Microemulsions from anionic surfactants

Differential scanning calorimetry (DSC) was used to determine the kinetics of polymerization and the glass transition temperature of the solid polymer. Preliminary results indicate the dependence of kinetics on the microstructure as determined using Borchardt and Daniels method (26). The reaction order, rate constant, and conversion were observed to be dependent on the initial microstructure of the microemulsions. The apparent glass transition temperature (Tg) of polystyrene obtained from anionic surfactant (SDS) microemulsions is significantly higher than the Tg of normal bulk polystyrene. In contrast, polymers from nonionic microemulsions show a decrease in Tg. Some representative values of Tg are shown in Table I. 

As a result of the intensive research done on microemulsions in connection with enhancing the recovery of petroleum from oil reservoir rock, a number of methods have been developed for determining the conditions under which a microemulsion is formed. Thus, for microemulsions with anionic surfactants, equation 8.10 has been suggested (Salager, 1979) to develop the optimum formulation (when the equation equals zero) ... 

Nonionics can function as cosurfactants in microemulsions. This cosurfactant role, which can also be performed by short-chain alcohols or glycol ethers, can make it possible to form microemulsions or other phases from anionic surfactant systems that would otherwise be unreachable in a pure anionic system. By one definition, a microemulsion system is one that achieves a zero or close-to-zero curvature [108]. This is easily achievable in nonionic systems, but very difficult in pure anionic surfactant systems due to the head group repulsions. Mixing the nonionic with the anionic makes these types of systems, which sometimes have greater cleaning ability, easily accomplished. 

Fig. 3.14 Electron micrograph of styrene polymerized in middle-phase microemulsion containing anionic surfactant SDS (from [71], With permission from John Wiley Sons, Inc.)...

The nature of surfactant used in microemulsion has a pronounced effect on the above mentioned properties of polymer products. Thus, if the surfactant has any polar or electrostatic interaction with the polymer, this may lead to an improvement in its tensile properties. However, if the surfactant is not compatible with the polymerized matrix, it may simply act as a low-molecular additive (plasticizer) and reduce the mechanical strength of the material. For polystyrene, it has been observed that the polymer produced from a nonionic surfactant-based microemulsion is ductile while that obtained from anionic surfactant (e.g., SDS)-based microemulsion is brittle in nature and has much higher glass transition temperamre than the bulk-polymerized polymer. 

In abroad sense, the model developed for the cobaloxime(II)-catalyzed reactions seems to be valid also for the autoxidation of the alkyl mercaptan to disulfides in the presence of cobalt(II) phthalocyanine tetra-sodium sulfonate in reverse micelles (142). It was assumed that the rate-determining electron transfer within the catalyst-substrate-dioxygen complex leads to the formation of the final products via the RS and O - radicals. The yield of the disulfide product was higher in water-oil microemulsions prepared from a cationic surfactant than in the presence of an anionic surfactant. This difference is probably due to the stabilization of the monomeric form of the catalyst in the former environment. 

Further information on the dependence of structure of microemulsions formed on the alcohol chain length was obtained from measurement of self diffusion coefficient of all the constitutents using NMR techniques (29-34). For microemulsions consisting of water, hydrocarbon, an anionic surfactant and a short chain alcohol and C ) the self diffusion... 

Khomane et al. prepared dodecanethiol-capped CdS QDs of 4 nm size by using a Winsor II microemulsion system [242], which are soluble in solvents such as n-heptane, toluene, n-hexane, thus demonstrating the dual role of the anionic surfactant, viz., forming the microemulsion and facilitating the extraction of oppositely charged ions from the aqueous to the organic phase. 

In this paper, a molecular thermodynamic approach is developed to predict the structural and compositional characteristics of microemulsions. The theory can be applied not only to oil-in-water and water-in-cil droplet-type microemulsions but also to bicontinuous microemulsions. This treatment constitutes an extension of our earlier approaches to micelles, mixed micelles, and solubilization but also takes into account the self-association of alcohol in the oil phase and the excluded-volume interactions among the droplets. Illustrative results are presented for an anionic surfactant (SDS) pentanol cyclohexane water NaCl system. Microstructur al features including the droplet radius, the thickness of the surfactant layer at the interface, the number of molecules of various species in a droplet, the size and composition dispersions of the droplets, and the distribution of the surfactant, oil, alcohol, and water molecules in the various microdomains are calculated. Further, the model allows the identification of the transition from a two-phase droplet-type microemulsion system to a three-phase microemulsion system involving a bicontinuous microemulsion. The persistence length of the bicontinuous microemulsion is also predicted by the model. Finally, the model permits the calculation of the interfacial tension between a microemulsion and the coexisting phase. 

It has been shown that the addition of a small amount of the anionic surfactant sodium dodecyl sulfate (SDS) to a microemulsion based on nonionic surfactant increased the rate of decyl sulfonate formation from decyl bromide and sodium sulfite (Scheme 1 of Fig. 2) [59,60]. Addition of minor amounts of the cationic surfactant tetradecyltrimethylammonium gave either a rate increase or a rate decrease depending on the surfactant counterion. A poorly polarizable counterion, such as acetate, accelerated the reaction. A large, polarizable counterion, such as bromide, on the other hand, gave a slight decrease in reaction rate. The reaction profiles for the different systems are shown in Fig. 12. More recent studies indicate that when chloride is used as surfactant counterion the reaction may at least partly proceed in two steps, first chloride substitutes bromide to give decyl chloride, which reacts with the sulfite ion to give the final product [61]. 

In the nonionic system observed under EVM, the initial microemulsion showed no tendency of gelation until it reached 60 C. After reaching 60<>C, the system gels and starts to polymerize after 10-12 hours. As polymerization proceeds, the water separates out. After about 20-24 hours, the gel starts to become a solid with an excess emulsion phase formed at the bottom. The polymerization is essentially complete after 36 hours. Due to different modes of polymerization in the anionic and nonionic surfactant systems, the mechanical properties of the solid are different. The polymers obtsuned from anionic microemulsions are brittle, while those obtmned from nonionic microemulsions are ductile. 

Polymerization of styrene in microemulsions has produced porous solid materials with interesting morphology and thermal properties. The morphology, porosity and thermal properties are affected by the type and concentration of surfactant and cosurfactant. The polymers obtained from anionic microemulsions exhibit Tg higher than normal polystyrene, whereas the polymers from nonionic microemulsions exhibit a lower Tg. This is due to the role of electrostatic interactions between the SDS ions and polystyrene. Transport properties of the polymers obtained from microemulsions were also determine. Gas phase permeability and diffusion coefficients of different gases in the polymers are reported. The polymers exhibit some ionic conductivity. 

Many surfactants have been used to formulate microemulsions (1). They were of three types anionic surfactants such as petroleum sulfonates, sodium octyl benzene sulfonate, sodium dodecyl sulfate, alkaline soaps cationic surfactants such as dodecyl ammonium and hexadecyl eimmonium chlorides or bromides and nonionic surfactants such as polyoxyethylene glycols. Furthermore, many exhibit liquid-crystalline properties (2) and in some cases the structure of the mesophases has been established (3). Nevertheless, nearly nothing is known about their compatibility with blood and tissues, and, from our own experience, some exhibit a high lytic power for red cells... 

A first attempt at hydroformylation in a micellar system using a water-soluble rhodium catalyst (Rh-TPPTS) was made by Tinicci and Platone from Eniricerche in 1994 [ 59 ]. They converted olefins with carbon numbers up to 12 using a mixture of an anionic surfactant (SDS) and butanol (as co-surfactant). It has been shown that microemulsions made with non-ionic surfactants of the alcohol ethoxylate type are advantageous compared to ionic... 

The synergisms of mixtures of anionic-cationic surfactant systems can be used to form middle-phase micro emulsions without adding short-chain alcohols [109, 110]. The surfactants studied were sodium dihexyl sulphosuccinate and benzethonium chloride. The amount of sodium chloride required for the middle-phase microemulsion decreased dramatically as an equimolar anionic-cationic surfactant mixture was approached. Under optimum middle-phase microemulsion conditions, mixed anionic-cationic surfactant systems solubilised more oil than the anionic surfactant alone. Upadhyaya et al. [109] proposed a model for the interaction of branched-tail surfactants (Fig. 8.16). According to this model the anionic-cationic pair allows oil to penetrate between surfactant tails and increases the oil solubilisation capacity of the surfactant aggregate. Detergency studies were conducted to test the capacity of these mixed surfactant systems to remove oil from... 

Figure 4 Viscosity of the microemulsion phase (made up with the commercial anionic surfactant mixture TRS 10-80, a sulfonate with an approximate molecular weight of 420) as a function of the salinity. (Data taken from Ref 89.)...

It can be seen from Table 6 that anionic, cationic, and nonionic surfactants have all been exploited in formulating microemulsions for materials synthesis. Anionic and nonionic surfactants appear to be the most popular types of surfactants, with Aerosol OT (AOT) and the polyoxyethylated alkylphenyl ether surfactants (e.g., NP-5) leading. Part of the attraction of AOT and the NP surfactants is related to the fact that they permit microemulsion formulation without the need for cosurfactants. Also, a large body of information is already available on the phase behavior and structure of AOT microemulsions [121], and this makes it convenient to work with this anionic surfactant. A unique advantage of the nonionic surfactants is the fact that their use does not involve the introduction of (potentially undesirable) counterions. The ability to alter the size of the hydrophilic (oxyethylene) groups and/or the hydrophobic (alkyl) groups provides additional flexibility in surfactant selection. 

Qutubuddin and coworkers [43,44] were the first to report on the preparation of solid porous materials by polymerization of styrene in Winsor I, II, and III microemulsions stabilized by an anionic surfactant (SDS) and 2-pentanol or by nonionic surfactants. The porosity of materials obtained in the middle phase was greater than that obtained with either oil-continuous or water-continuous microemulsions. This is related to the structure of middle-phase microemulsions, which consist of oily and aqueous bicontinuous interconnected domains. A major difficulty encountered during the thermal polymerization was phase separation. A solid, opaque polymer was obtained in the middle with excess phases at the top (essentially 2-pentanol) and bottom (94% water). The nature of the surfactant had a profound effect on the mechanical properties of polymers. The polymers formed from nonionic microemulsions were ductile and nonconductive and exhibited a glass transition temperature lower than that of normal polystyrene. The polymers formed from anionic microemulsions were brittle and conductive and exhibited a higher Tj,. This was attributed to strong ionic interactions between polystyrene and SDS. 

Specific roles of the so-called co-surfactants (commonly, but not necessarily alcohols) have been examined by various workers [122, 126, 136] some points are discussed here. For example, a critical thermodynamic analysis in conjunction with experimentations led Eicke [ 136] to the conclusion that a co-surfactant should decrease the interfacial free energy under isothermal conditions, while causing an uptake of water into the microemulsion and extension of its domain. The anionic surfactant AOT assists the formation of large reverse microemulsion domains (high water uptake) in different ternary systems without help from a co-surfactant (Section 2.2), but cationic surfactants do generally need this fourth component. In spite of this, enhanced solubilization by the addition of (small quantities of) a co-surfactant has been observed by various workers in AOT systems. Eicke [136] used cyclohexane, benzene, carbon tetrachloride and nitrobenzene in the system AOT/ isooctane/water and found considerable water uptake (the fraction of the oil phase, i.e. isooctane was 0.8 or more). With increasing polarizability or polarity of the CO-surfactant, the water uptake decreased. 

Wolf, L. Hoffmann, H. Watanabe, K. Okamoto, T., Microemulsions from Silicone Oil with an Anionic/Nonionic Surfactant Mixture. Phys. Chem. Chem. Phys. 2011,13, 3248-3256. 

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