一种阴离子表面活性剂的合成与性能研究

合成了一种阴离子型双醚双苯磺酸盐Gemini表面活性剂,测定该系列Gemini表面活性剂水溶液的表面张力(γcmc)分别为:32.00mN/m、28.41 mN/m、29.76 mN/m、33.20 mN/m,临界胶束浓度(cmc)分别为:0.79mmol/L、0.87 mmol/L、1.02 mmol/L、0.84 mmol/L;该Gemini表面活性剂(DPDAS-12)可在无碱,浓度为0.35%条件下,将油/水界面张力降至1.2×10-3mN/m的超低水平;可有效改变岩石表面润湿性,可将亲油表面(θ=114°)改变为弱亲油(θ=69.3°),可将亲水表面(θ=26.0°)改变为弱亲水表面(θ=34.0°)。     

Micellization of Anionic Sulfonate Gemini Surfactants and Their Interactions With Anionic Polyacrylamide

Anionic sulfonate gemini surfactants 8‐s‐8(SO₃)₂ and 12‐s‐12(SO₃)₂ (s = 3, 6) were synthesized, and their micellization in aqueous solution at 25.0 °C and pH 9 was investigated. The results show that the critical micelle concentrations (CMC) of 8‐s‐8(SO₃)₂ are more than 2 orders of magnitude larger than those of 12‐s‐12(SO₃)₂, but the spacer length has a relatively small impact on the CMC. Moreover, the interactions of n‐s‐n(SO₃)₂ (n = 8, 12; s = 3, 6) with anionic polyacrylamide (PAM) at 25.0 °C and pH 9 were investigated using surface tensiometry, rheolgy, and scanning electron microscopy (SEM). The results indicate that the surface tension and rheological properties of PAM depend on the concentration of n‐s‐n(SO₃)₂. Below the critical aggregation concentration of C₁, surface tension is sharply reduced, the surface tension of n‐s‐n(SO₃)₂/PAM is lower than n‐s‐n(SO₃)₂ alone, but viscosity is almost unchanged with increasing C_{n‐s‐n(SO3)2}. Above C₁, surface tension reduces very slowly until the saturated concentration of C₂ is reached. Above C₂, surface tension rapidly reduces until C_M is attained, suggesting free n‐s‐n(SO₃)₂ micelles begin to form. In the region of C₁–C_M, the viscosity significantly increases. Above C_M, surface tension is basically unchanged and these curves coincide with those of the single surfactant system. Moreover, the viscosity is almost constant. The SEM images indicate that fibrous aggregates are formed below C₁, then transformed into multilayer fibrous aggregates above C₁, and further into fiber‐braided‐structured and spider‐web‐structured aggregates above C_M. The variation of viscosity is closely associated with the transformation of aggregates.     

阴离子/非离子表面活性剂驱油技术研究

对上海石油化工研究院研制的阴离子/非离子表面活性剂进行了相关方面的适用性评价,通过岩心模拟驱替实验研究了改善驱油效果的能力。评价结果表明:该表面活性剂与明15块注入水具有良好的配伍性;降低界面张力能力显著,推荐使用的浓度范围为0.05%~0.30%;地层温度条件下,可稳定65 d;65℃时经过150 min达到析水平衡且析水率仅为60%,乳化能力较好;吸附量均在2.0 mg/g左右,抗吸附能力良好。模拟驱替实验表明:使水驱采收率提高约12%,最终采收率达到42%,驱油效率显著,具有较好的经济效益。     

琥珀酸磺酸盐双子表面活性剂的合成及性能

以顺丁烯二酸酐、正辛醇、乙二醇和亚硫酸氢钠为主要原料,经单酯化、双酯化、磺化反应合成了一种Gemi—ni双子表面活性剂——乙二醇双琥珀酸双辛酯磺酸钠。通过正交实验以及单因素实验确定最佳合成工艺条件为：单酯化反应,n（正辛醇）：n（顺丁烯二酸酐）-1.00：1．05,反应温度90℃,反应时间2h;双酯化反应,n（单酯）：n（乙二醇）=2．05：1．00,反应温度100℃,催化剂对甲苯磺酸用量1．0％。反应时间3h;磺化反应,n（双酯）：n（亚硫酸氢钠）-1．00：2．05．反应温度85℃．反应时间90min。利用红外光谱对反应中间体和产物进行了表征。产物的CMC为5．0×10^-4mol·L^-1,表面张力yCMC为37．98mN·m^-1。     

Synthesis and Surface Active Properties of a Gemini Imidazoline Amphoteric Surfactant

The gemini imidazoline amphoteric surfactant was prepared in two steps. We first reacted lauric acid and triethylenetetramine to obtain the intermediate called bisalkyl-bis-imidazoline. We analyzed it by ¹H NMR, and the yield was 82.45 % according to perchloric acid non-aqueous titration. The intermediate was then quaternized using sodium 2-chloroethanesulfonic acid in a mixture of isopropyl alcohol and water, during which we controlled the pH between 8 and 9 and the temperature between 80 and 90 °C to prepare C12-bis-imi. The air–liquid surface tension was measured by a tensiometer at 298 ± 0.1 K. The results show that the critical micelle concentration (CMC) was 2.25 × 10^?3 mol/L and the surface tension at the CMC (γ _CMC) was 30.42 mN/m. C12-bis-imi showed a synergistic effect in combination with lauric alcohol with nine ethylene oxide groups (AEO9). The synergistic effect is most striking when the mole ratio of C12-bis-imi/AEO9 was 1/1, and the corresponding CMC was 9.79 × 10^?5 mol/L and the γ _CMC was 37.61 mN/m.     

磺酸型双子表面活性剂大规模制备与性能研究

通过大规模工业化的方法来制备新型阴离子磺酸型双子表面活性剂DTM-12,该合成方法简单、反应条件温和、无需中间体的提纯,能够在可以接受的成本下进行大规模生产。对目标产物进行表征,对其表面活性进行测试,并将实验室制备、小试放大、中试生产的DTM-12各数据进行对比。结果表明,大规模制备的DTM-12分子结构与实验室制备的相同;其表面活性与实验室制备的相近,且均优于常用的传统表面活性剂。     

Surface and Biocidal Properties of Gemini Cationic Surfactants Based on Propoxylated 1,6-Diaminohexane and Alkyl Bromides

Two new classes of gemini cationic surfactants—hexanediyl-1,6-bis[(isopropylol) alkylammonium] dibromide {in the abbreviation form: C_nC₆C_n[iPr-OH] and C_nC₆C_n[iPr-OH]₂; alkyl: C_nH_{2n + 1} with n = 9, 10, 12 and 14}—have been synthesized by interaction of alkyl bromides with N,N′-di-(isopropylol)-1,6-diaminohexane and N,N,N′,N′-tetra-(isopropylol)-1,6-diaminohexane. The surface tension, electrical conductivity, and dynamic light scattering (DLS) techniques were used to investigate the aggregation properties of the gemini cationic surfactants in aqueous solution. The formation of critical aggregates at two concentrations in an aqueous solution from obtained gemini cationic surfactants were determined via the tensiometric method. Thus, these gemini cationic surfactants start to form aggregates at concentrations well below their critical micelle concentrations (CMC). The surface properties and the binding degree (β) of the opposite ion were tested against the length of the surfactant hydrocarbon chain and the number of the isopropylol groups in the head group. By applying the DLS technique, it was explored that how the number of isopropylol groups in gemini cationic surfactants with C₁₂H₂₅ chain affects the sizes of micelles at concentrations greater than CMC. It was discovered that the obtained gemini cationic surfactants have a biocidal character.     

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。     

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.     

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。     

非离子表面活性剂的表面膨胀性质研究

用毛细波 -纵向波技术研究了非离子表面活性剂octaethyleneglycolmonododecylether(C12 E8)的表面膨胀性质。利用毛细波 -纵向波的波数和衰减系数探索了非离子表面活性剂溶液的表面膨胀模量、表面膨胀弹性、表面膨胀粘度、静态膨胀弹性、表面粘度相角与浓度和表面变形频率的关系。还通过表面膨胀性质和Frumkin表面状态方程的研究 ,探讨了非离子表面活性剂溶液的表面吸附动力学性质     

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.     

Properties of a Binary System Containing Anionic and Cationic Gemini Surfactants

Surface tension, fluorescence, and dynamic light scattering were used to investigate the properties of a binary surfactant system comprising an anionic gemini surfactant (DLMC) and cationic gemini surfactant (II‐12‐EO₂). Surface tension measurements afforded the critical micelle concentration (cmc) of the mixture and the values are all lower than those of pure constituent surfactants. For the mixtures of II‐12‐EO₂/DLMC, the micelle aggregation number decreases with the increase of II‐12‐EO₂, and the micropolarity of the micelle is lowest when the molar fraction of II‐12‐EO₂ is 0.5; the hydrodynamic radius (R_h) of the mixed micelle first increases and then decreases with the addition of II‐12‐EO₂, and larger micelles are obtained when the molar fraction of II‐12‐EO₂ is 0.5 or 0.7.     

磺酸盐Gemini表面活性剂物化性能的研究

磺酸盐Gemini表面活性剂因具有较高的表面活性、耐温及抗盐性好等特点而受到国内外学者的广泛关注。分别采用量高法和搅动法测定了磺酸盐Gemini表面活性剂TADS-10的润湿性能和起泡性能,采用分水时间法测定了TADS-10对液体石蜡的乳化能力。结果表明:磺酸盐Gemini表面活性剂TADS-10亲油表面的接触角随浓度的增大而减小,而亲水表面的接触角随浓度的增大而增大;在临界胶束浓度附近,TADS-10的起泡性能趋于稳定;随着温度的升高,其起泡性能增强;与传统表面活性剂相比,TADS-10具有较强的乳化性能。     

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.     

非离子表面活性剂缔合结构的物理化学性能研究进展

从浊点,表面张力表面吸附、胶束形成热力上行为、与离子表面活性剂的复配,与聚合物的相互作用,微乳液的热力学性质,在非水体系中的物化性能等方面总结了近年来国内外应用现代实验技术对非离子表面活性剂缔合结构物理化学性能的研究现状况,得到了许多有益的规律和结论,并对各个研究领域进行了展望。这地丰富表面活性剂的基础理论和进一步开发利用非离子表面活性剂具有重要意义。     

Gemini表面活性剂的特性及耐盐活性研究

研究了疏水链长度不同和联接基长度不同的7种系列阴离子Gemini表面活性剂的表/界面活性。它们的表面张力和临界胶束浓度表明它们有很好的表面活性。它们有非常好的抗一价、二价盐的能力,在20%以上的NaCl盐水中仍能溶解。用高矿化度的中原油田盐水配制的活性剂溶液与原油间的界面张力能达到超低,表明它们可应用于特高矿化度油藏提高采收率。     

无机盐对磺酸盐型双子表面活性剂溶液表面性能的影响

在(30±0.2)℃下,用直接观察法、表面张力法和旋转液滴法考察了不同无机盐(NaCl、CaCl2和MgCl2)对磺酸盐型双子表面活性剂DJ溶液溶解性、临界胶束浓度(CMC)值和界面张力的影响。结果表明,磺酸盐型双子表面活性剂DJ具有良好的抗盐性,溶解度可以达到20 000 mg/L以上;在低盐度范围时(小于500 mg/L),随着无机盐质量浓度的增加,表面活性升高,CMC降低;随着阳离子(Na+、Ca2+和Mg2+)价数的增加,CMC降幅增大,且Ca2+的影响程度大于Mg2+;在无机盐质量浓度达到10 000 mg/L时,CMC呈上升趋势;无机盐的加入使溶液界面张力先降后升,然后趋于平稳。无机盐质量浓度在100～1 000 mg/L内,磺酸盐型双子表面活性剂DJ溶液的界面张力可以达到最低。     

Effects of Spacers on Surface Activities and Aggregation Properties of Anionic Gemini Surfactants

This present article employs four anionic Gemini surfactants with different spacer groups and investigates their physicochemical and aggregation properties. The critical micelle concentration (CMC), surface tension at CMC (γ_CMC) and C ₂₀ of these surfactants have been investigated using the du Nouy ring method. The aggregation number (N) was determined with intrinsic fluorescence quenching method using pyrene as a fluorescence probe and benzophenone as a quencher. Results show that these anionic Gemini surfactants have lower CMC and C ₂₀ values compared with those conventional ones and show higher surface activity. As expected, the spacer plays an important role in the aggregation properties of Gemini surfactants. Under experimental conditions, Gemini B–D with an alkoxylated group as spacer has a lower CMC and a higher aggregation number than Gemini A with methylene as spacer. For Gemini B–D, the CMC and aggregation number values decrease with the increasing flexible spacer length. The micropolarity also affects the aggregation of the present anionic Gemini surfactants. The micropolarity of micelle becomes low when the concentration of surfactants increases. Aggregation numbers of surfactants increase and fluorescence intensities decrease with the increasing concentration of NaCl. These results will help us to understand the relationship between the architectures of Gemini surfactants and their various properties in aqueous solution. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.

Solubilization of Phenanthrene and Fluorene in Equimolar Binary Mixtures of Gemini/Conventional Surfactants

abstract This study deals with the enhanced solubilization of polycyclic aromatic hydrocarbons (PAHs) such as phenan-threne (PHE) and fluorene (FLR) in a pure cationic gemini (G6) and three conventiona...