GENERAL PRINCIPLES OF EMULSION
POLYMERISATION WITH VEOVA
MONOMERS
VV 2.0
Issued January 2001
The emulsion polymerisation process
In an emulsion polymerisation process vinyl or acrylic monomers are
converted into a water-dispersed polymer (latex). The process starts with the
help of a free-radical initiator. The polymer particles are stabilised with
surface active materials (surfactants) to prevent undesired fusion or
coagulation. The final product is a polymer latex.
The emulsion polymerisation process has various advantages compared to
bulk or solution polymerisation as it proceeds at low viscosity. This allows an
adequate removal of the heat of reaction generated during the process and
the production of high molar mass polymers in combination with high
monomer conversion and short cycle-times. The final product is a waterbased system with a low viscosity.
The emulsion polymerisation process is applied on an industrial scale for the
production of latices used as binders in a variety of products such as
emulsions paints, adhesives, primers and sealers.
The different phases of the emulsion polymerisation process
At the start of the process, the monomers are dispersed into small droplets,
stabilised by surfactants. Most of the remaining surfactant molecules are
present as clusters (micelles) in the water phase (Figure 1). These micelles
are very small (10 nm) relative to the monomer droplets (1-10 m). Three
different stages of emulsion polymerisation can be distinguished. During
stage I the initial formation of polymer particles takes place. In stage II the
polymerisation proceeds with a constant supply of new monomer which
results in growth of the polymer particles. At the end of stage II monomer
supply ceases and subsequently the rate of polymerisation decreases
gradually (stage III).
The emulsion polymerisation processes normally used to produce VeoVabased latices proceeds via the three stages mentioned above. They are semicontinuous processes, during which the monomers are gradually added to the
reactor over a period of a few hours.
To begin with the reactor is charged with water, surfactants and part of the
initiator. The reactor is heated to the reaction temperature. Typically 5 to
10% of the total amount of monomers are subsequently added to the reactor
to produce a so-called in-situ seed latex which allows better control of the
particle formation step. The polymerisation is started by the initiator
generating free radicals by thermal decomposition in the aqueous phase. The
free radicals react with monomers present in the water phase to form
oligomer chains (stage I). These oligomers can be absorbed into the micelles
or can continue to grow and adsorb surfactant molecules. In either case this
results in the formation of new polymer particles (Figure 2). This process
continues until no micelles are left. In the case of a semi-continuous process,
stage I corresponds with the generation of the seed latex.
micelle
monomer
droplet
I-I
M
I-I
Initiator
I-I
monomer
droplet
I-I
micelle
2 R.
M
.RMMMM
I-I
I-I
surfactant
M
Monomers
surfactant
Figure 1: Initial situation
polymer particle
Figure 2: Stage I of the emulsion
polymerisation process
The polymer particles start to absorb additional monomer which migrates
from the monomer droplets through the water phase. The polymerisation
then proceeds mainly in the monomer-swollen polymer particles without the
formation of new particles (stage II). The monomers consumed by polymer
chain growth are replaced by new monomers which continue to migrate from
the monomer droplets (Figure 3). Depletion of monomer droplets is prevented
by the continuous addition of new monomers. The growing particles are
stabilised by adsorption and/or grafting of surfactants and colloids onto their
surface. Fresh initiator is continuously added to the reactor via a separate
initiator feed stream. For a semi-continuous process, stage II applies during
the monomer addition period.
When all the monomers have been added to the reactor, the polymerisation
continues with the conversion of residual monomer in the polymer particles.
Gradually the rate of polymerisation decreases to zero when no residual
monomer is left (Figure 4). Stage III corresponds with the post-cooking
period applied at the end of the semi-continuous process.
I-I
R.
R.
monomer swollen polymer particle
I-I
2 R.
I-I
MM
M
Monomers
M
surfactant
Figure 3: Stage II of the emulsion
polymerisation process.
VV 2.0
Figure 4: Stage III of the emulsion
polymerisation process.
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Stabilisation of the latex
There are two forms of stabilisation that prevent premature coagulation of
latex particles:
Electrostatic repulsion between the polymer particles. This can be
provided by means of anionic surfactants and negatively charged
functional groups located at the polymer/water interface.
Steric stabilisation by hydrophilic groups located at the surface of the
polymer particles. These hydrophilic groups originate from non-ionic
surfactants or protective colloids. They attract much water, thus creating
a so-called protective water-barrier between the particles that prevents
coagulation.
Electrostatic stabilisation is complementary to steric stabilisation. The two
are therefore usually combined to achieve the optimum result.
If protective colloids are used, normally in combination with surfactants, the
latex is referred to as a colloid-stabilised latex. If protective colloids are
absent, the latex is called a colloid-free latex. Idealised structures of a
colloid-stabilised and colloid-free latices are given in Figure 5.
Surfactant
Protective colloid
Figure 5: Idealised structures of a colloid-free and colloid-stabilised
latex particle.
Main ingredients in VeoVa-based latices
Monomers
VeoVa monomers are most commonly used in conjunction with vinyl
acetate. They can also readily co-polymerise with many other monomers, for
example most acrylic monomer types. These include functional monomers
used for latex stabilisation such as acrylic acid. VeoVa technical bulletin
VV 0.1 provides information with respect to the selection of suitable comonomers.
VV 2.0
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Initiators
The usual initiator for vinyl acetate polymerisation is potassium persulphate.
Ammonium persulphate is also sometimes used, as well as redox systems
that allow lower reaction temperatures. The amount of initiator should be
sufficient to provide an adequate number of free radicals. In colloid-stabilised
latices, too high amounts of free radicals should be avoided as this can cause
excessive degradation of the protective colloid and hence a reduction of the
latex viscosity. Using too much initiator also produces polymers with a low
molecular weight. This usually leads to lower mechanical performance.
The partition of the initiator between the initial reactor charge and the
initiator feed is also important. Good results are usually obtained using the
minor part in the initial reactor charge and the major part in the initiator feed
stream.
Following the addition of the monomer mixture to the reactor, it is common
practice to add extra initiator or a redox booster during the post-cooking
period to achieve high monomer conversion.
Surfactants and protective colloids
Surfactants play an essential role in providing good stability both during the
emulsion polymerisation process and during storage and transport. By
choosing specific types and amounts of surfactants the average particle size
of the latex can be controlled to a large extent. Surfactants also have an
effect on many performance properties of the latex, such as pigment binding
power and water sensitivity. Finally, some surfactant types are less favoured
for health and safety reasons. It is therefore important to pay some extra
attention in choosing the right surfactant types.
Most vinyl acetate/VeoVa latices, regardless of whether they are of the
colloid-stabilised or the colloid-free type, contain a combination of anionic
and non-ionic surfactants. Anionic surfactants provide shear stability to the
latex during the polymerisation reaction. They enable small particles to be
formed and minimise losses by coagulation. Non-ionic surfactants provide
electrolyte stability and contribute to mechanical and freeze-thaw stability.
The use of either surfactant type alone is insufficient; latices prepared using
only anionic surfactants are usually deficient in electrolyte stability whereas
high coagulation losses may occur when only non-ionic surfactants are used.
A combination of dodecyl benzene sulphonate as the anionic surfactant with
a suitable non-ionic surfactant delivers stable latices with good performance.
Nonyl phenol ethoxylates have been the standard type non-ionic surfactants
for many years, but they are now
under environmental pressure.
Alternatives have been selected from a wide range of non-ionic surfactants
with various chemical structures. Information on the relationship between
surfactant structure and latex properties is described in detail in Technical
Bulletins on the design and manufacture of the colloid-stabilised and colloidfree VeoVa-based latex types (VeoVa Technical Bulletins VV 2.1.1 and VV
2.2.1)
VV 2.0
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Many latices use a protective colloid for stabilisation (between 0.5% and 2%
on monomer weight) in addition to a combination of surfactants. The colloid
can have an effect on the emulsion polymerisation process because it reacts
with radicals. Details on colloid choice and the role the colloid plays in the
emulsion polymerisation process are given in dedicated bulletins on colloidstabilised latex manufacture (VeoVa Technical Bulletin VV 2.1.1).
Final latex
The product resulting from emulsion polymerisation is a white, stable
polymer dispersion with low residual monomer content and a solids content
typically around 44 to 56% m/m. Polymer molecular weight varies with the
polymerisation conditions but is usually in the range of 100,000 to
1,000,000 daltons. The average particle size (Dw) of colloid-free latices is
usually around 100-170 nm and that of colloid-stabilised latices about 200500 nm.
Other important aspects for the production of latices
The production and performance of latices are influenced by a variety of
other parameters. Some of the key issues to consider are:
Water quality
The concentration of electrolytes in the water used has an effect on the
latex stability and particle size. Therefore, the use of demineralised water is
recommended.
Nitrogen inlet
Oxygen can have an inhibiting effect on polymerisation. Therefore, the
reactor containing the initial reactor charge should be flushed with an inert
gas, such as nitrogen.
pH control and yellowing
A buffer is used to control the pH at a level of about 4 during the
polymerisation. In colloid-free systems, where acrylic acid is used as a costabiliser, the pH is increased to 7-8 after the reaction, in order to improve
latex stability.
Seed
An important factor, determining the maximum amount of monomers that
can be initially charged to the reactor, is the resulting exothermic heat of
reaction. The initial monomer amount should be chosen in such a way that
the temperature rises from the starting temperature up to the desired
reaction maximum temperature. It is recommended to avoid too strongly
exothermic reactions.
Effect of polymerisation conditions on latex properties
In general, high polymerisation temperatures lead to lower average molecular
weight polymers and hence lower mechanical strength. Specifically for
colloid-stabilised latices, a polymerisation temperature below 76C may lead
to lack of stability due to insufficient grafting of the colloid.
VV 2.0
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Solubility of monomers in water
For the required mass transport through the aqueous phase in any emulsion
polymerisation it is required that the monomers used possess a certain
degree of solubility in water. VeoVa monomers have a very low solubility in
water, however not to the degree that this is limiting for mass transport.
Vinyl acetate has a relatively high solubility, which leads to a somewhat
higher presence in the water phase, where initiation usually takes place. As a
result, chain ends may be relatively rich in vinyl acetate compared to the
average composition. Also, at the end of the polymerisation it is helpful to
use hydrophobic initiators to convert traces of VeoVa that are located in the
polymer phase rather than the water phase.
Stirring speed
Some latices have a relatively high viscosity. Problems, such as insufficient
heat transfer and insufficient mixing of re-fluxing monomer back into the
latex, can be avoided by adequate stirring. However, care should be taken
not to generate too much foam.
Stirring also causes significant shear, which necessitates the use of a good
stabilising system for the latex and proper reactor and stirrer design to avoid
the formation of grit and coagulum.
Solids content
Colloid-stabilised vinyl acetate/VeoVa 10 latices can be prepared at 54-56%
m/m solids without any difficulty. For low particle size latices, notably
colloid-free types the solids content should be reduced slightly in order to
avoid grit formation and very high viscosity during the latex preparation.
Laboratory reactor
During laboratory experimentation the preparation of vinyl acetate/VeoVa
latices can be carried out in 2 to 5 litre glass reactors equipped with an
anchor or turbine stirrer, a cooling mantle, a nitrogen flux and a reflux
condenser. The monomer mixture and initiator solution are fed into the
reactor with a pump. The monomer mixture should be kept under
continuous agitation throughout the polymerisation reaction.
N2 flushing
stirrer
condenser
thermo couple
pump
monomer pre-emulsion
heating water bath
Figure 6: Typical laboratory reactor equipment
VV 2.0
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Handling Precautions
For more detailed information on all aspects relating to Health, Safety and
Handling, reference should be made to the Safety Data Sheets of VeoVa
monomers, which are available from your local Resolution representative or
distributor. The precautions advised therein should be strictly observed. For
such details related to other products listed in this bulletin, please contact
the suppliers of those products.
Recommended Public Literature on Emulsion
Polymerisation
1. Piirma I., Emulsion Polymerisation, Academic Press, New York (1982)
2. Gilbert R.G., Emulsion Polymerisation a Mechanistic Approach, Academic
Press, London (1995)
3. Asua J.M., Polymeric Dispersions: principles and applications, NATO ASI
Series, Kluwer Academic Publishers, Dordrecht, (1997).
4. Lovell P.A., El-Aasser M.S., Emulsion polymerisation and emulsion
polymers, Wiley, Chichester (1997).
VeoVa is a trademark of Resolution Performance Products.
The information contained in this publication is, to the best of our knowledge, true and accurate, but any
recommendations or suggestions which may be made are without guarantee, since the conditions of use are
beyond our control. Furthermore, nothing contained herein shall be construed as a recommendation to use any
product in conflict with existing patents covering any material or its use.
VV 2.0
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