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| title | chunk | source | category | tags | date_saved | instance |
|---|---|---|---|---|---|---|
| Emulsion polymerization | 1/4 | https://en.wikipedia.org/wiki/Emulsion_polymerization | reference | science, encyclopedia | 2026-05-05T10:47:38.679050+00:00 | kb-cron |
In polymer chemistry, emulsion polymerization is a type of radical polymerization that usually starts with an emulsion incorporating water, monomers, and surfactants. The most common type of emulsion polymerization is an oil-in-water emulsion, in which droplets of monomer (the oil) are emulsified (with surfactants) in a continuous phase of water. Water-soluble polymers, such as certain polyvinyl alcohols or hydroxyethyl cellulose, can also be used to act as emulsifiers/stabilizers. The name "emulsion polymerization" is a misnomer that arises from a historical misconception. Rather than occurring in emulsion droplets, polymerization takes place in the latex/colloid particles that form spontaneously in the first few minutes of the process. These latex particles are typically 100 nm in size, and are made of many individual polymer chains. The particles are prevented from coagulating with each other because each particle is surrounded by the surfactant ('soap'); the charge on the surfactant repels other particles electrostatically. When water-soluble polymers are used as stabilizers instead of soap, the repulsion between particles arises because these water-soluble polymers form a 'hairy layer' around a particle that repels other particles, because pushing particles together would involve compressing these chains. Emulsion polymerization is used to make several commercially important polymers. Many of these polymers are used as solid materials and must be isolated from the aqueous dispersion after polymerization. In other cases the dispersion itself is the end product. A dispersion resulting from emulsion polymerization is often called a latex (especially if derived from a synthetic rubber) or an emulsion (even though "emulsion" strictly speaking refers to a dispersion of an immiscible liquid in water). These emulsions find applications in adhesives, paints, paper coating and textile coatings. They are often preferred over solvent-based products in these applications due to the absence of volatile organic compounds (VOCs) in them.
Advantages of emulsion polymerization include:
High molecular weight polymers can be made at fast polymerization rates. By contrast, in bulk and solution free-radical polymerization, there is a tradeoff between molecular weight and polymerization rate. The continuous water phase is an excellent conductor of heat, enabling fast polymerization rates without loss of temperature control. Since polymer molecules are contained within the particles, the viscosity of the reaction medium remains close to that of water and is not dependent on molecular weight. The final product can be used as is and does not generally need to be altered or processed. Disadvantages of emulsion polymerization include:
Surfactants and other polymerization adjuvants remain in the polymer or are difficult to remove For dry (isolated) polymers, water removal is an energy-intensive process Emulsion polymerizations are usually designed to operate at high conversion of monomer to polymer. This can result in significant chain transfer to polymer. Can not be used for condensation, ionic, or Ziegler-Natta polymerization, although some exceptions are known.
== History == The early history of emulsion polymerization is connected with the field of synthetic rubber. The idea of using an emulsified monomer in an aqueous suspension or emulsion was first conceived at Bayer, before World War I, in an attempt to prepare synthetic rubber. The impetus for this development was the observation that natural rubber is produced at room temperature in dispersed particles stabilized by colloidal polymers, so the industrial chemists tried to duplicate these conditions. The Bayer workers used naturally occurring polymers such as gelatin, ovalbumin, and starch to stabilize their dispersion. By today's definition these were not true emulsion polymerizations, but suspension polymerizations. The first "true" emulsion polymerizations, which used a surfactant and polymerization initiator, were conducted in the 1920s to polymerize isoprene. Over the next twenty years, through the end of World War II, efficient methods for production of several forms of synthetic rubber by emulsion polymerization were developed, but relatively few publications in the scientific literature appeared: most disclosures were confined to patents or were kept secret due to wartime needs. After World War II, emulsion polymerization was extended to production of plastics. Manufacture of dispersions to be used in latex paints and other products sold as liquid dispersions commenced. Ever more sophisticated processes were devised to prepare products that replaced solvent-based materials. Ironically, synthetic rubber manufacture turned more and more away from emulsion polymerization as new organometallic catalysts were developed that allowed much better control of polymer architecture.
== Theoretical overview == The first successful theory to explain the distinct features of emulsion polymerization was developed by Smith and Ewart, and Harkins in the 1940s, based on their studies of polystyrene. Smith and Ewart arbitrarily divided the mechanism of emulsion polymerization into three stages or intervals. Subsequently, it has been recognized that not all monomers or systems undergo these particular three intervals. Nevertheless, the Smith-Ewart description is a useful starting point to analyze emulsion polymerizations.