal care and household cleaning.     

Preparation and Characterization of an Anionic Gemini Surfactant for Enhanced Oil Recovery in a Hypersaline Reservoir

A new type of anionic Gemini surfactant (AGS) was designed and prepared by a simple, low–cost, and green method, and its properties were characterized. The results showed that the values of parameters such as critical micelle concentration (CMC) value, Γmax, Amin, and pC20 of AGS were 0.10 mmol L⁻¹, 1.62 mmol m⁻², 1.02 nm², and 4.60, respectively, indicating that AGS is highly surface active. AGS has a very good synergistic effect with lauryl diethanol amide (6501), and the mixture surfactant 6501DA (composed of AGS and 6501 with a mass ratio of 1:2.5) has good wetting and emulsifying ability of the crude oil and good resistance to calcium and magnesium ions. In the temperature range from 50 to 70 °C, salinity of 20,000–50,000 mg L⁻¹ of the simulated formation water, and dosage of 6501DA from 500 to 3000 mg L⁻¹, all the interfacial tension (IFT) values between the 6501DA solution and Bamianhe crude oil were lower than 10⁻² mN m⁻¹, and all the adsorption amounts of oil sand to 6501DA in solution were less than 2 mg g⁻¹, indicating that AGS has potential for application in EOR in a hypersaline reservoir.     

阳离子表面活性剂胶束和微乳液增溶过程的核磁共振谱法研究(英文)

运用高分辩NMR方法 ,研究了阳离子表面活性剂十六烷基三甲基溴化铵 (CTAB)胶束水溶液、KBr盐溶液对苯甲醇的增溶作用及CTAB/正丁醇 /10 %正辛烷 /水反向微乳液对丙烯酰胺(AM)的增溶作用。结果表明 ,在苯甲醇浓度低时苯甲醇主要增溶于CTAB胶束水溶液或KBr盐溶液的界面层 ,随着增溶物浓度的增大 ,苯甲醇主要增溶于胶束的栅栏层和胶束内核。在CTAB胶束水溶液中 ,当苯甲醇浓度达到 0 35 7(V/V)时 ,它沿烃链的增溶达到饱和 ,并开始进入胶束内核中心 ,并引起CTAB长链亚甲基峰分裂成两个单峰 ,一个在高场 ,一个在低场 ,而在CTAB胶束KBr盐溶液中 ,未得到长链亚甲基的分裂峰。在CTAB油包水 (W /O)微乳液中 ,通过 1H和 13CNMR谱讨论了丙烯酰胺与CTAB和正丁醇的相互作用 ,丙烯酰胺浓度较小时 ,其增溶在微乳液的Stern层 ,当丙烯酰胺与CTAB摩尔比接近 0 75时 ,丙烯酰胺分子增溶到栅栏层 ,并沿CTAB烃链进行分布     

A New Anionic Oxalamide Lauryl Succinate Sodium Sulfonate Gemini Surfactant: Microwave-Assisted Synthesis and Surface Activities

An anionic Gemini surfactant, oxalamide lauryl succinate sodium sulfonate, was synthesized successfully through amidation, esterification and sulfonation reactions under microwave irradiation conditions by using maleic anhydride, ethylenediamine, lauryl alcohol, sodium sulfite as the starting materials. The best reaction conditions for synthesize the target product were obtained by single factor and orthogonal optimization methods. FTIR, elemental analysis and ¹H‐NMR analysis were used to confirm the chemical structure of the surfactant. The critical micelle concentration (CMC) in aqueous solution, surface tension, emulsification capacity and foaming power were determined. The critical micelle concentration and γ_CMC are respectively equal to 3.5 × 10^?4 mol L^?1 and 21.5 mN m^?1. It was found that microwave‐assisted synthesis is an efficient means of preparation of this anionic Gemini surfactant with shorter times and higher yields.     

阳离子表面活性剂与LAS的复配性能研究

采用新开发的带有乙氧基链的含氮阳离子表面活性剂———十二烷基二甲基羟乙基氯化铵(K3)与LAS进行复配,考察了复配体系的物化性能,如:界面张力、乳化力、润湿力、去污力以及K3对大肠肝菌、金黄色葡萄球菌的杀菌性能等。实验证明K3与阴离子表面活性剂有良好的复配性能与杀菌性能,对洗涤剂配方的改进,产品性能的提高具有指导意义。     

Synthesis,Surface and Antimicrobial Activities of Novel Cationic Gemini Surfactants

A series of novel cationic gemini surfactants [C_nH_2n+1–O–CH₂–CH(OH)–CH₂–N⁺(CH₃)₂–(CH₂)₂]₂·2Br^? [ 3a (n = 12), 3b (n = 14) and 3c (n = 16)] having a 2‐hydroxy‐1,3‐oxypropylene group [?CH₂–CH(OH)–CH₂–O–] in the hydrophobic chain have been synthesized and characterized. Their water solubility, surface activity, foaming properties, and antibacterial activity have been examined. The critical micelle concentration (CMC) values of the novel cationic gemini surfactants are one to two orders of magnitude smaller than those of the corresponding monomeric surfactants. Furthermore, the novel cationic gemini surfactants have better water solubility and surface activity than the comparable [C_nH_2n+1–N⁺(CH₃)₂–(CH₂)₂]₂·2Br^? (n‐4‐n) geminis. The novel cationic gemini surfactants 3a and 3b also exhibit good foaming properties and show good antibacterial and antifungal activities.     

Novel Ester-linked Anionic Gemini Surfactant: Synthesis,Surface-Active Properties and Antimicrobial Study

A novel anionic gemini surfactant containing an ester bond in the spacer group was synthesized using cardanol as the raw material and characterized by IR, ¹H NMR and ¹³C NMR. The surface properties of the gemini surfactant were investigated and compared with its corresponding single chain surfactant counterpart. It was found that this novel gemini surfactant exhibited a low critical micelle concentration value (1.9 mM) and good efficiency in reducing surface tension of water (33.6 mN/m). The gemini surfactant was found to have antimicrobial activity against Gram-negative (Escherichia coli and Pseudomonas aeruginosa), Gram-positive (Bacillus subtilis and Staphylococcus aureus) bacteria and fungi (Aspergillus niger, Aspergillus flavus, Candida albicans and Rhizopus stolonifer). The gemini as well as the corresponding single chain surfactant showed good antimicrobial activity against all pathogenic microorganisms studied and can be employed as an antimicrobial agent. The synthesized novel anionic gemini surfactant possesses an excellent wettability and low foamability.