高分子表面活性剂的合成

介绍了高分子表面活性剂的合成方法及其不同于低分子表面活性剂的特点,重点从离子聚合、活性自由基聚合、缩合聚合、开环聚合、高分子化学反应、自由基胶束聚合等角度综述了近几-来高分子表面活性剂的合成研究进展.     

Synthesis and Aqueous Solution Properties of Polyoxyethylene Surfactants with Ultra-Long Unsaturated Hydrophobic Chains

Methoxypolyethylene glycols (M _n = 750, 1000, 2000, and 5000 g/mol) were hydrophobically modified by transestification with mono-unsaturated alkyl chains (UC18, UC22, and UC24), and the obtained ultra-long-chain nonionic surfactants were characterized by ¹H NMR, FTIR and gel permeation chromatographic, respectively. Aqueous solution properties of all these surfactants, including cloud point, surface activities, viscosifying ability, and phase diagrams were examined. It was found that all these ultra-long-chain polyoxyethylene surfactants exhibit good water solubility and typical Newtonian rheological behavior. For the surfactants with the same hydrophobic length, the CP, equilibrium surface tension (γ_cmc), as well as zero-shear viscosity (η₀) increase with increasing their hydrophilic length; for those with same hydrophilic head group, the critical micellar concentration and η₀ increase while the γ_CMC decreases with increasing hydrophobic tail length. Moreover, a decrease in the critical overlap concentration and an increase in the critical temperature were observed in phase diagrams of all these ultra-long-chain polyoxyethylene surfactants. (Supplemental materials are available for this article. Go to the publisher's online edition of the Journal of Dispersion Science and Technology to view the free supplemental file.)     

Enhancement of the Surface Activity for Some Monomeric and Polymeric Thiol Surfactants Using Silver Nanoparticles

In the present work, the self-assembling of some synthesized thiol surfactants namely (6-(3-amino phenoxy) hexane-1-thiol, 8-(3-amino phenoxy) octane-1-thiol, 10-(3-amino phenoxy) decane-1-thiol, 12-(3-amino phenoxy) dodecane-1-thiol, and their polymers on silver nanoparticles was investigated. The self-assembling of these surfactants on silver nanoparticles was characterized using different techniques such as ultraviolet (UV) spectroscopy, powder x-ray diffraction (XRD), electrone diffraction (ED), and transmission electron microscopy (TEM). The effect of the self-assembling of these surfactants on the stabilization of the silver nanoparticles (AgNPs) was studied using TEM images. The growth of the silver nanoparticles was investigated with respect to the increase of alkyl chain in the synthesized thiol surfactants. The effect of silver nanoparticles on the surface, interfacial tension, and the emulsion stability of these surfactants with paraffin oil was studied. The results show that the silver nanoparticles have the ability to effect on the behavior of these surfactants in solution and improve their surface activity.     

Antimicrobial Activity of Gemini Surfactants with Ether Group in the Spacer Part

Due to their large possibility of the structure modification, alkylammonium gemini surfactants are a rapidly growing class of compounds. They exhibit significant surface, aggregation and antimicrobial properties. Due to the fact that, in order to achieve the desired utility effect, the minimal concentration of compounds are used, they are in line with the principle of greenolution (green evolution) in chemistry. In this study, we present innovative synthesis of the homologous series of gemini surfactants modified at the spacer by the ether group, i.e., 3-oxa-1,5-pentane-bis(N-alkyl-N,N-dimethylammonium bromides). The critical micelle concentrations were determined. The minimal inhibitory concentrations of the synthesized compounds were determined against bacteria Escherichia coli ATCC 10536 and Staphylococcus aureus ATCC 6538; yeast Candida albicans ATCC 10231; and molds Aspergillus niger ATCC 16401 and Penicillium chrysogenum ATCC 60739. We also investigated the relationship between antimicrobial activity and alkyl chain length or the nature of the spacer. The obtained results indicate that the synthesized compounds are effective microbicides with a broad spectrum of biocidal activity.     

Phase Behavior in Mixtures of Cationic Dimeric and Anionic Monomeric Surfactants

The formation of mixed aggregates has been investigated in the mixture of oppositely charged surfactants vastly differing in molecular geometry and size. The systems considered is mixture of the cationic gemini surfactant, ethanediyl-1,2-bis(dodecyldimethylammonium bromide), and anionic surfactant, sodium dodecyl sulfate. Various mixed nano- and microaggregates (micelles, vesicles, thin lamellar sheets, and tubules) were formed depending on bulk composition and total surfactant concentration. Two types of aggregates were found in precipitate, the tubules as prevailing aggregates on the gemini-rich side, and vesicles as prevailing aggregates on the SDS-rich side. The tubules formation was ascribed to mutual influence of specific structure of cationic dimeric surfactant and electrostatic interactions at the bilayer/solution interface. The proposed mechanism involved the formation of lamellar sheets, which rolled-up into tubules.     

工业废水中阳离子表面活性剂的分光光度法测定

研究了阳离子表面活性剂溴化十六烷基三甲基胺和氯化十六烷基吡啶与二溴羧基苯基重氮氨基偶氮苯的显色反应 ,并提出了分光光度测定阳离子表面活性剂的新方法。结果表明 ,在碱性介质中 ,溴化十六烷基三甲基胺、氯化十六烷基吡啶等均能与二溴羧基苯基重氮氨基偶氮苯形成 1∶ 2的紫红色离子缔合物 ,最大吸收波长位于 5 80 nm处 ,表观摩尔吸光系数为 3.7× 1 0 4 L· mol- 1·cm- 1。表面活性剂的浓度在 0～ 80 μg/2 5 m L范围内符合比耳定律。方法直接应用于工业废水中阳离子表面活性剂的测定 ,获得了满意的结果     

Acid- and Oxidatively-Labile Vinyl Ether Surfactants: Synthesis and Drug Delivery Applications

Liposomes have now evolved into a commercially-important drug delivery vehicle by overcoming a host of problems that were initially encountered with first generation liposomes. In spite of these impressive advances, the great potential of liposomes as drug delivery vehicles will not be fully realized until more effective targeting and membrane fusion mechanisms have been incorporated into their formulations. Our laboratory has developed several plasmenyl-type lipids for use in acid- or photooxidatively-triggerable liposomes. This review summarizes our progress toward the design, synthesis, and triggered release of encapsulated agents upon acid-catalyzed hydrolysis or photosensitized oxidation of plasmenyl-type lipid systems. Application of these materials in cascade triggering and intracellular drug delivery schemes is also described.     

Polymeric Surfactants and Emerging Alternatives used in the Demulsification of Produced Water: A Review

Stable emulsions are frequently encountered in oil production and cause a series of environmental and operational issues. Chemical demulsification is widely used for the separation of oil from water or removal of water from oil. The chemicals used in the demulsification process have a strong affinity to the oil-water interface. This review presents the various types of chemical demulsifiers used for the demulsification of water-in-oil and oil-in-water emulsions. The review covers the relevant properties of polymeric surfactants such as polyether, dendrimers, and natural biodegradable polymeric surfactants. In addition, emerging alternatives like nanoparticles-based demulsifiers and ionic liquids are also reviewed. The factors affecting the demulsification efficiency of these demulsifiers and structure-property relationships are discussed. Copolymers with high hydrophilic content and molecular weight are more efficient demulsifiers. Similarly, the position isomerism (same carbon skeleton and functional groups but a different location of functional groups) strongly affects the HLB and demulsification performance. Generally, dendrimers show better performance compared to linear polymeric surfactants due to their relatively higher interfacial activity, better penetrability, and a larger number of reactive terminal groups. Techniques used to evaluate the performance of demulsifiers are also covered. The review also highlights the current developments and future prospects of chemical demulsifiers.     

Surfactants Used in Food Industry: A Review

The understanding of the formation, structures, and properties of emulsions is essential to the creation and stabilization of structures in food. The increasing use of surfactants, the identification of compounds with low toxicity and good surface activity properties is of great interest. The relevance of the major end points specified in the Organisation for Economic Co-operation and Development (OECD) guidelines for the hazard assessment of food chemicals is critically analyzed and main parameters are acute toxicity, subacute repeated studies, allergy, reproductive toxicity, long-term studies, and mutagenicity tests. We focus this article on surfactant association structures and food colloids. There is almost infinite number of combinations are organized and arranged in very complex internal microstructures with various types of assemblies such as dispersions, emulsions, foams, gels, etc. Low-mass surfactants are very mobile at the interface and they are particularly efficient reducing the interfacial tension. As a result, they rapidly coat the freshly created oil-water interface during emulsification. In this category, we mainly mentioned monoglycerides, lecithins, glycolipids, fatty alcohols and fatty acids. High-mass surfactants cover protein and polysacharide groups. The protein molecule may interpenetrate in the lipid phase to various degrees. The specific binding is predominantly electrostatic: The headgroups of the surfactants bind to groups of opposite charge on the protein. The saturation binding for anionic surfactants is pH-independent and seems to be controlled by the cooperative hydrophobic interactions. Polysaccharides and smallmolecule surfactants are two of the predominant groups of amphiphilic materials that have been explored for the stabilization of emulsions. One of the most important aspects of polymer-surfactant systems is their ability to control stability and rheology over a wide range of composition. Biocompatible, biodegradable, and/or nontoxic emulsion-based formulations have great potential for applications in the food. The combination of particular characteristics such as emulsifying, anti-adhesive and antimicrobial activities presented by biosurfactants suggests potential application as multipurpose ingredients or additives.     

Synthesis and Applications of Alkylbenzene Sulfonate Gemini Surfactants

A series of anionic Gemini surfactants with the same structure except for the spacer and side chain length of the alkylbenzene sulfonate were synthesized based on dodecyl benzene and toluene. The structures of the compounds were confirmed by infrared and nuclear magnetic resonance spectroscopy, and elemental analyses. The effect of spacer and side chain length on the interfacial tension of Gemini surfactant solution was investigated by comparison of the critical micelle concentration (cmc) of the surfactants in aqueous solution using the drop volume method, and the surface tension at the cmc (γcmc). The Gemini surfactant with the best properties was used as emulsifier in emulsion polymerization of methyl methacrylate, and its foam stability was also determined.     

正负离子表面活性剂复配系统

正负离子表面活性剂复配系统,由于其带有相反电荷的离子头基间的强静电相互作用,具有强协同效应和高表面活性,在水溶液中可形成丰富的微观结构,表现出复杂的相行为。本文在相关研究的基础上,对于正负离子表面活性剂复配系统在表面（界面）性质,囊泡的制备及稳定性,虫状胶束的生成和性质,双水相系统的性质及其在萃取方面的应用,拟相分离模型、热力学胞腔模型、分子热力学模型及分子模拟等理论研究和作为模板合成纳米材料等方面的研究进展进行了综述。对于双水相系统的研究,指出了一些有待于进一步解决的问题。     

Synthesis of Amphoteric Surfactants via Esterification Process

This article describes the synthesis of a novel amphoteric surfactant through esterification of 2‐hydroxy‐N,N,N‐trimethylethanaminium chloride with maleic acid alkyl ester of C₈, C₁₀, and C₁₂ chain length in the presence of base. Maleic acid alkyl esters were synthesized by the reaction of maleic anhydride with alkyl alcohol. Surface‐active properties were studied by different techniques such as surface tension and foaming property. Critical micelle concentrations (CMCs) were found by using surface tension values to learn the effect of chain length on CMC of synthesized surfactants. The best result obtained has minimal coproducts, an environmentally safer route, and a very good CMC value of surfactants.     

Solubilization Behaviors of Nonpolar Substrates Using Double Tailed Cationic Surfactants

A series of double hydrophobic tails of N-methyl diethanolammonium bromide cationic surface active agents were synthesized. Their chemical structures were elucidated using different analytical tools including elemental analyses, FTIR, mass fragmentation, and ¹H-NMR spectroscopy. Their surface parameters including critical micelle concentration (CMC), effectiveness (π _CMC ), efficiency (Pc ₂₀), maximum surface excess (Γ _max ), and minimum surface area (A _min ) were calculated. The behaviors of the synthesized molecules in their solutions were discussed based on the data of surface parameters, micellization and adsorption thermodynamics at 25°, 40°, and 55°C. The experimental data of surface activity showed that these molecules are tends to form micelles in the bulk of their solutions at lower temperatures. On contrarily, they prefer to adsorb at higher temperatures. The synthesized cationic surfactants were used as solubilizing agent for nonpolar substrate (paraffin oil) at 25°C. The results of solubilization measurements showed good ability for the used surfactants towards solubilizing paraffin oil in aqueous medium. The results showed that the chemical structure of the solubilizate plays an important rule in its solubilization. Several factors were found to influence the extent of solubilization including: number of alkyl chains within surfactant molecule, symmetry of molecules and chain length of hydrophobic parts. The results were rationalized by the Kraft point and HLB values of the used surfactants. Furthermore, solubilization curves showed the steady state solubilization of each surfactant used.     

An Unusual Variation of Surface Tension with Concentration of Mixed Cationic‐anionic Surfactants

There are two platforms in the surface tension vs. concentration curve (γ‐lgC curve) of cationic‐anionic surfactant mixtures. The first platform is the same as that of common surfactant solution, and the cross point is the CMC. After the CMC, the mixtures form precipitate. At higher concentration, the mixtures form homogeneous solution again. When the mixtures form homogeneous solution at high concentration, surface tension increases with concentration, then becomes constant. So the γ‐lgC curve exhibits the second platform. The surface tension at the second platform increases by increasing molar ratio of two surfactants and polar group size of surfactants, and decreases with adding inorganic salts.     

Synthesis and Evaluation of Some Schiff Base Surfactants for Treating Crude Oil Emulsions

Water soluble nonionic surfactants based on Schiff base monomers were prepared by their etherification with β,^` β- dichlorodiethylether and PEG 400 in presence of NaOH. The surface properties of the prepared surfactants were determined by measuring the surface tension at different temperatures. The prepared nonionic surfactants were evaluated as demulsifiers for synthetic water in crude-oil emulsions that were pronounced at different ratios of crude oil: water at 45°C and 60°C. The experimental results showed that the dehydration rate of the prepared demulsifiers reached 90% and 100% at some concentrations.     

Quantitative Structure—Property Relationship on Prediction of Surface Tension of Nonionic Surfactants

When a surfactant is solved into a solvent, it will adsorb onto the surface of the solution and reduce the surface free energy to a marked degree. The surface free energy, which is the minimum amount of work required to create that surface, is usually measured by surface tension. The minimum of surface tension 0g is the most useful key for characterizing the activity of surfactant. It is well known that 0g is determined by the molecular structure of surfactant, i.e., the contributions from …     

Synthesis,Properties, and Applications of Amino Acids Based Surfactants: A Review

Amino acids based surfactants belong to the class of surfactants with high biodegradability, low toxicity and excellent surface active properties. They possess excellent emulsifying, detergency properties and form fine lather. These surfactants are environment friendly, mild to skin and eyes, and have hard water tolerance. This article reviews types, synthesis, various surface properties such as cmc (critical micelle concentration), surface tension, phase behavior, Krafft temperature, and interfacial adsorption of these surfactants. The biological properties such as antimicrobial activity, aquatic toxicity, biodegradability and hemolytic activity have also been focused. The various applications of amino acid based surfactants in the area of life sciences such as gene transfection, formation of liposomes, and drug delivery systems have also been reviewed.     

连接基团链长度对季铵盐二聚表面活性剂C12-s-C12·2Br在水溶液中胶团化行为的影响

用电导法、稳态荧光法和粘度法研究了二聚表面活性剂C12-s-C12*2Br分子中的连接基团链长度(s=2, 3, 4, 6)对其在水溶液中聚集行为的影响. 实验发现, C12-s-C12*2Br的胶团生成能力远比其单体C12TABr强得多, 前者cmc值较后者降低一个数量级. 胶团聚集数N随表面活性剂浓度c的增大而增大, 其中当s=2时的N值在c=7.7 mmol/L后开始急剧增大. 计算结果表明, 此时胶团形状发生了明显变化, 形成了椭球形的胶团. 粘度测定结果也证实了这一点.     

Synthesis and Surface Activity of Heterogemini Imidazolium Surfactants

A series of heterogemini imidazolium surfactants with two-methylene spacer groups ([C_m-2-C_nim]Br_{2, m, n}=8, 10, 12, 14, 16; m≠n) have been synthesized and characterized by 1H NMR and ESI-MS spectroscopy. The effects of various reaction parameters, including stoichiometry, reaction temperature and time, were investigated. In addition, the surface activity study about heterogemini imidazolium surfactants was carried out and the influences of dissymmetric degree on the surface properties were also discussed.