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Emulsion Polymerization
CELLOSIZE
HYDROXYETHYL CELLULOSE
For Emulsion Polymerization
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Contents
3 Introduction
4 Latex types
5 Latex manufacturing techniques
5 Stabilization of emulsion polymers
6 The role of CELLOSIZE™ HEC as a protective colloid
10 Chemistry of CELLOSIZE HEC in emulsion polymerization
Table of Contents

11 Hydroxyethyl cellulose characteristics

12 CELLOSIZE HEC in polymerization of vinyl ester monomers
15 CELLOSIZE HEC in polymerization of acrylic monomers
16 Water adsorption of latex films
16 CELLOSIZE HEC as part of the total stabilizing system
17 Emulsion polymerization formulations
17 A. Poly(vinyl acetate) latex
18 B. Poly(vinyl acetate) latex
19 C. Persulfate initiated vinyl acetate - vinyl versatate
copolymer latex
20 D. t-Butyl hydroperoxide - sodium formaldehyde sulfoxylate
initiated vinyl acetate - vinyl versatate copolymer latex
21 E. Persulfate - metabisulfite initiated vinyl acetate - vinyl
versatate copolymer latex
22 F. Vinyl acetate - vinyl versatate latex binder for premium
quality paints
23 G. Vinyl acetate - butyl acrylate-latex
24 H. All-acrylic latex
25 References
25 Glossary

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CELLOSIZE Hydroxyethyl Cellulose:

A Protective Colloid for Emulsion Polymerization

Introduction
Synthetic latices are extensively used as binders in paints,
adhesives, paper, textile and various other end-applications.1 They
can be characterized as aqueous dispersions of polymer particles
produced by a chemical process known as emulsion polymeriza-
tion. In this process, monomers are converted into polymers in an
aqueous emulsion system in the presence of emulsion stabilizers
and catalyzed by water-soluble radical initiators.
Latices offer a unique combination of interesting physical
CELLOSIZE hydroxyethyl
properties. They are low viscosity polymer systems which are cellulose (HEC) can be used as
used in water-borne, environmentally friendly systems. Stability part of the latex stabilizer system
and rheology dominate the physical properties required for where it acts as a protective col-
loid. In this respect CELLOSIZE
most applications.
HEC will contribute to both
Latices should remain colloidally stable when stored over a long stability and rheology of the
system. CELLOSIZE HEC is
period, when subjected to shear forces or when incorporated into
available in a wide range of grades,
a formulation. In the presence of other formulation ingredients, allowing the customer to select the
the latex stability should be maintained. When latices are appropriate protective colloid for
destabilized, coagulation or agglomeration of the polymer any given application requirement
of stability and rheology. The
particles occurs which can be accompanied with layering of the
narrow specification limits of the
system. This will have a negative impact on the performance of various CELLOSIZE HEC grades
the latex and, therefore, stability is of utmost importance. This offer a highly reproducible and
stability is obtained largely from the stabilizer system used in the reliable product needed for the
production of emulsion polymers.
manufacturing of the latex.
Each application requires a certain rheology of the binder-latex.
In some cases, good flow after application is required in semi-
gloss emulsion paints where brush or roller marks must be leveled
out, while in other cases flow of the formulation after application
must be avoided in some special textile applications. The required
flow properties can usually be obtained by control of particle
size and particle size distribution of the latex. For a given
polymerization process or technique, the particle properties are
strongly influenced by the type and level of the stabilizer system.

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Latex Types
Emulsion polymers are normally
classified based on the monomer(s)
used in their production. The
basic monomer composition
determines primarily the abrasion
resistance, the water adsorption,
and the minimum film forming
temperature (MFFT) of the latex.
Monomers are classified based Table 1: Classification of common latex types
on the hardness of their
homopolymer.
Latex type Main applications Use of HEC
• Monomers producing rubber-
like polymers are called “soft Carboxylated styrene -
monomers.” Examples of these butadiene (SBR) latex Textile, Paper, Adhesives –
include acrylates, butadiene, Vinyl acetate homopolymer Adhesives, Construction +
ethylene and vinyl versatate†.
Vinyl acetate copolymer
• Monomers producing glass-like (with acrylates, vinyl versatate,
polymers are called “hard maleates, fumarates) Paint ++
monomers.” Examples of
these include methacrylates, Methyl methacrylate-acrylate
vinyl acetate, styrene and copolymers Paint +
vinyl chloride. Styrene - acrylics Paint –
To obtain optimal film building Vinyl acetate - ethylene -
properties at a given temperature, vinyl chloride (pressure polymers) Paint ++
combinations of hard and soft
monomers are frequently used. ++ Very frequent use
The soft monomer functions as + Frequent use
an internal plasticizer. If only – Normally not used
hard monomers are used, like in
poly(vinyl acetate) latices, an
external plasticizer like n-butyl
phthalate must be added to
obtain good film building.
Typical industrial latices are pre-
sented in Table 1. Hydroxyethyl
cellulose is extensively used in
the polymerization of vinyl
homopolymers and vinyl
copolymers, including vinyl-
acrylics. To some extent it is
also used in the polymerization
of all-acrylics.

†
Vinyl versatate refers to the vinyl ester
of versatic 10 acid (vinyl neodecanoate,
CAS 5100-52-3)

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Latex Manufacturing Techniques

There are basically four different In the full batch process, the Stabilization of
techniques to produce latices: the catalyst is added when all the Emulsion Polymers
semi-batch process, the full batch ingredients have been charged to
process, the staged adiabatic or the reactor. In this process, all To stabilize the polymer particles
shot process and the continuous monomers are present from the in the continuous aqueous phase,
process. beginning of the polymerization. the particles must be sheathed
The most important industrial The staged adiabatic or shot by a transitional layer which
manufacturing technique is the process is derived from the batch prevents the particles from
semi-batch process. Most of the process in which the monomers agglomerating. Two stabilization
water used in the batch is charged are added in different “shots.” mechanisms can be distinguished:
initially. The stabilizer system, The process is mainly used for a. Electrostatic stabilization: This
buffer, and other miscellaneous redox initiated polymerizations stabilization arises from ionic
components are added and dis- at modest temperature. groups, present at the surface
solved in the water. Subsequently, of the particle, which repel
The continuous process is carried
some initial monomer (5-10%) each other. These ionic groups
out in a series of connected
is charged and the mixture is can be anionic surfactants,
stirred-tank reactors where the
then heated to the reaction (e.g., alkyl or aryl sulfates or
recipe ingredients are supplied
temperature. Initial catalyst sulfonates); anionic end-groups
to the first tank and the final
(radical initiator) is fed in to start (e.g., sulfates from persulfate
product is removed from the
the pre-polymerization (seeding). catalysts or anion-containing
last tank.
After the exothermic reaction has monomers such as carboxylic
ceased, the remaining monomer(s) or sulfonic acid monomers).
is fed to the reactor at such a
rate that the heat generation is b. Steric stabilization: This
controlled. The reaction is con- stabilization arises from bulky
ducted at a constant temperature. groups present at the surface
of the polymer particles. These
There are many variations of the groups can be polymeric
semi-batch process. For instance, surfactants or protective
a catalyst stream and/or a colloids like CELLOSIZE
stabilizer solution may be fed hydroxyethyl cellulose.
along with the monomer. The
monomer can also be added as In most latex-systems, stabilization
an aqueous emulsified monomer- is obtained by a combination
system (emulsion addition technique). of the two basic stabilization
The key process technique involved mechanisms described above.
in the semi-batch process, however, This is achieved by using as
is the delayed monomer addition stabilizer-system a combination of
which permits easy control over anionic and nonionic surfactants
the polymerization rate, polymer- next to a hydrophilic polymer
ization temperature, the copolymer acting as a protective colloid.
composition, particle size and
polymer molecular weight.

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The Role of CELLOSIZE HEC as a Protective Colloid

Figure 1: The structure of hydroxyethyl cellulose (idealized)

O
O OH OH
O
O HO
O O
HO O
HO
O OH
O

To gain some insight into how surfactant-stabilized droplets in The protective colloid action of
CELLOSIZE hydroxyethyl a continuous aqueous phase. CELLOSIZE HEC in the final
cellulose (HEC) acts as a protective Monomers used in emulsion latex is presented in Figure 2.
colloid around the polymer polymerization have a limited The water molecules surrounding
particles, the structure of HEC solubility in water. The total level the polymer particles are “bound”
(Figure 1) should be considered. of surfactants is high enough to onto the surface due to the
Under emulsion polymerization have surfactant micelles in the hydrophilic nature of the HEC
conditions, free radicals are aqueous phase which can solubilize chains. The polar end groups of
produced to initiate the polymer- some monomers. The CELLOSIZE the polymer, polar monomer
ization. These radicals can induce HEC is also present in the segments, as well as polar
free radical sites on the hydroxy- aqueous phase. surfactant species also contribute
ethyl cellulose backbone by in binding part of the aqueous
When the water-soluble initiator
hydrogen abstraction of the acetal phase onto the polymer particles.
is added (Step 2 – latex particle
hydrogen (see Scheme 1). These
nucleation), the polymerization The “bound” water provides a
reactive sites can initiate the
starts in the micelles where transition between the hydrophobic
emulsion polymerization of the
monomer is present. The initiator polymer phase and the “free” or
monomers. By this reaction
also forms radicals with the normal water in the continuous
sequence, the hydroxyethyl
monomers and the protective phase. This sheath or transitional
cellulose becomes chemically
colloid present in the aqueous layer provides the stability to the
bonded onto the formed polymer.
phase. The protective colloid colloidal system. This type of
The protective colloid is in this
radicals migrate to the micelles stabilization is referred to as steric
case firmly and irreversibly grafted
where they are grafted onto the stabilization. The size of the
onto the polymer surface which
growing polymer. The polymeriza- polymer particles, coupled with
gives an optimal protective colloid
tion continues because monomers the transitional layer, largely
action. If this grafting reaction
diffuse continuously from the determines the rheological
does not occur, there is the
large monomer droplets into the properties of the system. For
possibility for the hydroxyethyl
aqueous phase where they are example, the viscosity of the
cellulose chain to adsorb onto the
adsorbed onto the growing polymer system can be considered as a
particle surface. This loosely
particles (Step 3– growth of measure of the balance between
reversible physical adsorption
polymer particles by adsorption of the volume fraction of polymer
leads, however, to an inferior
monomer). The polymerization in particle and “bound” water on
protective colloid action.
each monomer-swollen particle one hand and “free” water on the
To visualize the action of continues until the monomer other. Of course, the “bound” and
CELLOSIZE HEC in an emulsion droplets are depleted and no “free” water are in a state of
polymerization process, the monomer and/or initiator is left dynamic equilibrium.
following description is helpful (Step 4– polymerization in
(see Scheme 2, Harkins’ Theory). monomer-swollen polymer
In the initial polymerization particles).
mixture (see Step 1–initial mixture),
the monomers are present as large

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Scheme 1: Grafting of hydroxyethyl cellulose onto the latex polymer

O
O OH OH
O
O HO
O
O
HO O
HO
O OH
O

Free radical initiator

O
O OH OH
O
O HO
O
O
HO O
HO
O OH
O

CH2=CHX

O
O OH OH
O
O HO
O
O
HO O
HO
O OH
O
• CHX-CH2-(CHX-CH2)n

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Scheme 2: Emulsion polymerization process (Harkins’ Theory)

Surfactant Nascent latex particle

R

Monomer Monomer
droplet droplet

R
Micelle
Protective
colloid Monomer
molecule Radical initiator

Step 1: Initial mixture Step 2: Latex particle nucleation

R R

R
Monomer
droplet Grafted
protective
colloid
R

Step 3: Growth of polymer particles by Step 4: Polymerization in monomer-swollen

adsorption on monomer polymer particles

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Figure 2: Dynamic equilibrium of “bound” and “free” water

Latex particle

Surfactant

Protective colloid

Bound water

Free water

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Chemistry of CELLOSIZE HEC in Emulsion Polymerization

The grafting of hydroxyethyl two possible reaction routes will Acrylic monomers like methyl
cellulose (HEC) onto the polymer normally occur simultaneously; methacrylate, butyl acrylate
particles is not the only reaction however, either grafting or or 2-ethylhexyl acrylate are
occurring during emulsion degradation will be favored very reactive toward radical
polymerization. Next to grafting, depending on the reactivity of intermediates and the grafting
the cellulosic backbone will be the monomer and the chemical reaction route is predominant in
cleaved to some extent, leading structure of the HEC. these systems. The different
to smaller molecular weight reaction paths of hydroxyethyl
Vinylic monomers such as vinyl
HEC fragments.2 cellulose with vinylic versus
acetate or vinyl versatate have a
acrylic systems will also give
A general reaction pattern in relatively low reactivity toward
rise to different chemical and
which degradation and grafting radical intermediates. Therefore,
structural requirements of the
are competitive reactions has HEC radicals generated in the
CELLOSIZE HEC as a
been proposed.3 In Scheme 3, presence of vinylic monomers
protective colloid.
this pattern is presented with will prefer the degradation route.
persulfate as the initiator. The Normally only 15% to 25% of
radical HEC intermediate is the the protective colloid is grafted
common intermediate for both in vinylic polymers.
grafting and degradation. The

Scheme 3: Proposed scheme of HEC reaction chemistry

under standard emulsion polymerization conditions
H O
OR
HO + O = S= O
O
O
O O
OR

Initiator transfer
to protective colloid

OR O
HO O + O =S = O
O
O OH
OR

Degradation of HEC Grafting of monomer

CH2=CHX

CH2-CHX•
OR O OR
HO HO O
O O
O O
OR OR
Degradation Grafting

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Hydroxyethyl Cellulose Characteristics

Because CELLOSIZE hydroxyethyl CELLOSIZE hydroxyethyl WP and QP refers to the
cellulose is used as a chemical cellulose grades for emulsion degree of retardation during
reagent in emulsion polymeriza- polymerization are produced in dissolution in water. Like all
tion, its chemical structure can an MS range of 1.8 to 2.7 and a water-soluble polymers, care
profoundly affect its performance. corresponding DS of 0.8 to 1.4. must be taken to prevent lump
The structure of hydroxyethyl As a general rule, high MS and gel formation when HEC
cellulose is mainly characterized products are recommended for is dissolved in water. If gel or
by molecular weight, molar vinylics, while lower MS lump formation occurs, adverse
substitution (MS) and degree of products are recommended for effects on latex viscosity,
substitution (DS). acrylics. The reason for this is stability and grit formation can
that grades showing a high result. These problems can be
• As already discussed, the most
DS/MS ratio tend to favor the avoided by understanding those
important characteristics for
grafting route upon initiation factors which control the
HEC, in relation to the emulsion
(see Scheme 3). dissolution characteristics of
polymerization process, are the
CELLOSIZE HEC.
ethylene oxide MS and DS or • The molecular weight of
fundamentally the “substitution hydroxyethyl cellulose is related CELLOSIZE HEC is surface-
pattern” of the ethylene oxide to its viscosity development in treated to have a retarded
groups on the cellulose back- aqueous solution. In Table 2, dissolution behavior, and this
bone. The molar substitution is the viscosity limits of the surface-treatment permits the
defined as the average number CELLOSIZE hydroxyethyl powder to disperse easily before
of hydroxyethyl groups per cellulose grades are presented. the process of swelling and
anhydroglucose unit and this The normal protective colloid dissolution starts. The time
number is theoretically unlimited. grades are the lower molecular available to disperse the powder
However, for practical reasons, weight type such as the 09, 3, in the water before the onset
commercial low viscosity grades 300 and 4400 grades. of dissolution is called the
of HEC are usually not produced hydration time. The hydration
All CELLOSIZE hydroxyethyl
above an MS of 3.0. The time is affected by pH and
cellulose grades have very
degree of substitution is defined temperature. QP types are
narrow viscosity limits, or
as the average number of more retarded and show a
molecular weight distributions,
substituted hydroxyl groups substantially longer hydration
necessary to obtain a good
per anhydroglucose unit. This time than WP types. EP types
emulsion polymerization
number is limited to a theoretical have an intermediate hydration
reproducibility.
maximum of 3.0. For the time. High pH and/or high
idealized structure of HEC • Most of the CELLOSIZE HEC temperatures decrease the time
shown in Figure 1, the MS is grades are offered in a WP and between dispersion and the
2.5 and the DS is 1.5. a QP version. The designation onset of dissolution of HEC in
water (the hydration time).

Table 2: Viscosity ranges of CELLOSIZE HEC grades

Grade Concentration, Solution viscosity Spindle rpm Typical molecular
% by weight Brookfield LVT, weight (Mn)
(dry basis) 25°C, mPa•s
QP 09 5 75-150 1 30 65,000
EP 09† 5 90-160 1 30 65,000
QP 3L 5 215-282 2 60 75,000
QP 300 2 300-400 2 60 200,000
EP 300† 2 250-400 2 60 200,000
WP 300 2 300-400 2 60 200,000
QP 4400H 2 4800-6000 4 60 475,000
†
EP 09 and EP 300 are special CELLOSIZE HEC products, developed to enhance grafting in emulsion polymerization of vinylic systems.

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Ideally, CELLOSIZE HEC should CELLOSIZE HEC in

be added under conditions which Polymerization of Vinyl
lead to a good dispersion such as
neutral to acidic pH and/or cold
Ester Monomers
to ambient temperature. Rapid In this part, the performance of
dissolution can be subsequently CELLOSIZE HEC in vinylic
obtained by increasing pH by polymerization is discussed.
the addition of the buffer Typical examples of these latices
(e.g., sodium acetate, sodium are vinyl acetate homopolymers,
bicarbonate, borax) and/or by vinyl acetate - vinyl versatate
raising the temperature. copolymers and vinyl acetate -
vinyl chloride - ethylene pressure
• CELLOSIZE HEC is a water-
terpolymers. As already indicated,
soluble polymer with very
hydroxyethyl cellulose undergoes
narrow specifications on the
preferential degradation in these
amount of water-insolubles
systems and only limited grafting
present in the polymer. Water-
occurs. The severe degradation of
insoluble material can either
hydroxyethyl cellulose is illustrated
be unreacted cellulosic fibers,
in Table 3, where the influence of
overdried HEC or small
CELLOSIZE HEC molecular
gel-like particles. The level of
weight on later viscosity in a
water-insoluble material in
persulfate-initiated standard vinyl
CELLOSIZE HEC is controlled
acetate - vinyl versatate emulsion
very closely to prevent the
polymerization is presented. We
formation of grit (scrap) in the
have found that there is very little
emulsion polymerization
correlation between the viscosity
process.
of the protective colloid and
• CELLOSIZE HEC contains a the final latex viscosity in these
limited amount of residual salt particular systems. For all
and volatiles. The salt present standard HEC grades, similar
in the product is sodium acetate latex viscosities are obtained.
which is a known buffering Under these polymerization
agent in the latex production conditions, CELLOSIZE HEC is
process. The volatiles content degraded to a constant molecular
of all CELLOSIZE HEC weight nearly independent from
grades is kept within tight the starting molecular weight.
specifications during production Because high viscosity grades
and packaging. However, as can lead to process problems, it
hydroxyethyl cellulose is a is usually recommended to use a
hygroscopic powder, it should QP 300 or lower viscosity
be stored in closed containers CELLOSIZE HEC grade.
to prevent adsorption of
moisture. As packaged, the
levels of salt and volatiles
in CELLOSIZE HEC are
controlled to ensure that the
percentage of active polymer
does not vary significantly
between batches.

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Table 3: Influence of molecular weight of CELLOSIZE HEC on the final latex viscosity
in a persulfate initiated vinyl acetate-vinyl versatate emulsion polymerization†

Protective colloid Approximate molecular Average latex viscosity

weight (Mn) of HEC (Brookfield RVT, spindle #6,
50 rpm, 20°C)
CELLOSIZE QP 300 200,000 2500 mPa•s
CELLOSIZE QP 4400H 475,000 2400 mPa•s
CELLOSIZE QP 15000H 850,000 2260 mPa•s
CELLOSIZE QP 30000H 1,000,000 2600 mPa•s
†
For formulation and typical properties, see Section C of the polymerization formulations section, p. 19.

Degradation and grafting reactions acrylic systems, a lower level soluble chain transfer agents like
are of utmost importance to the protective colloid is more 1-dodecanethiol5 can be used.
final rheology and stability of the appropriate (see next section). The effect of triethanolamine
latex. These properties can be (TEA) present in an all-vinylic
• Addition of chain transfer
controlled by various factors: latex is shown in Table 4. An
agents. These additives reduce
increased level of TEA results in
• Level of protective colloid. In the formation of HEC polymer
a higher latex viscosity due to
vinylic polymerizations, it is radicals, thereby suppressing
reduced degradation of HEC.
recommended to use a protec- both the oxidative degradation
tive colloid level of 1% to 3% and the grafting reaction. However, in doing so, care must
by weight relative to monomer. Water-soluble chain transfer be taken not to affect the stability
Increasing the level results in agents like triethanolamine of the emulsion because the
higher latex viscosities and (TEA)4 or 2-mercaptoethanol5, reduction of grafting can increase
better stabilizing effect. For as well as oil- and polymer- the level of grit formation.

Table 4: Influence of triethanolamine on the latex viscosity of a persulfate-initiated

vinyl acetate-vinyl versatate emulsion polymerization††

Protective colloid TEA level (% by weight, Latex viscosity Grit level

based on monomers)
CELLOSIZE QP 300 — 2000 mPa•s 30 ppm
CELLOSIZE QP 300 0.1% 2520 mPa•s 45 ppm
CELLOSIZE QP 300 0.3% 3600 mPa•s 120 ppm
CELLOSIZE QP 300 0.5% 3800 mPa•s 259 ppm
††
For formulation and typical properties, see Section C of the polymerization formulations section, p. 19.

• Process variables. Process The above techniques can be used needed and some of them reduce
variables known to have to increase the viscosity and the grafting efficiency of the
an effect on grafting and stability of all-vinylic latices. HEC, leading to a lower emulsion
degradation of the HEC are5: However, these techniques show stability.
- seed-feed initiator balance serious limitations because special
- monomer feed rates additives, higher products levels
- seed-feed HEC balance or special process techniques are

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A better way to obtain vinylic CELLOSIZE EP 09 in a vinyl colloid has little impact on final
latices, giving a higher latex acetate - vinyl versatate emulsion latex viscosity. However, for
viscosity and improved stability, polymerization are presented. polymerizations conducted with
is to use CELLOSIZE EP 300 The polymerization procedures redox initiation, an important
or CELLOSIZE EP 09 as the are described in Sections C, D effect of the molecular weight
protective colloid. These and E of the polymerization of CELLOSIZE HEC on latex
CELLOSIZE products are formulations section. viscosity is observed. A lower
hydroxyethyl celluloses with a molecular weight HEC leads
Three polymerization initiator
different chemical structure than to a lower latex viscosity
systems have been considered: a
the standard CELLOSIZE types. (CELLOSIZE EP 09 versus
thermal initiation with ammonium
The different hydroxyethyl CELLOSIZE EP 300). Next
persulfate and two redox initiations
substitution pattern leads to a to the structure of the
using the system persulfate -
lower tendency for cleavage of CELLOSIZE HEC protective
metabisulfite and the system
the cellulosic backbone during colloid, this case demonstrates
t-butyl hydroperoxide - sodium
polymerization and also promotes the important influence of the
formaldehyde sulfoxylate (TBHP-
the grafting of the protective initiator system on latex viscosity.
SFS). Under all of these initiator
colloid onto the polymer particles.
systems, CELLOSIZE EP grades
In this way, a firmly bound
offer a higher latex viscosity
protective layer can be formed
compared to the equivalent
around the latex particles,
standard CELLOSIZE QP type.
imparting high viscosity and
As already indicated, in the case
good stability of the emulsion. In
of thermal initiation of vinylic
Table 5, latex viscosities obtained
emulsion polymerization, the
with CELLOSIZE EP 300,
molecular weight of the
CELLOSIZE QP 300 and the
CELLOSIZE HEC protective
lower molecular weight

Table 5: Latex viscosities of vinyl acetate - vinyl versatate copolymer

(Brookfield RVT, spindle 6, 50 rpm, 20°C)

Protective colloid THERMAL REDOX REDOX

ammonium persulfite t-butyl hydroperoxide
persulfate metabisulfate sodium formaldehyde sulfoxylate
CELLOSIZE EP 300 3500 mPa•s 2000 mPa•s > 10,000 mPa•s
CELLOSIZE QP 300 2500 mPa•s 1300 mPa•s 5000 mPa•s
CELLOSIZE EP 09 2500 mPa•s 1000 mPa•s 7000 mPa•s

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CELLOSIZE HEC Polymerization of Acrylic Monomers

In the polymerization of all- • The concentration of hydroxy- CELLOSIZE HEC can also be
acrylic latices such as methyl ethyl cellulose should be used effectively in the preparation
methacrylate - butyl acrylate or minimized. A concentration of vinyl-acrylic copolymers like
2-ethylhexyl acrylate - acrylic maximum of 0.2% by weight vinyl acetate - butyl acrylate or
acid copolymers, hydroxyethyl of CELLOSIZE HEC based on vinyl acetate - 2-ethylhexyl
cellulose undergoes extensive the monomers is recommended. acrylate latices. In these cases, no
grafting reactions. When the straight recommendation on
• Preferably, hydroxyethyl
polymerization conditions are not grade choice of CELLOSIZE
cellulose should be added near
well controlled, the high degree of HEC can be given because their
the end or even after addition
grafting can easily lead to latex properties range between pure
of the monomers to reduce
particle bridging by grafting of vinylic and pure acrylic latices.
excessive grafting.
one HEC chain onto multiple In general, one can say that
polymer particles. This leads to • The addition of chain-transfer increasing the CELLOSIZE HEC
agglomeration of the latex during agents like triethanolamine, concentration will impart higher
polymerization. As discussed 2-mercaptoethanol or viscosities and improve the
above, the grafting reaction of 1-dodecanethiol4,5 during stability. Higher viscosities can
HEC can be controlled in polymerization can effectively also be obtained by using higher
several ways. For acrylic control agglomeration. HEC viscosity grades. In principle,
systems, the following general all CELLOSIZE HEC protective
recommendations can be given: The advantage of using colloid grades can be used in
CELLOSIZE HEC in all-acrylic these systems, but laboratory or
• A low molecular weight latices is to make use of its good pilot plant tests will be required
hydroxyethyl cellulose like stabilizing capacity which allows to assess the optimum stability
CELLOSIZE EP 09 is preferred for a reduction in the total and rheology at an acceptable
to prevent possible particle amount of stabilizer ingredients protective colloid level.
bridging (short chain (surfactants and protective
protective colloid). colloid). This can lead to a
significant reduction of the sur-
• A low molar substitution
factant level, yielding a reduction
hydroxyethyl cellulose is
in both raw material cost and
recommended to reduce
water adsorption of the latex.
grafting tendency. Preferably
the molar substitution should
not be higher than 2.0.

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Water Adsorption of Latex Films

An important property of latices In Figure 3, the water adsorption CELLOSIZE HEC as Part
used in coatings is a reduced of vinyl acetate-vinyl versatate of the Total Stabilizing
tendency to adsorb water. A good latex films is plotted as a function System
water barrier property is required of the molar substitution (MS) of
for exterior coatings to prevent the hydroxyethyl cellulose used as A typical stabilizing system used
surface corrosion to metal and a protective colloid. An important in vinylic emulsion polymeriza-
water damage to wood, and to increase in water adsorption is tion consists of an anionic
improve washability of interior observed when the molar substi- surfactant, a nonionic surfactant
coatings. The level of hydrophilic tution is increased. Although the and a protective colloid. This
components like hydroxyethyl major determining factors in the system will make use of the
cellulose in the production of water adsorption of a latex film synergy between electrostatic and
latices should therefore be are the monomer composition steric stabilization to lead to an
minimized. Next to the level and level of stabilizers, the use of optimal stabilization performance
of hydroxyethyl cellulose, the a hydroxyethyl cellulose with under various conditions. The
chemical structure of HEC is also lower molar substitution is an surfactants play an important
an important factor in the water advantage. role in the stabilization of the
adsorption of a latex film. initial monomer emulsion and
also in the nucleation of the
polymer particles which occurs
in the surfactant micelles. The
Figure 3: Water adsorption of vinyl acetate - vinyl versatate latex† protective colloid plays an
important role in the stabilization
40 of the final latex. In this light,
CELLOSIZE HEC offers good
storage and shear stability as
well as an excellent freeze-thaw
35 stability.
% Water Adsorbed

30

25

20
1.5 2.0 2.5 3.0 3.5
MS of Hydroxyethyl Cellulose
†
Formulation: see Section C of the polymerization formulation section, p.19.

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The components of the stabilizing on latex particle size and viscosity. higher pigment binding capacity,
system have an important influ- With an increasing level of but if the particle size becomes
ence on the particle size of the anionic surfactant, the particle too small, the leveling performance
latex. Both nonionic surfactants size decreases and the latex of the paint will be impaired.
and hydroxyethyl cellulose tend viscosity increases substantially. Latices must therefore have a
to impart a large particle size well defined particle size and
Good control over particle size is
while anionic surfactants tend to this can be obtained by proper
needed in emulsion polymeriza-
induce a small particle size. selection of the stabilizer system.
tion because specific properties of
Latices prepared with hydroxy-
the latex in an application are CELLOSIZE HEC is an important
ethyl cellulose normally have an
related to the particle size. In a aspect of the total stabilizing
average latex particle size above
paint system, for instance, small system.
0.2 microns. The level of anionic
particle size latices will lead to a
surfactants has a high influence

Emulsion Polymerization Formulations

A. Poly(Vinyl Acetate) Latex
A.1 Formulation (percent by weight)
1. Initial aqueous charge:
Deionized water 40.902%
CELLOSIZE QP 4400H 1.0 %
Sodium dodecylbenzene sulfonate (as 6.5% aqueous solution) 3.15 %
Nonylphenol (20) ethoxylate (as 80% aqueous solution) 0.48 %
Sodium bicarbonate 0.074%
Antifoam 0.004%

2. Monomer:
Vinyl acetate 50.8 %

3. Catalyst mixtures:
1. Water 1.0 %
Ammonium persulfate 0.05 %
2. Water 2.0 %
Ammonium persulfate 0.03 %
3. Water 0.5 %
Ammonium persulfate 0.01 %

A.2 Procedure
1. Place the initial aqueous charge in the reactor.
2. Add 7.8% of the vinyl acetate and stir the mixture at 150 rpm.
3. Raise the temperature to 70°C and add catalyst mixture 1.
4. After 10 minutes, add the remaining monomer and catalyst mixture 2 over a period of three hours.
Maintain the temperature of the reaction mixture at 75°C.
5. Add the catalyst mixture 3 and hold the latex at 75°C for one hour (cook-out period).
6. Cool the latex to room temperature.

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A.3 Latex properties

Brookfield RVT viscosity
(50 rpm, spindle 5, 20°C) 2000 to 2500 mPa•s
pH 4.3 to 4.4
Solids content 52%
Grit level (200 mesh) 60 to 75 mg/kg

B. Poly(Vinyl Acetate) Latex

B.1 Formulation (percent by weight)
1. Initial charge:
Deionized water 41.30 %
Sodium bicarbonate 0.05 %
Sodium lauryl sulfate 0.25 %
Octylphenol (40) ethoxylate 1.10 %
CELLOSIZE QP 300 1.20 %

2. Monomer charge:
Vinyl acetate 52.00 %

3. Catalyst charge:
Ammonium persulfate 0.10 %
Deionized water 4.00 %

B.2 Procedure
1. Add 5% of the monomer and 20% of the catalyst charge to the reactor.
2. Prepolymerize the mixture at 75°C for 10 minutes.
3. Add the remaining monomer and catalyst over a period of 3 hours.
4. Postpolymerization at 75°C for one additional hour.

B.3 Latex properties

Brookfield LVT viscosity at 20°C (spindle 3)
At 12 rpm 5500 mPa•s
At 30 rpm 3500 mPa•s
At 60 rpm 3000 mPa•s
pH 4.6 to 4.8
Solids content 54 to 55%
Grit level (200 mesh) 20 to 40 mg/kg

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C. Persulfate Initiated Vinyl Acetate - Vinyl Versatate Copolymer Latex

C.1 Formulation (percent by weight)
1. Initial charge:
Deionized water 42.0 %
CELLOSIZE EP 300 1.0 %
Sodium dodecylbenzene sulfonate (70% active, 10% aqueous solution) 2.8 %
Nonylphenol (20) ethoxylate (80% aqueous solution) 0.6 %
Sodium bicarbonate 0.076%
Antifoam 0.04 %

2. Monomer charge:
Vinyl acetate 34.8 %
Vinyl versatate 15.1 %

3. Initiator 1:
Deionized water 1.0 %
Ammonium persulfate 0.051%

4. Initiator 2:
Deionized water 2.0 %
Ammonium persulfate 0.031%

5. Initiator 3:
Deionized water 0.5 %
Ammonium persulfate 0.011%

C.2 Procedure
1. Charge the reactor with the initial charge. Adjust the reactor temperature control bath to 75°C and
reactor stirrer speed to 150 rpm.
2. Add 7.8% of the monomer charge and adjust the temperature of the bath to 85°C.
3. When the temperature inside the reactor is stabilized, add initiator 1 and control the temperature
of the mixture at 80°C.
4. After prepolymerizing for 10 minutes, start feeding in the remainder of the monomer charge and
initiator 2 over a period of 3 hours.
5. When the addition is completed (after 3 hours), add initiator 3 and maintain the temperature at 80°C for 1 hour.
6. After this additional hour of cook-out, cool down and discharge the reactor.

C.3 Latex properties

Brookfield RVT viscosity
(50 rpm, spindle 5, 20°C) 3000 to 4000 mPa•s
pH 4.2 + 0.1
Solids content 51%
Grit level (200 mesh) 20 to 60 mg/kg

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D. t-Butyl Hydroperoxide - Sodium Formaldehyde Sulfoxylate

Initiated Vinyl Acetate - Vinyl Versatate Copolymer Latex
D.1 Formulation (percent by weight)
1. Initial charge:
Deionized water 41.95%
CELLOSIZE WP 300 1.0 %
Nonylphenol (20) ethoxylate (80% aqueous solution) 0.61%
Sodium dodecylbenzene sulfonate (10% aqueous solution) 2.8 %
Antifoam 0.04%

2. Initiator system:
a. TBHP emulsion
Deionized water 1.72%
t-Butyl hydroperoxide (TBHP) 0.27%
Sodium dodecylbenzene sulfonate 0.01%

b. SFS solution:
Deionized water (pH 5) 1.82%
Sodium formaldehyde sulfoxylate (SFS) 0.18%

3. Monomer mixture:
Vinyl acetate 34.6 %
Vinyl versatate 15.0 %

D.2 Procedure
1. Place the initial charge and 8% of monomer mixture in the reactor.
2. Heat the reactor content to 60°C.
3. Add 25% of the TBHP emulsion (a) and 25% of the SFS solution (b).
4. Hold the reactor at 60°C for 10 minutes.
5. Charge the remaining monomer mixture, TBHP emulsion and SFS solution to the reactor over
a period of 3 hours at 60°C.
6. After the addition of the monomer mixture is complete, hold at 60°C for one hour.
7. Cool down to ambient temperature and discharge reactor.

D.3 Latex properties

Brookfield RVT viscosity
(50 rpm, spindle 5, 20°C) 4500 to 5000 mPa•s
pH 4.8 to 5.2
Solids content 51 to 52%
Grit level (200 mesh) 20 to 35 mg/kg

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E. Persulfate - Metabisulfite Initiated Vinyl Acetate - Vinyl Versatate

Copolymer Latex
E.1 Formulation (percent by weight)
1. Initial charge:
Water 41.975%
CELLOSIZE EP 300 1.0 %
Nonylphenol (20) ethoxylate (80% aqueous solution) 0.61 %
Sodium dodecylbenzene sulfonate (10% aqueous solution) 2.8 %
Antifoam 0.04 %
Sodium bicarbonate 0.075%

2. Initial system:
Initiator 1:
Water 1.72 %
Ammonium persulfate 0.18 %
Initiator 2:
Water 1.72 %
Sodium metabisulfite 0.18 %

3. Monomer mixture:
Vinyl acetate 34.6 %
Vinyl versatate 15.0 %

E.2 Procedure
1. Charge the reactor with the initial charge and 8% of monomer mixture.
2. Heat the reactor content to 60°C.
3. Add 25% of initiator 1 and 25% of initiator 2 over 10 minutes at 60°C.
4. While holding the reactor at 60°C, charge the remaining monomer mixture and
initiators 1 and 2 over a period of 3 hours.
5. After the addition of the monomer mixture and initiators is complete, hold for one hour at 60°C
(cook-out period).
6. Cool to ambient temperature and discharge reactor.

E.3 Latex properties

Brookfield RVT viscosity
(50 rpm, spindle 5, 20°C) 1600 to 2100 mPa•s
pH 4.7 to 4.8
Solids content 50 to 51%
Grit level (200 mesh) 30 to 250 mg/kg

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F. Vinyl Acetate - Vinyl Versatate Latex Binder For Premium Quality Paints†
F.1 Formulation (percent by weight)
1. Initial charge:
Water, demineralized 31.026%
RHODACAL™ DS10 (10% aqueous solution) 1.55 %
Potassium persulfate 0.052%
Borax 0.26 %
Acetic acid 0.103%
CELLOSIZE QP 300 1.03 %

2. Monomer pre-emulsion:
Water, demineralized 6.93 %
DESHCOFIX™ 202 1.03 %
Vinyl acetate 36.19 %
Vinyl versatate 15.51 %

3. Initiator solution:
Water, demineralized 6.20 %
Potassium persulfate 0.119%

F.2 Procedure
1. Heat the initial reactor charge to 60-65°C while flushing the reactor with nitrogen.
2. Add 5% of the monomer pre-emulsion to the reactor and heat to 76°C.
3. Add the remaining monomer pre-emulsion during a period of 3 hours. In the meantime, add the initiator
solution into the reactor by a separate stream for a period of 3 hours and 15 minutes.
4. At the end of the initiator solution addition period, heat the latex to 80°C. Maintain this temperature for
an additional period of 2 hours.

F.3 Latex properties

Brookfield RTV viscosity 2100 mPa•s

pH 4.4
Solids content 53.5 %

The latex is suitable for the manufacture of high quality interior and exterior emulsion paint types. Optionally the vinyl
versatate/vinyl acetate ratio is changed from 70/30 to 75/25 for economy exterior paints, or 80/20 for economy interior
paint types. This can be done without further changes in the latex formulation, but the hydrolytic stability of the
latex will be slightly lower.
The latex shows an excellent overall stability, as can be expected from colloid-stabilized vinyl versatate latex types.
The formulation contains a nonionic surfactant which is NPE-free.
This latex is also characterized by a good water absorption resistance.

†
This formulation has been developed by Resolution Performance Products, previously Shell Chemicals Europe,
which has given us the permission to include it in our literature.

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G. Vinyl Acetate - Butyl Acrylate Latex

G1. Formulation (percent by weight)
1. Initial charge:
Deionized water 40.0 %
Sodium acetate 0.13 %
Nonylphenol (50) ethoxylate 1.6 %
Sodium lauryl sulfate 0.27 %
Ethylene glycol 0.5 %
CELLOSIZE EP 09 1.0 %

2. Monomer charge:
Vinyl acetate 43.3 %
Butyl acrylate 10.0 %

3. Initiator system:
Ammonium persulfate 0.1 %
Deionized water 3.1 %

G.2 Procedure
1. Charge the reactor with the initial charge, add 10% of the monomer charge and adjust the
temperature to 70°C, allowing the monomer to be emulsified for 10 minutes.
2. Add 15% of the initiator and heat the reactor to a temperature of 75°C,
prepolymerization for 10 minutes.
3. The remainder of the monomer charge is added over a period of 3 hours together
with 80% of the initiator.
4. Postpolymerization for 30 minutes with the remaining 5% initiator solution.

G.3 Latex properties

Brookfield RVT viscosity
(50 rpm, spindle 4, 20°C) 1000 to 2000 mPa•s
pH 4.6
Solids content 55%
Grit level (200 mesh) 20 to 30 mg/kg

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H. All-Acrylic Latex
H.1 Formulation (percent by weight)
1. Initial charge:
Deionized water 16.53 %
Triethanolamine 0.4 %

2. Monomer pre-emulsion:
Deionized water 16.8 %
LUTESOL™ A030 2.07 %
EMULPHOR™ OPS 2.07 %
Butyl acrylate 23.1 %
Methyl methacrylate 22.4 %
Methacrylic acid 0.7 %

3. Initiator 1:
Ammonium persulfate 0.11 %
Deionized water 2.82 %

4. Initiator 2:
Sodium formaldehyde sulfoxylate 0.045%
Deionized water 2.815%

5. Protective colloid charge:

CELLOSIZE EP 09 0.14 %
Deionized water 10.0 %

H.2 Procedure
1. Prepare pre-emulsion first: dissolve the surfactants in water and then add the monomers under high shear.
2. Place the initial charge in the reactor and heat to 65°C under nitrogen.
3. Feed pre-emulsion and initiators into the reactor over a period of 3 hours at 65°C.
4. After 2 hours of addition, feed the CELLOSIZE HEC solution during the remaining 1 hour.
5. After all reactants are charged, hold at 65°C for 30 minutes (postpolymerization cook-out).
6. After cooling to room temperature, adjust the pH to 8.0 with ammonium hydroxide.

H.3 Latex properties

Brookfield LVT viscosity
(60 rpm, spindle 3, 20°C) 1000 to 2000 mPa•s
pH 8.0
Solids content 50%
Grit level (200 mesh) 10 to 40 mg/kg

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References
1. “Polymer Latices and their Applications,” edited by K.O. Calvert, Applied Science Publishers, 1982.
2. D. Donescu et al, in “Emulsion Polymerization of Vinyl Acetate,” edited by M.S. El-Aasser and
J.W. Vanderhoff, Applied Science Publishers, p 203-213, 1981.
3. D.H. Craig, in “Water Soluble Polymers, Beauty with Performance,” edited by J.E. Glass, Advances in
Chemistry Series 213, American Chemical Society, Chapter 18, p 351-367, 1986.
4. D.H. Craig, Polym. Mater. Sci. Eng., 51, 172, 1984.
5. K.R. Geddes in “Cellulose Sources and Exploitation, Industrial Utilization, Biotechnology and Physico-
Chemical Properties,” edited by J.F. Kennedy, G.O. Philips and P.A. Williams, Ellis Horwood Series in
Polymer Science and Technology, Chapter 36, p 287-294, 1990.

Glossary
BINDER: See latex.
BOUND WATER: The water layer around a latex particle which is bound onto the surface
of the particle by the hydrophilic molecules (e.g., HEC) present on that
surface. This “bound” water stands in dynamic equilibrium with the
“free” water of the continuous phase.
CHAIN TRANSFER AGENT: A chemical capable of reaction with a radical (growing polymer, HEC
radical) which results in a termination of the existing radical. The chain
transfer agent becomes thereby a radical which can induce further
polymerization on a new site.
COAGULATION: Phenomenon where the latex system becomes a solid mass.
COAGULUM: See grit.
COLLOID: Polymeric substance swellable or soluble in water.
DEGREE OF POLYMERIZATION: The number of monomers per polymer molecule. There is normally a
distribution of the degree of polymerization which is characterized by
an average degree of polymerization.
DEGREE OF SUBSTITUTION: Average number of hydroxyl positions on each anhydroglucose unit that
have been substituted. Abbreviation: DS. Maximum value: 3.
EMULSION: System composed of two liquids, not soluble in each other, where one
acts as a continuous phase in which droplets of the second component
are dispersed. For instance, monomers dispersed in an aqueous system
stabilized by surfactants.
EMULSION POLYMERIZATION: A process in which an emulsion of water-insoluble monomers in water
is converted to a dispersion of polymer particles in water (see latex)
under the influence of a water soluble initiator system.
GRAFTING: The process whereby the hydroxyethyl cellulose becomes chemically
attached onto the latex particle.

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CEL46017_EmulPoly_INTR.qxd 10/25/02 3:23 PM Page 26

GRIT: Large polymer particles formed during or after polymerization which

have to be removed by filtration or otherwise can create application
problems.
HYDRATION TIME: The time after which CELLOSIZE HEC starts to build viscosity after
being introduced into water. This time depends on temperature, water
quality (including pH) and the type of CELLOSIZE HEC.
INITIATOR: A chemical or a chemical system which, under certain temperature
conditions, produces radicals which initiate the polymerization
reaction. Initiators are classified as either thermal initiators [chemicals
such as ammonium persulfate which decompose at elevated tempera-
tures (+80°C) to generate radicals] or redox initiators [chemical
systems such as persulfate/bisulfite reacting under modest temperatures
(40-60°C) to generate radicals].
LATEX: An aqueous dispersion of stabilized polymer particles.
MICELLE: Agglomeration of surfactant molecules in aqueous media. The
hydrophobic moieties of the surfactant molecules are oriented to the
inside of the micelle and the hydrophilic part is oriented outward to the
aqueous phase.
MOLAR SUBSTITUTION: Average number of ethylene oxide molecules that have reacted with
each anhydroglucose unit. Abbreviation: MS.
MONOMER: A molecule capable of undergoing polymerization. It is typically
characterized by an activated carbon-carbon unsaturated bond.
Examples include vinyl acetate, vinyl versatate, 2-ethylhexyl acrylate,
butyl acrylate, methyl methacrylate, styrene, etc.
PROTECTIVE COLLOID: A colloid like HEC capable of stabilizing a latex by steric stabilization
due to its presence at the surface of the polymer particles.
POLYMER: A substance which consists of polymeric molecules. These molecules
are composed of a repetition of one or a few building blocks. These
building blocks or monomers are converted during the polymerization
process to chain formed polymers. If only one building block is used to
produce the polymer, then the polymer is called a homopolymer. If two
or more building blocks are used to produce the polymer, then the
polymer is called a copolymer.
RADICAL: A chemical entity characterized by an atom bearing a lone electron
which makes this chemical entity reactive. Radicals are produced by the
initiator and these radicals react with the monomer to produce
monomer radicals which propagate with other monomers to form a
polymeric molecule.
SURFACTANT: Chemical compound which contains in the same molecule a hydrophilic
(water-liking) and a hydrophobic (water-hating) group.
SYNERESIS: Phenomenon whereby during storage of a latex an aqueous layer is
formed on top of the formulation. The latex can be homogenized easily
by stirring.

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CEL46017_USCVR.qxd 10/25/02 3:12 PM Page 2

For more information, complete literature, and product samples,

you can reach a Dow representative at the following numbers:

From the United States and Canada:

call 1-800-447-4369
fax 1-989-832-1465

In Europe:
toll-free +800 3 694 6367†
call +32 3 450 2240
fax +32 3 450 2815

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call 1-989-832-1560
fax 1-989-832-1465

[Link]

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The Netherlands (00), Norway (00), Portugal (00), Spain (00),
Sweden (00), Switzerland (00) and the United Kingdom (00).

NOTICE: No freedom from any patent owned by Seller or others is to be inferred. Because use conditions and applicable laws may differ from one
location to another and may change with time, Customer is responsible for determining whether products and the information in this document are
appropriate for Customer’s use and for ensuring that Customer’s workplace and disposal practices are in compliance with applicable laws and other
governmental enactments. Seller assumes no obligation or liability for the information in this document. NO WARRANTIES ARE GIVEN; ALL IMPLIED
WARRANTIES OF MERCHANTABILITY OR FITNESS FOR A PARTICULAR PURPOSE ARE EXPRESSLY EXCLUDED.

Published October 2002.

Printed in U.S.A. *Trademark of The Dow Chemical Company Form No. 325-00032-1002 AMS