阴-非离子型Gemini表面活性剂的合成研究进展

介绍了磺酸盐型、羧酸盐型和其他类型阴-非离子型Gemini表面活性剂的合成研究进展，简述了阴-非离子型Gemini表面活性剂与其他表面活性剂复配体系的性能特点及相关应用，并对阴-非离子型Gemini表面活性剂的发展趋势进行了展望。     

非离子型Gemini表面活性剂的性质

Gemini表面活性剂具有的优良表面活性,使之有望作为三次采油用的表面活性剂。用界面张力仪及HAAKERS600流变仪研究了非离子型Gemini表面活性剂的表面活性及流变特性。结果表明,25℃下,氧乙基数(EO数)分别为8,10,12的3种非离子型Gemini表面活性剂8-NP-8、10-NP-10及12-NP-12的临界胶束浓度(cmc)值分别为:0.99,0.15和0.032 mmol/L;非离子型Gemini表面活性剂的表面活性及cmc值受电解质的影响较小;氧乙基数为12的非离子型Gemini表面活性剂可以使亲水及亲油固体表面的接触角明显降低,水润湿性增强;非离子型Gemini表面活性剂溶液的粘度随剪切速率增加基本保持不变,呈现出牛顿流体的特性。     

双子表面活性剂的合成及应用研究进展

综述了近年来国内外双子(Gemini)表面活性剂的合成、性能及应用研究的进展。介绍了目前离子型、非离子型、两性离子型及不对称型Gemini表面活性剂的主要合成方法以及它们的主要性能;阐述了Gemini表面活性剂在日用化工、乳液聚合、金属防腐、生物技术和三次采油等各领域的应用状况。最后对Gemini表面活性剂的发展方向进行了展望。     

磺酸盐/硫酸酯盐Gemini表面活性剂的合成及应用进展

Gemini表面活性剂又作“双子表面活性剂”,其分子结构类似于两个表面活性剂分子的聚合体,故又称二聚表面活性剂。Gemini表面活性剂具有较单烷基链烃和单离子头基组成的普通表面活性剂更好的表面活性。根据双子表面活性剂所含亲水基团电荷差异,将其分为阴离子型、阳离子型、非离子型和混合型四大类。其中磺酸盐型和硫酸酯型属阴离子型双子。     

Gemini型表面活性剂的合成进展

综述了Gemini型表面活性剂,包括阴离子型、阳离子型、非离子型、两性型及一些特殊类型Gemini表面活性剂的合成方法研究进展。有参考文献23篇。     

表面加溶

本文首次报导了有关表面加溶的定量研究。文中测定了负离子型染料铬天青S(CAS)在两种硅胶(大孔硅胶和小孔硅胶)上的非离子型表面活性剂TX100、TX305和癸基甲基亚砜(DMS)的吸附层中的表面加溶。实验表明CAS单独存在时不被硅胶吸附;但当硅胶一旦吸附了一定量的非离子型表面活性剂后,CAS即被表面加溶,硅胶被染成紫红色(与CAS加溶于非离子型表面活性剂胶团溶液的颜色相似)。CAS的表面加溶量与非离子型表面活性剂的吸附量皆成直线关系;而直线的斜率,即加溶能力,只与表面活性剂的性质有关,而与硅胶的种类无关。三种表面活性剂被加溶的能力(gmol~(-1))依次是TX305>DMS>TX100。我们设想:对于TX100和TX305CAS可能是被表面加溶于吸附的氧乙烯链双层之间;对于DMS,则可能是表面加溶于双分子吸附层的碳氢链栅栏之中。     

非离子Gemini表面活性剂分子在水中的聚集行为

通过实验和耗散粒子动力学模拟相结合的方法,研究了非离子型Gemini表面活性剂在水溶液中的聚集行为和表面活性剂分子在水-气界面的分布情况。结果表明:10个环氧乙烷(EO)的α,α'-[2,4, 7, 9-四甲基-5-癸炔-4, 7-二醇]双[ω-羟基-聚(环氧乙烷)](S-10)的单体和团簇共存于低浓度溶液中。随着浓度的增加,表面活性剂分子聚集成球状胶束且尺寸增大;当球状胶束的尺寸增加到一定程度时,它们不能稳定存在并聚集成棒状胶束。在水-气界面处,表面活性剂分子或垂直或水平分布,但是随着浓度的增加,疏水基团垂直插进空气,而EO段在水中呈不规则的锯齿形分布。随着EO链段长度的增加,S-4、S-10和S-30的最小吸附分子截面积逐渐增大,这就是随着表面活性剂的EO段长度增加而润湿性降低的原因。实验与模拟相结合的方法为研究非离子Gemini表面活性剂的聚集行为提供了新的思路,通过模拟结果可以快速判断实验的准确性。     

聚氧乙烯十二烷基醚类在石腊/水溶液界面上的吸附性质

本文以非离子型表面活性剂聚氧乙烯十二院基醚类水溶液为体系,测定溶液表面张力γ和对固体的接触角θ。根据Young方程和Gibbs等温吸附方程的关联,求取固/液界面吸附量,并得到Langmuir型吸附等温线。推算了饱和吸附量、平均分子面积以及石腊临界表面张力等数值,结果和文献值接近。因此,本法可用于活性较高(CMC值低)的非离子表面活性剂在各种低能固体表面吸附性质的研究。     

Gemini磺酸盐类表面活性剂与非离子型表面活性剂在悬浮剂中的复配应用

将Gemini磺酸盐类表面活性剂与农药中常用的几种非离子型表面活性剂复配使用,成功研制出性能优良的20%虫酰肼悬浮剂、50%多菌灵悬浮剂及380g/L噁草酮悬浮剂。实验表明,使用Gemini磺酸盐类表面活性剂与非离子型表面活性剂复配后的产品乳化性能和稳定性得到很大的改善,协同效应明显,大大优于单独使用非离子型表面活性剂的产品。     

阴非离子型Gemini表面活性剂驱油体系性能评价

为提高低渗透油藏采收率,开发了一种阴非离子型Gemini表面活性剂ANG7-Ⅳ-7,并测定体系的界面张力、乳化性能和吸附量。结果表明,ANG7-Ⅳ-7表面活性剂浓度在1⁴ g/L范围内,油水界面张力均可达到10-3m N/m的超低数量级,当ANG7-Ⅳ-7浓度为4 g/L时,能使油水界面张力达到最低值6.025×10-3m N/m;在注入浓度为4 g/L时,表面活性剂在油砂上的吸附量为2.035 mg/g。室内岩心驱油试验结果表明,4 g/L的ANG7-Ⅳ-7表面活性剂驱可在水驱后提高采收率11个百分点。     

The energetics of surfactant adsorption at the air-water interface

The standard free energy, enthalpy, and entropy changes (ΔG, ΔH, and ΔS, respectively) for the adsorption at the air-water interface of a commercial ethylene oxide (EO) adduct of straight chain nonylphenol from monomer solution at the critical micelle concentration (CMC) have been calculated from surface tension-concentration data at 21C–45C using the Gibbs equation, the standard free energy change equation ΔG=−RT (In interfacial monomer concentration/CMC), and the Gibbs-Helmholtz equation which gave ΔH directly from the slope of the (ΔG/T) vs (1/T) function. The CMC and surface tension at the CMC (γCMC) decreased, and −ΔG and molecular area increased slightly, with increasing temperature. The ΔH and ΔS values were positive, and appear explainable by the postulations applied to micellization. At ambient temperature (28C) an increase in the (EO) mol ratio of straight chain nonylphenol and C₁₃ secondary alcohol ethoxylates resulted in increases of CMC, γCMC, and molecular area, and slight decreases in −ΔG. A comparison of the 9 (EO) mol ratio adducts of C₁₃ straight chain primary and secondary alcohols showed that the CMC and molecular area of the secondary alcohol ethoxylate were larger, and the γCMC and −ΔG smaller, than the corresponding values of the primary alcohol ethoxylate.     

Surface Activity and Performance Properties of Gemini Salts of Linear Alkylbenzene Sulfonate in Aqueous Solution

Gemini salts of linear alkylbenzene sulfonate (LABS) were prepared by neutralization of sulfonic acid with a series of low-molecular-weight diamines in aqueous solution. The equilibrium surface activity of Gemini salts of LABS was determined by measuring the surface tension as a function of surfactant concentration to determine the critical micelle concentration (CMC), surface tension at the CMC (γ_CMC), and the area per molecule at the air-water interface (Ų). Electrical conductivity was measured as a function of surfactant concentration to determine the CMC and counterion binding. Dynamic surface tension was measured using a bubble pressure tensiometer to infer the rate at which the surfactant migrates to the air-water interface. Equilibrium interfacial tension against mineral oil was measured using a spinning drop tensiometer. Dynamic interfacial tension was measured using a drop volume tensiometer. The surface tension, CMC, and interfacial tension of Gemini salts of LABS decreased compared to monovalent organic and inorganic salts. The CMC decreases with increasing molecular weight of the diamine spacer group. Dynamic surface and interfacial tension of Gemini salts of LABS are lower than monovalent salts. The foam volume of Gemini salts of LABS was determined using a high shear blender test. The foam volume of Gemini salts of LABS is lower than monovalent salts and depends on the size of the spacer group. Hard-surface cleaning was measured using artificial soil applied to white Formica tiles. Soil removal was determined by optical reflectance as a function of abrasion cycles. Gemini salts of LABS show reduced hard-surface cleaning performance compared to monovalent salts. Detergency of different types of soils on cotton and polyester/cotton fabric was determined by optical reflectance measurements. Gemini salts of LABS show improved cleaning performance compared to monovalent salts. Cleaning performance increases with increasing molecular weight of the diamine spacer group. In situ neutralization of LABS with organic diamines is a simple and efficient way to prepare anionic Gemini surfactants for industrial scale applications.     

The molecular mechanism for destabilization of foams by organic ions

The effect of tetraalkylammonium ions on the destabilization of foam has been studied by measuring the half-life of foam (τ_1/2), area/molecule at the air/water interface, surface viscosity and critical micelle concentration (CMC) of sodium dodecyl sulfate (SDS). The area/molecule of SDS in organic salt solutions, calculated from the Gibbs isotherm, increases as the size of organic ion increases, and surface viscosity of the film decreases with the size of organic ions. The interaction of tetraalkylammonium ions with SDS decreases the CMC of the solution, and hence the concentration of SDS monomers decreases. The CMC of SDS decreases with the increase in the size and concentration of organic ions. The decrease in the CMC, increase in the area/molecule of SDS at the air/water interface and the decrease in surface viscosity by tetraalkylammonium ions all work to decrease the foam stability. The results indicate that the change in intermolecular distance between surfactant molecules in the adsorbed film by organic ions can significantly influence the surface viscosity and foam stability. The foam destabilizing efficiency of tetra-alkylammonium ions was superior or equivalent to that of tributyl phosphate and 2-ethyl hexanol, which are used in many antifoaming formulations.     

MD膜驱剂与阳离子表面活性剂混合体系的胶束性质

通过电导率法测定临界胶束浓度(CMC),研究了MD膜驱剂的浓度、温度及不同无机盐对MD膜驱剂与十二烷基三甲基溴化铵(DTAB)混合体系CMC的影响。研究表明:MD膜驱剂与DTAB混合后,可降低DTAB的CMC,并且CMC随着MD膜驱剂浓度的增加而减小。温度从25℃升高到50℃时,4 mmol/L MD膜驱剂/DTAB混合体系的CMC增大。无机盐的加入有利于混合体系CMC的降低,相同价态的阴离子对CMC的影响相近,高价阴离子降低CMC的效果好于低价阴离子。     

Synthesis and Self-Aggregation of a Hydroxyl-Functionalized Imidazolium-Based Ionic Liquid Surfactant in Aqueous Solution

This paper deals with the synthesis and self-aggregation of a hydroxyl-functionalized imidazolium-based ionic liquid (IL) surfactant, namely 1-hydroxyethyl-3-dodecylimidazolium chloride ([C₂OHC₁₂im]Cl). The molecular structure was confirmed by means of electrospray ionization mass spectrometry (ESI–MS), ¹H nuclear magnetic resonance (¹H NMR) and elemental analysis. Many important physicochemical parameters, such as the critical micelle concentration (CMC), the surface tension at CMC (γ_CMC), the adsorption efficiency (pC ₂₀), the surface pressure at CMC (Π_CMC), the maximum surface excess (Γ _m ), the minimum molecular cross-sectional area (A _min), the value of CMC/C ₂₀, the average number of aggregation (N _m ) and the micellar microenvironment polarity were determined by surface tension-concentration curves, fluorescence spectra, and electrical conductivity. The phenomena of the second CMC, the concentration dependence of N _m , and the critical average aggregation number (N _m,c) of imidazolium-based IL surfactants are reported for the first time in this paper.     

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.     

由六氟丙烯二聚体合成阳离子表面活性剂及其性能

以六氟丙烯二聚体和,N,N-二甲基丙二胺为主要原料,合成了N,N-二甲基N′-(2-三氟甲基-1-五氟乙基)全氟烯丙基丙二胺(Ⅰ),然后通过季铵化反应制得溴化[N,N-二甲基-N-乙基-N′-(2-三氟甲基-1-五氟乙基)全氟烯丙基氨丙基]铵(Ⅱ)阳离子表面活性剂。利用碱性溴酚蓝方法对季铵盐阳离子进行了定性测定,并通过红外光谱和19FNMR、1HNMR对其分子结构进行了表征。性能测试结果表明,该阳离子表面活性剂的表面张力为24．5 mN／m(20℃),其临界胶束浓度为2．04×10-3mol/L,克拉夫特点低于0℃,具有良好的水溶稳定性。     

A kinetic study of ultrasonic degradation of carboxymethyl cellulose

In this study, the effect of power of ultrasound, temperature, and concentration of carboxymethyl cellulose (CMC) solution on the rate of ultrasonic degradation were investigated, and a kinetic model based on viscometry data was used to calculate the rate constants in different conditions. To investigation of effect of ultrasonic power on the degradation of CMC, the power of ultrasound was increased and observed that the viscosity of the CMC solution was decreased with an increase in the power of ultrasound, but the extent of the degradation in a constant power was found to decrease with an increase in concentration or temperature. The ultrasonic degradation of CMC solutions was carried out at different temperatures to investigate the effect of the temperature on the rate of degradation. The calculated rate constants indicated that the degradation rate of the CMC solutions decreased as the temperature increased. The degraded CMCs were characterized by gel permeation chromatography, and average molecular weights of ultrasonicated CMCs were compared in different reaction conditions. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

利用Gemini联接链上生色基团测定临界胶团浓度

利用Gemini表面活性剂分子聚集使联接链上生色基团吸光截面积增大的原理,发展了自吸收光谱测定水溶液中临界胶团浓度(CMC)的方法。实验测得C11pPHCNa水溶液(pH=12)的CMC值0．0891 mmol／L,与表面张力法测定的结果(CMC=0．0925 mmol／L)吻合。当这些分子聚集形成较完整胶团后造成联接链上生色基团的荧光猝灭,由此可测定形成较完整胶团的临界点(≈0．451 mmol／L)。     

Surface Activity,Thermodynamics of Micellization and Adsorption Properties of Quaternary Salts Based on Ethanolamines and Decyl Bromide

The surface-active properties of ionic-liquid type salts synthesized by the interaction of ethanolamines and decyl bromide have been studied. Surface tension as a function of concentration of the surfactant in aqueous solution was measured at 10, 20, 30 and 40 °C using a drop volume stalagmometer. From these measurements, the maximum surface excess concentration and the minimum area per molecule at the aqueous solution/air interface, the critical micelle concentration (CMC), the surface pressure at the CMC, and the standard thermodynamic parameters of adsorption and micellization were calculated. The structural effects on adsorption, micellization, and the effectiveness of surface tension reduction are discussed in terms of these parameters.