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。     

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.     

长链烷基苯磺酸钠Gemini表面活性剂的合成和表面活性

以脂肪酸、苯酚、乙二醇为原料,经酰化反应、酯化反应、Fries重排、氢化还原反应、磺化以及中和反应等步骤,合成出3种长链烷基苯磺酸钠Gem in i表面活性剂。用IR、1HNMR和ESI-MS对产物进行了结构鉴定。以W ilhelmy-p late法测定了30℃时它们在水溶液中的临界胶束浓度(CMC)和临界胶束浓度下的表面张力(γCMC)。纯水溶液中其临界胶束浓度(CMC)为10-4~10-5mol/L,γCMC为35~37 mN/m;随着苯环上长链烷基碳数(n=8、10、12)的增加,CMC分别为5.94×10-4、1.53×10-5、0.46×10-5mol/L;γCMC分别为36.9、34.4、34.4 mN/m。结果表明,此类表面活性剂具有比较好的表面活性。     

Synthesis,Characterization and Evaluation of the Surface Active Properties of Novel Cationic Imidazolium Gemini Surfactants

New imidazolium gemini surfactants were synthesized by reaction of epichlorohydrin with long chain fatty alcohols furnishing products 2-(alkoxymethyl)oxirane followed by their subsequent treatment with imidazole resulting in the formation of 1-(1H-imidazol-1-yl-3 alkoxy)propane-2-ol which on subsequent treatment with 1,2-dibromoethane and 1,3-dibromopropane resulted in the formation of title gemini surfactants:1,2-bis(1(3-alkoxy-2-hydroxypropyl)-1H-imidazol-3-ium)ethane bromide (7), 1,3-bis(1(3-alkoxy-2-hydroxypropyl)-1H-imidazol-3-ium)propane bromide (8), 1,2-bis(1(3-alkoxy-2-hydroxypropyl)-1H-imidazol-3-ium)ethane bromide (9), 1,3-bis(1(3-alkoxy-2-hydroxypropyl)-1H-imidazol-3-ium)propane bromide (10), 1,2-bis (1(3-alkoxy-2-hydroxypropyl)-1H-imidazol-3-ium)ethane bromide (11) and 1,3-bis (1(3-alkoxy-2-hydroxypropyl)-1H-imidazol-3-ium)propane bromide (12). Their identification was based on IR, ¹H-, ¹³C-NMR, DEPT, COSY and mass spectral studies. Their surface active properties were also evaluated on the basis of surface tension and conductivity measurements.     

Gemini Pyridinium Surfactants: Synthesis and Their Surface Active Properties

New pyridinium Gemini surfactants have been synthesized by esterification of renewable fatty acids with halogenated alcohols furnishing respective esters (2‐chloroethyl hexadecanoate, 2‐chloroethyl tetradecanoate, 2‐chloroethyl dodecanoate, 2‐bromoethyl hexadecanoate, 2‐bromoethyl tetradecanoate and 2‐bromoethyl dodecanoate) followed by their subsequent treatment with 4,4′‐trimethylenedipyridine resulting into the formation of title Gemini surfactants: (4,4′‐(propane‐1,3‐diyl)bis(1‐(2‐(hexadecanoyl oxy) ethyl) dipyridinium chloride(7), (4,4′‐(propane‐1,3‐diyl)bis(1‐(2‐(tetradecanoyl oxy) ethyl) dipyridinium chloride (8), 4,4′‐(propane‐1,3‐diyl)bis(1‐(2‐(dodecanoyl oxy) ethyl) dipyridinium chloride (9), (4,4′‐(propane‐1,3‐diyl)bis(1‐(2‐(hexadecanoyl oxy) ethyl) dipyridinium bromide (10), (4,4′‐(propane‐1,3‐diyl)bis(1‐(2‐(tetradecanoyl oxy) ethyl) dipyridinium bromide (11), 4,4′‐(propane‐1,3‐diyl)bis(1‐(2‐(dodecanoyl oxy) ethyl) dipyridinium bromide (12). Their identifications are based on IR, ¹H‐, ¹³C‐NMR, DEPT, COSY and mass spectral studies. Their surface active properties are also evaluated on the basis of surface tension and conductivity measurements and thermal stability of these long chain cationics Gemini surfactants have been measured by thermal gravimetric analysis under nitrogen atmosphere.     

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 %.     

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。     

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。     

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。     

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。     

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 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.     

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。     

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。     

Synthesis and Surface Activity of Cationic Amino Acid-Based Surfactants in Aqueous Solution

I studied the possibility of using amino acid-based surfactants as emulsifiers at the same time as preservatives. Fourteen lipopeptides were synthesized employing a solid phase peptide synthesis procedure. All compounds were designed to be positively charged from +1 to +4 and acylated with fatty acid chain—palmitic and miristic. The surface activity of the obtained lipopeptides was tested using a semi-automatic tensiometer to calculate parameters describing the behavior of lipopeptides in the air/water interface. Such parameters as CMC, surface tension at the CMC point (σ _CMC), effectiveness (π _CMC), and efficiency (pC20) were measured. Emulsifying properties of all lipopeptides were also examined. The studies reveal that the surface active properties of synthesized compounds strongly depend on the length of alkyl chains as well as on the composition of amino acid polar heads. The critical micelle concentration decreases with increasing alkyl chain length of lipopeptides with the same polar head. The effectiveness and efficiency decrease when the number of amino acids in the polar head increases. All lipopeptides established a very weak emulsification power and created unstable water/Miglyol 812 and water/paraffin oil emulsions. Results suggest that lipopeptides cannot be used as emulsifiers; nonetheless, it is possible to use them as auxiliary surfactants with disinfectant properties in combination with more potent emulsifiers.     

Progress in the Synthesis of Zwitterionic Gemini Surfactants

Zwitterionic gemini surfactants have hydrophilic head groups consisting of two polar groups with different charges. Species synthesized to date can be classed as anionic–cationic, anionic–nonionic, and cationic‐nonionic. These surfactants not only have a small repulsion between the hydrophilic head groups, but also have a more compact arrangement at the interface, which greatly reduces the surface and interfacial tensions. In addition, owing to the existence of zwitterions, they are endowed with a unique aggregation morphology and unique rheology in solution, so they has the potential for a number of applications. The present research situation and potential research directions of the synthesis methods of the three types of zwitterionic gemini surfactants are discussed in this paper.     

Synthesis,Surface Activities and Toluene Solubilization by Amine-oxide Gemini Surfactants

A series of amine-oxide gemini surfactants featuring amide groups [N, N’-dimethyl-N, N’-bis(2-alkylamideethyl)-ethylenediamine oxide (alkyl = C₁₁H₂₃, C₁₃H₂₇, C₁₅H₃₁, C₁₇H₃₅)] have been synthesized via a three-step synthetic route, and their chemical structures were confirmed by mass spectra, FTIR and ¹H-NMR spectra. The surface activities of these compounds have been measured. The results show that these synthesized amine-oxide gemini surfactants reduced the surface tension of water to a minimum value of approximately 26.91 mN m^?1 at a concentration of 2.92 × 10^?5mol L^?1. Furthermore, their critical micelle concentration (CMC) values and solubilization of toluene decrease with an increase of the hydrophobic chain length from 12 to 18. Isoelectric point measurements revealed that their pI values range from 4.0 to 10.5.     

Synthesis and Investigation of Surface Active Properties of Counterion Coupled Gemini Surfactants

Three counterion coupled gemini (cocogem) surfactants in the series 1,6‐bis(N,N‐alkyldimethylammonium) adipate, referred as n‐6‐n (n = 12, 14, 16), were synthesized, purified and characterized by ¹H NMR and ¹³C NMR. Their physicochemical properties were investigated by electrical conductivity and surface tension measurements. The degree of ionization, critical micelle concentration (CMC), surface excess at the air/solution interface (Γ_max), minimum area per surfactant molecule at the air/solution interface (A_min), surface tension at the CMC (γ_CMC), and pC₂₀ (negative log of the surfactant molar concentration, required to reduce the surface tension of water by 20 mN m^?1) were calculated. Increase in tail length of the surfactants increases the efficiency of surfactants to decrease the surface tension of water. Thermodynamic parameters, viz. molar free energy at the maximum adsorption attained at CMC (G_min), standard Gibb's energy of micellization (), and standard Gibbs energy of adsorption (), were also calculated. The and values show that the monomers were preferred to be adsorbed at the air/water interface and then in the micellar formation in the bulk. Additionally, fluorescence measurements were used to find the aggregation number. Other relevant surface properties (Krafft point, emulsion stability, foaming ability, micellar stability and dye solubilization ability) were also evaluated. These results suggest that with respect to emulsion formation, micellar stability and dye solubilization, the cocogem with a 16‐carbon chain gives better results, producing 89 % more stable foams and shows better aggregational behavior.     

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。