Pigment & Resin Technology

Large scale emulsion polymerisation

Henry Warson, BSc, PhD, CChem, FRSC
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To cite this document:
Henry Warson, BSc, PhD, CChem, FRSC, (1984),"Large scale emulsion polymerisation", Pigment & Resin Technology, Vol.
13 Iss 7 pp. 4 - 7
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 4 PIGMENT AND RESIN TECHNOLOGY
This article is intended to indicate some of the
problems involved in obtaining latices which have
practical utility. I shall be mainly concerned w i t h
copolymers of vinyl esters and the various acrylic
monomers and also w i t h latices which are applied
as such—not merely polymerised in emulsion as a
convenient method of obtaining the solid polymer in
particulate f o r m .
Practical requirements
(1) The polymerisation must be repeatable w i t h i n
agreed limits in each production batch, in
particular the time-temperature schedule should
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be approximately the same.
(2) The formulation should be a reasonably robust
one, so that minor changes in formulation w i l l
have a zero or negligible effect. This may involve
(a) minor changes in the source of raw
materials.
(b) The human effect—minor variations in
weighing or temperature control should have
no marked effect on the final latex.
In this connection, a specification should be
easily reproducible. Usually this refers to solids
content, viscosity under standard test conditions,
or a viscosity profile under varying shear; p H , free
monomer, and possibly a mechanical stability
test, and freedom from precipitate.
User requirements
Continuing the genera! requirements, it is
essential that a formulation should be suitable for the
requirements of the user. The author often tends to
lose patience w i t h some academic workers who have
heard of no other emulsifier than Na dodecyl sulphate,
carefully purified, and whose obsession for kinetic
equations, useful as they are, contributes relatively
little to a practical art in w h i c h , in its early stages,
empirical experiment far outran any possible theory.
Much of the work of this Institute!, concentrat­
ing as it does on the particle morphology, may not
merely be of more practical use, but may contribute
more significantly to future developments. As an
example the investigations into the location of reactive
groups, such as carboxyl and methylolamide, whether
* This article (not previously published) is based on a lecture
given at Lehigh University, Bethlehem Penn, USA on 11th
October, 1983.
† Emulsion Polymers Institute, Lehigh University.
JULY 1984
Large scale emulsion
polymerisation*
Henry Warson, BSc, PhD, CChem, FRSC
Solihull Chemical Services, Solihull B92 7AF
these tend to be on the surface or are " b u r i e d " has a
very marked effect indeed on the properties of a latex,
e.g. the effect of mild alkalis which would have a
negligible immediate or a very slow long-term effect
on " b u r i e d " carboxyl, but might readily solubilise
surface carboxyl, usually with a marked viscosity
increase.
The following are some effects in a little more
detail:—
(1) Resistance to cycles of freezing and thawing—
a necessity in most climates
It is not possible to go into many details here.
A volume by the current author 1 gives the position
up to 12 years ago. If the second order transition
point Tg is above the freezing point, there is a greater
chance of stability; water soluble polymers such as
polyvinyl alcohol may improve stability as in most,
but not all latices of polyvinyl acetate. A " b u i l t - i n "
charge on the particles themselves tends to impart
freeze-thaw stability. Thus practically it has been
noted that many acrylic ester copolymer latices
intended for emulsion paints and which are based
on an anionic-nonionic blend of emulsifiers acquire
stability if 2% of copolymerised acid is present, but
stability is uncertain if the acid weight percentage
on monomer is reduced to 1½%. W i t h acrylic ester
copolymer latices, methacrylic acid, being more
monomer compatible, is in general preferred to acrylic
acid.
The presence of propylene glycol or higher
alkylene glycols such as hexylene glycol or blends also
helps the problem by reducing the freezing point of
the aqueous phase. They have a plus point too, in that
they are desirable additives to emulsions intended
for paints because of the slower evaporation problems.
(2) Stability to tropical temperatures
In some desert regions drums exposed to
direct sun may reach 6 0 ° C , and local overheating may
be even higher—conditions conducive to some
coagulation. Oven tests with small samples at 60°
may give some qualitative idea, but a 25-or 50-gallon
drum may behave quite differently.
There are several factors against which to
guard; some emulsifiers may slowly hydrolyse, e.g.
C9H16C6H14SO3Na + H2O = C9H19C6H3 + NaHSO 4
If the protective envelope around the particles
begins to hydrolyse, especially as the pH progressives
lowers, coagulation occurs. Some nonionic stabilisers
 JULY 1984 PIGMENT AND RESIN TECHNOLOGY
are not truly soluble at elevated temperature, possibly
above 5 0 ° , and may result in reduced stability. The
change in polymer properties above the Tg may itself
be a major factor as particle-particle collisions may
readily result in coagulation, acting as a nucleus for
further coagulation.
Recently it has been noted that a perfectly
standard vinyl acetate—Veova (VV10)copolymer, in
tropical conditions, developed what can only be
described as a " s p i d e r w e b " w i t h i n the latex on
standing. This latex included a nonionic surfactant
w i t h a low cloud point and hydroxyethyl cellulose.
The cause is still uncertain; it might have been
collapsed foam, possibly including an addition com­
pound between the cellulose ether and the surfactant,
or even a reaction of surplus monomer. It is substan­
tially water insoluble—and analysis seems to indicate
that it is substantially polyvinyl acetate.
Heat transfer
The heat transfer problems are fairly simple
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to understand. The average polymerisation kettle has
a height which is about 1½ times the diameter. The
surface area varies with the diameter; the volume w i t h
the square of the diameter; therefore the cooling
surface becomes progressively less. The heat of poly­
merisation is very appreciable. Various figures have
been published as shown in Table 1.2
Table 1
Heats of polymerisation
kcals per mol
Styrene
16.5
Methyl acrylate 20.2
Acrylic acid 18.5
Methacrylic acid 15.8
Methyl methacrylate 12.9
n-butyl methacrylate 13.5
Vinyl acetate 21.3
Ethylene (gas to solid, 25°) 25.4
There is thus a colossal amount of heat to
remove from a vigorous polymerisation; in addition
a considerable amount of heat must be put into the
reactor to start a polymerisation in many cases,
although some redox procedures avoid this. Thus
adequate cooling is desirable. In some cases cooling
is augmented by reflux, e.g. in some vinyl acetate
polymerisations. I am not generally in favour of this
procedure since it requires re-emulsification of the
condensed vapour, and there may be problems w i t h
vapour polymerisation causing incrustation on the
reactor, and possibly loss of monomer to the atmos­
phere giving rise to some pollution.
In considering temperature, the accuracy of
measuring and of positioning the thermometers,
thermocouple type usually, is important. In a large
reactor, e.g. 25,000L two internal thermometers at
different levels may give an indication of slow mixing
and heat transfer, i.e. a measurement too near the
5
reactor walls may not be a true indication of that
nearer the centre of the reactor. Several thermocouples
may be even more desirable in the jacket. In the
latter the engineering design should be such that the
water is evenly heated, otherwise overshooting, in
both heating and cooling, of the jacket may cause
trouble in proper temperature control, and possibly
the loss of a valuable batch. In a few cases w i t h large
reactors, especially where heavy reflux may occur, the
upper part of the jacket may be held at a lower
temperature than the lower section.
The simplest way to heat a reactor to the
starting temperature and to dissolve emulsifiers is by
the injection of live clean steam. The temperature of
the cold water is known, say 2 0 ° , likewise the latent
heat of steam, about 540 cals, and it is a simple
matter to calculate the amount of condensed water to
bring the temperature to the required level.
In some reactions, in particular the polymerisa­
tion of vinyl acetate and copolymers when the reaction
has started, in a kettle which is 1,000L or more,
control has been effected by emptying the jacket com­
pletely and regulating the reaction w i t h slowly rising
temperature by the rate of addition of monomer. In
larger reactors a heat interchanger through which the
reaction mixture is pumped has been used, but this
assumes that the polymerising emulsion is stable and
is unlikely to form coagulum.
This type of regulation is also possible in
various redox systems where both redox initiators and
parts of the monomers are added in batches. More
difficulty arises in closed reactor systems where in
most cases all the monomer is added at the start, e.g.
most polymerisations involving vinyl chloride or
butadiene, in which case temperature control is of
major importance in ensuring a reaction that does
not become uncontrollable.
Stirring conditions
The mechanism of emulsion polymerisation is
complex, and there are many papers on the subject.
One especially useful paper may be quoted. 3 Emulsion
polymerisation varies, of course, w i t h the nature of the
monomers and the system as a whole. A significant
feature, however, is the fact that for a large part of the
polymerisation, polymer swollen w i t h monomer can be
considered as a viscous liquid, and in presence of an
emulsifier can be divided into smaller particles by the
energy of agitation alone, a simple mechanical fact
often forgotten by theoreticians.
There are two major problems involved in
scale-up, these are particle size and stirring condi­
tions.
The particle size of a latex, whilst partly
controlled by the nature of the emulsifier and the
monomers as well as temperature, has a much greater
dependence on stirring conditions than is usually
accepted. This is not particularly easy to show on a
laboratory scale, but even the change in stirrer type
 6 PIGMENT AND RESIN TECHNOLOGY
and stirring conditions on a 25L scale is likely to show
significant differences, and this w i l l also apply to
vicosity variations. In general very fast stirring of a
potentially viscous water phase, e.g. based on part-
hydrolysed polyvinyl acetate which is used as a latex
stabiliser may reduce viscosity by shearing the
hydrated layer on the surface of the particles. This
was known over 4 0 years ago in the product of the
" M o w i l i t h " latices in Germany.
The control of particle size w i t h i n desired
limits is essential in a commercial product. Too small
a particle may be objectionable in some cases, e.g.
certain adhesive formulations where it is undesirable
that the particles should soak into the capillaries of a
subtrate such as w o o d . Whilst, as mentioned pre­
viously, the emulsifier system may to some degree
govern particle size, there are many complications to
be overcome. The efficiency of a stirrer depends to
some degree on the distance of each individual particle
at any one moment from the stirrer. Furthermore,
whilst the rpm may be the same it w i l l be readily
seen that the peripheral speeds of the stirrer w i l l
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increase w i t h the diameter of the vessel. This w i l l ,
of course, increase the energy required considerably
more than the increase in reactor size, and w i l l also
increase the coagulation risk by excessive shear.
Nevertheless w i t h a stirrer, usually of the turbine type
which is ½ to ⅔ the diameter of the reactor, there may
be less agitation nearer the walls of the reactor. This
varies very markedly w i t h the viscosity of the poly­
merising emulsion and its thixotropic characteristics.
In practice a compromise is achieved. I have found
practically that between a pilot plant and large scale
reactors, the rpm must be reduced somewhere between
the third and fourth roots of the increase in speed.
This implies practically that on scaling from 25L to
2,500L, if the initial speed is 150 rpm, that on the
larger scale w i l l be between 15 and about 48 rpm.
Whilst a single stirrer w i l l be adequate for small plant,
probably up to 1,000L w i t h larger installations, extra
stirrers are necessary at intervals, and a 25-75,000L
reactor w o u l d need two or three extra stirrers. These
are often simple bars, but some pitch of the blades
may be desirable. There is likely to be a minor problem
of surface splash during any form of gradual addition
reaction, especially via the surface. This may cause
some incrustation on the sides, which if detached may
cause some troublesome coagulum and act as a
nucleus for further coagulum.
Regarding the inclusion of baffles on the walls,
I have never been convinced that they are really useful
in assisting agitation—it is more than probable that
they give a " d e a d " surface for formation of coagulum.
W i t h the very viscous latices, of the order of
50P, anchor stirrers are sometimes used in a vessel
which tends to be hemispherical. These are the types
mentioned in the reports on German factories pub­
lished in the late nineteen forties. 4 For the normal
types of latex prepared today, they are highly unsatis­
JULY 1984
factory, liable to cause excessive shear near the
reactor walls, and giving unsatisfactory turbulence
towards the centre, unless accompanied by bars to aid
stirring. There is also a risk of " d e a d space" under­
neath the base of the anchor.
Effects of temperature variation
The adequate control of temperature is one
of the major problems in large scale operation.
Polymers and copolymers of vinyl acetate may be
taken as examples since possibly they show some of
the major variations. The azeotrope of vinyl acetate
and water is 66½°; however, as polymer absorbs
monomer, the temperature of reflux increases. At 8 0 ° ,
polyvinyl acetate w i l l hold about 20° of its weight of
monomer without reflux. Thus control by reflux has
no real meaning since absence of reflux may denote
anything from zero to 2 0 % free monomer at 8 0 ° , and
below this temperature even bigger variations are
possible.
It is usual in the standard delayed addition
of monomer to add about 5-10% of monomer at the
start, and to add monomer over about four hours, w i t h
a temperature profile which may be constant over
about 2° from 74°-76° or possibly a higher range,
thence a gradual rise to about 9 0 ° , where temperature
is maintained for about half an hour.
Sometimes it is necessary to add a gradual
feed of initiator, usually sodium or ammonium persul­
phate, at a total usually of not more than 0 . 1 % of
monomer, to maintain the reaction. There are some
side reactions which consume initiator in slightly
irregular fashion and some skill is needed to control
the extra addition, for which a plant operator must
be trained. A t the same time, if a standard profile
is not followed there may be marked differences in the
final properties. Such items as viscosity in particular
may vary, and possibly mechanical stability. Whilst
this is particularly noteworthy when polyvinyl alcohol
is used as a stabiliser, particularly because of its
tendency to act as a graft base, it has been quite
noticeable w i t h other systems, e.g. w i t h latices mainly
intended for emulsion paint with hydroxyethyl cellulose
as stabiliser, and anionic/nonionic stabilisers. I have
known this to effect both latex viscosity, particle
size, and the formation of coagulum after filtration
and storage in drums.
Formulation variations and their control
Many formulations involve copolymers. We
therefore have the additional problem of ensuring
that the copolymerisation follows the same pattern
every time. It may not necessarily be desirable to have
an even copolymerisation. A n uneven copolymerisa­
tion may be desirable, w i t h alkali thickenable latices,
e.g. of vinyl acetate, ethyl acrylate and acrylic acid.
It may also be preferable with latices intended for
sound and vibration damping where it is desirable to
have the Tg, the point at which energy absorption
 JULY 1984 PIGMENT AND RESIN TECHNOLOGY
takes place should be spread over a temperature
range of 15°-20° to account for normal variations. 5
Many early literature claims, particularly on
the application side, ignored this problem of uneven
copolymerisation, with the result therefore that
statements have been made in technical journals that
butyl acrylate is a superior internal plasticiser to
2-ethylhexyl acrylate, which is, of course, incorrect.
The r1:r2 ratios of an acrylate ester and vinyl acetate
are of the order of 6 0 - 9 0 : 1 . This is modified by the
much greater solubility of vinyl acetate in water, and
probably the increased solubility of growing aqueous
radicals which are substantially vinyl acetate. If how-
ever monomers are added in a gradual addition
without assuring, preferably by a GLC test, that there
is no build up of the slower polymerising monomer,
the final product may consist of a substantial per-
centage of almost pure homopolymer of vinyl acetate
which is incompatible w i t h the high acrylic copolymer
produced at an early stage. There w i l l thus be a
product, which although giving an apparently clear
film w i l l have a much higher modulus than an even
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copolymer. This has been known in industry for about
25 years. Where reactions are performed under
pressure, extra care is needed. It may be best in some
diene copolymerisations to add one or more of the
monomers throughout the reaction, especially where
carboxylated types are involved. Pressure polymerisa-
tions are necessary with vinyl chloride copolymerisa-
tions, where it is usually necessary to stop short as the
final polymer interferes w i t h desirable properties
because of molecular weight changes.
W i t h ethylene copolymerisations, again careful
control is necessary—there are some complications
because of analysis difficulties w i t h the final copoly-
mer; pressures should be controlled and some partial
solvent, e.g. ter-butanol, for ethylene may be a useful
additive.
Raw material variations
It is only possible to mention this subject
briefly, but marked variations have been observed on
many occasions w i t h raw materials of nominally the
same specification, but which may behave very
differently in practice. Sometimes trace impurities
may retard or inhibit polymerisation, particularly of
the more sensitive monomers such as vinyl acetate.
Crontonic acid has been known to have shown a
marked batch to batch variation, although the nature
of the inhibiting chemical could not be determined.
The problem is greatest w i t h polymeric materials, and
in particular polyvinyl alcohol (partially hydrolysed
polyvinyl acetate). A t least ten types of variation have
been quoted." In addition the possibility exists that the
hydroxyl groups of polyvinyl alcohol may take part in
a redox reaction.
As water consists of about half of a latex, its
variation in properties are rather surprisingly ignored.
7
The practice of using filtered river water, prevalent in
some developing countries, is not to be commended,
even if passed through a water softener. Some ions
may still be present, whilst biological impurities may
have quite a marked, and probably undesirable effect.
Drinking water grade is desirable. Where " s o a p " type
emulsifiers are used, water softening is preferable, but
in most cases where stabilisation is by sulphate/
sulphonate emulsifiers, or nonionic surfactants it is
necessary.
Subsequent treatments
A latex must not merely be stable and have
all the indicated properties in its own right, but it
must withstand any compounding that may be neces-
sary in application. Emulsion paints are the simplest
example. Exceptionally pigments may be ground
directly into an emulsion where there is a surfeit of
stabiliser. More usually a pigment is ground separately
but the interactions between pigment paste and
emulsifier may cause precipitation, e.g. Ca+ ions may
react w i t h polymer carboxyl and cause gradual thicken-
ing; in other cases a thickener may be absorbed so
strongly on the pigment that there is an unaccountable
viscosity drop. This occurs, e.g. when a vinyl acetate
copolymer is stabilised with amylopection dextrin.
The latex properties resemble those of an HEC stabil-
ised latex; on adding rutile TiO 2 to a dextrin stabilised
latex all viscosity is lost and the paint is too thin for
use without further thickener. This is because TiO 2
absorbs dextrin strongly without it having any dispers-
ing effect. External plasticisers may need heat treat-
ment to ensure that they enter the polymer particles;
addition of solvents, often in the adhesive industry,
must be treated w i t h caution, particularly if they are
partly or wholly water soluble. I hardly need mention
the importance of pH stability under specific condi-
tions. There are numerous other examples, e.g. in
adhesive compounding, paper coating and cement
additives inter alia.
Conclusions
This article must necessarily summarise only
some of the factors involved in practical polymerisa-
tions. It may be concluded by the starting quotation
in a publication by the current author " V i n y l acetate
is not polymerised commercially in dilatometers". 7
References
1 Warson, H., Applications of Synthetic Resin Emulsions,
Ernest Benn, London, 1972, pp 137-40.
2 Schildknecht, C. E., Vinyl & Related Polymers, John Wiley,
N.Y., 1952, p 245.
3 Hicks, R. W., Gates, L. E. Chem Eng. Progress, 1975 71 (8)
74-7.
4 Dunlop, R. D., F.I.A.T. 1102, 1947, p 4.
5 Warson, H., see ref. 1, pp 979-84.
6 Warson, H., in Etylene and Its Industrial Derivatives, Ed.
Miller, S. A. Ernest Benn, London, 1969, pp 980-2.
7 Warson H., In Emulsion Polymerisation of Vinyl Acetate,
Ed. El-Aaser, M. S. Vanderhoff, J. W., Applied Science
Publishers, 1981, p 1.