正丁醇对二(2-乙基己基)琥珀酸酯磺酸钠微乳液体系的影响

通过在二(2-乙基己基)琥珀酸酯磺酸钠(AOT)/正庚烷/水的三元体系中加入正丁醇,得到了新的四元体系。绘制了25℃时AOT/正丁醇/正庚烷/水四元体系能够稳定存在的相图,发现在一定R值(水和AOT的摩尔比)条件下该相图出现了分为两个区域的现象。利用电导率数据研究了由W/O型微乳液→双连续微乳液→棒状液晶→层状液晶→双连续微乳液→O/W型微乳液的结构转变。通过稀释法求得AOT/正丁醇/正庚烷/水微乳液体系的结构参数,结果表明:含水量增加,两个区域的自由能-△G0c→i都减小,对微乳液体系的稳定不利;含水量越低,越有利于微乳液的形成和稳定;AOT/正丁醇/正庚烷/水四元体系比以AOT作表面活性剂的三元体系有更大的微乳液区域,是一个适合制备所需功能性纳米粒子的体系。     

Triton X-100/正构醇/石油醚/水反相微乳液性质的研究

通过测定微乳液的电导率值,确定配制W/O型Triton X-100/正构醇/石油醚/水微乳液的最大增溶水量;根据微乳液含水量与电导率关系曲线及体系的拟三元相图,讨论了正构醇种类、正构醇含量、乳化剂与油相质量比对W/O型微乳液的结构、电导率、增溶水量的影响。结果表明:乳化剂与油相质量比大于1时,正戊醇、正己醇和正庚醇为助剂配制的Triton X-100/正构醇/石油醚/水体系微乳液有较大的增溶水量,而乳化剂与油相质量比大于1.5时,以正丁醇为助剂配制的Triton X-100/正构醇/石油醚/水体系微乳液才有较大的增溶水量;正构醇的链长及加入量影响微液滴界面膜的强度,从而影响微乳液的增溶水量、电导率及微乳液形成区域的大小;对于Triton X-100/正构醇/石油醚/水体系,正戊醇是形成W/O型微乳液的较好助剂,当正戊醇与Triton X-100的质量比为0.5时,W/O型微乳液的形成区域最大。     

十二烷基硫酸钠/正丁醇/正庚烷/水微乳液性质研究

25℃时,绘制十二烷基硫酸钠(SDS)/正丁醇/正庚烷/水体系在不同R值(水和SDS的摩尔比)时的相图,得出该体系能形成W/O微乳液的配比为:正丁醇的质量分数在25%~60%,正庚烷的质量分数在0~80%。该体系在室温下能够形成较大范围的W/O单相微乳液区,R值对微乳区的面积和所在的位置无太大的影响。采用电导率曲线讨论了加水稀释过程中,体系由W/O型→双连续型→棒状液晶→层状液晶→双连续型→O/W型的微观结构转变。采用稀释法求得其W/O型微乳液体系的结构参数,结果表明:体系的水内核半径Rw在讨论的范围内随VH2O、R值的增加而增大。含水量增加,自由能-ΔGcO→i降低,对微乳液体系的稳定不利;含水量越低,越有利于微乳液的形成和稳定。     

水基性透明液体剂型的加工、性能和差异(Ⅱ)

4 微乳剂 早在20世纪40年代,Hoar和Schulman等人发现油-水混合物借助表面活性剂可以自发地形成透明的分散体系,由于所形成的液滴粒径非常小,后来将这种体系命名为微乳液.此后证明,它是一个热力学上稳定的、均相的水包油型乳液可溶体系,加工的微乳液剂型即为微乳剂. 微乳液存在3种结构类型,即O/W型、W/O型和双连续相结构(也称为中间相微乳型).这3种类型可以在一定条件下互相转变[10].农药上的微乳剂大都为以水为连续相的O/W型乳液.     

有机物系固-液相平衡理论研究进展

评述了采用活度系数方程、状态方程、经验模型、人工神经网络和拓扑方法研究有机物系固-液相平衡的理论和方法,其中活度系数模型是研究有机物系固-液相平衡的主要方法。     

含非离子表面活性剂吐温-80的微乳液结构研究

采用非离子表面活性剂吐温-80,以石油醚为油相,正丁醇为助表面活性剂来制备微乳液。用稀释法测定并计算了Tween-80/石油醚/正丁醇/水体系O/W型微乳的结构参数。测量微乳液体系在15~30℃温度范围内的pH及电导,考察温度对微乳液体系的影响。向微乳液体系中加入PVP,测量体系的电导和接触角,考察水溶性高分子对微乳液体系的影响。结果表明微乳液体系的电导随温度的上升而变大,相同温度时,加入PVP会使体系的电导变大,接触角变小。     

真空下C_(10)与DMP体系汽液相平衡的研究

在7.36 k Pa下采用汽液相平衡釜测定了正癸烷-1-癸烯、正癸烷-邻苯二甲酸二甲酯(DMP)、1-癸烯-邻苯二甲酸二甲酯(DMP)和正癸烷-1-癸烯-邻苯二甲酸二甲酯的等压汽液相平衡数据。二元体系的实验数据通过了Herington面积法和热力学一致性校验,利用NRTL模型、Wilson模型和UNIQUAC模型对实验数据进行关联,得到相应的模型参数和关联偏差。实验结果表明:正癸烷-1-癸烯、正癸烷-邻苯二甲酸二甲酯和1-癸烯-邻苯二甲酸二甲酯二组分物系均不形成共沸物,模拟结果与实验值接近。最后用关联得到的模型参数预测了三元体系的汽液平衡数据。实验值与预测值吻合,可满足萃取精馏工艺设计的需要。     

协同效应在WO型微乳液中的作用

本文通过拟三元相图、增溶、电导和表面张力测定等方法,研究了烷基羧酸盐(CnH_(2n+1)COONa)与十六烷基三甲基溴化铵(CTAB)复配在正戊醇存在下对煤油—水体系W/O型微乳液形成的协同效应,发现在整个复配范围内同时出现协同效应和反协同效应。而且,发生协同效应的复配范围是在羧酸盐的高比例区,此时,体系的W/O型微乳区域面积扩大。     

微通道内传递对液液分散过程的影响规律

在同轴环管微通道中,采用水/正辛醇形成两相体系,利用硫酸向水中传质并释放热量以实现伴随传质传热的微分散过程,研究了两相流速、硫酸浓度对两相流型和液滴大小的影响规律。结果发现,传递会引发O/W/O新流型的产生和流型分布区域变化。探讨了传递强度对于分散液滴尺寸的影响,通过计算液滴脱落时的动态界面张力,分析了传质和传热对于液液微分散影响的大小。     

无尼泊金酯类化妆品防腐体系的应用研究

本文以二醇类和苯氧乙醇为主要防腐剂,复配1,2-戊二醇、1,2-己二醇、对羟基苯乙酮、乙基己基甘油、辛酰羟肟酸、甘油辛酸酯、氯苯甘醚、山梨坦辛酸酯中的几种组成防腐体系,应用于含油量30%、p H值为5~7的O/W配方,通过防腐挑战实验和过敏性斑贴实验对复配防腐体系进行综合评价。由实验结果可知,优选出的两组低刺激、高效率的防腐体系分别为:(1)0.224%1,2-己二醇、0.056%乙基己基甘油、0.056%辛酰羟肟酸、0.084%甘油辛酸酯,总添加量为0.42%;(2)0.40%苯氧乙醇、0.10%氯苯甘醚、0.15%山梨坦辛酸酯,总添加量为0.65%。这两种防腐体系可通过化妆水剂、O/W乳液、O/W霜、W/O霜配方防腐挑战实验,说明上述两种防腐体系具有一定普适性。     

Synthesis of dioctyl sulfosuccinate-doped polypyrrole grains by aqueous chemical oxidative polymerization and their use as light-responsive liquid marble stabilizer

Polypyrrole grains are synthesized by aqueous chemical oxidative polymerization using ferric chloride as an oxidant in the presence of bis(2-ethylhexyl) sulfosuccinate sodium salt as both a dopant and a hydrophobizing agent. The resulting grain products are characterized in terms of their size, morphology, surface and bulk chemical compositions, hydrophilicity-hydrophobicity balance, (photo) thermal property, and electrical conductivity. Scanning electron microscopy studies indicate that the grains are aggregates of atypical primary grains with submicrometer size. Elemental microanalysis and thermogravimetric analysis confirm that the polypyrrole is preferably doped with dioctyl sulfosuccinate compared with chloride ion, and dioctyl sulfosuccinate/chloride ion dopant ratio increases with an increase of bis(2-ethylhexyl) sulfosuccinate sodium salt concentration in the polymerization systems. The grains show near-infrared light-to-heat photothermal property, which is confirmed by thermography. The data obtained through X-ray photoelectron spectroscopy indicate the presence of dioctyl sulfosuccinate dopants on the surface of the grains, and therefore the dried polypyrrole grains show hydrophobic character. The dried grains can work as a light-responsive liquid marble (LM) stabilizer. Motions of the LM can be driven by near-infrared laser irradiation-induced Marangoni flow on planar air-water surface. The release of internal liquid can be achieved by controlled disruption of the LM via external stimulus application.     

Synthesis and evaluation of a ruthenium–copper oxide/silica catalyst derived from microemulsion processing

Bimetallic Ru–Cu catalysts supported on SiO₂ have been synthesized in microemulsions using sodium metasilicate (Na₂SiO₃), copper nitrate (Cu(NO₃)_2·3H₂O) and ruthenium chloride (RuCl₃) at 28 °C. The microemulsion system consists of sodium 1,4‐bis(2‐ethylhexyl) sulfosuccinate (AOT) and sodium dodecyl sulphate (SDS), cyclohexane, and an aqueous solution of sodium metasilicate or metal salts. The catalysts have been characterized by XPS, EDX/SEM with line scanning and they possess a very narrow pore size distribution (around 38 Å) and relatively high specific surface areas (around 400 m²/g). The catalytic results of the N₂O decomposition reveal that higher conversions of N₂O can be achieved by the catalysts synthesized from the microemulsion process at lower temperatures (around 400 °C).     

Polymerization of acrylamide in styrene containing inverse microemulsions: polymerization kinetics and polymer product composition studies

The kinetics of free‐radical homopolymerization and copolymerization of acrylamide (AAm) and styrene (S) initiated by water‐soluble ammonium peroxodisulfate, (APS) or by toluene‐soluble dibenzoyl peroxide (DBP) in inverse microemulsion toluene/S/AOT (sodium bis(2‐ethylhexyl)sulfosuccinate)/water/AAm characterized by a low volume fraction of the aqueous phase (Φ_aw ≈ 0.08) as a function of the concentration of S in the oil phase of the inverse microemulsion system have been studied. S strongly decreases the rate of AAm/S (co)polymerization. This is valid for both APS and DBP initiators. Kinetic measurements indicate the important role for cross‐initiation of water soluble AAm growing chains and of oil soluble S analogues activated by the primary free‐radicals generated from APS (or from DBP) in the dispersed water droplets (or in the continuous oil‐phase) of the inverse microemulsion, respectively. With inverse microemulsions containing toluene (70.73 %)/S (2.44 %)/AOT(17.56 %)/water (7.32 %)/AAm (1.95 %), after polymerization (initiator APS, 3.04 × 10⁻² mol dm⁻³ of water) and separation of the polymeric components, the following yields were obtained: AAm/S (co)polymer (89.20 mass%; ie 62.24 mass% of AAm structural units and 26.96 mass% of S structural units), polyacrylamide (9.4 mass%) and polystyrene (1.4 mass%). © 2000 Society of Chemical Industry     

Synthesis,Stabilization and Activation of Pt Nanoparticles for PEMFC Applications

Amongst the main challenges of catalyst materials for Proton Exchange Membrane Fuel Cells (PEMFCs) are activity and durability. Here we report on the synthesis of monodisperse nanoparticles and stabilization with traces of the surfactant, here Na‐AOT (bis‐(2‐ethylhexyl) sulfosuccinate sodium salt), used in the synthesis procedure. The surfactants prevent agglomeration and reduce Ostwald ripening. We compare the performance of Pt catalyst nanoparticles synthesized in dense microemulsions, Na‐AOT/heptane/water and Triton X‐100/toluene/water, with a commercial state‐of‐the‐art catalyst for the Oxygen Reduction Reaction (ORR). The produced catalyst nanoparticles were extracted onto a carbon support, Vulcan XC‐72R, washed and activated by heat‐treatment, which led to heavy agglomeration, or by electrochemical treatment, which led to an enhanced activity for ORR. Additionally, in comparison to the other two catalysts an increased durability of the platinum nanoparticles synthesized in the microemulsion of Na‐AOT/heptane/water was observed.     

琥珀酸二异辛酯磺酸钠的制备

介绍了一种在常压、无外加相转移催化剂的条件下制备琥珀酸二异辛酯磺酸钠的新方法。研究了合成标题产物中磺化反应的主要影响因素 ,并得出该反应的优惠工艺条件     

Alcohol-free diphenyl oxide disulfonate middle-phase microemulsion systems

Diphenyl oxide disulfonate (DPDS) surfactants were successfully used to formulate Winsor Type III middlephase microemulsion systems with tetrachloroethylene (PCE) and decane. To our knowledge this is the first time that monochain DPDS surfactant phenyloxide monohexadecyl disulfonate surfactant (C16MADS) and commercially available DOWFAX 8390 were found to form middle-phase microemulsion systems with oils. Hydrophobic dioctyl sodium sulfosuccinate (Aerosol OT) was also used as a cosurfactant to lower the systems' hydropholic-liphophilic balance. Two organic acids (hydrophobic octanoic acid and hydrophilic l-tartaric acid) were used in place of the alcohol to formulate middle-phase microemulsion. The middle-phase microemulsion systems dramatically increased organic solubility when compared to micellar DPDS surfactant systems. Winsor Type I systems near the Type I–III boundary produced “super” solubilization for hydrophobic oils. Findings from this study enable us to improve DPDS solubilization enhancement of hydrophobic compounds.     

Salts of poly(4-vinylpyridinium) with bis(2-ethylhexyl) sulfosuccinate: Coils and globules of the single molecules observed by dynamic light scattering,stabilization of the reversed emulsions

Poly(4-vinylpyridine) derivatives alkylated with dimethylsulfate, octylbromide and dodecylbromide were synthesized. Counter ions in the polymer salts were substituted with bis(2-ethylhexyl)sulfosuccinate. The solutions of the polyelectrolyte-surfactant complexes in the mixtures of decane with chloroform were studied by dynamic light scattering. At high decane content all the complexes have expanded coil conformations. The increase of chloroform content over 60 vol.% leads to folding of the coils to globule state and to the appearance of the second peak on the DLS curves corresponding to the small fraction of large particles with hydrodynamic radii R ca 40–80 nm. The ability of the synthesized complexes to stabilize reversed emulsions was studied. It was shown that polymer complexes of AOT with comb-like polycations stabilize emulsions of water in 4:1 mixture of decane with chloroform. Addition of sodium chloride to the system markedly increases stabilizing effect of the comb-like polycations with AOT.     

Preparation of cadmium sulfide/poly(methyl methacrylate) composites by precipitation with compressed CO2

Cadmium sulfide (CdS) nanoparticles and poly(methyl methacrylate) (PMMA) were first synthesized in methyl methacrylate (MMA)/sodium bis(2‐ethylhexyl) sulfosuccinate (AOT) microemulsion, in which MMA acts as the solvent and monomer. Then compressed CO₂ was used as an antisolvent to precipitate the CdS and PMMA simultaneously. Using this method, a CdS/PMMA composite was successfully prepared. The CdS nanoparticles dispersed in the polymer matrices were characterized by transmission electron microscopy. The higher pressure is favorable to producing CdS nanoparticles of smaller size. The phase structure of the obtained composite was characterized by X‐ray diffraction, which reveals that cubic CdS particles were formed. The FTIR spectra of the composite showed that there is no chemical bonding or strong interaction between CdS and PMMA. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1643–1648, 2004     

Partitioning of Polymeric Plutonium(IV) in Winsor II Microemulsion Systems

Abstract

The hydrolysis and polymerization of Pu(IV) can cause serious problems during the aqueous processing of spent fuel and nuclear wastes. Several studies describing the liquid/liquid extraction behavior of polymeric Pu(IV) have been reported in the literature. In many cases, poor plutonium extraction was accompanied by the appearance of an interfacial crud or third phase. Invariably, poor mass balances were observed during the extraction of aged, colloidal Pu(IV). Extraction of colloidal Pu(IV) by microemulsion-based solvent extraction systems, however, is capable of attaining bulk phase mass balances for Pu of 100%. The Winsor II microemulsions discussed in this paper consisted of sodium bis(2-ethylhexyl) sulfosuccinate in hexane with either octylphenyl-N,N-diisobutylcarbamoylmethyl-phosphine oxide or tributyl phosphate as coextractant. Backextraction of plutonium from microemulsion phases was achieved by Pu encapsulation in silica particles that were produced by the acid-catalyzed hydrolysis and polymerization of tetraethoxysilane within the aqueous microdroplets of the microemulsion.     

Enzymatic esterification of DL‐menthol with propionic acid by lipase from Candida cylindracea

This work deals with the resolution of DL ‐menthol with propionic acid by Candida cylindracea lipase (Ccl) in organic solvent reaction systems and a reverse micelles system of sodium 1,4‐bis (2‐ethylhexyl) sulfosuccinate (AOT). The activity and stability as well as enantioselectivity of the lipase in two systems were studied. The results indicate that the lipase showed higher stability in reverse micelles than in organic solvent, which proved that the reverse micelles system has potential application for maintaining the activity of the enzyme for a long time. This is because lipase molecules can be entrapped in water‐containing micro‐drops of reverse micelles, avoiding direct‐contract with unfavorable organic medium. The enantioselectivity (E > 30, ee_p = 92.5) in the two systems is relatively high, although the conversion is moderate. The influence of the characteristic parameters of the two systems, such as pH, temperature, w₀ (molar ratio of water to AOT in reverse micelles systems) and water content (organic solvent) on the conversion of DL ‐menthol was also investigated. Copyright © 2005 Society of Chemical Industry