Droplet size monomer emulsions

Emulsion polymerisation represents the next stage in development from the suspension technique and is a versatile and widely used method of polymerisation. In this technique droplets of monomer are dispersed in water with the aid of an emulsifying agent, usually a synthetic detergent. The detergent forms small micelles 10-100 /im in size, which is much smaller than the droplets that can be formed by mechanical agitation in suspension polymerisation. These micelles contain a small quantity of monomer, the rest of the monomer being suspended in the water without the aid of any surfactant. 

Furthermore, should free radicals be present, the vinyl groups would much more rapidly polymerise depleting the emulsion droplets of monomer, providing the control required for a particular particle size. The composition of the solution thus determines not only the phase behaviour, but the rate of polymerisation and the particle size. If, the organism has in its genetic code, the abihty to synthesise the monomer, it presumably has... 

The micelles are present at a concentration of about lO per ml of liquor and each micelle contains around 100 monomer molecules. In contrast, the number of monomer droplets is only about 10 ° per ml. Thus, despite the larger volume of monomer droplets, the micelles offer a very much larger surface area. A radical formed in the aqueous phase will thus encounter a monomer-filled micelle much more often than a monomer droplet. Therefore, the polymerization takes place practically only in the micelles and not in the monomer droplets. The monomer consumed in the micelles is replaced by diffusion from the monomer droplets through the aqueous phase. According to the theories of Harkins and of Smith and Ewart, the kinetic course of an emulsion polymerization is divided into three intervals At first some of the micelles increase rapidly in size as the polymerization advances and are transformed into so-called latex particles, containing both monomer and polymer. These are still very much smaller than the monomer droplets and have an initial diameter of about 20-40 pm, corresponding to about... 

If the monomer droplet size in a conventional emulsion polymerization can be reduced sufficiently (see below), the loci of polymerization become the monomer droplets. This system is referred to as a miniemulsion polymerization and will be discussed in detail below. The particle diameter will range from 50 to 500 nm. 

Mouran et al. [105] polymerized miniemulsions of methyl methacrylate with sodium lauryl sulfate as the surfactant and dodecyl mercaptan (DDM) as the costabilizer. The emulsions were of a droplet size range common to miniemulsions and exhibited long-term stability (of greater than three months). Results indicate that DDM retards Ostwald ripening and allows the production of stable miniemulsions. When these emulsions were initiated, particle formation occurred predominantly via monomer droplet nucleation. The rate of polymerization, monomer droplet size, polymer particle size, molecular weight of the polymer, and the effect of initiator concentration on the number of particles all varied systematically in ways that indicated predominant droplet nucleation. 

Claverie et al. [325] have polymerized norbornene via ROMP using a conventional emulsion polymerization route. In this case the catalyst was water-soluble. Particle nucleation was found to be primarily via homogenous nuclea-tion, and each particle in the final latex was made up of an agglomeration of smaller particles. This is probably due to the fact that, unlike in free radical polymerization with water-soluble initiators, the catalyst never entered the polymer particle. Homogeneous nucleation can lead to a less controllable process than droplet nucleation (miniemulsion polymerization). This system would not work for less strained monomers, and so, in order to use a more active (and strongly hydrophobic) catalyst, Claverie employed a modified miniemulsion process. The hydrophobic catalyst was dissolved in toluene, and subsequently, a miniemulsion was created. Monomer was added to swell the toluene droplets. Reaction rates and monomer conversion were low, presumably because of the proximity of the catalyst to the aqueous phase due to the small droplet size. 

Polymerizations of the monomer emulsions were carried out with oil-soluble initiators. Oil-soluble initiators have often been employed in emulsion polymerization recipes and are generally used in suspension polymerization. Whereas in the latter case the initiation naturally takes place in the monomer droplets, the locus of initiation and growth of particles in emulsion polymerization with oil-soluble initiators has been open to some doubt. However, the fact that the particle size and size distribution is not very different from the results with water-soluble initiators and that the particles are generally much smaller than the droplets in the monomer emulsions indicates that with... 

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