Preparation of microlatex dispersions using oil-in-water microemulsions

The preparation of microlatex dispersions from microemulsions of a monomer (styrene, methylmethacrylate or vinyl acetate) is described. A simple method for preparing the microemulsion has been devised. This consists of forming a water-in-oil (w/o) emulsion using a low (HLB) surfactant (nonylphenol with 5, 6 or 7 moles ethylene oxide) and then titrating with an aqueous solution of a high HLB surfactant (nonylphenol with 15 or 16 moles ethylene oxide). A small amount of anionic surfactant (sodium lauryl sulphate, sodium dodecyl benzene sulphonate or dioctyl sulphosuccinate) was also incorporated to enhance the stability of the w/o emulsion and facilitate the inversion to an o/w microemulsion. The droplet-size distribution of the resulting microemulsion was determined using photon-correlation spectroscopy.Three different methods of polymerising the microemulsion were used. These were thermally induced polymerisation using potassium persulphate, azobis-2-methyl propamidinium dichloride (AMP-water-soluble initiators) or azobisisobutyronitrile (AIBN, an oil-soluble initiator). All these initiators required heating to 60°C, i.e. above the stability temperature of the microemulsion. In this case, the microlatices produced were fairly large (37–100 nm diameter) and had a broad particle-size distribution. The second polymerisation procedure was chemically induced using a redox system of hydrogen peroxide and ascorbic acid. This produced microlatices with small sizes (18–24 nm diameter) having a narrow-size distribution. The microlatex size was roughly two to three times the size of the microemulsion droplets. This showed that collision between two or three microemulsion droplets resulted in their coalescence during the polymerisation process. The third method of polymerisation was based on UV irradiation in conjunction with K₂S₂O₈, AMP or AIBN initiators. In this case, the microlatex size was also small (30–63 nm) with a narrow particle-size distribution.Microlatex particles were also prepared using a mixture of monomers (styrene plus methylmethacrylate) or mixture of monomers and a macromonomer, namely methoxy (polyethylene glycol)methacrylate. The latter was used to produce hairy particles, i.e. with grafted polyethylene oxide (PEO) chains.The stability of the microlatices was determined by adding electrolytes (NaCl, CaCl₂, Na₂SO₄ or MgSO₄) to determine the critical flocculation concentration (CFC). The nonionic latices were very stable giving no flocculation up to 6 mol dm^–3 NaCl or CaCl₂ and a CFC of 0.6 mol dm^–3 for Na₂SO₄ or MgSO₄. Charged latices were less stable than the nonionic ones. The critical flocculation temperatures (CFT) of all latices were determined as a function of electrolyte concentration. With the nonionic latices, CFC was higher than the -temperature for polyethylene oxide at the given electrolyte concentration. This indicated enhanced steric stabilisation as a result of the dense packing of the chains and hence an elastic contribution to the steric interaction. This was not the case with the charged latex, which showed CFT values lower than the -temperature. The hairy latices [i.e. those containing methoxy polyethylene glycol (PEG) methacrylate] were also less stable towards electrolyte (CFT was much lower than -temperature), indicating a low density of PEO layers.     

微乳液法制备纳米粒子

介绍了W／O型微乳液内超细颗粒的形成机理、制备的技术关键，综述了近年来国内外微乳法制备纳米粒子的最新进展。引用文献37篇。     

Styrene and methylmethacrylate oil-in-water microemulsions

 A simple procedure for the preparation of styrene-in-water and methylmethacrylate (o/w) micro-emulsions was established. This consisted of the preparation of a w/o emulsion using a low HLB number surfactant (Synperonic NP4, nonyl phenyl with 4 mol ethylene oxide) and a small amount of an anionic surfactant (Aerosol OT, diethyl hexyl sulphosuccinate, or sodium dodecyl benzene sulphonate). The w/o emulsion was then titrated with an aqueous solution of a high HLB number surfactant (Synperonic NP15, nonyl phenyl with 15 mol ethylene oxide). The droplet size and poly-dispersity were determined using photon correlation spectroscopy (PCS). The temperature range within which a microemulsion remained stable decreased with increase in the concentration of styrene or methylmethacrylate and this could be explained in terms of the phase diagram of the microemulsion system. Conductivity measurements as a function of temperature showed that the systems are oil-in-water microemulsions. Received: 20 December 1996 Accepted: 5 March 1997     

Preparation of organic nanoparticles using microemulsions: their potential use in transdermal delivery

Organic nanoparticles of cholesterol and retinol have been synthesized in various AOT (Aerosol OT; sodium bis(2-ethylhexyl) sulfosuccinate)/heptane/water microemulsions by direct precipitation of the active principle in the aqueous cores. The nanoparticles are observed by transmission electron microscopy (TEM) using the adsorption of a contrasting agent, such as iodine vapor. The size of the nanoparticles can be influenced, in principle, by the concentration of the organic molecules and the diameter of the water cores, which is related to the ratio R=[H2O]/[surfactant]. The particles remain stable for several months. The average diameter of the cholesterol nanoparticles varies between 3.0 and 7.0 nm, while that of retinol varies between 4.0 and 10 nm. The average size of the cholesterol nanoparticles does not change much either as a function of the ratio R or as a function of the concentration of cholesterol. The constant size of the nanoparticles can be explained by the thermodynamic stabilization of a preferential size of the particles. Chloroform is used to carry the active principle into the aqueous cores. Retinol molecules form J-complexes composed of two or three molecules, as detected by UV-visible spectroscopy.     

Preparation of amorphous aluminum oxide-hydroxide nanoparticles in amphiphilic silicone-based copolymer microemulsions

Organo-inorgano nanocomposites with colloidal dimensions have interesting optical, catalytic, and mechanical properties, particularly when such hybrids are reinforced with transition metal oxide nanoparticles. Nanoparticles with a mean size of 1.0-2.4 nm are obtained through hydrolysis of aluminum isopropoxide in the L(2) phase of amphiphilic (PDMS-POE) polydimethylsiloxane-polyoxyethylene Silwet L-7607-octanol/acetylacetone-water mixtures. The particle sizes are related weakly to the microemulsion composition: 0.8-1.2 nm for 20 wt% Silwet L-7607 and 2.0-2.4 nm for 50 wt% Silwet L-7607. Protection of the particles against aggregation is ensured through their confinement in the intraaggregate colloidal domains. Factors affecting the hydrolysis-condensation process of acetylacetone-complexed aluminum isopropoxide in copolymer-poor and copolymer-rich regions of PDMS-POE W/O microemulsions are studied by Fourier transform infrared spectroscopy, small angle X-ray scattering, and transmission electron microscopy. Prepared nanoparticulate dispersions possess long-term stability and form clear mixtures in different organic polar and nonpolar solvents.     

Normal micelles and oil-in-water microemulsions in a water-toluene-Tween 80 ternary system

It is revealed that oil-in-water microemulsions of type I according to Winsor’s classification are formed at 293 K in a ternary water-toluene-Tween 80 system. Water-rich corner of the phase diagram is plotted, and the domains of the existence of micellar and microemulsion systems are determined. Different methods (refractometry, precision tensiometry, dynamic and static light scattering, and UV and NMR spectroscopies) are employed to study the properties (hydrodynamic particle radii, the aggregation numbers of nonionic surfactant molecules, and the degrees of hydration) of normal micelles and particles of dispersed phase in oil-in-water microemulsions at different toluene concentrations. The polarity of a microenvironment of the solubilizate is estimated. Original Russian Text ? M.V. Poteshnova, N.M. Zadymova, 2006, published in Kolloidnyi Zhurnal, 2006, Vol. 68, No. 2, pp. 226–236.     

Preparation of metal nanoparticles in water-in-oil (w/o) microemulsions

The use of an inorganic phase in water-in-oil microemulsions has received considerable attention for preparing metal particles. This is a new technique, which allows preparation of ultrafine metal particles within the size range 5 nm相似文献   

Organic nanoparticles from microemulsions: Formation and applications

Microemulsions have already been recognized as convenient templates for nanoparticle synthesis. Spontaneous formation of the compartmentalized domains within the microemulsions leads to facile and low-cost preparation processes.In the past, microemulsions were mainly explored as precursors for the synthesis of inorganic nanoparticles. However, there is a constantly growing number of publications offering to exploit these systems to produce organic nanoparticles, and in recent years, a variety of methods have emerged in this field. The aim of this review is to survey the methods recently used to produce organic nanomaterials from microemulsions, and to give a perspective on particle design possibilities that can be achieved by various techniques. The structure of the initial microemulsion system, the chemical and technical aspects of preparation, the nature of additives and surface active agents, as well as the possible outcomes in terms of final particle characteristics, will be discussed for the various methods.     

Formation of silica nanoparticles in microemulsions

Silica nanoparticles for controlled release applications have been produced by the reaction of tetramethylorthosilicate (TMOS) inside the water droplets of a water-in-oil microemulsion, under both acidic (pH 1.05) and basic (pH 10.85) conditions. In-situ FTIR measurements show that the addition of TMOS to the microemulsion results in the formation of silica as TMOS, preferentially located in the oil phase, diffuses into the water droplets. Once in the hydrophilic domain, hydrolysis occurs rapidly as a result of the high local concentration of water. Varying the pH of the water droplets from 1.05 to 10.85, however, considerably slows the hydrolysis reaction of TMOS. The formation of a dense silica network occurs rapidly under basic conditions, with IR indicating the slower formation of more disordered silica in acid. SAXS analysis of the evolving particles shows that approximately 11 nm spheres are formed under basic conditions; these are stabilized by a water/surfactant layer on the particle surface during formation. Under acidic conditions, highly uniform approximately 5 nm spheres are formed, which appear to be retained within the water droplets (approximately 6 nm diameter) and form an ordered micelle nanoparticle structure that exhibits sufficient longer-range order to generate a peak in the scattering at q approximately equal to 0.05 A-1. Nitrogen adsorption analysis reveals that high surface area (510 m2/g) particles with an average pore size of 1 nm are formed at pH 1.05. In contrast, base synthesis results in low surface area particles with negligible internal porosity.     

Measurement of the correlation radius in oil-in-water microemulsions by dynamic light scattering

The diffusion coefficient and correlation radius associated with the droplet particles in oil-in-water microemulsions (CTAB, octane, butanol, NaBr and water) were determined by dynamic light scattering- Unlike the case of CTAB micelles, there is a maximum in the correlation radius versus temperature plot.     

Polymer-induced recovery of nanoparticles from microemulsions

A new isothermal approach to the recovery of inorganic nanoparticles (NPs) is demonstrated. The NPs can be incorporated into a background microemulsion (ME) supporting fluid, and they can be recovered by addition of non-adsorbing polymer. A clean liquid-liquid (L-L) phase transition can be readily induced by addition of polymer to the MEs. Furthermore, the L-L transitions are also observed in the presence of added NPs, but now the nanoparticles concentrate in the lower co-existing ME phases. Once recovered, the NPs can be redispersed by adding extra ME as a solvent.     

A novel approach for the preparation of AgBr nanoparticles from their bulk solid precursor using CTAB microemulsions

Microemulsions are suitable reaction media to prepare a wide variety of nanoparticles and provide control over their sizes. However, as typically used, microemulsions limit rates of rapid reactions and suffer from low reactant solubilization capacity. This work presents a new application of a novel approach aimed at minimizing these limitations. This approach, which was previously applied for AgCl nanoparticle preparation, involves solubilization of a bulk silver halide in the form of higher halides, by means of reaction with the surfactant counterion of a microemulsion, and the reprecipitation of silver halide nanoparticles in the water pools of individual reverse micelles. CTAB microemulsions were employed because they possess a reactive counterion and are known to have a high solubilization capacity for ionic reactants. Despite their high solubilization capacity, CTAB microemulsions achieved lower nanoparticles uptake (molar concentration of the colloidal nanoparticles) for the same surfactant concentration when compared to our previous study. The effect of the following variables on the nanoparticle uptake and the particle size was investigated: (1) operation variables, including rate of mixing and temperature; and (2) microemulsion variables, including CTAB and n-butanol concentrations, and water-to-surfactant mole ratio, R. These variables provide a comprehensive test to the proposed mechanism and expose the role of the surfactant layer rigidity. The nanoparticle uptake increased as the rate of mixing, temperature, and CTAB concentration increased, and decreased as n-butanol concentration and R increased. High n-butanol concentration and R values reduced the effective surfactant concentration and contributed to less surfactant layer rigidity and to particle aggregation.     

Magnesium hydroxide nanoparticles synthesized in water-in-oil microemulsions

Well-dispersed magnesium hydroxide nanoplatelets were synthesized by a simple water-in-oil (w/o) microemulsion process, blowing gaseous ammonia (NH(3)) into microemulsion zones solubilized by magnesium chloride solution (MgCl(2)). Typical quaternary microemulsions of Triton X-100/cyclohexane/n-hexanol/water were used as space-confining microreactors for the nucleation, growth, and crystallization of magnesium hydroxide nanoparticles. The obtained magnesium hydroxide was characterized by field-emission scanning electron microscopy (FESEM), high-resolution transmission election microscopy (HRTEM), X-ray powder diffraction (XRD), laser light scattering, Fourier transform infrared spectroscopy (FT-IR), and thermogravimetric analysis-differential scanning calorimetry (TGA-DSC). The mole ratio of water to surfactant (omega(0)) played an important role in the sizes of micelles and nanoparticles, increasing with the increase of omega(0). The compatibility and dispersibility of nanoparticles obtained from reverse micelles were improved in the organic phase.     

Generation of metal oxide nanoparticles in optimised microemulsions

The phase behavior and structure of aqueous-in-n-heptane microemulsions, stabilized by surfactant mixtures of di-n-didodecyldimethylammonium bromide, DDAB, and Brij(R)35 were studied by small angle (neutron or X-ray) scattering techniques. The aqueous nanodroplets contain either a precursor reactive salt or a precipitating agent, so that simple mixing induces nanoparticle formation. These formulated microemulsions display good phase stability against added polar additives such as monovalent, divalent, trivalent metal ions, ammonia solution, tetrabutylammonium hydroxide, and their mixtures. Nanoparticle formation was demonstrated via precipitation of metal oxides inside the water nanodroplets, affording control over the resulting particle size. Nanoparticle characteristic size (XRD- and HR-TEM derived sizes) and specific surface areas (S(BET) (m(2)g(-1))) for iron oxide and CeO(2) prepared in these mixed microemulsions, are compared with those stabilized by single surfactants DDAB and Pure AOT.     

Reaction of carboxylic acid esters with phenolates in oil-in-water microemulsions based on cetyltrimethylammonium bromide

A kinetic study of reactions of carboxylic acid esters with phenols activated with alkalis or amines in microemulsions based on cationic surfactants showed that the phenolates formed upon activation exhibit different nucleophilicity depending on the value of the negative charge on the oxygen atom, which is determined by the properties of the phenol, ionizing agent, and solvent.     

Growth of silica nanoparticles in methylmethacrylate-based water-in-oil microemulsions

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 (R _w) 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 R _w 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 R _w, but adjusting the particle growth period produces particles between 10 and 70 nm.     

A versatile approach to affinitychromic polythiophenes

The preparation of both postfunctionalizable and chromic poly[3-(N-succinimido-p-phenylcarboxylate(tetraethoxy)oxy)-4-methylthiophene] is reported. The N-hydroxysuccinimide ester side group can easily react with different amine-bearing molecules in the solid state to yield a library of new polythiophene derivatives. The resulting polymers can be dissolved in various solvents, and interactions between the side chains (ligands) and different analytes (targets) can be detected from modifications of both the side-chain and the backbone conformations resulting in important color changes (i.e., affinitychromism). This colorimetric polymeric transducer could therefore lead to highly valuable, versatile, and inexpensive tools for highthroughput screening and drug discovery.     

Preparation of nanoparticles of silver halides,superconductors and magnetic materials using water-in-oil microemulsions as nano-reactors

Water-in-oil microemulsions have been used for the synthesis of a variety of nanoparticles since the technique was first introduced in 1982. In this paper we have reviewed several articles pertaining to the synthesis of nanoparticles in microemulsions and described in some detail our research efforts in the past decade in the field of synthesis of nanoparticles of silver halides, superconductors and magnetic materials using water-in-oil microemulsions as nano-reactors.     

A versatile method for grafting polymers on nanoparticles

We report a simple and versatile method for grafting polymers on nanoparticles. A procedure was developed for the synthesis and subsequent functionalization of silica nanoparticles with a perfluorophenylazide. Polymers were then grafted by the photochemically induced insertion reactions of the perfluorophenylnitrene. Polystyrene, poly(4-vinylpyridine), and poly(2-ethyl-2-oxazoline) were successfully grafted on silica nanoparticles. Grafting density was studied with regard to polymer concentration and molecular weight.     

Formation of zinc sulfide and hydroxylapatite nanoparticles in polyelectrolyte-modified microemulsions

The paper is focused on the formation of nanoparticles, i.e., zinc sulfide (ZnS) and hydroxylapatite, in a microemulsion template phase consisting of heptanol, water, and a surfactant with a sulfobetaine head group in the absence and presence of an added polyelectrolyte. In the absence of a polyelectrolyte, beside larger particles, spherical ZnS nanoparticles with a diameter below 10 nm can be redispersed after solvent evaporation. In the presence of the synthetic cationic polyelectrolyte poly(diallyldimethylammonium chloride), a reloading of the particle surface is observed, and cationic charged ZnS nanoparticles, of about 5 nm in size, can be redispersed as a main fraction. When hydroxylapatite is formed in the presence of the more stiff biopolymer chitosan hydroxylapatite, hybrid structures were formed. Transmission electron micrographs show fiber-like aggregate structures, consisting of individual small nanoparticles ordered along the polymer chain.