双子表面活性剂的性能、合成及应用

综述了新型表面活性剂一双子表面活性的性能、合成方法。与普通表面活性剂比较Gemini表面活性剂具有特殊的分子结构,使其在诸多常规领域及分子筛、纳米材料合成和生物分子分离等新领域中具有广泛的应用前景。     

双子表面活性剂的合成研究进展

双子表面活性剂作为新一代表面活性剂,具有传统单链表面活性剂所不具备的优越性能,在化妆品、三次采油、聚合反应、催化剂制备等领域具有巨大的应用价值。文章对双子表面活性剂的合成研究进行了综述。     

非离子Gemini表面活性剂的合成进展

双子（Gemini）表面活性剂是近年来迅速发展的一类新型表面活性剂,它是指分子中具有双亲水基和双亲油基的由一个间隔基团连接的表面活性剂,与传统表面活性剂相比,Gemini表面活性剂具有许多优异性能。相对而言,近年来非离子Gemini表面活性剂研究远较阴离子和阳离子的Gemini表面活性剂研究少。本文对非离子Gemini表面活性剂的研究现状进行了概述,以期对非离子Gemini类表面活性剂的研究与应用开发有所裨益。     

新型阴离子孪连表面活性剂的合成

系列长链环氧烷与不同短链二醇在75~80℃、NaH作用下合成了系列中间体孪连长链二醇,此中间体再与1,3-丙烷磺酸内酯在THF、NaH中反应得到了疏水链长度和连接基长度不同的7种磺酸盐孪连表面活性剂。核磁共振氢谱及红外光谱的结构分析证实了它们的结构。它们的表面张力为26.5~34 mN/m,临界胶束浓度为0.001~0.01 mmol/L,结果表明,它们的表面活性比相应碳链的常规表面活性剂强很多。疏水链长度和连接基长度的增长,有助于表面活性的提高。     

烷基苯磺酸盐Gemini表面活性剂的结构与界面性质

以烷基酰氯为原料,经傅克酰基化反应、格林反应、催化氢化还原及磺化、中和等步骤,合成了10-4-10、12-4-12和10-6-10(10和12代表疏水基碳数,4和6代表连接基团碳数)3种不同结构的双烷基双苯双磺酸盐Gemini表面活性剂,并用核磁共振氢谱和电喷雾质谱对产物进行了结构鉴定。用旋滴法测定了其水溶液与正庚烷的界面张力,发现磺酸盐Gemini表面活性剂的CMC比对应的传统的表面活性剂的CMC低两个数量级,并且随着疏水基碳数或连接基团碳数的增加而降低。10-4-10、12-4-12和10-6-10的饱和吸附面积(Amin)分别为0.23、0.35和0.97 nm2,饱和吸附量(Γmax)分别为7.37×10-10、4.65×10-10和1.72×10-10mol/cm2,临界胶束浓度下的界面张力(γCMC)分别为3.60、3.06和1.89 mN/m。     

季铵盐双子表面活性剂的合成和表面活性

以吗啉和溴代烷为原料,合成了两种季铵盐双子表面活性剂(m-6-m,m=10,12),并用IR和1HNMR表征了其结构。测得28℃时,12-6-12和10-6-10的表面张力(γCMC)分别为26.45 mN/m和25.55 mN/m;临界胶束浓度(CMC)分别为1.0 mmol/L和3.1 mmol/L;pC20值分别为3.48和3.03;比表面过剩(Γmax)分别为2.72×10-6mol/m2和2.80×10-6mol/m2;分子最小截面积(Amin)分别为0.611 nm2和0.593 nm2。结果表明,该季铵盐双子表面活性剂与相同离子头基及烷基链的单季铵盐表面活性剂相比,CMC低一个数量级,γCMC相差不大。     

阴离子磺酸盐双子表面活性剂的合成研究

以乙二胺,顺丁烯二酸酐、亚硫酸氢钠和十二醇为原料,通过三步法合成阴离子磺酸盐双子表面活性剂。通过正交实验考察了反应物投料比、反应温度和反应时间对目标产物收率的影响。研究表明合成目标产物的最优工艺条件为:中间体二乙胺双-(酰基丙酸-α-磺酸钠)b:十二醇摩尔比为1∶2.2,反应温度为145℃,反应时间为6h。产物结构经IR、1 H NMR表征为目标产物。     

Synthesis and Properties of Dissymmetric Gemini Surfactants

A series of novel dissymmetric gemini surfactants, [C _m H_2m+1COOC₂H₄(CH₃)₂N(CH₂)₃N(CH₃)₂C₂H₄OOCC _n H_2n+1]Br₂ was synthesized and symbolized as m-s–n. The Krafft temperatures and surface tension curves of the dissymmetric gemini surfactants were measured using an electrical conductivity method and a drop volume method. The low Krafft temperatures indicate very good solubility of these esterquat gemini surfactants. With the increasing numbers of carbon atoms in the hydrophobic alkyl chain, the critical micelle concentration (CMC) and the minimum surface area (A _min) decrease, and the efficiency of surface tension reduction (pc₂₀) increases. With the same numbers of carbon atoms in the hydrophobic alkyl chain, the dissymmetric gemini surfactant has a lower CMC and a smaller A _min than the corresponding symmetric gemini surfactant due to the enhanced hydrophobic interactions.     

Synthesis of Ester Based Cationic Pyridinium Gemini Surfactants and Appraisal of Their Surface Active Properties

New pyridinium gemini surfactants have been synthesized by esterification of halogenated carboxylic acids with long chain fatty alcohols furnishing respective esters (dodecyl-2-chloroacetate, tetradecyl-2-chloroacetate, hexadecyl-2-chloroacetate, dodecyl-2-bromoacetate, tetradecyl-2-bromoacetate and hexadecyl-2-bromoacetate) followed by their subsequent treatment with 4,4′-trimethylene dipyridine resulting in the formation of title Gemini surfactants: 4,4′-(propane-1,3-diyl)bis1-{2-(dodecyloxy)-2-oxoethyl}; 4,4′-(propane-1,3-diyl)bis{1-(2-(tetradecyloxy)-2-oxoethyl}; 4,4′-(propane-1,3-diyl)bis{1-(2-(hexadecyloxy)-2-oxoethyl} dipyridinium chlorides; 4,4′-(propane-1,3-diyl)bis{1-(2-(dodecyloxy)-2-oxoethyl}; 4,4′-(propane-1,3-diyl)bis{1-(2-(tetradecyloxy)-2-oxoethyl} and 4,4′-(propane-1,3-diyl)bis{1-(2-(hexadecyloxy)-2-oxoethyl} dipyridinium bromides. Their identifications are based on IR, ¹H-NMR, ¹³C-NMR, DEPT, COSY and Mass spectral studies. Their surface active properties were also evaluated on the basis of surface tension and conductivity measurements.     

Synthesis and Properties of Novel Phenylenediamine Gemini Surfactants

In the present work, a two-step method was adopted to synthesize a series of novel Gemini surfactants using N,N-dimethylalkyl amines (alkyl length = C₁₂, C₁₆ and C₁₈), epichlorohydrin, and n-phenyllenediamine as starting materials. The products were characterized using mass spectroscopy (MS) and nuclear magnetic resonance spectroscopy (¹H NMR). Systematic experiments were conducted to evaluate their surface activity, foaming properties, and antibacterial performance. Results showed the critical micelle concentrations (CMC) of the C₁₂-based, C₁₆-based, and C₁₈-based phenylenediamine surfactants were 3.295 × 10⁻³, 2.532 × 10⁻⁴, and 3.140 × 10⁻⁴ mol L⁻¹ at 298 K, respectively, with corresponding surface tension (γ_cmc) values of 28.24, 31.95, and 35.06 mN m⁻¹ under the same conditions. The Gemini surfactants showed not only good surface activity and foaming properties, but also demonstrated good antimicrobial performance against Gram-positive and Gram-negative bacteria and fungi.     

Gemini表面活性剂的结构特点及在采油中的应用

文章简要地介绍了Gemini表面活性剂的结构特点；从表面活性剂的作用原理出发，介绍了Gemini表面活性剂的优良性能：如表面张力、泡沫力、润湿力、优异的协同效应、耐温抗盐性等；在此基础上，阐述了该类表面活性剂在油田三次采油上的应用前景。     

磺酸盐类表面活性剂合成进展

本文主要综述了磺酸盐类表面活性剂的合成路线和方法,同时综述了类型新颖的磺酸盐表面活性剂的结构与性能的关系。对今后的磺酸盐表面活性剂的合成发展方向提出了一些看法,希望能对磺酸盐表面活性剂的发展起到一定的积极作用。     

Synthesis, Surface Active Properties of Novel Gemini Surfactants with Amide Groups and Rigid Spacers

A series of novel cationic gemini surfactants, bis-(N-(3-alkylamido-propyl)-N,N-dimethyl)-p-phenylenediammonium dichloride, were synthesized. The structures of the gemini surfactants were characterized by IR, ¹H NMR and ¹³C NMR. The Krafft temperatures of surfactants were determined through conductivity, the surface active properties in aqueous solution were studied at various temperatures by surface tension and conductivity. The thermodynamic functions of micellization process of the surfactants were also calculated by conductivity. The Krafft temperatures of the surfactants were 12, 13 and 28 °C. The values of CMC and Γ _max decreased with increasing the length of hydrophobic chains, but the values of CMC and α increased with increasing temperature. The process of micellization is a spontaneous, exothermic and entropy-driven process.     

Synthesis,Characterization, and Viscosification of Amidosulfobutaine and Zwitterionic Gemini Surfactants

The viscoelastic surfactants (VES)-based acid diverters are frequently used to divert acid flow from high-permeability layers into low-permeability for enhanced overall productivity of the treated well. In general, an optimum VES-based system possesses advantages of decrease in absorption loss, damage of reservoir, and improved adaptability of active agents to high salinity. Herein, we report the synthesis of three new zwitterionic gemini surfactants ( 1 – 3 ) and previously known amidosulfobutaine ( C ₁₈ AMP3SB ) has been accomplished for the investigation of diverting acid performance. The synthesis of these surfactants was achieved by the amidation of the acid chlorides of commercially available fatty acids with 3-(dimethylamino)-1-propylamine followed by subsequent reactions with appropriate sultone or ethyl 4-bromobutanoate. The synthesized surfactants were well characterized by spectroscopic methods including IR and NMR spectroscopy. The thermogravimetric analysis (TGA) results suggested that surfactants ( 1 – 3 ) and C ₁₈ AMP3SB possess excellent thermal stability, with no appreciable loss of mass up to 300°C. The viscosity measurements of the neat surfactants ( 1 – 3 ) and C ₁₈ AMP3SB were performed under various temperatures, in the presence of different concentration of calcium chloride salt with the aid shear viscosimetry. The analysis revealed that the viscosity of neat C ₁₈ AMP3SB increases with increase in concentration of CaCl₂. With 10% CaCl₂ solution, the viscosity was increased from 7.5 to 33.55 cPs, whereas in 20% CaCl₂ the viscosity reached to 102 cPs with rise in temperature from ambient to 90°C. Moreover, the viscosity of neat surfactants ( 1 – 3 ) did not exhibit any appreciable viscosity change under the experimental conditions. However, the mixture of surfactants ( 1 – 3 ) each in combination with C ₁₈ AMP3SB (1:1) displayed significant upsurge in the viscosity, up to more than 10 folds.     

双子表面活性剂的研究进展

双子表面活性剂（gemini或dimeric）是由两个单链单头基普通表面活性剂在离子头基处通过化学键联接而成，这种特殊的结构使其具有比传统表面活性剂更优的性能，本文介绍了双子表面活性剂的发展简史、研究概况以及结构特点，表明这种表面活性剂具有重要的实用价值。     

Synthesis and Antibacterial Activity of Novel Amido-Amine-Based Cationic Gemini Surfactants

A series of novel cationic gemini surfactants were synthesized from corresponding amido-amines in a single step reaction. The amido-amines were obtained from long chain carboxylic acids and 3-N,N-dimethylamino-1-propyl-amine with excellent isolated yield (up to 95 %). All the synthesized quaternary ammonium compounds (QACs) were further investigated for surface active properties. The critical micelle concentration (CMC) and the effectiveness of surface tension reduction were determined. The surface tension measurements of newly synthesized gemini surfactants showed good water solubility, and low CMC values, had great efficiency in lowering the surface tension and a strong adsorption at the air/water interface than the corresponding monomeric surfactants. Further, the antibacterial activity of the synthesized QACs against both Gram-positive and Gram-negative bacteria was also investigated.     

Gemini（孪联）表面活性剂的界面性质与应用

全面地评述Gemini(孪联）表面活性剂在界面吸附,不溶膜和协同效应等方面近两年国际上的研究进展,总结了部分有代表性Gemini(孪联）表面活性剂的界面物理化学性质。并介绍了这类表面活性剂在增溶,乳液聚合,抗菌和新材料制备等领域的优良应用性能。     

Synthesis and Surface Activity of Bisphosphate Gemini Surfactants

Anionic bisphosphodiester gemini surfactants with two different spacer moieties and varying alkyl chain lengths were synthesized and investigated for their surface active properties. The equilibrium and dynamic surface tension studies were carried out using the Wilhelmy plate technique and maximum bubble pressure method respectively. It was found that these gemini surfactants possess lower critical micellar concentration values, and reduce the surface tension to a greater extent in comparison with the conventional analogues. The efficiency of the synthesized gemini surfactants was also evaluated. The results of surface activities obtained were correlated with the structures of gemini surfactants. The dynamic surface tension measurements showed that the geminis with long chains adsorb very slowly at the air/water interface within the time span of measurements. These gemini surfactants showed low foamability.     

Synthesis,Physico-Chemical Properties and Enhanced Oil Recovery Flooding Evaluation of Novel Zwitterionic Gemini Surfactants

In this work, a novel series of zwitterionic gemini surfactants with different hydrophobic tails were synthesized and characterized. The physico‐chemical properties of these products (such as surface tension, oil/water interfacial tension, foaming ability, and the wetting ability of paraffin‐coated sandstone) were fully studied. The CMC of the synthesized surfactants ranged from 2.17 × 10^?4 mol L^?1 to 5.36 × 10^?4 mol L^?1 and corresponding surface tension (γ_CMC) ranged from 26.49 mN m^?1 to 29.06 mN m^?1, which showed excellent efficiency among the comparison surfactants. All the products can reduce the interfacial tension to a relatively low level of about 0.1–1.0 mN m^?1. Additionally, results from applying different hydrocarbons suggested that the synergy will be clearer and oil/water interfacial tension will be lower if the oil components are similar to the surfactants. Contact angle and foaming measurements indicated that the surfactants exhibited good wetting and foaming abilities. The results of oil flooding experiments using an authentic sandstone microscopic model showed that C‐12 and CA‐12 could effectively improve the displacement efficiency by 21–29 %.     

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.