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Emulsion polymerization

physical science Maturity 11-13 Next article →

Emulsion polymerization is a specialized form of radical polymerization. This chemical process creates polymers by using an emulsion of water, monomers, and surfactants. A monomer is a small molecule that serves as a building block for larger chains. A surfactant, often called soap, helps mix substances that usually do not blend. Most often, this process uses an oil-in-water emulsion. In this setup, monomer droplets act like oil in a continuous phase of water.

Emulsion Polymerization Cartoon 3
Emulsion Polymerization Cartoon 3

Though it is called emulsion polymerization, the name is actually a misnomer. The polymerization does not happen inside the large monomer droplets. Instead, it occurs within tiny latex or colloid particles. These particles form spontaneously during the first few minutes of the reaction. They are typically about 100 nm in size. Each particle is made of many individual polymer chains. To prevent these particles from sticking together, surfactants provide an electrostatic charge. This charge causes the particles to repel one another. Some processes use water-soluble polymers as stabilizers instead of soap. These create a "hairy layer" around each particle to keep them apart.

Scientists explain this mechanism using the Smith-Ewart-Harkins theory. This theory divides the process into three distinct intervals. In the first interval, the monomer is dispersed in water with surfactants. This creates large monomer droplets and many tiny micelles. A water-soluble initiator is added to the water phase. This initiator reacts with the monomer inside the micelles. As the monomer converts to polymer, the micelles transform into polymer particles.

Emulsion Polymerization Cartoon 3
Emulsion Polymerization Cartoon 3

In the second interval, the system reaches a steady state. The large monomer droplets act as reservoirs. They supply monomer to the growing particles through diffusion. During this stage, the number of radicals per particle is very important. Smith-Ewart theory suggests that Case 2 is most common. In Case 2, a particle usually contains either zero or one growing chain. A single radical allows a chain to grow until a second radical enters. This second radical causes the chain to terminate quickly. The particle then remains dormant until a third radical arrives.

In the third interval, the free monomer droplets eventually disappear. All the remaining monomer is then located within the polymer particles. Depending on the specific product, extra monomer or initiator may be added. This helps maintain the levels as the particles continue to grow. The final result is a dispersion of polymer particles in water. This dispersion is often called a latex or a polymer colloid. Even though "emulsion" is technically incorrect here, the term is still widely used.

History shows that this field grew from the study of synthetic rubber. Before World War I, researchers at Bayer tried to mimic natural rubber. Natural rubber forms in dispersed particles stabilized by colloidal polymers. Early Bayer workers used starch, gelatin, or ovalbumin as stabilizers. These were actually suspension polymerizations rather than true emulsion polymerizations. The first true emulsion polymerizations occurred in the 1920s using isoprene. Following World War II, the process expanded to include plastic production.

Emulsion Polymerization Cartoon 3
Emulsion Polymerization Cartoon 3

Emulsion polymerization offers several technical advantages for industry. It can produce high molecular weight polymers at very fast rates. In other methods, like bulk polymerization, there is a tradeoff between speed and molecular weight. This process also uses water as a continuous phase. Water is an excellent conductor of heat. This helps maintain temperature control during fast reactions. Additionally, the viscosity of the mixture stays close to that of water. This is because the polymer molecules are contained within small particles.

These polymers are vital for many everyday products. They are used to create adhesives, paints, and paper coatings. They are also used in textile coatings. Many of these products are preferred because they lack volatile organic compounds (VOCs). Using water-based dispersions instead of solvent-based ones is better for the air. However, there are some challenges to consider. Surfactants can remain in the final polymer and are hard to remove. Also, removing water to create dry polymers requires a lot of energy.

Emulsion Polymerization Cartoon 3
Emulsion Polymerization Cartoon 3
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