Emulsion polymerization

When radicals generated in the aqueous phase encounter the monomer within the micelle, they initiate polymerization. The conversion of monomer to polymer within the micelle lowers the monomer concentration and generates a monomer concentration gradient. Consequently, the monomer from monomer droplets and uninitiated micelles begin to diffuse to the growing, polymer-containing, particles. Those micelles that did not encounter a radical during the earlier stage of conversion begin to disappear, losing their monomer and surfactant to the growing particles. The theory predicts that after the end of this interval, the number of growing polymer particles remains constant.

This interval is also known as steady state reaction stage. Throughout this stage, monomer droplets act as reservoirs supplying monomer to the growing polymer particles by diffusion through the water. While at steady state, the ratio of free radicals per particle can be divided into three cases. When the number of free radicals per particle is less than ​¹⁄₂, this is called Case 1. When the number of free radicals per particle equals ​¹⁄₂, this is called Case 2. And when there is greater than ​¹⁄₂ radical per particle, this is called Case 3. Smith-Ewart theory predicts that Case 2 is the predominant scenario for the following reasons. A monomer-swollen particle that has been struck by a radical contains one growing chain. Because only one radical (at the end of the growing polymer chain) is present, the chain cannot terminate, and it will continue to grow until a second initiator radical enters the particle. As the rate of termination is much greater than the rate of propagation, and because the polymer particles are extremely small, chain growth is terminated immediately after the entrance of the second initiator radical. The particle then remains dormant until a third initiator radical enters, initiating the growth of a second chain. Consequently the polymer particles in this case either have zero radicals (dormant state), or 1 radical (polymer growing state) and a very short period of 2 radicals (terminating state) which can be ignored for the free radicals per particle calculation. At any given time, a micelle contains either one growing chain or no growing chains (assumed to be equally probable). Thus, on average, there is around 1/2 radical per particle, leading to the Case 2 scenario. The polymerization rate in this stage can be expressed by

$${\displaystyle R_{p}=k_{p}[\mathrm {M} ][\mathrm {P} ^{\bullet }]}$$

where ${\textstyle k_{p}}$is the homogeneous propagation rate constant for polymerization within the particles and ${\displaystyle [\mathrm {M} ]}$ is the equilibrium monomer concentration within a particle. ${\textstyle [\mathrm {P} ^{\bullet }]}$ represents the overall concentration of polymerizing radicals in the reaction. For Case 2, where the average number of free radicals per micelle are ${\displaystyle 1/2}$, ${\textstyle [\mathrm {P} ^{\bullet }]}$ can be calculated in following expression:

$${\displaystyle [\mathrm {P} ^{\bullet }]={\frac {N_{\mathrm {micelles} }}{2N_{\mathrm {A} }}}}$$

where ${\displaystyle N_{\mathrm {micelles} }}$is number concentration of micelles (number of micelles per unit volume), and ${\displaystyle N_{\mathrm {A} }}$ is the Avogadro constant (6.02×10²³ mol⁻¹). Consequently, the rate of polymerization is then

$${\displaystyle R_{p}=k_{p}[\mathrm {M} ]{\frac {N_{\mathrm {micelles} }}{2N_{\mathrm {A} }}}.}$$

Separate monomer droplets disappear as the reaction continues. Polymer particles in this stage may be sufficiently large enough that they contain more than 1 radical per particle.

Typical monomers are those that undergo radical polymerization, are liquid or gaseous at reaction conditions, and are poorly soluble in water. Solid monomers are difficult to disperse in water. If monomer solubility is too high, particle formation may not occur and the reaction kinetics reduce to that of solution polymerization.

Ethene and other simple olefins must be polymerized at very high pressures (up to 800 bar).

Copolymerization is common in emulsion polymerization. The same rules and comonomer pairs that exist in radical polymerization operate in emulsion polymerization. However, copolymerization kinetics are greatly influenced by the aqueous solubility of the monomers. Monomers with greater aqueous solubility will tend to partition in the aqueous phase and not in the polymer particle. They will not get incorporated as readily in the polymer chain as monomers with lower aqueous solubility. This can be avoided by a programmed addition of monomer using a semi-batch process.

Ethene and other alkenes are used as minor comonomers in emulsion polymerization, notably in vinyl acetate copolymers.

Small amounts of acrylic acid or other ionizable monomers are sometimes used to confer colloidal stability to a dispersion.

Both thermal and redox generation of free radicals have been used in emulsion polymerization. Persulfate salts are commonly used in both initiation modes. The persulfate ion readily breaks up into sulfate radical ions above about 50 °C, providing a thermal source of initiation. Redox initiation takes place when an oxidant such as a persulfate salt, a reducing agent such as glucose, Rongalite, or sulfite, and a redox catalyst such as an iron compound are all included in the polymerization recipe. Redox recipes are not limited by temperature and are used for polymerizations that take place below 50 °C.

Although organic peroxides and hydroperoxides are used in emulsion polymerization, initiators are usually water soluble and partition into the water phase. This enables the particle generation behavior described in the theory section. In redox initiation, either the oxidant or the reducing agent (or both) must be water-soluble, but one component can be water-insoluble.

Selection of the correct surfactant is critical to the development of any emulsion polymerization process. The surfactant must enable a fast rate of polymerization, minimize coagulum or fouling in the reactor and other process equipment, prevent an unacceptably high viscosity during polymerization (which leads to poor heat transfer), and maintain or even improve properties in the final product such as tensile strength, gloss, and water absorption.

Anionic, nonionic, and cationic surfactants have been used, although anionic surfactants are by far most prevalent. Surfactants with a low critical micelle concentration (CMC) are favored; the polymerization rate shows a dramatic increase when the surfactant level is above the CMC, and minimization of the surfactant is preferred for economic reasons and the (usually) adverse effect of surfactant on the physical properties of the resulting polymer. Mixtures of surfactants are often used, including mixtures of anionic with nonionic surfactants. Mixtures of cationic and anionic surfactants form insoluble salts and are not useful.

Examples of surfactants commonly used in emulsion polymerization include fatty acids, sodium lauryl sulfate, and alpha olefin sulfonate.

Some grades of polyvinyl alcohol and other water-soluble polymers can promote emulsion polymerization even though they do not typically form micelles and do not act as surfactants (for example, they do not lower surface tension). It is believed that growing polymer chains graft onto these water-soluble polymers, which stabilize the resulting particles.[14]

Dispersions prepared with such stabilizers typically exhibit excellent colloidal stability (for example, dry powders may be mixed into the dispersion without causing coagulation). However, they often result in products that are very water sensitive due to the presence of the water-soluble polymer.

Other ingredients found in emulsion polymerization include chain transfer agents, buffering agents, and inert salts. Preservatives are added to products sold as liquid dispersions to retard bacterial growth. These are usually added after polymerization, however.