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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
I-I M
monomer droplet
micelle M 2 R.
I-I
monomer droplet
M Initiator I-I M I-I M Monomers
I-I
M .RMMMM I-I M polymer particle
surfactant
surfactant
Figure 1: Initial situation
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. I-I
monomer swollen polymer particle MM M Monomers M surfactant M
I-I
2 R.
Figure 3: Stage II of the emulsion polymerisation process.
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.
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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)
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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.
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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 pump thermo couple
monomer pre-emulsion heating water bath

Figure 6: Typical laboratory reactor equipment
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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.
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GENERAL PRINCIPLES OF EMULSION POLYMERISATION WITH VEOVA MONOMERS

VV 2.0 Issued January 2001

The emulsion polymerisation process

The different phases of the emulsion polymerisation process

M Initiator I-I M I-I M Monomers

M .RMMMM I-I M polymer particle

Figure 1: Initial situation

Figure 2: Stage I of the emulsion polymerisation process

monomer swollen polymer particle MM M Monomers M surfactant M

Figure 3: Stage II of the emulsion polymerisation process.

Figure 4: Stage III of the emulsion polymerisation process.

Stabilisation of the latex

Surfactant Protective colloid

Figure 5: Idealised structures of a colloid-free and colloid-stabilised latex particle.

Main ingredients in VeoVa-based latices

Surfactants and protective colloids

Other important aspects for the production of latices

pH control and yellowing

Effect of polymerisation conditions on latex properties

Solubility of monomers in water

monomer pre-emulsion heating water bath

Recommended Public Literature on Emulsion Polymerisation

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