A nucleophilic substitution reaction between 4-tert-butylbenzyl bromide and a series of iodide salts has been performed in oil-in-water microemulsions based on either a fatty alcohol ethoxylate or a sugar surfactant. The reaction kinetics was compared with the kinetics of the same reaction performed in a microhomogeneous reaction medium, d-MeOH. Previous results showing a particularly high reactivity in the microemulsion based on the fatty alcohol ethoxylate was confirmed. It was shown that in both microemulsions the reaction rate was almost independent of the choice of counterion to iodide. This indicates that complexation of the cation with the surfactant headgroup, which, in particular, could have taken place with surfactants containing oligooxyethylene chains (a “crown ether effect”), seems not to be of importance.
127I NMR studies, as well as quadrupole splitting experiments performed by 2H NMR, indicate that there is a certain accumulation of iodide at the oil–water interface of the microemulsions. It is difficult to draw any quantitative conclusions in this respect, however.
The results obtained in this study, combined with results from previous investigations of the same reaction, indicate that the unexpectedly high reactivity obtained in the microemulsion based on a surfactant containing an oligooxyethylene headgroup is most probably due to the nucleophile being poorly solvated when present in the headgroup layer of such a microemulsion. Poorly solvated anions are known to be highly reactive nucleophiles. 相似文献
Sub-zero temperature DSC measurements were conducted to evaluate the behavior of water in non-ionic microemulsions. Two surfactant
systems were studied. The first, based on ethoxylated fatty alcohol, octaethylene glycol monon-dodecylether [hereafter referred to as C12(EO)8] and also containing water, pentanol and dodecane at a fixed weight ratio of 1:1. The second system, based on oligomeric
ethoxylated siloxanes, water and dodecanol as oil phase. In both systems it was found that in up to 30 wt.% of the total water
content, all water molecules solubilize in the amphiphilic phase and are bound to the ethylene oxide (hereafter referred to
as EO) head-groups. No free water exists in the surfactant aggregates’ core. Up to three molecules of water are bound to each
EO group.
In the first system, the behavior changes significantly upon adding more water. The added pentanol allows further swelling
and the water penetrates into the amphiphile structures and forms a reservoir of free water. Structures are deformed and grow
from elongated channels (up to 15–20 wt.% water), via illdefined (one-dimensional growth) local lamellar structures (up to
ca. 60 wt.% water) to spherical normal, O/W micelles (at ≥85 wt.% water).
In contrast, the oligomeric systems, due to geometrical restrictions of the amphiphiles and the nature of their curvature
that prevents inversion, cannot further solubilize water in the surfactant aggregates’ core, causing phase separation to occur.
Part of the results presented in this paper were included in S. E.’s doctoral thesis in Applied Chemistry at The Hebrew University
of Jerusalem, Israel. 相似文献
The kinetics of alkaline hydrolysis of O-ethyl O-p-nitrophenyl chloromethylphosphonate in a sodium bis(2-ethylhexyl)sulfosuccinate—n-nonane—polyethylene glycol—water reverse micellar system was studied in a wide range of concentrations of the surfactant
and water. The sign of the catalytic effect of micelles is inverted in the presence of the polymer. A sharp change in the
apparent rate constant of hydrolysis of the phosphonate was found in a region of the temperature percolation threshold.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 60–67, January, 2007. 相似文献
Dynamic light scattering experiments have been performed at various concentrations, of pharmaceutical oil-in-water microemulsions
consisting of Eutanol G as oil, a blend of a high (Tagat O2) and a low (Poloxamer 331) hydrophilic–lipophilic balance surfactant,
and a hydrophilic phase (propylene glycol/water). We probe the dynamics of these microemulsions by dynamic light scattering.
In the measured concentration range, two modes of relaxation were observed. The faster decaying mode is ascribed classically
to the collective diffusion Dc (total droplet number density fluctuation). We show that the slow mode is also diffusive and suggest that its possible origin
is the relaxation of polydispersity fluctuations. The diffusion coefficient associated with this mode is then the self-diffusion
Ds of the droplets. It was found that Dc and Ds had opposite volume fractions of oil plus surfactants (ϕ) dependence and a common limiting value D0 for ϕ=0. Average hydrodynamic radius (Rh=10.5 nm) of droplets was calculated from D0. Rh is supposed to compose the inner core, a surfactant film including possible solvent molecules, which migrate with the droplet.
The concentration dependence of diffusion coefficients reflects the effect of hard sphere and the supplementary repulsive
interactions which arises due to loss of entropy, when absorbed chains of surfactant intermingle on the close approach of
the two droplets. This mechanism could also explain the observed stability of our systems. The estimated extent of polydispersity
is 0.22 from the amplitude of slower decaying mode. The polydispersity in microemulsion systems is dynamic in origin. Results
indicate that the time scale for local polydispersity fluctuations is at least three orders of magnitude longer than the estimated
time between droplet collisions. 相似文献
By the orthogonal design, the optimal formation conditions for the middle-phase microemulsions in the system dioctadecyldimethylammonium
chloride (DODMAC)/ sodium dodecyl sulfate (SDS)/n-butanol/n-hep-tane/brine were obtained as follows: WDODMAC: WSDS = 1:4-1:5,Cπ-butanol (%) = 11.0-12.0, andCNaCl (%) = 3.25
Investigations have been made on the effects of the concentrations of NaCl and n-butanol (l.0%-14.0%), the ratios ofWDODMAC: to WSDS, and the kinds of alcohols (n-propanol, n-butanol, and n-pentanol) on the formation, the phase behaviour, the ultralow interfacial
tensions, the optimal salinity (S*), and the length of salinity (δS). Some rules and data were worked out about the formation and characteristics of the middle-phase
microemulsions. The mi-crostructures of the middle-phase microemulsions were also studied by using FT-IR, ESR, and freeze
fracture electron microscopy techniques. The results from the three methods show that the microstructures of the middlephase
mi-croemulsions undergo the change from O/W to bicontinuous (B.C.) and to W/O. The distribution rule of the orga-nized molecule
assemblies in the middle-phase microemulsions is conducible to constructing the model of microemulsion systems, to recognizing
the microstructures of the middle-phase microemulsions, and to setting forth the relationship between the microstructures
and macro-properties of rnicroemulsions.
Project supported by the Niltional Natural Science Foundation of China and the Chinese Postdoctoral Science Foundation. 相似文献
Geometrical calculations of aggregate sizes in the reversed micellar solution phase of the system water/sodium octanoate/decanol at 20 °C have been tested by dynamic light scattering studies. The autocorrelation functions were interpreted in the simplest possible way (monodisperse aggregates, Stokes-Einstein diffusion equations) since the geometrical model does not account for detailed changes in shapes or micellar interactions. The model predicts the main features of micellization in these solutions, i. e., the micelles grow continuously as the concentration of water or the molar ratio water/octanoate increases, association begins at quite low concentrations of water and the surrounding decanolic solvent behaves as pure decanol which is saturated with water. 相似文献
Microemulsions used in enhanced oil recovery are usually used in conjunction with a polymer solution that provides mobility control by reducing the permeability of the formation and/or increasing the viscosity of the injected fluid. Microemulsions, which are mixtures of at least four components — water, oil, surfactant and cosurfactant (and, usually, inorganic salts) are complex even in the absence of polymer and consequently, studies of their phenomenon tend to be phenomenological. An approach found to be useful to circumvent this has been to consider the microemulsion particles dispersed in their external phase to be macromolecules which retain their integrity when diluted with external phase or when mixed with polymers. Thus the dispersed phase components are treated as a pseudocomponent. If this approach is followed, many features of the phase diagram of polymer-microemulsion mixtures can be rationalized. It is therefore of some interest to determine whether a similar approach can be used to understand or predict the viscosity of mixtures in which a simple mixing rule for viscosities can be utilized to gain further insight into the polymer-microemulsion interaction. 相似文献
The mechanism of silica particle formation in monomer microemulsions is studied using dynamic light scattering (DLS), atomic
force microscopy, small-angle X-ray scattering (SAXS), and conductivity measurements. The hydrolysis of tetraethylorthosilicate
(TEOS) in methylmethacrylate (MMA) microemulsions (MMA = methylmethacrylate) is compared with the formation of SiO2 particles in heptane microemulsions. Stable microemulsions without cosurfactant were found for MMA, the nonionic surfactant
Marlophen NP10, and aqueous ammonia (0.75 wt%). In the one-phase region of the ternary phase diagram, the water/surfactant
ratio (Rw) could be varied from 6 to 18. The DLS and SAXS measurements show that reverse micelles form in these water-in-oil (w/o)
microemulsions. The minimum water-to-surfactant molar ratio required for micelle formation was determined. Particle formation
is achieved from the base-catalyzed hydrolysis of TEOS. According to atomic force microscopy measurements of particles isolated
from the emulsion, the particle size can be effectively tailored in between 20 and 60 nm by varying Rw from 2–6 in heptane w/o microemulsions. For MMA-based microemulsions, the particle diameter ranges from 25 to 50 nm, but
the polydispersity is higher. Tailoring of the particle size is not achieved with Rw, but adjusting the particle growth period produces particles between 10 and 70 nm. 相似文献
The polymerization of styrene in ternary microemulsions stabilized by the cationic surfactant tetradecyltrimethylammonium bromide was studied as a function of concentrations of water-soluble (potassium persulfate, KPS) and oil-soluble (AIBN) initiators. At a particular molar ratio of the initiators, similar maximum rates of polymerization can be achieved from using both types of the initiators. In addition, both initiated systems produced microlatexes with similar hydrodynamic radius, number of polymer particles, molecular weight of polystyrene and number of polymer chain per latex particle. But the dependencies of these latex parameters on concentrations of KPS and AIBN may not be the same. The polymerization mechanism appears to be similar, irrespective of using KPS or AIBN. It is discussed in terms of effective radicals produced for the polymerization. While the different dependencies of some latex parameters on concentrations of the initiators are attributed to the different efficiencies of the initiators in producing effective radicals. 相似文献