The first successful theory to explain the distinct features of emulsion polymerization was developed by Smith and Ewart,[10] and Harkins[11] 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.

Schematic diagram of emulsion polymerization

The Smith-Ewart-Harkins theory for the mechanism of free-radical emulsion polymerization is summarized by the following steps:

A monomer is dispersed or emulsified in a solution of surfactant and water forming relatively large droplets of monomer in water.

Excess surfactant creates micelles in the water.

Small amounts of monomer diffuse through the water to the micelle.

A water-soluble initiator is introduced into the water phase where it reacts with monomer in the micelles. (This characteristic differs from suspension polymerization where an oil-soluble initiator dissolves in the monomer, followed by polymer formation in the monomer droplets themselves.) This is considered Smith-Ewart Interval 1.

The total surface area of the micelles is much greater than the total surface area of the fewer, larger monomer droplets; therefore the initiator typically reacts in the micelle and not the monomer droplet.

Monomer in the micelle quickly polymerizes and the growing chain terminates. At this point the monomer-swollen micelle has turned into a polymer particle. When both monomer droplets and polymer particles are present in the system, this is considered Smith-Ewart Interval 2.

More monomer from the droplets diffuses to the growing particle, where more initiators will eventually react.

Eventually the free monomer droplets disappear and all remaining monomer is located in the particles. This is considered Smith-Ewart Interval 3.

Depending on the particular product and monomer, additional monomer and initiator may be continuously and slowly added to maintain their levels in the system as the particles grow.

The final product is a dispersion of polymer particles in water. It can also be known as a polymer colloid, a latex, or commonly and inaccurately as an 'emulsion'.

Smith-Ewart theory does not predict the specific polymerization behavior when the monomer is somewhat water-soluble, like methyl methacrylate or vinyl acetate. In these cases homogeneous nucleation occurs: particles are formed without the presence or need for surfactant micelles.

High molecular weights are developed in emulsion polymerization because the concentration of growing chains within each polymer particle is very low. In conventional radical polymerization, the concentration of growing chains is higher, which leads to termination by coupling, which ultimately results in shorter polymer chains. The original Smith-Ewart-Hawkins mechanism required each particle to contain either zero or one growing chain. Improved understanding of emulsion polymerization has relaxed that criterion to include more than one growing chain per particle, however, the number of growing chains per particle is still considered to be very low.

Because of the complex chemistry that occurs during an emulsion polymerization, including polymerization kinetics and particle formation kinetics, quantitative understanding of the mechanism of emulsion polymerization has required extensive computer simulation. Gilbert has summarized a recent theory.

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