Latex dispersion polymerization

The polymeric latex obtained in a hydrophobic organic solvent is poorly dispersed in water because of the presence of an emulsifier with a low HLB value. For this reason, a wetting agent is added to water or emulsion prior to the dissolution. The wetting agent (a surface active substance with a high HLB value) facilitates the inversion of latex phases to produce a direct type emulsion. Usually, it belongs to oxyethylated alkylphenols, fatty alcohols, or fatty acids. 

In this chapter, the polymerization methods used for the production of uniform latex particles in the size range of O.I-lOO /Ltm are described. Emulsion, swollen emulsion, and dispersion polymerization techniques and their modified forms for producing plain, functionalized, or porous uniform latex particles are reviewed. The general mechanisms and the kinetics of the polymerization methods, the developed synthesis procedures, the effect of process variables, and the product properties are discussed. 

Figure 9 The schematical representation of dispersion polymerization process, (a) initially homogeneous dispersion medium (b) particle formation and stabilizer adsorption onto the nucleated macroradicals (c) capturing of radicals generated in the continuous medium by the forming particles and monomer diffusion to the forming particles (d) polymerization within the monomer swollen latex particles, (e) latex particle stabilized by steric stabilizer and graft copolymer molecules (f) list of symbols.

Table 5 Typical Dispersion Polymerization Recipes Providing Uniform Latex Particles...

Paine et al. [99] tried different stabilizers [i.e., hydroxy propylcellulose, poly(N-vinylpyrollidone), and poly(acrylic acid)] in the dispersion polymerization of styrene initiated with AIBN in the ethanol medium. The direct observation of the stained thin sections of the particles by transmission electron microscopy showed the existence of stabilizer layer in 10-20 nm thickness on the surface of the polystyrene particles. When the polystyrene latexes were dissolved in dioxane and precipitated with methanol, new latex particles with a similar surface stabilizer morphology were obtained. These results supported the grafting mechanism of stabilization during dispersion polymerization of styrene in polar solvents. 

The dispersion polymerization of alkylcyanoacry-lates provides degradable uniform polyalkylcyanoacry-late latex particles in submicron size range. These particles are termed as biodegradable nanoparticles in the common literature [102-107]. The general structure of alkylcyanoacrylates is ... 

Another group of uniform latex particles were prepared by the dispersion polymerization of acrolein in an aqueous medium by Margel and coworkers [96], A typical polymerization was conducted in the aqueous alkaline medium having a pH of 10.5, which was obtained by the aqueous NaOH solution. Polyglutaraldehyde-NaHS03 conjugate was synthesized by the reaction of... 

Table 10.4 summarizes the compositions of some experiments as well as the colloid-analytical data of the final polystyrene lattices. A particle diameter of about lOOnm (including the shell of the adsorbed block copolymers in an extended conformation) is rather low for the product of a dispersion polymerization in unpolar solvents. In addition, a mean deviation (a) of about 20% of the particle size indicates a well-controlled and stable latex. 

The nucleation mechanism of dispersion polymerization of low molecular weight monomers in the presence of classical stabilizers was investigated in detail by several groups [2,6,7]. It was, for example, reported that the particle size increased with increasing amount of water in the continuous phase (water/eth-anol), the final latex radius in their dispersion system being inversely proportional to the solubility parameter of the medium [8]. In contrast, Paine et al.[7] reported that the final particle diameter showed a maximum when Hansen polarity and the hydrogen-bonding term in the solubility parameter were close to those of steric stabilizer. 

Canelas, D. A. Betts, D. E. DeSimone, J. M. Yates, M. Z. Johnston, K. P. Poly(vinyl acetate) and Poly(vinyl acetate-co-ethylene) Latexes via Dispersion Polymerizations in Carbon Dioxide. Macromolecules 1998, 31, 6794-6805. 

Both aqueous polymer-based systems (latex), made by emulsion or dispersion polymerization, and oil-modified alkyd resin-based systems are still in wide use [781], Table 12.2 shows the composition of a typical water-based emulsion paint. There is a wide variety of coatings, ranging from broad applicability to highly specialized, including latexes, amino resins, isocyanates, epoxy resins, acrylic resins, polyester... 

The reaction engineering aspects of these polymerizations are similar. Excellent heat transfer makes them suitable for vinyl addition polymerizations. Free radical catalysis is mostly used, but cationic catalysis is used for non-aqueous dispersion polymerization (e.g., of isobutene). High conversions are generally possible, and the resulting polymer, either as a latex or as beads, is directly suitable for some applications (e.g., paints, gel-permeation chromatography beads, expanded polystyrene). Most of these polymerizations are run in the batch mode, but continuous emulsion polymerization is common. 

Dispersion polymerization is defined as a type of precipitation polymerization by which polymeric microspheres are formed in the presence of a suitable steric stabilizer from an initially homogeneous reaction mixture. Under favorable circumstances, this polymerization can yield, in a batch process, monodisperse, or nearly monodisperse, latex particles with a relatively large diameter (up to 15 pm) [103]. The solvent selected as the reaction medium is a good solvent for both the monomer and the steric stabilizer, but a non-solvent for the polymer being formed and therefore a selective solvent for the graft copolymer. This restriction on the choice of solvent means that these reactions can be carried out... 

In choosing an epoxy and polymeric latex, it is important that they have compatibility. Incompatibility usually occurs when the pH of the epoxy resin dispersion alters the pH of the latex into a range where the ionically stabilized latex is broken, causing agglomeration of the latex polymer. The pH of the epoxy resin s emulsion may need to be adjusted before blending with the polymeric latex. 

Colloidal stability is usually controlled by the type and amount of the employed surfactant. In miniemulsions, the fusion-fission rate equilibrium during sonication and therefore the size of the droplets directly after primary equilibration depends on the amount of surfactant. For sodium dodecylsulfate (SDS) and styrene at 20% dispersed phase, it spans a range from 180 nm (0.3% SDS relative to styrene) down to 32 nm (50 rel.% SDS) (Fig. 4a). Again, it is anticipated that rapidly polymerized latexes also characterize the parental miniemulsion. As... 

Series I Acrylic Latex Emulsions. A series of four acrylic latex emulsions varying in glass transition temperature (Tg) (3) were applied first. Tg is the temperature at which the resin changes from a relatively flexible to a relatively stiff material. The acrylic latexes are made from water-insoluble monomers such as acrylates and alkyl acrylates polymerized in emulsion form to produce an aqueous dispersion or latex of the polymer. Upon drying, the emulsion is irreversibly broken so that the applied material becomes wash-fast. The application requires no catalyst or high temperature heating. 

In the conventional emulsion polymerization, monomer droplets are dispersed ip an aqueous phase containing micellar aggregates of surfactant. In this case, the dispersed phase represents a relatively small volume fraction of the system and the micellar aggregates constitute the sites of the polymerization process. In the gel(paste)-like emulsions employed here, the volume fraction of the dispersed phase can be as high as 0.99, and the cells of the concentrated emulsion lead to the polymerized latex particles. 

Examples of aqueous coating solutions include water-soluble low molecular weight cellulose ethers, emulsion polymerization latexes of polymethacrylates, and dispersions of water-insoluble polymers such as ethyl-cellulose in the form of pseudolatex. These solvent-free coating solutions provide a range of different coatings... 

In dispersion polymerization, by contrast to emulsion or suspension polymerization, a monomer which is soluble in the reaction medium is polymerized. In analogy to fhe aforementioned types of polymerization, an insoluble polymer is obtained. The reaction is carried out in the presence of non-ionic surfactants or soluble polymers, which can stabilize the polymer particles generated to form a stable latex. Wifh particle sizes of ca. 1 to 15 pm, dispersion polymerization can cover the particle size range between emulsion and suspension polymerization. 

Stable aqueous emulsions of poly(2-ethylhexyl acrylate) (PEHA) were also produced by RESAS from CO2 (68). In this case, a polymer suspension in CO2 was expanded instead of a dissolved solute. A C02-philic surfactant, Monasil PCA (PDMS-g-pyrrolidonecarboxylic acid), was utilized in dispersion polymerization to form a stable polymer suspension at 65°C and 345 bar. A hydrophilic surfactant, (e.g., SAM 185, Pluronic L61, or Pluronic L62), that is soluble in CO2 and CO2/2-EHA monomer mixtures as well as water was added to CO2 to stabilize the suspension after it had been rapidly expanded through a capillary into aqueous solution. The resulting aqueous emulsion with up to 15.6 wt % polymer content was stable for weeks with an average particle size of 2 to 3 pm. Another approach is to introduce the hydrophilic surfactant in the aqueous phase in addition to the surfactant in the CO2 phase. This approach is more general, since many hydrophilic surfactants are not soluble in CO2. During expansion of the suspension into an aqueous solution, the hydrophilic surfactant—for example, triblock Pluronic copolymers—dilfuses to the particle surface to provide stabilization. The resulting aqueous latexes were stable for 100 days for a polymer content reaching 12.7 wt %. 

Young JLS, Richard J, DeSimone Joseph M. Synthesis of two-stage composite latex particles by dispersion polymerization in carbon dioxide. Pol5mr Prepn (ACS Div Polym Chem) 1999 40 829-830. 

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