Emulsion polymerization kinetic regimes

At low values of a, the emulsion polymerization system is characterized by (a) the very slow overall rate of absorption of free radicals by the latex particles and/or the very large population of latex particles (i.e., pJNp ) and (b) the very large rate constant for desorption of free radicals out of the latex particles and/or the very large ratio of the surface area to volume of a single latex particle (i.e., /CdesV p ) tliis regime, desorption of free radicals out of the latex particles plays an important role in the emulsion polymerization kinetics. The value of n is smaller than 0.5 [Smith-Ewart Case 1 kinetics, Eq. (4.6)] and n increases rapidly with increasing a. At medium values of a, the emulsion polymerization system is characterized by (a) the very small rate... 

Heterophase processes should be primarily distinguished based on their emulsion structure (oil-in-water or water-in-oil) and type of stability (kinetic or thermodynamic). This identifies four mutually independent polymerization regimes, each with unique colloidal and chemical behavior. L Macroemulsion, II. Inverse-Macroemulsion, HI. Microemulsion, IV. Inverse-Microemulsion. The macroemulsion and inverse-macroemulsion domains can be further subdivided into Suspension (la), Emulsion (lb), Inverse-suspension (Ha) and Inverse-emulsion (lib) subdomains based on a transition at the critical micelle concentration. 

The small droplet size (in the nm regime), high kinetic stability and optical transparency of miniemulsions enable the further application of these materials compared to conventional emulsion systems. In particular, miniemulsions have been primarily used to prepare well-defined nanometer-sized polymeric nanoparticles, using the monomer as the dispersant phase. Surfactants containing a polymerizable group (otherwise known as a surfmers) can be used to protect, stabilize and functionalize the polymer particles. 

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