Abstract
Although it has been generally accepted for the past 45 years that the latex particles which are the principal locus of the emulsion polymerization reaction are nucleated from monomer solubilized in emulsifier micelles, conclusive evidence to support this supposition has been lacking. Twenty years ago it became apparent that in the case of monomers such as methyl methacrylate and vinyl acetate which have significant solubility in water, latex particles are nucleated by precipitation of oligomeric radicals formed in aqueous solution. Then it was found that even styrene, which has a very low solubility in water, could be polymerized in emulsion without an emulsifier or below the critical micelle concentration of the emulsifier when the latex particles must also be nucleated by oligomeric precipitation. However, such ‘emulsifier-free emulsion polymerization’ proves impossible with p-tert-butyl styrene which has only one tenth of the water solubility of styrene. Subsequently much evidence has been published to show that the ultimate latex particles are formed by coalescence of unstable precursor particles. It is argued that in the case of water-insoluble monomers, precursor particles may be formed by coalescence of monomer-swollen micelles destabilized by polymerization.
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