双子表面活性剂体系的界面活性研究

测定了阳离子型双子表面活性剂烷基 α ,ω 双二甲基烷基溴化铵以及它与普通表面活性剂复配体系的表面张力。结果表明 :双子表面活性剂的表面活性大大高于普通表面活性剂 ,双子表面活性剂溶液的表面活性受其联接基团的影响远大于其烷基链的影响。通过研究阳离子型双子表面活性剂 /阴离子普通表面活性剂复配体系和阴 /阳普通表面活性剂复配体系的协同效应 ,发现双子表面活性剂与普通表面活性剂有很好的复配协同效应 ,这主要是由双子表面活性剂的特殊结构造成的。     

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。     

吗啉双子表面活性剂的性能研究

通过对新型阳离子双子表面活性剂α,ω-二(烷基吗啉鎓)烷烃的性能测定,研究了表面活性剂结构中疏水基和连接基碳链长度对表面性能、润湿性能、泡沫性能以及乳化性能的影响,确定了产物结构与其性能的关系.结果表明,α,ω-二(烷基吗啉鎓)烷烃双子表面活性剂的表面张力、泡沫性能以及乳化性能均优于其相应单子表面活性剂,润湿性能单子表面活性剂要比双子表面活性剂好;双子表面活性剂中,疏水基相同时,缩短连接基,表面活性剂的性能更优;连接基相同时,缩短疏水链,表面活性剂性能下降.     

磺酸盐Gemini表面活性剂的合成与表面活性

以单链表面活性剂SCT及1,3-丙二胺为原料,通过一步取代反应,合成了4种含三嗪环的磺酸盐Gemini型表面活性剂Cn-3-Cn(n=6,8,12,14),测定了25℃时4种表面活性剂的临界胶束浓度CMC。结果表明,Cn-3-Cn的临界胶束浓度CMC均随着疏水烷基链长度的增加而减小,C12-3-C12(实际疏水基碳原子数为14)达到最小值7.23×10-5mol/L,当实际疏水基中碳原子数增加到16时,CMC有所增加。同传统单烷基离子型表面活性剂十二烷基硫酸钠(SDS)相比,该类表面活性剂的CMC值低1～2个数量级,显示出很高的表面活性。此外,表面张力随着疏水烷基链长度的增加呈现先减小后增大的趋势,最低γcmc为35.48 mN/m。     

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.     

一种有色表面活性剂的合成及其表面活性研究

以邻氨基酚为原料,经过酰化、偶合反应合成了一系列不同碳链长度的3′ 脂肪酰氨基 4′ 羟基偶氮苯 4 磺酸,它们具有表面活性剂和偶氮染料的特征结构。这些褐色产物溶于强碱性溶液,其中脂肪酰氨基为12,14和16碳的产物具有表面活性,是有色的表面活性剂。其CMC以及CMC下的表面张力值均随着碳链增加而降低,由12碳酰氨基产物的0 0023mol/L及56 4mN/m下降到最低的16碳酰氨基产物的0 0009mol/L及48 6mN/m,表现出较好的表面活性,符合典型表面活性剂的规律。     

哌嗪系列双子表面活性剂的合成

为了探索哌嗪类双子表面活性剂在三次采油(EOR)、新材料制备及生物技术领域中的应用,合成了两个以哌嗪为基的双子表面活性剂Ⅰ和Ⅴ,一个含有两种阴离子的Bola型表面活性剂Ⅱ和一个大环表面活性剂Ⅲ。表面张力测定结果显示,Ⅰ的临界胶束浓度(CMC)为6.47×10-4mol/L,优于传统的表面活性剂;Ⅴ的CMC为1.17×10-3mol/L,说明连接基团长度一定时,增加疏水链的数目,表面活性降低。Ⅱ和Ⅲ水溶性较好,可应用于生物技术领域或在新材料中作为模板剂。MM2能量最小法计算结果显示,在有限长连接基团中引入较多疏水链的化合物不易合成。用溶剂可接触面积说明了Ⅲ水溶性较好的原因。     

辛基-[ω-烷氧基-聚(氧乙烯)]基-苯磺酸钠的合成及表面活性

以正辛酸、苯酚、多缩乙二醇和溴代烷烃为原料,经酰化、酯化、Fries重排、催化加氢、威廉逊醚化及磺化等反应,合成了8种辛基-[ω-烷氧基-聚(氧乙烯)]基-苯磺酸钠表面活性剂。经红外、核磁和电喷雾质谱对产物进行了结构鉴定。用W ilhelmy法测定了该系列表面活性剂的表面张力。结果表明,合成的辛基-[ω-烷氧基-聚(氧乙烯)]基-苯磺酸钠结构明确,具有良好的表面活性,水溶液中CMC达到10-5mol/L数量级,γCMC最低达25.79mN/m;固定烷基碳数,随着EO数的增加,CMC和γCMC先降低后升高,当EO数为4时,增加烷基碳数,CMC显著降低,γCMC减小。     

非对称阳离子双子表面活性剂的合成和性能研究

采用十六烷基二甲基叔胺和十八烷基二甲基叔胺分别与盐酸、环氧氯丙烷反应,制备得中间产物N-(3-氯-2-羟基)丙基-N,N-二甲基十六烷基氯化铵和N-(3-氯-2-羟基)丙基-N,N-二甲基十八烷基氯化铵。2种中间产物在碳酸钠催化下先后与乙二胺反应生成一种含长亲水链非对称阳离子双子表面活性剂(16-X-18)。采用IR和~1H NMR对中间体和产物进行表征,采用电导率法研究了所制备的表面活性剂的表面活性。结果表明,所制备的非对称阳离子双子表面活性剂的Krafft点低于0℃,cmc在25℃时为2.935×10~(-5)mol/L,反离子结合度随温度的上升而降低。     

新型羧酸盐类双子阴离子表面活性剂合成工艺及表面性能研究

用自制的双十二烷基乙二胺与丁二酸酐进行酰胺化反应,制备了一种新型羧酸盐类双子阴离子表面活性剂C12H25N(COC2H4COOH)C2H4N(COC2H4COOH)C12H25,并采用正交实验的方法优化了其工艺条件。结果表明:较佳工艺条件是n(双十二烷基乙二胺)∶n(丁二酸酐)=1∶2.8;60℃下反应20 h,在此条件下产品的平均收率达91.5%。通过高效液相色谱、IR、1HNMR及元素分析对产品的结构进行了表征,并测定了该表面活性剂的表面活性。结果表明这种双子阴离子表面活性剂在水溶液中的临界胶束浓度为4.31×10-6mol/L,γcmc=28.74 mN/m。     

季铵盐型Gemini表面活性剂气液界面行为研究

合成了不溶于水的季铵盐型Gemini表面活性剂18-s-18(=3,4,6,8,10,12),研究了联结基团长度对Gemini表面活性剂在气液界面上的性质的影响.结果表明:对不同长度的联结基团,表面压-分子面积曲线很相似;极限面积在s≤6时几乎成直线快速增加,并在s=10时达到最大值,s>10时稍微下降.     

双子表面活性剂的结构特点与表面活性

双子型表面活性剂由于极性头基区域的键合,阻抑了极性头之间的斥力,突破了传统表面活性剂的结构概念,具有比传统表面活性剂高得多的表面活性,现有的研究数据表明并联结构的双子表面活性剂具有比串联结构的双子表面活性剂高的降低表面张力的能力。     

羟基和酯基型Gemini双季铵盐表面活性剂在煤沥青表面的润湿特性

以自制的羟基和酯基型Gemini双季铵盐表面活性剂为研究对象,在考察其表面活性的基础上,进一步研究了表面活性剂在煤沥青表面的润湿性。研究表明,羟基型Gemini表面活性剂在煤沥青表面的接触角随疏水链长度的增长呈先减小后增大趋势,其中C₁₂-OH在煤沥青表面的润湿效果最好;对于m-n-m酯基型Gemini表面活性剂而言,接触角随疏水链长度的增长而降低。当疏水链长度一定时,m-6-m在煤沥青表面的润湿效果比m-2-m好。在一定浓度范围内,C₁₀-OH、C₁₂-OH和12-2-123种Gemini表面活性剂的表面张力与其在煤沥青表面黏附张力呈线性关系。煤沥青表面的Zeta电位随Gemini表面活性剂浓度的增大呈先增大后趋于平稳的趋势。     

唑型双子表面活性剂的合成和性能研究

以咪唑、以咪唑,溴乙酸,溴代十四烷和二元醇为主要原料,采用三步法合成了三种新的咪唑型双子表面活性剂,简记[C_(14)-n-C_(14)]Br_2。通过核磁氢谱和红外光谱对三种产物的结构进行表征,证明合成的产物为目标产物。并采用表面张力法得出三种表面活性剂的表面张力曲线,进而计算临界胶束浓度(CMC)等一系列表面性能参数,结果表明,连接基越短的咪唑型双子表面活性剂拥有更低的CMC,更高的界面活性。     

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。     

Insights into the Optimization of Alkyl Phenol/Alkyl Halide Ratio in Gemini Surfactant Synthesis

¹H NMR and thin layer chromatography (TLC) were applied to analyze the component of two series of synthesized sulfonated Gemini surfactants with different spacer lengths (2, 4, and 6 carbons) and hydrophobic chain lengths (9, 12 carbons). Gemini surfactants were prepared by reacting alkylphenol with alkyl halide followed by sulfonation with chlorosulfonic acid. The influence of the molar ratio of alkyphenol to alkyl halide on the mono‐ to diether ratio was investigated and the results indicated that the molar ratio is a key factor to minimize impurities in the target material, due to the high reactivity of alkyl halide. In addition, the results showed that alkyl halide with a shorter spacer group length required a higher molar ratio of alkyl halide to alkylphenol. To synthesize the intermediate Gemini product with 80 % diether content, the molar ratios were optimized using n(alkylphenol):n(1,6‐dibromohexane) = 1:0.55, n(alkylphenol):n(1,4‐dibromobutane) = 1:0.7, and n(alkylphenol):n(1,2‐dibromoethane) = 1:2.5, respectively.     

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.

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.     

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.