Basics of Emulsion Polymerization: Raw Materials and Mechanism

Study and Compilation by: Anuj Agrawal

Date: 9th March 2022

In the early days, emulsion polymerization technique was explored in the effort for producing synthetic
rubber latexes (e.g., Styrene butadiene rubber), but the versatility of emulsion polymerization was quickly
recognized and led to an extremely wide range of polymers being produced in this way, including synthetic
elastomers, bulk plastics, and polymer latexes for use in variety of coating applications.

Emulsion polymerization is one of the types of free radical polymerization techniques ( the other common
ones being bulk, solution and suspension polymerization). But amongst all emulsion polymerization has
attracted most interest in industrial and academic setting because of the advantages it provides over other
types of polymerization techniques:

1. Fast dissipation of heat during polymerization

2. Forms high molecular weight polymers at lower viscosity
3. Ability to control submicron particle size and morphology
4. Polymers can be used directly
5. Can be used for tacky polymers

Emulsion polymerization usually produces latexes with spherical particles, which have a higher
packing factor, hence do not show high viscosity as a different latex would show at equal
concentration.

Before discussing the mechanism and intricacies of emulsion polymerization, it is important to study the
key raw materials required for this process:

Monomers:
Main requirement is that the monomers can undergo free radical chain polymerization and they do not
react with water. Monomers with limited solubility in water (neither very high nor very low) are most
useful. Major classes of latexes used on coatings are based on acrylic, methacrylic esters, and on vinyl
esters.

Methacrylic acid and acrylic acid improve colloidal stability, affect flow properties, improve adhesion, and
give carboxylic acid groups to serve as cross linking sites.

Hydroxyethyl acrylate and hydroxyethyl methacrylate provide hydroxyl groups for crosslinking.

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Initiators:
Initiators selected should be such that they are soluble in water. Most preferred initiators are persulfate
(SO52- or S2O82-) salts (ammonium persulfate/ potassium persulfate)

For polymerization at lower temp, addition of reducing agents accelerate radical production. Common
reducing agents include mixture of ferrous, thiosulfate (S2O32-), and persulfate salts. Processes using this
type of initiation are called redox emulsion polymerization.

It is common to add more lipophilic “chaser” initiator in the late stages of the semicontinuous process
to facilitate conversion of monomer to high levels (>99%). E.g., t-butyl hydroperoxide.

Surfactants:
Both anionic (sodium lauryl sulfate - SLS) and nonionic (NP ethoxylates) surfactants are used. Typically,
concentration of anionic surfactants varies from 0.5-2.0% of monomer concentration; and concentration
of nonionic surfactants varies from 2.0-6.0% of monomer concentration.

Surfactants help in stabilizing the hydrophobic monomer particles, forming micelles in the water phase
and promotes particle nucleation for polymerization.

Anionic surfactants lead to formation of rigid particles resulting in latexes which have low viscosity at high
solids. Whereas nonionic surfactants lead to lower polymer solids at high viscosity.

At the same surfactant concentration, a surfactant with lower CMC will give smaller particle size.

Particle size is much broader when anionic surfactants are used and approaches a monodisperse
particle size when nonionic surfactants are used.

Figure 1: Schematic diagram of emulsion polymerization

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Process mechanism

Emulsion polymerization mechanism can be divided into 3 intervals.

Interval 1: Waterborne free radicals first polymerize with monomer molecules dissolved in the continuous
aqueous phase. This results in the increased hydrophobicity of oligomeric radicals. When a critical chain
length is achieved, these oligomeric radicals become so hydrophobic that they show a strong tendency to
enter the monomer-swollen micelles and then continue to propagate by reacting with those monomer
molecules therein. Consequently, monomer-swollen micelles are successfully transformed into particle
nuclei. Hence increase in particle number and occurrence of particle nucleation is observed in Interval 1.
These embryo particles continue to grow by acquiring the reactant species from monomer droplets and
monomer-swollen micelles, exhausting most of the surfactants by the end of this phase.

Interval 2: Polymerization continues, and polymer particles increase in size until monomer droplets get
exhausted. Monomer droplets act as reservoirs to supply the growing particles with monomer and
surfactant species.

Interval 3: The polymer size increases as latex particles become monomer-starved and the concentration
of monomer in the reaction loci continues to decrease toward the end of polymerization.

Particle size is larger when the turbulence and agitation intensity is high.

Figure 2: Intervals in emulsion polymerization

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Typical emulsion polymerization formulation

Styrene butadiene Polyacrylate

Ingredients
copolymer emulsion
Water 190 133
Butadiene 70 -
Styrene 30 -
Ethyl acrylate - 93
2-chloroethyl vinyl ether - 5
p-divinylbenzene - 2
Sodium lauryl sulfate 5 3
Potassium persulfate 0.3 1
n-Dodecyl mercaptan 0.5 -
Sodium pyrophosphate - 0.7
Conditions
Time 12 hrs 8 hrs
Temperature 500C 500C
Yield 65% > 98%

References

1. Biomacromolecules. Fundamentals of Emulsion Polymerization. Peter Lovell. 2020-2021.

2. Intech Open Book Series. Emulsion Polymerization Mechanism. Abdelaziz Nasr Moawed Bakr El-hoshoudy.
January 2018.
3. Progress in Polymer Science. Emulsion polymerization mechanisms and kinetics. C.S. Chern. April 2006.
4. Organic Coatings – Science and Technology. 3rd Edition. Wiley 2007.