MINIEMULSION POLYMERIZATION

Introduction
Miniemulsions

are a special class of emulsions that are stabilized against

coalescence (by a surfactant) and Ostwald ripening (by an osmotic pressure
agent).

Miniemulsions

are produced by the combination of a high shear which is

provided by a sonicator or a mechanical homogenizer to break the
emulsion into submicron monomer droplets with a size ranging from 50 to
500 nm.
Surfactant/co-stabilizer is added to retard monomer diffusion/droplet
coalescence caused by Brownian motion settling or Stokes law creaming
by prevents Ostwald ripening*. Therefore, when a liquid emulsion is
subjected to high shear, small droplets will obtain.

The droplet surface area in these systems is very large where most of the
surfactant is adsorbed at the droplet surface.
Particle

nucleation is primarily via radical (primary or oligomeric) entry

into monomer droplets, since little surfactant is present in the form of
micelles.

The

important feature is that the reaction proceeds by polymerization of

the monomer in the droplets, thus there is no true Interval II in
miniemulsion.
A

polar droplets can be dispersed in a polar liquid to give direct

miniemulsions (oil-in-water), whereas polar droplets in a non-polar liquid
leads to inverse miniemulsions (e.g., water-in-oil, w/o).

Interval I
Monomer
swollen
micelle ~
100

Interval IParticle nucleation

Emulsified
monomer
droplet
~ 10
Emulsifier
Monomer swollen
polymar particle ~
500

Interval II
Continuous aqueous phase

Interval IIParticle growth

Emulsified
monomer
droplet ~ 10

Particle size increase

Monomer swollen
polymar particle ~
500
Interval III

Continuous aqueous phase

Monomer
swollen
polymar
particle ~
1000

Interval IIIMonomer droplet

depletion
a

Continuous aqueous phase

Particle of same size

NO TRUE interval II
in miniemulsion
b

a) Macroemulsion polymerization versus b) miniemulsion polymerization.

Example of polymers produced by miniemulsion polymerization.

Polymer class

Polymerization

Year

polystyrene

radical

1973

polyvinyl chloride

radical

1984

silicone

anionic

1994

polyethylene

catalytic

2000

epoxy

polyaddition

2000

polyurethane

polyaddition

2001

saturated polyester

polycondensation

2003

polyamide

anionic

2005

polyimide

polycondensation

2009

Ostwald ripening
Ostwald

ripening is a phenomenon which smaller particles

in solution dissolve and deposit on the larger particles in
order to reach more thermodynamically stable wherein the
surface to area ratio is minimized.
The small particle disappears while the size of large particle
increases at the end of process.
Small particle

Large particle

Small particle
disappears

Larger particle size

Ostwald

ripening occurs because molecules on the surface

of particles are more energetically unstable than those at the
centre.
The surface particle
gone after 7.8 sec,
migrates into solution

The

unstable surface molecules often migrate into solution,

thus shrinking the particle over time and increasing the
number of free molecules in solution.

When

the solution is supersaturated with the molecules of the shrinking

particles, those free molecules will redeposit on the larger particles.
Small particles decrease in size until they disappear and large particles grow
even larger, thus resulting a larger mean diameter of a particle size
distribution (PSD).

Ostwald

ripening is often found in oil-in-water emulsions where oil

molecules will diffuse through the aqueous phase and join larger oil
droplets.
Over

time, this causes emulsion instability and eventually phase separation.

Free molecule of particles

Larger particle

Factors affect miniemulsion

Miniemulsions are produced by the combination of a high shear device (to
break up the emulsion into submicron monomer droplets) and a waterinsoluble, monomer-soluble component (to retard monomer diffusion
from the submicron monomer droplets) where both steps are necessary
to effect predominant droplet nucleation.

1. Surfactant/co-stabilizer

The vast majority of miniemulsion polymerizations have been stabilized

with anionic surfactants due to their compatibility with neutral or
anionic (acid) monomers and anionic initiators.

Co-stabilizer used either cetyl alcohol (CA) or hexadecane (HD) to

retard Ostwald ripening in submicron monomer droplets.

Both CA and HD possess requisite properties for a co-stabilizer i.e. high

monomer solubility, low water solubility and low molecular weight.

High

monomer solubility will give a large Flory Huggins interaction

parameter between the co-stabilizer and the monomer, thus giving a higher
volume fraction of co-stabilizer in the droplet.
Low molecular weight co-stabilizer will give a high ratio of co-stabilizer
molecules to monomer molecules in the droplet.
These factors will enhance swelling or retard monomer loss via Ostwald
ripening.
2.

Choice of Initiator

Most miniemulsion polymerizations have been run using water-soluble

initiators. However, a number of researchers have looked at the
possibility of using an oil-soluble initiator instead.
In most cases the oil-soluble initiator is used as a finishing initiator to
increase final monomer conversion.

3. Shear Device

High shear device (or sonication) is needed to break up the emulsion into
submicron monomer droplets.
In the absence of a high-shear device, miniemulsion systems revert to
macroemulsion polymerizations, indicating that the presence of a costabilizer alone is not sufficient to cause predominant droplet nucleation.
Firstly, a coarse pre-emulsion is formed by vigorous stirring of the
monomer, water, surfactant to form a macroemulsion.
For reasons of practicality, the costabilizer is dissolved in the monomer
before pre-emulsification.
Then, the coarse pre-emulsion particle is subjecting the system to high
shear device to form submicron droplet.
The intensity of shearing depends on the rotor speed, normally from 535
krpm for most modern equipment.
However, at higher speeds the shearing action generates a significant
amount of heat, which may harm the sample being emulsified or the
machine itself.

Advantages of miniemulsion
1.

2.

The most prominent advantage is no step of monomer

diffusion through the aqueous phase - from the monomer
droplets to the polymer particles during the course of
polymerization because the monomer droplets are
directly polymerized.
The micellar nucleation in conventional emulsion
polymerization is extremely sensitive to a large number
of factors such as amount of surfactant, amount of
initiator, agitation speed, temperature of the
polymerization reaction, mode of addition of the
monomers, etc. These factors are eliminated in
miniemulsion.