硫酸酯盐双子表面活性剂的合成和界面张力的研究

实验室条件下,以长链羧酸(月桂酸)、聚乙二醇等为主要原料,通过赫尔-乌尔哈-泽林斯基反应等和酯化反应,用醚键加入方式加入联接基团,用浓硫酸加成反应加入硫酸酯键,从而在实验室条件下合成具有特殊结构的双子表面活性剂-GA12-S-12.通过用旋转液滴法测合成的硫酸酯盐阴离子双子表面活性剂的表面张力,测得其临界胶束浓度(CMC)为438 mg/L,临界胶束浓度下表面张力为30.9 mN/m,并对比十二烷基硫酸钠水溶液表面张力,显示GA12-S-12[低聚二醇(α-硫酸酯钠)月桂酸双酯阴离子双子表面活性剂]具有更优的表面活性.进一步配制不同浓度的GA12-S-12表面活性剂溶液,测定它们与长庆五里湾原油的界面张力,效果显示其适用于五里湾区原油采收率的提高.     

磺酸盐双子表面活性剂的合成及其性能研究

以间苯二酚和甲醛、亚硫酸氢钠为原料,在100℃通过磺甲基化制得中间体,再与溴代十二烷通过威廉姆森醚化得到阴离子磺酸双子表面活性剂,总收率46.7%。研究了反应时间、反应温度和反应物摩尔比对收率的影响。用红外光谱和元素分析确认了其化学结构。测得其cmc和γcmc分别为0.81 mmol/L、γcmc=28.5 mN/m。对其与其他表面活性剂进行复配,在最佳配比下,有更低的cmc和γcmc。     

一种不对称阴离子Gemini表面活性剂的合成及表面活性研究

以α-溴代十四酸乙酯和4-癸基苯酚为原料,经Williamson醚化、磺化及皂化反应制备了一种不对称阴离子Gemini表面活性剂α-(4-癸基-2-磺基)-苯氧基十四酸钠,简写为C12CO2Na-p-C10SO3Na,考察了醚化反应条件,并用FTIR和1HNMR表征了中间体及目标产物结构。结果表明,醚化反应的最佳条件为:以N,N-二甲基甲酰胺(DMF)和甲苯作溶剂,无水K2CO3作缚酸剂,物料比n(α-溴代十四酸乙酯)∶n(4-癸基苯酚)=1.05∶1,回流反应3 h,醚化产物收率为77.2%(以4-癸基苯酚计)。采用吊片法测定了目标产物的表面活性,其表面张力最低可降至26 mN/m左右,临界胶束浓度(CMC)为3.28×10-6mol/L,比相应常规单链表面活性剂十四烷酸钠和间癸基苯磺酸钠的CMC低3个数量级,体现出Gemini表面活性剂优异的表面活性。     

Micellization of Carboxylic Acid Gemini Surfactant and Its Interaction with Amino Acid Surfactant in Aqueous Solution

The carboxylic acid-type Gemini surfactant (CGS12) was synthesized, and its micellization in aqueous solution at different pH values at 25.0 °C was investigated. The results show that the critical micelle concentration (CMC) of CGS12 at different pH values is only 10⁻⁶ order of magnitude, and the pH has little effect on the CMC. Moreover, the interaction of CGS12 with amino acid surfactant of sodium N-lauroyl sarcosinate (SLS) at 25.0 °C and pH 7.0 was investigated using surface tension, dynamic light scattering (DLS), cryogenic transmission electron microscopy (Cryo-TEM), and Ross–Miles foam measurements. The CGS12/SLS mixture shows a low CMC, and as a whole the CMC value becomes smaller with increasing molar fraction of CGS12 (X_CGS12). Under different X_CGS12, the mixtures form soluble aggregates with different hydration radii (R_h). Moreover, the mixture aggregates are mainly in the form of vesicles. The foaming height of CGS12 is worse than that of SLS, but the CGS12/SLS mixture has good foaming stability. This work reveals that the surfactant mixture has good surface activity and good foam stability.     

Development of a Stimuli-Responsive Gemini Zwitterionic Viscoelastic Surfactant for Self-Diverting Acid

A Gemini zwitterionic viscoelastic surfactant named self diverting acid - gemini sulfonated surfactant (SDA-GS), which has double quaternary ammonium groups, double sulfonate groups, and two hydrophobic tails, was synthesized from oleylamidopropyl dimethylamine, 1,3-propanesultone, and 2, 2-bis(bromomethyl)propane-1, 3-diol. The viscosity of an SDA-GS aqueous solution varies with acid and calcium chloride concentrations. With a decrease in the HCl concentration, the viscosity of the acid solution prepared with SDA-GS increases to a maximum value, followed by a decrease, which results from the aggregation of the surfactant into wormlike micelles and the following disaggregation. Calcium ions generated by the reaction of acid and calcium carbonate can enhance the aggregation of the surfactant to increase the peak viscosity of the acid solution. The peak viscosity of the acid solution prepared by 5 wt.% SDA-GS without calcium ions could only reach 73.2 mPa.s when the HCl concentration was 4 wt.%, but that of the acid solution with calcium carbonate powder added could reach over 200 mPa.s when the HCl concentration was consumed to 4 wt.% and the calcium chloride concentration 21.6 wt.%. The viscoelastic measurements proved that calcium ions can drive the growth of the wormlike micelle. The acid and Ca²⁺ response of SDA-GS can be applied in self-diverting acid to improve the acid displacement in the heterogeneous reservoir. Experimental evaluation showed that the acid solution prepared by SDA-GS and the selected corrosion inhibitor showed a good corrosion inhibition performance and a viscosity variation that makes it an efficient self-diverting acid. The spent acid (21.6 wt.%) with 4 wt.% HCl retained high viscosity over 80 mPa.s at a 170 s⁻¹ shearing rate and at 120°C after 90 min. The parallel core flood tests to simulate in situ application of SDA-GS acid showed that the permeability improvement ratios (K₁/K₀) of the cores could reach 182.3 and 278.4 at 60 and 90°C, respectively.     

Surface and Aggregation Properties of Synthesized Cetyl Alcohol Based Bis-Sulfosuccinate Gemini Surfactants in Aqueous Solution

A series of cetyl alcohol based anionic bis‐sulfosuccinate gemini surfactants (BSGSCA1,4; BSGSCA1,6 and BSGSCA1,8) with different spacer lengths was prepared using dibromoalkanes. The surfactant structure was elucidated using elemental analysis, Fourier transform infrared spectroscopy (FT‐IR) and nuclear magnetic resonance spectroscopy (NMR). Surface tension measurements were used to determine the critical micelle concentration (CMC), the surface tension at the CMC (γ_CMC), surface pressure at the CMC (π_CMC) and efficiency of adsorption (pC20). On the basis of surface studies, the CMC and γ_CMC decreases with increasing length of the spacer group. The micelle aggregation number, determined by fluorescence quenching studies, increases with increasing surfactant concentration above the CMC. The micropolarity in the micelle increases with increasing length of the spacer and decreases with increasing surfactant concentration.     

一种新型双联两性表面活性剂的合成与性能

采用1,4-丁二醇、马来酸酐、环氧氯丙烷、十六烷基叔胺为主要原料,合成了一种新型双联(Gemini)两性表面活性剂--丁二醇双琥珀酸一氯羟丙基季铵双酯磺酸钠(HDBC).红外光谱和质谱分析确证,合成的表面活性剂为目标产物.该表面活性剂水溶液最低表面张力为25.92 mN.m-1、临界胶束浓度为0.01 g.L-1;并考察了其发泡、稳泡性、乳化力和钙皂分散力.     

羧酸钠Gemini表面活性剂水溶液的表面活性及其pH影响

羧酸钠Gemini表面活性剂C11pPHCNa与相同烷烃链的月桂酸钠(SL)水解产生的酸式分子,使水溶液表面张力曲线呈现下凹状,电导曲线的转折点明显向较大浓度偏移(SL曲线),甚至消失(C11pPHCNa曲线)。添加10mmol·L-1NaBr仅表现出盐效应,不影响其水解。在临界的pH=8.2时,它们的水解影响被初步抑制,表面张力曲线表现出通常的上凸状。在pH=12时,CMC、c20和γCMC分别为9.30×10-2mmol·L-1、3.33×10-3mmol·L-1和35.4mN·m-1(C11pPHCNa)以及25.1mmol·L-1、5.37mmol·L-1和37.2mN·m-1(SL)。     

Synthesis and Physicochemical Investigation of Long Alkylchain Betaine Zwitterionic Surfactant

An effective and economic two-step route was developed to synthesize the long alkyl chain betaine zwitterionic surfactant directly from natural fatty acids. The optimal processing conditions for synthesizing the intermediate and final product were probed and the yields of 96.4% and 88.3% were obtained for each step, respectively. The surface active behavior of the synthesized decylbetaine surfactant was investigated using the surface tension method. The related thermodynamic parameters were calculated and discussed. The fluorescence probe technology was applied to determine the micropolarity of decylbetaine micelles.

Mixed Micellar Properties and Related Interaction Parameters of Butanediyl-1,4-bis(dodecyl dimethyl ammonium bromide) Gemini Surfactant with Nonionic Amphiphiles

Mixed micellization of cationic gemini surfactant butanediyl-1,4-bis(dimethyldodecylammonium bromide) with nonionic surfactants (sorbitan esters, alcohols and phenol ethoxylates) and triblock copolymers has been studied tensiometrically. Various physicochemical parameters of the studied systems including ideal CMC values, experimental and ideal micellar compositions, interaction parameters, activity coefficients of the components, etc. have been evaluated by considering theoretical models of Clint, Rubingh, Rosen and Maeda. The experimental critical micelle concentration (CMC) values of the mixed micelles were lower than the CMC values of the individual components and showed a negative deviation from ideal CMC (CMC*) values. The analysis reveals that the mole fractions of gemini are lower compared to the nonionic surfactants/triblock polymers and the values of ΔG _m ^° , ΔG _ad ^° , G _min and ΔG _ex ^m show that the spontaneity of the studied mixed micelles relatively decreases as the content of the gemini in the bulk phase increases.     

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.     

Synthesis and Surface Properties of Anionic Gemini Surfactants having N-acylamide and Carboxylate Groups

A straightforward synthetic strategy to an anionic gemini surfactant having both N-acylamide and carboxylate groups in a molecule has been demonstrated. The surface properties of the anionic gemini surfactant, such as CMC (critical micelle concentration), C₂₀ (the concentration required to reduce the surface tension of the solvent by 20 mN/m), γ _CMC (the surface tension at the CMC), ∏ _CMC (the surface pressure at the CMC), Γ _max (the maximum surface excess concentration at the air/aqueous solution interface), A _min (the minimum area per surfactant molecule at the air/water interface), and the CMC/C₂₀ ratio (a measure of the tendency to form micelles relative to adsorbtion at the air/water interface), have been studied. The influence of the different concentrations of NaCl on the surface properties of the gemini surfactant has been discussed. The results have shown that the CMC values decreased with an increase in the concentration of NaCl indicating that the Na⁺ preferentially adsorbs onto the surface of the charged aggregate and facilitates the aggregate growth by suppressing the main impediment of electrostatic repulsion among head groups. Additionally, the values of Γ _max are always higher in salt solutions as compared to those in pure water due to their salting out effect. The larger pC₂₀ value indicates that the surfactant adsorbs more efficiently at the air/water interface and reduces surface tension more efficiently. In addition, the geminis in water show little or no break in their specific conductance versus surfactant molar concentration plots. This is attributable to protonation of the carboxylate group and strong Na⁺ release during micellization.     

水相中表面活性剂与盐类的物理化学关系及其在水处理过程中的作用

探讨无机盐类对表面活性剂溶液体系相态、表面张力、流变等性质的影响。盐类的离子效应通过多种微观机理使微乳液相态、表面张力、临界胶束浓度、流变性质、浊点等物理化学性质产生明显变化，从而影响体系的动力学和热力学参数；较全面地考虑这些盐效应的影响对改善废水处理技术具有重要意义。     

Synthesis and Surface Properties of a Novel Anionic Gemini Surfactant using Dioxaoctane as a Linking Group

A novel anionic Gemini surfactant containing oxygen atoms in the linking group was designed and synthesized. The surface properties of the anionic Gemini surfactant were investigated by measuring the surface tension and conductivity. The Gemini surfactant showed a low critical micelle concentration value, which decreases with increasing concentration of NaCl. The calculated physicochemical properties indicate that oxygen atoms in the linking group interact with water molecules stronger than CH₂.     

磺酸盐型双基表面活性剂的合成与表面性能

以壬基酚和甲醛为原料,合成了一种新型的磺酸盐型双基表面活性剂(Gemini-A)。利用元素分析、红外光谱确定了Gemini-A的结构。研究了Gemini-A水溶液的润湿性,比较了Gemini-A与传统表面活性剂的增溶能力。试验结果表明,Gemini-A水溶液具有较低的表面张力(33.51 mN/m)和临界胶束浓度(0.141 mmol/L)及良好的润湿性,显示出了较好的表面性能,具有很强的增溶能力,是符合3次采油要求的表面活性剂。     

Effects of the Polypropylene Oxide Number on the Surface Properties of a Type of Extended Surfactant

The surface properties of 5 extended surfactant C_12–14P _mE₂S solutions in pure water and 0.1 M NaCl were investigated through surface tension and electrical conductivity measurements. The surface properties measured include the critical micelle concentration (CMC), critical surface tension (γ_cmc), maximum surface excess concentration (Γ_max), minimum area occupied per surfactant molecule (A_min), and efficiency in surface tension reduction (pC₂₀). The CMC values of the 5 surfactants decreased with increasing polypropylene oxide number (PON) and were higher than those obtained in 0.1 M NaCl. The Γ_max values showed a downward trend whereas the A_min values exhibited an upward trend with increasing PON without NaCl. The Γ_max values were higher and the A_min values were lower than those obtained without 0.1 M NaCl. The CMC values increased at elevated temperatures. The CMC values of C_12–14P₃E₂S, C_12–14P₅E₂S, and C_12–14P₈E₂S were similar but were markedly lower than those of C_12–14E₂S at different temperatures. When PON was less than 12, the log CMC value decreased linearly with increasing PON in the absence of salt, and the relationship between pC₂₀ and PON was linear. But in the presence of 0.1 M NaCl, the log CMC value decreased exponentially with increasing PON.     

Interaction of a Novel Anionic Gemini Surfactant Containing a Triazine Ring with Cetyltrimethylammonium Bromide in Aqueous Solution

The interaction between a novel anionic gemini surfactant containing a triazine ring, denoted as C8‐G, and cetyltrimethylammonium bromide (CTAB) has been investigated in aqueous solution. The surface tension vs log. molar concentration plots of the individual surfactants and their mixtures were measured at different temperatures (298, 303, 308, and 313 K) by the drop volume method. The surface properties and the interaction parameters of the adsorption monolayer and the mixed micelle were obtained from the plot. The results showed that the CMC of the C8‐G/CTAB mixture reached a minimum value of 3.20 × 10^?5 mol/L when α_G (the mole fraction of C8‐G in the mixed system) was 0.7 at 308 K, and the minimum γ_CMC was 28.1 mN/m obtained for the molar ratio of 0.9 at 308 K. Interaction between the two components was strongest () when α_G was 0.7 at 303 K. All the C8‐G/CTAB mixtures exhibited synergism in both surface tension reduction efficiency and mixed micelle formation except when the mole fraction of C8‐G (α_G) was 0.1, 0.5 and 0.9 at 313 K, and became greatest for the molar ratio of 0.7 at 303 K. The C8‐G/CTAB mixtures exhibited synergism in surface tension reduction effectiveness for all the complex ratios at 303 K, α_G = 0.1, 0.3, 0.9 at 308 K and α_G = 0.7 at 313 K, whereas the other surfactant mixtures did not show this synergism.     

Mixed Micelles of Trisiloxane Based Silicone and Hydrocarbon Surfactants Systems in Aqueous Media: Dilute Aqueous Solution Phase Diagrams, Surface Tension Isotherms, Dilute Solution Viscosities, Critical Micelle Concentrations and Application of Regular Solution Theory

Mixtures of trisiloxane type nonionic silicone surfactant (SS) with sodium dodecylsulfate, tetradecyltrimethylammonium bromide or tert-octylphenol ethoxylated with 9.5 ethylene oxide groups were studied in water at 30 °C by dilute aqueous solution phase diagrams, surface tension and dilute solution viscosity methods. The cloud points for the silicone surfactant aqueous solutions increased upon addition of hydrocarbon surfactants indicating the formation of hydrophilic complexes in mixture solutions. The scrutiny of the surface tension isotherms plotted as a function of SS concentration revealed that competitive adsorption effects are the characteristic features in these mixtures depending upon the SS concentration. Otherwise the isotherms exhibited two break points and the difference of concentration between the two break points increased with the increase in SS concentration indicating the cooperative nature of interactions. The micellar mole fractions of individual surfactants were determined by Rublingh's regular solution theory; interaction parameters and activity coefficients were evaluated and interpreted in terms of synergistic type interactions in these mixtures. The surface active parameters in mixture solutions were estimated and their analysis shows that the molecular species in the mixture solutions have a preferential tendency for adsorption at the air/water interface than in association form in the bulk solution. The effect of hydrocarbon surfactants on the intrinsic viscosity of SS micelles was monitored and related to the enhanced hydration in mixed micelles.     

Investigation of Mixing Behavior of both a Conventional Surfactant and Different Inorganic Salts with a Cationic Gemini Surfactant in Aqueous Solution

N,N′-bis [3-(dodecanoylamino)propyl]-N,N,N′,N′-tetramethylhexane-1,6-diaminium dibromide is a cationic Gemini surfactant including quaternary ammonium salt with amide groups. Critical micelle concentration (CMC) and some thermodynamic parameters of the cationic Gemini surfactant were investigated using surface tension and conductivity methods. Mixed micellization of binary mixtures of the cationic Gemini surfactant with a conventional surfactant cetyl trimethylammonium bromide (CTAB) was investigated using the conductometric method at five different temperatures ranging from 303.15 to 323.15 K. CMC, micellar ionization degree (α_m), counterion binding constant (g₁), interaction parameter (β), and activity coefficients ( and ) of mixed systems were found out from data of conductivity at different mole fractions for all studied temperatures. Additionally, the effects of some inorganic salts with different concentrations on the surface properties of cationic Gemini surfactant were examined by surface tension measurements. Some surface properties of the pure cationic Gemini surfactant and mixed salts systems were calculated using the data of surface tension.     

Structural and Physicochemical Properties of a Polymerizable Surfactant Synthesized from <Emphasis Type="Italic">N</Emphasis>-Methylol Acrylamide

A new polymerizable nonionic surfactant with reactive vinyl groups has been synthesized from N‐methylol acrylamide using a two‐step procedure. The structure of the surfactant molecule was characterized by Fourier transform infrared, ¹H nuclear magnetic resonance and mass spectroscopy. The surface active properties alongside its self‐assembly properties were investigated by surface tension, electrical conductivity, and fluorescence spectroscopy measurements. As compared with other nonionic surfactants, this study showed that this polymerizable surfactant possesses slightly a higher critical micelle concentration (CMC) value and the surface tension value at CMC. The obtained CMC values were compatible among measurements, ca. 0.02–0.038 M. The evidence of micelle formation also provided by the zeta potential measurements and the obtained zeta potential values showed that the polymerizable surfactant solutions had limited stability. The hydrolysis stability and solubility of the polymerizable surfactant were also investigated. The solubility results have shown that it was soluble in polar solvents while insoluble in nonpolar solvents both at room temperature and 40 °C. The acidic and basic hydrolysis of the surfactant increased as the temperature increased and the hydrolysis stability was 180 min (basic medium) and 55 min (acidic medium) at 80 °C.