碳氢表面活性剂在超临界CO2中形成微乳液的研究进展

在超临界CO₂中形成微乳液可以克服CO₂对高分子量和亲水性物质溶解能力差的缺点。碳氢表面活性剂成本低,对环境友好,利用碳氢表面活性剂形成超临界CO₂微乳液有利于工业应用,但绝大部分碳氢表面活性剂不能形成微乳液,所以需要对碳氢表面活性剂进行选择和设计。本文介绍了微乳液的形成、表征和评价,从表面活性剂的亲CO₂性能和界面活性两方面,综述了碳氢表面活性剂的设计思想和进展。另外介绍了助表面活性剂对形成超临界CO₂微乳液的作用,并对常规碳氢表面活性剂在助表面活性剂的作用下形成超临界CO₂微乳液的体系进行了综述。最后,介绍了含碳氢表面活性剂的混合表面活性剂在形成超临界CO₂微乳液方面的研究情况。     

超临界二氧化碳微乳液中的表面活性剂

介绍了在超临界二氧化碳(SC-CO_2)下形成微乳液的原理和概念,并且按照所应用各种表面活性剂的结构特点对其在SC-CO_2下形成微乳液的能力分别进行比较和归纳,为今后筛选和设计在SC-CO_2下形成微乳液的表面活性剂提供了重要信息。     

助表面活性剂对阴/阳离子表面活性剂复配形成微乳液的影响

中相微乳液;盐度扫描;助表面活性剂对阴/阳离子表面活性剂复配形成微乳液的影响     

在超临界CO2聚合反应中应用的表面活性剂的研究

概括了表面活性剂在以超临界CO2 为介质的分散反应和乳化反应中的应用研究进展。重点介绍了几种重要的表面活性剂的结构、机理及应用 ,并指出在应用超临界CO2 技术进行的聚合反应中 ,表面活性剂具有重要的作用及广阔的应用前景。     

离子液体微乳液体系的应用研究

室温离子液体具有诸多优异的物理化学性质及功能,是一类备受关注的新型介质和材料,应用于诸多领域。特别是近年来,由离子液体参与形成的微乳液因其在生物、医药、催化以及材料制备等领域具有潜在的应用前景而备受关注。本文综述了近年来咪唑类离子液体作为极性、非极性和表面活性剂组分,分别取代微乳液体系中的水相、油相和表面活性剂相,形成的一系列新型的微乳液体系的研究进展,归纳了水、有机溶剂、高聚物、助表面活性剂、温度等因素对离子液体微乳液性质的影响。重点介绍了离子液体微乳液的热点应用,包括以离子液体微乳液液滴为模板合成纳米材料,离子液体微乳液作为酶反应的介质及其在有机反应等方面的研究进展。     

碳氟表面活性剂复配体系的中相微乳液研究

全氟辛酸钠(OBS)/十六烷基三甲基溴化铵(CTAB)-正丁醇/正丙醇-油-盐水体系能形成多相微乳液, 本文应用正交试验设计寻找了最佳中相微乳液体系组成, 然后系统地研究了含盐量、表面活性剂总浓度, 醇总浓度, 油的种类对该体系中相微乳液的形成, 相态和其特性参数的影响。并且应用红外光谱对微乳液的微观结构进行了测定。最后还对碳氢表面活性剂和碳氢/碳氟表面活性剂复配体系进行了比较。本文结果对三次采油和日用化工等领域的应用以及对理论研究都具有重要的意义。     

微乳液催化苯乙烯聚合反应

微乳液催化苯乙烯聚合反应１）郝京诚汪汉卿２）（中国科学院兰州化学物理研究所兰州７３００００）石元昌李干佐（山东大学胶体与界面化学研究所济南２５０１００）关键词微乳液催化苯乙烯聚合微乳液［１］是油、水、表面活性剂和助表面活性剂在适当比例下自发形成的热力...     

以非离子型表面活性剂形成微乳液的碳原子数相关性研究

由非离子型表面活性剂、助表面活性剂（醇）、水和油形成微乳液,用拟三角相图中微乳区的面积确定形成微乳液的最佳条件,实验证明,油的碳原子数加上醇的碳原子数等于表面活性剂的碳原子数对为微乳液形成最佳条件,也符合ＢＳＯ规律。     

超临界CO2中的表面活性剂

介绍了超临界CO2中表面活性剂的结构特征以及聚合物表面活性剂和小分子表面活性剂的研究进展。指出了开发亲CO2表面活性剂的一些基本原则,其中降低表面活性剂在H2O／CO2表面的界面张力和提高表面活性剂的吸附能力比溶解度更为重要。建议加强CO2表面活性剂的研究与开发。     

阴离子型微乳液的电导行为及其溶液结构

根据电导测量,研究了属于W/O→双连续→O/W一类微乳液的十二烷基硫酸钠(SDS)/正丁醇/辛烷/水体系的溶液结构.并探讨了表面活性剂离子对微乳液导电行为的贡献,以及表面活性剂与助表面活性剂含量、油含量对微乳液溶液结构的影响.微乳液的导电行为在W/O子区域中主要是由于SDS阴离子和在O/W子区域中是由于Na离子的影响.在双连续区(IZ)中SDS阴离子和Na阳离子都能影响导电行为增加表面活性剂含量有助于形成O/W微乳液,而助表面活性剂和油含量都增加有助于于形成W/O微乳液.     

Microemulsions with CO2 as a solvent

Supercritical CO₂ is considered as a promising alternative for volatile organic solvents currently used in certain industrial processes and products, however, the poor solubilizing power of CO₂ towards polar substances remains a significant barrier to applications. Employing effective surfactants which generate stable dispersions and water/CO₂ microemulsions is accepted as one way to improve the physico-chemical properties of CO₂. This article reviews recent studies on microemulsions in liquid CO₂, as well as the development of CO₂-philic surfactants.     

Ions,ion pairs and inverse micelles in non-polar media

This paper begins with a review of the studies dedicated to the electrochemistry of non-polar liquids performed during last century. There is a list of dozens of liquids that have been studied, as well as variety of electrolytes. There is an overview of 13 different experimental methods which have been employed for this task. The theoretical part of the review emphasizes the work done by Onsager, Debye, Fuoss, Kraus, Bjerrum and others in 1920s and 30s. They initiated and justified the fundamental ideas that serve as the scientific basis for modern handbooks on non-aqueous electrochemistry. Many of these papers from 1930s and later are reviewed here.The second part of this paper is dedicated to the electrochemistry of non-polar liquids containing surfactants. These substances can serve as electrolytes if ionic. However, their main function is to enhance the solvation of ions, providing steric stabilization that minimizes ion re-association and ion-pair formation. Consequently, the classical “dissociation model” requires some modification when applied to surfactant solutions. There are also two additional theoretical models suggested specifically for surfactant solutions in non-polar liquids: the “disproportionation model” for dry inverse micelles, and the “fluctuation model” by Eicke, Borkovec, and Das-Gupta for microemulsions. Charged microemulsion droplets can serve as ions, which justifies the inclusion of this theory in this review. In addition, we can study (with a well defined theory) the transition from microemulsion droplet to dry inverse micelle ion by reducing water content. Studying this transition reveals some important features of both systems.We present here these three theories and apply them for interpreting experimental data (mostly conductivity) in four different systems, all of which are non-polar systems containing surfactants: solutions of ionic surfactants, solutions of non-ionic surfactants, microemulsions with ionic surfactants, and microemulsions with non-ionic surfactants.     

Phase equilibriums,self-assembly and interactions in two-, three- and four medium-chain length component systems

The Scandinavian surface (surfactant) and colloid science owes much of its success to Per Ekwall and Björn Lindman. In this review the main topics shared by their research groups at Åbo Akademi University in Finland and at Lund University in Sweden are described. The nature of surface active substances (cosolvents, co-surfactants and surfactants) and microemulsions are evaluated. It is shown that the properties of medium-chain length surfactants differ dramatically from long-chain surfactants. The phase equilibriums of binary systems are related to the phase equilibriums of ternary and quaternary systems referred to as microemulsions or more recently also as nanoemulsions. A distinction is made between hydrotrope liquids, detergentless microemulsions, surfactant mixture systems and microemulsions. Three component systems are assembled to “true” quaternary microemulsions. An exceptionally comprehensive network of thermodynamic parameters describing molecular site exchange and micelle formation are derived and related mutually. Gibbs free energy, enthalpy, entropy, volume, heat capacity, expansivity and compressibility can be used to illustrate the degree of aggregation cooperativity and to evaluate whether micelle formation is of a first-, second- or intermediate order phase transition. Theoretical simulations and experimental results show that the associate structures of medium-chain length surfactants are quite open and may be deformed due to small aggregation numbers. The self-assembly occurs over a number of distinct steps at a series of experimentally detectable critical concentrations. Despite the low aggregation tendency their phase behavior equals those of long-chain homologs in surfactant mixture and microemulsion systems. A number of models describing the self-assembly are reviewed. Nuclear magnetic resonance (shift, relaxation rate and diffusion), Laser Raman and infrared spectroscopies were chosen as key instruments for molecular interaction characterization since they were used in the collaboration between the research groups in Åbo and in Lund. A new method is introduced in order to evaluate the traditional procedure for extracting limiting parameters which also enables an illustration of the degree of cooperativity. The focus is laid mainly on aqueous, alcoholic, saline and, to a limited extent oil phases of one-, two-, three- and four component systems of water–sodium carboxylates–alcohol–oil. The extensive thermodynamic characterization of these liquid phases and liquid crystalline phases is left out due to space restrictions.     

The effect of structure of oil phase, surfactant and co-surfactant on the physicochemical and electrochemical properties of bicontinuous microemulsion

Efforts were made to prepare bicontinuous microemulsions with ten different oil phases involving aliphatic, linear, and aromatic hydrocarbons as oil phases, two co-surfactants (n-butanol and n-pentanol) and two surfactants: cationic (CTAB) and anionic (SDS). Different weight percentages were employed for the preparation of cationic and anionic surfactant based microemulsions as reported in the literature. Out of the 40 compositions (10 oil phasesx2 co-surfactantsx2 surfactants) thus selected only 28 systems showed stable bicontinuous microemulsion phase. This behavior is explained on the basis of the structures of various constituents present in the microemulsions. Viscosity variations of stable bicontinuous microemulsions are found to depend mainly on the nature of co-surfactant. Conductivity behavior on the other hand depends mainly on the weight percentage and composition of aqueous phase. The solubility of pyrene in the oil phase determines the excimer formation and fluorescence behavior in microemulsions. The electron transfer property of both the water-soluble and the oil-soluble redox systems does not depend on the oil phase and the co-surfactant. The significance and importance of characterizing well defined bicontinuous microemulsions is thus highlighted.     

柴油中相微乳液的制备和相图分析

制备了柴油/复合表面活性剂/正戊醇/MnCl2盐水五元微乳液;研究了MnCl2浓度、表面活性剂浓度及正戊醇浓度对五元微乳液体系中相微乳液的形成和鱼尾相图的影响.结果表明,用MnCl2扫描时形成的中相微乳液范围较窄;在鱼尾相图中,当复合表面活性剂D0821(双(C8-10烷基)二甲基氯化铵)和AEO-3(脂肪醇聚氧乙烯醚)的质量比为4∶6时,形成单相微乳液的表面活性剂效率最高,最佳表面活性剂的质量分数为8.3%.     

Structural Parameters of Mixed Nonionic Surfactants Microemulsions

In this study, we estimated the structural parameters of water/mixed nonionic surfactants/R (+)-limonene microemulsions. The mixed surfactants are sucrose laurate and ethoxylated mono-di-glyceride. U-type microemulsion region was observed in these systems. It was found that changes in the surfactants mixing ratio, surfactants contents and oil/water weight ratio in the microemulsions incite a considerable change in the aggregation number, core radius and interfacial area per mixed surfactants head groups in the formed microemulsions. The interfacial area per mixed surfactant head groups increases while the aggregation number decreases with the increase in the ethoxylated mono-di-glyceride mass fraction in the mixed surfactants. The For an oil/water weight content equals unity, the interfacial area per mixed surfactants head groups is constant for mixed surfactants contents below 35 wt%. For mixed surfactants contents above 35 wt% the interfacial area per mixed surfactants head groups decrease and stabilizes at the lower value. The aggregation number decreases with the increase in the mixed surfactants contents. The aggregation number decreases also with the increase in the oil/water weight ratio at fixed mixed surfactants content.     

Microemulsions as microreactors for food applications

Major recent advances. Structured self-assembled liquids have been considered as efficient microreactors for organic and enzymatic reactions. Only recently scientists learned to use food-grade cosolvents and coemulsifiers together with hydrophilic non-ionic surfactants and to construct U-type phase diagrams with large isotropic regions ranging continuously from the oil-rich corner to the water-rich corner without any phase separation. The U-type microemulsions facilitate triggering and control of certain reactions by changing water activities. Maillard thermal degradation between sugars and amino acids is the main, and almost the only, chemical reaction that has been studied in food-grade microemulsions. Some examples of recent studies include: Maillard processes in binary structured fluids composed of monoglycerides of fatty acids and water forming microemulsions and lyotropic liquid crystalline structures; pseudoternary and pseudoquaternary W/O microemulsions; U-type microemulsions (W/O, O/W and bicontinuous microemulsions); enzymatic reactions aimed to prepare other surfactants such as sugar esters, monoglycerides and lysolecithins or triglycerides. Reactions in microreactors lead to unique new products. The reaction products and rates are controlled by the hydrophilicity/lipophilicity of the reagents (guest molecules), their molar ratios, type of oil phase, nature of surfactants and oil/surfactant ratios, nature of curvature and its elasticity (adjusted by cosolvent and coemulsifier) and by the water activity. The field is in its infancy and will need work of many more model reactions before it will be used in industrial food applications. Enzymatic reactions in non-food microemulsions are common practice but only few examples of food microemulsions as enzymatic microreactors have been extensively studied.     

Catanionic surfactants: microemulsion formation and solubilization

We review and summarize the three-phase behavior and solubilization of microemulsions with catanionic surfactants. Particular emphasis is placed to the three-phase behavior of mixtures of oil, water and alcohol with mixed surfactants containing one anionic and one cationic surfactant. The effect of salt and catanionic surfactant on the HLB composition and solubilizing capacity of surfactants to form microemulsions is discussed.