碳氢表面活性剂在超临界CO_2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路和进展。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。     

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。     

介观模拟研究表面活性剂分支结构对W/O型微乳液的影响

本文采用耗散颗粒动力学模拟方法从介观水平上研究了表面活性剂分支结构对W/O型微乳液形成的影响。结果表明:对于不同链分支结构的表面活性剂/油/水体系在一定的油水比和表面活性剂浓度下可以形成W/O型微乳液,此时体系的平均界面张力值最低。但在表面活性剂浓度相同时,随着油水比的增加,直链表面活性剂H2T2最利于其形成;而在油水比相同条件下,随着表面活性剂浓度的增加,直链表面活性剂H2T2在较大浓度范围内依然为稳定的微乳液。也就是说直链表面活性剂最利于W/O型微乳液的形成。此模拟结果从介观水平上提供了表面活性剂分支结构对W/O型微乳液形成的影响,为微乳液的实际应用提供理论指导。     

阴/阳离子表面活性剂复配体系的中相微乳液研究

阴离子表面活性剂双-2-乙基己基磺化琥珀酸钠(简称AOT), 和阳离子表面活性剂十六烷基三甲基溴代铵(简称CTAB), 在有醇、正辛烷、盐水存在的情况下,能形成多相微乳液。本文系统地研究了阴/阳离子表面活性剂配比、醇的种类、醇的浓度对该体系的中相微乳液的形成及特性的影响, 得到了中相微乳液的特性参数(最佳含盐量S^*, 最佳中相微乳液体积V^*, 界面张力r~E、盐宽△S等)。这些性质对与阴/阳离子表面活性剂复配体系, 三次采油及日用化工上的应用开发具有重要意义。最后还开展单独阴离子表面活性剂体系和阴/阳离子表面活性剂复配体系进行了比较, 得到一些有价值规律, 并从理论上进行了探讨。     

表面活性剂分支结构对O/W型微乳液影响的介观模拟研究

采用耗散颗粒动力学模拟方法从介观水平上研究了表面活性剂分支结构对O/W型微乳液形成的影响。研究结果表明:对于不同链分支结构的表面活性剂/油/水体系在一定的油水比和表面活性剂浓度下可以形成O/W型微乳液,此时体系的平均界面张力值最低。当表面活性剂浓度相同时,随着油水比的降低,直链表面活性剂H2T2最利于O/W型微乳液的形成;而在油水比相同时,随着表面活性剂浓度的增加,直链表面活性剂H2T2在较大浓度范围内依然为稳定的微乳液。也就是说直链表面活性剂最利于O/W型微乳液的形成。此模拟结果从介观水平上提供了表面活性剂分支结构对O/W型微乳液形成的影响,为微乳液的实际应用提供理论指导。     

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%.     

无表面活性剂微乳液体系：N,N－二甲基甲酰胺/呋喃甲醛/水

通常微乳液一般由四个组分构成：水相、油相、表面活性剂和助表面活性剂。本文报道了一种不含表面活性剂的微乳液体系(简称SFME),由呋喃甲醛(油相),水和N,N－二甲基甲酰胺(DMF)三组分构成,不含传统的表面活性剂。对其相行为进行了研究,发现存在一个单相微乳液区和一个两相平衡区。采用电导率法和冷冻蚀刻电镜(FF-TEM)考察了单相区域中微乳液的微结构,结果表明可分为油包水(O/W)、双连续(BC)和水包油(W/O)三个区域。液滴直径介于40-70nm。     

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.     

阳离子表面活性剂中相微乳的形成和特性

自1943年SdriAn。等人山发现微乳液体系并予以命名以来，对微乳液研究不断深入·微乳液是由油、水、表面活性剂和助表面活性剂组成的各向同性、透明的、热力学稳定的分散体系，微乳液可分为单相微乳液和多相微乳液问．中相微乳液是多相微乳液中，与过剩盐水相和过剩油相达到三相平衡的Winsor皿型微乳液，它在三次采油、日用化工、微环境、酶催化等方面具有特殊重要的应用I‘，‘］．近年来对阴离子表面活性剂中相微乳液的形成和特性进行了较多研究［5。8］．但对阳离子表面活性剂中相微乳液的研究，目前尚未见报导，本文以澳代十四烷基毗…     

油酸-正丙醇-水无表面活性剂反相微乳液电导研究

本文对油酸-正丙醇-水三元体系的相行为进行了研究,表明可形成微乳液.由于体系中无传统表面活性剂,故所形成的微乳液为无表面活性剂微乳液.在反相微乳液区,固定正丙醇/油酸体积比(RP/O)为3∶5、1∶1和2∶1,考察了体系电导率(κ)随分散相体积分数(φd)的变化,结果表明κ随φd的增大先缓慢增加,后急剧增大,符合渗滤特...     

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     

Studies in the phase behavior of the microemulsions formed by mixed cationic and nonionic surfactants

The middle-phase behavior for the systems of cetyltrimethylammonium bromide (CTAB)/poly-ethyleneglycol-9-monododecyl ether (AEO₉)/alcohol/oil/brine and CTAB/octylphenolpolyoxyethylene-10-ether (Triton X-100)/alcohol/oil/brine have been studied with ɛ-β fishlike phase diagram method. The interfacial layer composition was determined, and some significant physicochemical parameters are derived from the hydrophilic-lipophilic balance plane equation. The effects of different alcohols, oils, temperature and inorganic salt (NaCl) on the middle-phase behavior of microemulsion formed by composite CTAB/AEO₉ systems were also investigated systematically. The effects of different factors on the phase behavior of microemulsions formed by CTAB/AEO₉ and CTAB/TX-100 systems were compared. The results suggest that the solubilization of CTAB/AEO₉ microemulsion is higher than that of CTAB/TX-100 system under the same conditions.     

反相微乳液中苯酚硝化反应选择性的研究

采用气相色谱内标法研究了苯酚在AOT/异辛烷/水、CTAB/正癸醇/异辛烷/水、DBSA/异辛烷/水3种反相微乳液中进行硝化反应的选择性;考察了表面活性剂种类、反应时间、反应温度以及反相微乳液的含水量等因素对反应选择性的影响.研究结果表明,苯酚在微乳液体系中的硝化反应具有明显的邻位选择性,阴离子表面活性剂DB-SA体系的邻位选择性最高,这与它同时具有微乳催化和酸催化作用有关.     

Application of tetrahydrofuran dispersant in microemulsion for fabricating titania mesoporous thin film

A new strategy was used to fabricate titania mesoporous thin film by incorporating tetrahydrofuran (THF) into the CTAB/n-butyl alcohol/cyclohexane/water reverse microemulsion as a micelle disperser. Highly dispersed and congregated TiO(2) particles in the microemulsion with and without THF were observed by transmission electron microscopy (TEM), respectively. The photographs observed by field-emission scanning electron microscopy (FE-SEM) show that a uniform titania mesoporous thin film with monodisperse TiO(2) spherical nanoparticles of ca. 20 nm was obtained using the microemulsion with THF.     

Phase behavior, interfacial composition and thermodynamic properties of mixed surfactant (CTAB and Brij-58) derived w/o microemulsions with 1-butanol and 1-pentanol as cosurfactants and n-heptane and n-decane as oils

Phase diagrams of pseudo-quaternary systems of cetyltrimethylammonium bromide (CTAB)/polyoxyethylene(20)cetyl ether (Brij-58)/water/1-butanol (or 1-pentanol)/n-heptane (or n-decane) at fixed omega (=[water]/[surfactant]) of 55.6 were constructed at different temperatures (293, 303, 313, and 323 K) and different mole fraction compositions of Brij-58 (X(Brij-58)=0, 0.5, and 1.0 in CTAB + Brij-58 mixture). Pure CTAB stabilized systems produced larger single-phase domains than pure Brij-58 stabilized systems. Increasing temperature increased the single-phase domain in the Brij-58 stabilized systems, whereas the domain decreased in the CTAB stabilized systems. For mixed surfactant systems (with X(Brij)=0.5) negligible influence of temperature in the studied range of 293 to 323 K on the phase behavior was observed. Interfacial compositions of the mixed microemulsion systems at different temperature and different compositions were evaluated by the dilution method. The n(a)(i) (number of moles of alcohol at the interface) and n(a)(o) (number of moles of alcohol in the oil phase) determined from dilution experiments were found to decrease and increase respectively for CTAB stabilized systems, whereas an opposite trend was witnessed for Brij-58 stabilized systems. The energetics of transfer of cosurfactants from oil to the interface were found to be exothermic and endothermic for CTAB and Brij-58 stabilized systems, respectively. At equimolar composition of CTAB and Brij-58, the phase diagrams were temperature insensitive, so that the enthalpy of the aforesaid transfer process was zero.     

Effects of salinity on the viscosity and birefringence of a microemulsion system

Oil/water/surfactant systems form complex equilibrium phases which are sensitive to a number of parameters, including amount and concentration of cosurfactant (often an alcohol), salinity, and temperature. If one of these variables is changed systematically as, for example, the salinity, an interesting transition may be observed in which at low salinities a microemulsion is in equilibrium with an excess oil phase, at moderate salinities a middle phase microemulsion is in equilibrium with both excess oil and excess water phases, and at higher salinities brine is in equilibrium with a microemulsion phase. To help elucidate the structure of the microemulsion, studies of viscoelasticity and streaming birefringence in oscillatory shear flow have been conducted of a middle phase-forming system as a function of salinity. It is found that the viscoelastic properties of the microemulsions are unchanged for shear rates varying from 0.1 to 100 sec⁻¹. Both the birefringence and the viscosity maximize near the salinity marking the transition from lower phase to middle phase microemulsion. Further inflections in these properties occur at a salinity marking the midrange of the middle phase microemulsion. For all cases the dominent relaxation time is near 3 to 5 msec while the birefringence changes by two orders of magnitude. The birefringence is a sensitive indicator of the elastic structure of the microemulsion.     

不同阴/阳离子表面活性剂复配体系的缔合结构研究

测定了十二烷基磺酸钠(AS)/十六烷基三甲基溴化铵(CTAB)/正丁醇(n-C4H9OH)/正庚烷(n-C7H16)/水(H2O),十二烷基硫酸钠(SDS)/十六烷基三甲基溴化铵(CTAB)/正丁醇(n-C4H9OH)/正庚烷(n-C7H16)/水(H2O)体系的微乳液正四面体相图,并用电导法划分了AS/CTAB/n-C4H9OH/n-C7H16/H2O体系微乳液的结构(W/O,B.C.和O/W);同时研究AS/CTAB/n-C4H9OH/n-C7H16/H2O/盐类(NaCl,CaCl2或AlCl3)体系和SDS/CTAB/n-C4H9OH/n-C7H16/H2O/盐类(NaCl,CaCl2或AlCl3)体系形成中相微乳的盐宽,从中得出上述两体系中相微乳的盐宽随盐类阳离子价态的增大而的规律。     

半微分电分析研究CTAB/n-C_4H_9OH/n-C_7H_(16)/H_2O微乳结构

制备了十六烷基三甲基溴化铵/正丁醇/正庚烷/水四组分体系的相图。讨论了 体系中助表面活性剂与表面活性剂的质量比k_m对形成微乳状液单相区域大小的影 响。以二茂铁为电活性探针用半微分电分析法测定系列微乳样品的表观扩散系数 D_(app)，从表观扩散系数D_(app)随含水量Φ_w的变化确定微乳液的微结构和结构 转变。电导率数据证实了半微分电分析的实验结果。     

影响反相微乳液导电性能的因素

分别以聚乙二醇辛基苯基醚(Triton X-100)或十六烷基三甲基溴化铵(CTAB)为表面活性剂, 与正己烷、正己醇和水构成反相微乳液. 研究了水相H+浓度、表面活性剂、助表面活性剂等对微乳液导电性能的影响. 结果表明, 增加水相H+浓度可大幅度提高反相微乳液的导电能力, 当H+浓度由1.0 mol•L-1增加到10 mol•L-1时, 微乳液的电导率可提高1~2个数量级. 当水相H+浓度为10 mol•L-1时, 微乳液的电导率随溶水量的增大而增大, 水油体积比为3:10时, 两种体系的电导率均达到3200 μS•cm-1. Triton X-100浓度对微乳液的电导率影响较大, 电导率随其浓度增加而增大；而CTAB浓度对微乳液电导率的影响较小, 电导率随其浓度增加略有减小；助表面活性剂正己醇使非离子型反相微乳液的电导率下降, 而使阳离子型反相微乳液的电导率先增大, 然后减小, 呈骆峰状变化.