Microlatexes

Manufacturing processes have been improved by use of on-line computer control and statistical process control leading to more uniform final products. Production methods now include inverse (water-in-oil) suspension polymerization, inverse emulsion polymerization, and continuous aqueous solution polymerization on moving belts. Conventional azo, peroxy, redox, and gamma-ray initiators are used in batch and continuous processes. Recent patents describe processes for preparing transparent and stable microlatexes by inverse microemulsion polymerization. New methods have also been described for reducing residual acrylamide monomer in finished products. 

Larpent and Tandros [102] prepared microlatex particles by polymerization of PEO-MA macromonomer with MMA, styrene, and vinyl acetate. The nonionic latexes are very stable, giving no flocculation up to 6 mol dm 3 NaCl or CaCl2 and a critical flocculation concentration (CFC) of 0.6 mol dm 3 for Na2S04 or MgS04 was estimated. Charged latexes are less stable than the nonionic ones. The CFC of all latexes are determined as a function of electrolyte concentration. With the nonionic latexes, however, the critical flocculation temperature (CFT)... 

Microemulsion Polymerization for Microlatexes with High Polymer-... 

Abstract This review describes how the unique nanostructures of water-in-oU (W/0), oil-in-water (0/W) and bicontinuous microemulsions have been used for the syntheses of some organic and inorganic nanomaterials. Polymer nanoparticles of diameter approximately 10-50 nm can easily be obtained, not only from the polymerization of monomers in all three types of microemulsions, but also from aWinsor l-like system. A Winsor 1-like system with a semi-continuous process can be used to produce microlatexes with high weight ratios of polymer to surfactant (up to 25). On the other hand, to form inorganic nanoparticles, it is best to carry out the appropriate chemical reactions in W/0- and bicontinuous microemulsions. 

Polymerizations in Globular and Bicontinuous Microemulsions for Producing Microlatexes... 

Candau and co-workers were the first to address the issue of particle nu-cleation for the polymerization of AM [13, 14] in an inverse microemulsion stabilized by AOT. They found that the particle size of the final microlatex (d 20-40 nm) was much larger than that of the initial monomer-swollen droplets (d 5-10 nm). Moreover, each latex particle formed contained only one polymer chain on average. It is believed that nucleation of the polymer particle occurs for only a small fraction of the final nucleated droplets. The non-nucleated droplets also serve as monomer for the growing particles either by diffusion through the continuous phase and/or by collisions between droplets. But the enormous number of non-nucleated droplets means that some of the primary free radicals continuously generated in the system will still be captured by non-nucleated droplets. This means that polymer particle nucleation is a continuous process [ 14]. Consequently, each latex particle receives only one free radical, resulting in the formation of only one polymer chain. This is in contrast to the large number of polymer chains formed in each latex particle in conventional emulsion polymerization, which needs a much smaller amount of surfactant compared to microemulsion polymerization. 

The polymerization of acrylamide (AM) and the copolymerization of acrylamide-sodium acrylate in inverse microemulsions have been studied extensively by Candau [10,11,13-15], Barton [16, 17], and Capek [18-20]. One of the major uses for these inverse microlatexes is in enhanced oil recovery processes [21]. Water-soluble polymers for high molecular weights are also used as flocculants in water treatments, as thickeners in paints, and retention aids in papermaking. 

Core-shell nanoparticles can also be fabricated using microemulsions. This was performed using a two-stage microemulsion polymerization beginning with a polystyrene seed [62]. Butyl acrylate was then added in a second step to yield a core-shell PS/PBA morphology. The small microlatex led to better mechanical properties than those of similar products produced by emulsion polymerization. Hollow polystyrene particles have also been produced by microemulsion polymerization of MMA in the core with crosslinking of styrene on the shell. After the synthesis of core-shell particles with crosslinked PS shells, the PMMA core was dissolved with methylene chloride [63]. The direct cross-... 

Fig. 3 Changes in PMMA particle size during long term storage at 60 °C for microlatexes stabilized by different surfactants (filled triangles) TTAB (filled squares) TTAC (filled circles) CTAB (empty triangles) OTAC...

The polymerization of styrene in Winsor I-like systems by semi-continuous feeding of monomer stabilized by either DTAB, TTAB or CTAB has been systematically investigated by Gan and coworkers [69a]. Rather monodisperse polystyrene microlatexes of less than 50 nm with molecular weights of over one million were obtained at a polymer/surfactant weight ratio of 14 1. The Winsor I-like (micro)emulsion polymerization of styrene stabilized by non-ionic surfactant and initiated by oil-soluble initiators has also been reported very recently [69b]. The sizes of the large monomer-swollen particles decreased with conversion and they merged with growing particles at about 40-50% conversion. 

High PMMA content (30-40%) microlatexes [70] stabilized with low concentrations of anionic SDS were also prepared by microemulsion polymeriza-... 

High polymer/surfactant weight ratios (up to about 15 1) of polystyrene microlatexes [73] have been produced in microemulsions stabihzed by polymerizable nonionic surfactant by the semi-continuous process. The copolymerization of styrene with the surfactant ensures the long-term stabihty of the latexes. Nanosized PS microlatexes with polymer content (<25 wt%) were also obtained from an emulsifier-free process [74] by the polymerization of styrene with ionic monomer (sodium styrenesulfonate, NaSS), nonionic comonomer (2-hydroxyethylmethacryalte, HEM A), or both. The surfaces of the latex particles were significantly enriched in NaSS and HEMA, providing better stabilization. 

Nanoparticles of PS (M =1.0xl0 -3.0xl0 mol ) microlatexes (10-30 nm) have also been successfully prepared from their respective commercial PS for the first time [75]. The dilute PS solutions (cyclohexane, toluene/methanol or cyclohexane/toluene) were induced to form polymer particles at their respective theta temperatures. The cationic CTAB was used to stabihze th microlatexes. The characteristics of these as-formed PS latex particles were quite similar to those obtained from the microemulsion polymerization of styrene as reported in literature. These microlatexes could also be grown to about 50 nm by seeding the polymerization of styrene with a monodisperse size distribution of D /Djj=1.08. This new physical method for preparing polymer nano-sized latexes from commercial polymers may have some potential applications, and therefore warrants further study. 

In other techniques of oil production, the microlatices can be usefully employed for ground consolidation, manufacture of drilling muds and as completion or fracturation fluids. Another use concerns the prevention of water inflows into production wells. The method consists injecting from the production well into the part in the field to be treated, an aqueous solution of polymer prepared by inverse microlatex dissolution in water. The polymer is adsorbed on the walls of the formation surrounding the well. When the latter is brought in production, the oil and/or the gas selectively traverse the treated zone whereas the passage of water is inhibited. 

Alternatively, they can act as flotation and draining adjuvants (26), for example in the manufacture of paper the addition of the polymer in stable microlatex improves water draining from the paper sheets. 

Preparation of Microlatex nith Functionalized Polyesters as Surfactants... 

Microlatex, l.e. particles having a diameter of less than lOOnm, can be obtained, especially with polyesters MD 90 and MD 120. 

It was also shown that stable latexes of high solid content, and small particle size could be practically obtained by this emulsion polymerization technique. Such microlatexes based on acrylic polymers modified by polyesters are an interesting approach to waterborne coatings leading to high gloss paint films (9). 

Riess G. Block copolymers as polymeric surfactants in latex and microlatex technology. Colloids Surf 1999 A 153 99-110. 

In this paper I review the salient features of polymerization in microemulsions at the present state of knowledge. I discuss the formulation of polymerizable microemulsions and show how the incorporation of monomers can modify the initial structure of the systems. The kinetic and mechanistic aspects are given and compared to those experienced in conventional emulsion polymerization. I also describe some recent results obtained on the formation of porous solid materials and functionalized microlatex particles, which seem quite promising for future applications. 

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