1158 Ind. Eng. Chem. Res.

1997, 36, 1158-1162

Why Are Polymerization Reactors Special?

Brian W. Brooks*
Department of Chemical Engineering, Loughborough University,
Loughborough, Leicestershire LE11 3TU, U.K.

Unlike many other products from the chemical industries, polymer molecules cannot easily be
separated from each other. Therefore, the material has to be produced with the required
specification at the reactor stage. The correct choice of reaction model is crucial for the prediction
of reactor behavior. Allowance must be made for the effects of high viscosities on both heat
transfer and reaction kinetics. In suspension polymerization, drop sizes, drop mixing, and
sedimentation all require particular attention. With emulsion polymerization, a change in the
reactor start-up procedure can lead to changes in dynamic behavior, monomer conversion, and
product quality. If we can learn from nature, polymerization reactors may take new forms in
the future.

Introduction
Chemical reactors can take many forms, but in
principle, most of them can be assigned to three
groups: batch reactors, continuous-flow reactors with-
out back-mixing, and continuous-flow reactors with
back-mixing. Simplistic diagrammatic representations
of these reactor types are shown in Figure 1. These
representations indicate the desired mixing conditions;
they do not show the physical manipulations which may
be necessary to achieve these conditions. Some mul-
tiphase reactors do not fit simply into these groups,
especially if mixing is confined to one phase only.
Reactors can take a wide variety of shapes and sizes
from small pipes to large fluidized beds. In each case,
the size, residence time, mixing patterns, and temper-
ature profiles are all important. It should be realized
that, although a tube may be a simple piece of equip-
ment, the events occurring inside the tube may be far
from simple.
Chemical reactions of industrial interest often proceed
via complex reaction schemes, and the distribution of
products depends on the nature of the mixing pattern
in the reactor. Usually, the reaction products must be
separated into distinct components. The success of a
separation process depends on the differences, in the
chemical or physical properties, between the product
components. A wide variety of separation processes can
be used including distillation, extraction, absorption,
adsorption, crystallization, membrane methods, and
filtration.
Polymeric Products
Chemical products such as ammonia, benzene, phe-
nol, or sodium carbonate have a unique and distinct
composition. They can be separated from process
streams and obtained in pure form. In contrast, the
constituent molecules of a polymer product have a
variety of sizes. For example, the term poly(ethylene
oxide) may be used to describe s[-CH2CH2O]ns but in
reality, there is not a single species present but a range
of polymers which have different molecular weights. The
physical properties which determine the usefulness of
the polymer mixture depend on the range of values for
n. The chemical differences between the various mo-
lecular sizes are not sufficiently wide to permit easy
* Telephone: +44(0)1509 222510. Fax: +44(0)1509 223923.
E-mail: B.W.Brooks@Lboro.ac.uk.
S0888-5885(96)00375-2 CCC: $14.00
Figure 1. Basic types of chemical reactors.
fractionation; also, most polymers are involatile and
cannot be fractionated by distillation. Therefore, the
product mix must be correct at the reaction stage; i.e.,
the required molecular weight distribution must be
obtained in the reactor. There is little scope for chang-
ing the size range afterwards.
Polymerization reactions also have unusual physical
features which pose problems for reactor design. Mono-
mer feeds usually have a relatively low viscosity, but
the polymer-containing fluids which are produced in the
reactors often have very high viscosities. This imposes
severe constraints on the choice of mixing pattern and
limits the extent of heat transfer (Carloff et al., 1994).
Restricted heat transfer is particularly important when,
as often happens, the polymerization is exothermic.
Polymerization Reactors
Reactors of various types, mentioned above, are used
for polymer manufacture, but it can be seen that
polymerization reactors have a number of special fea-
tures which affect design choices. Detailed information
about all the constituent chemical and physical steps
in a reaction process is often unavailable. Therefore,
in order to design a reactor successfully, it is necessary
to construct serviceable models which account for
important reaction phenomena. A model can take many
forms depending on the center of interest. For a
chemical reactor, a working model should take into
account chemical kinetics, fluid mixing, changes in
physical properties, and temperature variations (So-
roush and Kravaris, 1993). In this paper, special
features of polymerization reactors will be discussed
with particular reference to free-radical polymerization.
Choosing acceptable simplifications in a model is not
always easy. This can be illustrated by considering the
dynamic behavior of a continuous-flow reactor which is
used for the first stage in a styrene polymerization
process. During this process, changes in density and
specific heat are relatively small, but if they are
© 1997 American Chemical Society

Figure 2. Styrene polymerization in a stirred-flow reactor. (A)
No allowance for changes in properties. (B) Allowance for changes
in properties.
Figure 3. Instantaneous molecular weight distribution of poly-
(methyl methacrylate) at high viscosity. (A) Experimental results.
(B) “Ideal model”. (C) New model.
neglected, then the predicted variation of temperature
with time takes a somewhat spectacular form as shown
by plot A in Figure 2 (Brooks, 1981). A real reactor
would become unstable well before the first temperature
peak was reached; in effect, our model is telling us that
this process is not feasible. However, if the model is
modified to allow for the real (but small) changes in
density and specific heat, then the prediction is changed
dramatically, as shown by plot B in Figure 2. This
modified prediction corresponds accurately with reality.
Fortunately, in this particular case, workers in industry
discovered experimentally that the process is safe long
before anyone diverted them with inadequate models.
Viscosity Effects
The high viscosity which is often encountered in
polymerizing fluids not only inhibits mixing and im-
pedes heat transfer but also affects the reaction kinetics.
Fast reaction steps can become “diffusion controlled”
(Stickler et al., 1984). To allow for this, many workers
have devised models for molecular diffusion which can
be used to correlate changes in rate coefficients and to
predict kinetic behavior (Ray et al., 1995; Vivaldolima
et al., 1994; Soh and Sundberg, 1982). These changes
in the rate coefficients affect both the overall polymer-
ization rate and also the molecular weight distribution
of the polymer product. Therefore, it is important that
models account for both of these effects simultaneously.
Figure 3 shows the results for the instantaneous
polymerization of methyl methacrylate at high viscosity
(Bogunjoko and Brooks, 1983a). It can be seen that the
molecular weight distribution for the polymer is bimo-
dal., Models which assume a variable, but single, value
for the chain-termination rate coefficient all predict an
instantaneous molecular weight distribution which is
monomodal, as shown by plot B in Figure 3. Changing
values for key parameters alters the location of curve
B but not the shape.
By constructing a model which distinguishes between
different sizes of growing polymer molecules, even in a
very crude fashion, the essential features of the molec-
ular weight distribution can be reproduced. This is
shown by plot C in Figure 3. Thus, a model which is
not highly detailed can be sufficient for predicting the
Ind. Eng. Chem. Res., Vol. 36, No. 4, 1997 1159
Figure 4. Changes in average drop size at low polymer content.
performance of a polymerization reactor (the model also
predicts reaction kinetics accurately without further
parameter changes (Bogunjoko and Brooks, 1983b)). To
test this model, it is necessary to devise a method for
distinguishing and characterizing a newly-formed poly-
mer in a reaction fluid which already has a substantial
polymer content.
Suspension Polymerization
In suspension polymerization, the problems with heat
transfer are avoided by dispersing monomer drops in a
continuous aqueous phase before polymerization begins.
Heat transfer, from the small drops to the aqueous
phase and from the aqueous phase to the reactor
surroundings, is rapid. Therefore, control of the reactor
temperature is better than that which is possible in bulk
polymerization. Drop size distribution, which depends
on reactor geometry and stirrer speed, is important
because it determines the size distribution of the
finished polymer particles. The presence of a drop-
stabilizing agent in the continuous phase is usually
necessary. If the product is to be used in particulate
form, then the particle size distribution is part of the
product specification. It might be expected that, for a
given monomer system, the relationships between rate
coefficients and physical conditions, which are observed
in bulk polymerization, should apply to suspension
polymerization (Kalfas and Ray, 1993).
Most studies of drop size distribution, in liquid-liquid
dispersions, have been concerned with liquids of low
viscosity with attention focused on drop size distribution
in the steady state. In these cases, the time required
to achieve a steady state is often very short and is not
considered to be important. However, when the drops
are highly viscous or when their physical properties
change during the process, some considerable time may
be required to achieve a stable drop size distribution.
This is the case with suspension polymerization (Lange
and Reichert, 1981). Even when the fluid viscosity is
low, Figure 4 shows that an appreciable time is required
to achieve a stable drop size distribution (Brooks and
Richmond, 1994); this could be a significant fraction of
the reaction time. Drop sizes which are predicted by
“classical” relationships with the Weber number are not
always obtained in practice (Zerfa and Brooks, 1996).
At higher conversions, viscosity increases and changes
in the drop size distribution require even more time.
The drop size distribution is obtained by breakage and
coalescence of drops. If these processes, which are not
well understood (Chatzi and Kiparissides, 1995), become
slow, as the viscosity increases, then the mixing of any
new ingredient by postaddition to the reactor will not
be effective. The presence of drop stabilizers also
inhibits drop coalescence and mixing (Zerfa et al., 1995).
Also, it is important to consider the possibility of phase
inversion (in which the drop phase becomes continuous
1160 Ind. Eng. Chem. Res., Vol. 36, No. 4, 1997
Figure 5. Dangerous consequences of density changes in suspen-
sion polymerization as density and viscosity increase.
Figure 6. Schematic representation of dispersed phases in
emulsion polymerization.
and the phase which is initially continuous is turned
into drops (Brooks and Richmond, 1991)).
The drop density often increases during suspension
polymerization. This increase may be small (say 10%),
but it is important because it can have dangerous
consequences. Figure 5 shows an example in which the
monomer is less dense than hot water but the polymer
is more dense than hot water. If the agitator design is
not good, the polymerizing drops sediment and may
coalesce. Heat transfer from the sedimented mass is
much slower than heat transfer from the small drops,
and since the reaction is usually exothermic, the tem-
perature inside the polymerizing fluid will rise. Rapid
vaporization of monomer can then occur, leading to
disaster. The high potential for thermal runaway is one
feature of polymerization reactors which cannot be
ignored (Barton and Nolan, 1984; Nemeth and Thyrion,
1995).
Emulsion Polymerization
In emulsion polymerization, monomer drops are
dispersed in water but an assembly of very small
polymer particles is generated in the aqueous phase as
shown in Figure 6. This is not to scale; drop diameters
range between 0.05 and 2.0 mm, whereas the particle
diameters are usually less than 0.001 mm. The pres-
ence of emulsifiers is required, and the essential chem-
istry occurs mostly in the polymer particles and in the
aqueous phase. In conventional emulsion polymeriza-
tion, virtually no reaction occurs in the monomer drops
which act as reservoirs. However, very small monomer
drops can be transformed into polymer particles (Vander-
hoff, 1993). In addition to the physical advantages of
suspension polymerization, the mechanism of emulsion
polymerization often allows the simultaneous occur-
rence of high polymerization rate and high polymer
molecular weight. The final reaction product is a
dispersion of very small polymer particles which may
be used directly (e.g., for surface coatings or adhesives).
In emulsion polymerization, particle nucleation and
particle growth are important steps which are not fully
understood (Giannetti, 1993). This lack of understand-
ing does not present an insurmountable problem with
batch reactors because particle nucleation is usually
completed early in the polymerization so that particle
Figure 7. Conversion changes with time for the isothermal
emulsion polymerization of styrene in a continuous-flow reactor.
nucleation and particle growth are virtually consecutive
rate processes. However, continuous-flow reactors usu-
ally require agitation, and as a result of back-mixing,
particle nucleation and particle growth become simul-
taneous processes. The particle size distribution now
becomes wide so that the latex which is produced is
significantly different from that obtained with a batch
reactor (which gives a narrow particle size distribution).
Particle nucleation now requires characterization. If a
tubular flow reactor is used, then back-mixing can be
restricted and a narrow particle size distribution is
obtained (Paquet and Ray, 1994).
Early work predicted that, even when feed streams
to a continuous-flow back-mixed emulsion polymeriza-
tion reactor were steady and the reactor temperature
was constant, both the monomer conversion and the
particle concentration in the reactor could oscillate with
time during the reaction. Even so, some workers
believed that any oscillatory behavior was solely the
result of inadequate temperature control and that the
conversion would stabilize quickly (after the initial
stages when particles were being generated). Early
experimental results were deceptive. Figure 7A shows
the results obtained from regular sampling of a reactor
effluent. It can be seen that, after the start-up peak,
the conversion appears to become steady. Figure 7B
shows the “obvious” line to draw through the points, but
is this correct?
If, in addition to the regular samples, data points are
acquired at other times, then a different picture emerges
(Brooks et al., 1978). Figure 7C shows data in addition

Figure 8. Effect of start-up conditions for the emulsion polym-
erization of methyl methacrylate in a continuous-flow reactor.
Identical feed streams with small differences in start-up condi-
tions.
Figure 9. Start-up effects in the emulsion polymerization of
styrene in a continuous-flow reactor. Identical feed streams with
small differences in start-up conditions.
to the results that would have been gained from regular
measurements. Clearly, the estimate of the best line
through the original points must be revised, as shown
in Figure 7D. In this example, the oscillations are
relatively small and may eventually die out. In other
cases, substantial oscillations are sustained throughout
the process even though the reactor is isothermal and
the feed rate is steady (Greene and Poehlein, 1975).
The long-term behavior of a continuous-flow emulsion
polymerization reactor depends noticeably on the way
in which the reactor operation is started up (Brooks and
Raman, 1987). Figure 8 shows the results of two
experiments in which monomer conversion is oscillating
around quite different values. In both cases, the feed
streams and temperature are identical; the only differ-
ence is in the order in which the reactants were first
introduced to the reactor. These differences in conver-
sion are accompanied by differences in particle size
distribution. In effect, two different products are being
made from identical feed streams. Even when condi-
tions are arranged so that conversion does become
steady, bifurcation may still be observed; also, the
particle sizes may continue to change. Figure 9 shows
that, for identical reactor conditions (using identical feed
streams), a small change in start-up procedure leads to
two different (but almost steady) conversions (Baddar
and Brooks, 1984). However, it can be seen that, in one
case, the particle size is increasing rapidly (as nucle-
ation almost ceases). In spite of a stable conversion,
catastrophic coagulation can be expected to occur very
late in this process, when nucleation re-commences
(Kiparissides et al., 1980; Brooks and Raman, 1987). Not
only is the “wrong” product formed but the physical
properties of the emulsion will change so that the
emulsion will no longer flow out of the reactor (Brooks
and Raman, 1987). Ten tons of immobile gel inside a
reactor is most unwelcome. Oscillatory behavior can be
avoided by using a prereactor as a continuous seeder
(Penlidis et al., 1989).
Ind. Eng. Chem. Res., Vol. 36, No. 4, 1997 1161
Table 1. Relative Strengths of Fibersa
material tenacity (g/denier)
nylon 6,6 5.2
polyester 5.1
poly(acrylonitrile) 3.2
steel 3.5
spider silk (drag line) 7.8
a Data from Lucas, 1964.
Often, a number of monomers are polymerized simul-
taneously to make copolymers. Then, product composi-
tion becomes important. In these circumstances, a
semibatch reactor may be chosen. Here, there is an in-
flow but no out-flow so that the volume of the reactor
contents changes with time. With reactors of this type,
particle nucleation can be manipulated and polymer
composition can be controlled. The order in which the
reaction ingredients are added is now crucial because
it determines the nature of the final product. New ways
of describing semibatch polymerization reactors are now
being developed (Li and Brooks, 1993; Powell and
Brooks, 1995).
The Future
Products of the polymer industry are becoming more
complex with precise quality requirements. Reactor
processes are becoming more effective as our under-
standing improves. However, although substantial
advances have been made, the range of our processes
is still narrow. Most polymerization reactions require
sensitive catalysts, very clean conditions, controlled
monomer feed ratios, effective mixing, and precise
temperatures. Often, large cumbersome equipment and
toxic feedstocks must be used. Perhaps we should ask
if anything can be learned from nature.
All around us, many green plants are quietly copoly-
merizing carbon dioxide and water to make polymeric
materials (cellulose and carbohydrates). How would we
set about copolymerizing carbon dioxide and water (just
supposing that we knew how to do it)? Judging by
existing technology, extensive apparatus with large
compressors, sensitive catalysts, and a variety of control
equipment would be required. But green plants work
at atmospheric temperature and pressure with a so-
phisticated (and effective) catalyst which copes with a
highly contaminated feedstock (dirty air and water) and
functions in all weathers. Trees produce a variety of
“grades” of timber with complex polymeric structures
(already “laminated”) having very useful physical prop-
erties; some trees produce latex rubber. Although latex
rubber can be made in polymerization reactors, it does
not match the material from the rubber tree.
The garden spider (Araneus diadematus) produces
webs from very fine silk. The silk is composed of a
variety of polyamides (proteins), and the fiber properties
are changed to fulfill many functions (Vollrath and
Edmonds, 1989). Five types of silk have been identified,
each with a controlled composition (Lucas, 1964). From
the precursor materials, spiders produce their silk with
much-envied ease at atmospheric temperature. In spite
of high humidity, they manage to displace reaction
equilibrium very rapidly, achieving high conversion to
polymer before vaporization of volatiles occurs. In the
web, the drag lines are very strong. Table 1 shows that
spider silk is stronger than many man-made polymers.
Some specialized man-made fibers are as strong as
spider silk, but the extension at break is much lower.
Although it might be claimed that spiders have been
1162 Ind. Eng. Chem. Res., Vol. 36, No. 4, 1997
“developing their processes” for a few million years, we
must ask if our processes will eventually match those
of the spider.
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Received for review July 2, 1996
Revised manuscript received October 16, 1996
Accepted October 16, 1996X
IE960375M
X Abstract published in Advance ACS Abstracts, February
15, 1997.