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Polymerization Processes
Archie E. Hamielec, Institute for Polymer Production Technology, Department of Chemical Engineering,
McMaster University, Hamilton, Ontario, L8S 4L7, Canada
Hidetaka Tobita, Department of Materials Science and Engineering, Fukui University, Fukui, 910, Japan
3.3.6. Process Variables, Reactor Dy- 3.3.6.1.2. Monomer Coupling Without Ter-
namics/ Stability, On-Line Moni- mination Plug Flow and Batch Re-
toring and Control . . . . . . . . . 97 actors (CPFR/BR) . . . . . . . . . 103
3.3.6.1. Influence of Reactor Type and 3.3.6.1.3. Polymer Coupling . . . . . . . . . 104
Configuration on Molecular Mass 3.3.6.1.4. Copolymerization . . . . . . . . . . 107
and Copolymer Composition Dis-
3.3.6.1.5. Long-Chain Branching and Cross-
tributions, and on Long-Chain
Linking . . . . . . . . . . . . . . . . 109
Branching and Cross-Linking . . 97
3.3.6.1.1. Monomer Coupling with Bimo- 3.3.6.2. Reactor Dynamics and Stability . 111
lecular Termination Plug Flow and 3.3.6.3. On-Line Monitoring and Control 112
Batch Reactors (CPFR/BR) . . . . 99 4. References . . . . . . . . . . . . . . 114
F̄j mole fraction of monomer of type j K p∗ rate constant for polymeric radicals
chemically bound in accumulated poly- adding to pendant double bonds on
mer polymer chains
F̄ 1 mole fraction of monomer 1 (containing K p j , Kij propagation rate constant for
i
an abstractable atom) in accumulated monomer of type j adding to polymeric
polymer active center of type i
F̄ 2 mole fraction of monomer 2 (containing K p ij rate constant for polymeric radical of
a reactive carbon – carbon bond type i adding to a double bond on
F pi, in molar flow rate of monomer of type i a monomer unit of type j chemically
chemically bound in polymer into the bound in the polymer
reactor K p ijk propagation rate constant for monomer
Fr Froude number of type k adding to a polymeric active
F T, in molar flow rate of chain-transfer agent center of type ij
T into the reactor Kt total bimolecular termination constant
G+ counterion (K tc + K td )
GPC gel permeation chromatography K t0 total bimolecular termination constant
HCSTR homogeneous CSTR at zero conversion of monomer
HDPE high-density polyethylene K tc rate constant for bimolecular termina-
H – H Hui – Hamielec styrene polymerization tion by combination
model K tc ij termination by combination rate con-
HIPS high-impact polystyrene stant for polymeric radicals of types i
I initiator or catalyst and j (chemical control)
[I] concentration of initiator or catalyst K̄ tcN number-average bimolecular termina-
K chemical rate constant; equilibrium tion constant by combination
constant K td rate constant for bimolecular termina-
Ka absorption constant for oligomeric rad- tion by disproportionation
icals entering polymer particles K td ij termination by disproportionation rate
KA adsorption rate constant constant for polymeric radicals of types
Kd initiator decomposition constant i and j (chemical control)
K dp depropagation constant K̄ tdN number-average bimolecular termina-
KD desorption rate constant tion constant by disproportionation
Kfj rate constant for polymeric radical K̄ tN total number-average bimolecular ter-
i
of type i abstracting an atom from mination constant
monomer of type j chemically bound K tp termination rate constant in polymer
in polymer particles
K fm transfer to monomer rate constant K t (r, s) total bivariate distribution for
K fp rate constant for chain transfer to poly- diffusion-controlled bimolecular ter-
mer mination of polymeric species of chain
K fT rate constant for chain transfer to CTA lengths r and s
K fT i rate constant for chain transfer from K tw termination rate constant in aqueous
polymeric radical of type i to CTA phase
K fX transfer to small molecule X rate con- K̄ tW , K̄ tZ total weight- and z-average bimolec-
stant ular termination constants
Ki rate constant for monomer adding to a L characteristic length of energy-con-
primary radical taining large eddies
Kp propagation rate constant L length of path traversed by a growing
K ′p propagation rate constant for transfer radical from its point of origin to the
radical point where it precipitates
K− p propagation rate constant for free ion L reactor length
± LALLS low-angle laser light scattering
Kp propagation rate constant for ion pair
LCB long-chain branching
4 Polymerization Processes
ical reaction engineering, had little background the models, groups of rate constants often appear
in polymer chemistry, polymerization kinetics, when calculating rates and polymer properties.
and polymer characterization techniques. This A knowledge of the Arrhenius equation (over-
has changed dramatically in the last two decades, all frequency factor and activation energy) is
as evidenced by the rapid growth of the field of usually sufficient. Another factor which should
polymer reaction engineering within the chemi- be noted is that process models, no matter how
cal reaction engineering discipline. Process pa- detailed, cannot track polymerization rates and
rameters, such as residence-time distribution, polymer properties in real time without feed-
micromixing, and segregated flow, whose in- back from online sensors. The variability in trace
fluence on productivity and selectivity of small impurity levels cannot be accounted for with-
molecule reactions has been studied for many out periodically adjusting kinetic parameters in
years, appear to be far more important for poly- a process model. The great effort made by chem-
merization reactors in that they influence poly- ical kineticists to measure individual elemen-
mer properties dramatically [1–7]. tary rate constants are not in vain. Elementary
The development of engineering and spe- rate constants can be related to the structure of
cialty polymers with a better balance of prop- the reactants, but more importantly for process
erties or with a particular unique property has modelers, elementary rate constants can be used
been growing rapidly. In this regard, it has been to discriminate kinetic models (for example, the
found to be often more economic to produce terminal and penultimate models in copolymer-
a new polymer from existing commodity poly- ization). At this point it is appropriate to em-
mers rather than to start with a new monomer phasize the need for on-line sensors to monitor
and produce polymer in the usual manner. Tech- polymer properties so that process models can
niques such as polymer alloying and blending be used more effectively in state estimation and
are particularly attractive. These and other tech- control.
niques use chemical modifications of existing
polymers by chain scission, long-chain branch-
ing, cross-linking and grafting. These chemical 2. Polymerization Mechanisms and
modifications are usually carried out with poly- Kinetics
mer melts in an extruder reactor [1]. This pro-
cess is often called reactive polymer processing. Polymerization reactions can be classified as ei-
This is a new and commercially promising area ther step-growth or chain-growth reactions. It
where the principles of polymer reaction engi- has been proposed that these mechanisms should
neering could be profitably exploited. be termed random and sequential polymeriza-
Since 1980, modeling of polymerization re- tions [18], [19] since these terms have more sig-
actors has become more comprehensive. Inter- nificance statistically and are devoid of infer-
est has focussed on the prediction of polymer ence concerning the chemistry of the reactions
properties (chemical composition and molecular involved in the polymerizations. In this article,
mass distribution, long-chain branching, cross- however, the conventional terms step-growth
link density, polymer particle size distribution, and chain-growth polymerization are used. It is
and particle morphology). To develop a pre- important to note that this is a classification of
dictive model, account must be taken of the reaction mechanisms, not of the structure of the
chemistry and physics of all of the relevant mi- repeating unit, since many polymers can be syn-
croscopic processes which occur in the poly- thesized either by step-growth or chain-growth
merization process. Detailed physical property polymerization. Generally, however, polymer
and thermodynamic data on the partitioning of physical properties can differ significantly de-
species among phases is required to quantita- pending on the polymerization mechanism, and
tively calculate the concentrations of reactants this is often due to the difference in molecu-
at the loci of polymerization. Valid kinetic rate lar masses, i.e., polymers synthesized by chain-
constants (frequency factors and activation en- growth polymerization often have higher molec-
ergies) are also required. In this regard, one ular masses.
should note that the values for individual ele- These two types of growth reaction differ
mentary rate constants are often not required. In basically in terms of the time-scale of vari-
8 Polymerization Processes
ous reaction events, namely, the size of poly- hours. Chain-growth polymerizations require an
mer molecules increases at a relatively slow active center, which may be a free radical, cation,
rate over a much longer period of time in step- or anion. Once an active center is created, a poly-
growth polymerization. With step-growth poly- mer chain grows extremely rapidly, and when the
merization, the reactions that link monomers, growing chain is deactivated by a termination re-
oligomers, and polymers involve the same reac- action, the polymer chain is dead and no longer
tion mechanism, and any two molecular species takes part as a reactant. With free-radical poly-
(monomer, oligomer, or polymer) can be cou- merization, however, the so-called dead polymer
pled. The growth of a polymer chain proceeds chain is not always truly dead because under cer-
slowly from monomer to dimer, trimer, tetramer, tain circumstances it may itself react with rad-
and so on, until full-sized polymer molecules are icals. The active center may initiate the growth
formed at high monomer conversions. Polymer of many polymer chains.
chains continue to grow from both ends through-
out the polymerization and, therefore, both chain
lifetimes and polymerization times are usually
of the order of hours.
The kinetic study of such reactions would be above example), namely, the number-average
extremely difficult if the rate constant for the chain length P̄N and the conversion of func-
coupling reaction depended on the size of both tional groups p for linear step-growth polymer-
species. Fortunately, various kinetic studies have ization was first derived by Carothers [20]. P̄N
shown that the rate constant is effectively in- is simply given as the total number of monomer
dependent of chain length except perhaps for molecules initially present divided by the total
oligomers. This is often referred to as the con- number of molecules present at time t.
cept of equal reactivity of functional groups.
P̄N =NA0 /NA = 1/ (1 −p) (2.6)
Consider the example of step-growth poly-
merization shown below.
nA−A+nB−B→—
[ A − A − B − B—
—
] n (2.2)
As conversion p approaches unity, P̄N ap- reasons why bulk polymerization is quite often
proaches (1 + α)/(1 − α). Thus if α = 0.99, the used commercially for the production of poly-
maximum number-average chain length is only esters and polyamides.
199. This example illustrates the importance of The molecular mass distribution can most
precise control of the stoichiometric ratio to ob- easily be derived by using statistical methods for
tain a desired chain length. a stoichiometric ratio of unity [21]. The conver-
In general, in order to produce high molecular sion p can be interpreted as the probability that
mass polymer by step-growth polymerization, a functional group selected at random has re-
the system must satisfy the following require- acted. Consider the probability that a randomly
ments: selected molecule consists of r monomer units
(this quantity is equal to the number chain length
1) Very accurate control of the stoichiometric distribution). This polymer molecule possesses
ratio of functional groups r − 1 reacted functional groups, and one unre-
2) Absence of side reactions acted functional group. Therefore, the number
3) Availability of high-purity monomers chain length distribution, N (r) is given by
4) Reasonably high polymerization rate
5) Little tendency towards cyclization reactions N (r) =p(r−1) (1 −p) (2.8)
3) No intramolecular reactions occur in finite a molecule with many functional groups, the gel
species once formed acts like a giant sponge, rapidly
consuming sol polymer molecules.
This tree-like concept was generalized by
Gordon et al. [45], [46] based on the theory of
stochastic branching processes, which is consid-
ered to be a part of Graph Theory [47], [48]. This
technique involves abstract mathematics and re-
quires the derivation of the probability generat-
ing functions. The method is general but rather
difficult to use for real problems. To avoid the use
of probability generating functions, other prob-
abilistic methods have been proposed [49–52].
Figure 5. A schematic drawing of Flory’s tree-like model Among them the Macosko – Miller model [50–
(functionality f = 3) 52] using conditional probabilities is becoming
The tree-like model is called the Bethe Lattice or Cayley popular due to its simplicity. All the models
tree by physicists mentioned above are fully equivalent, that is,
only the mathematical language is slightly dif-
ferent. These statistical models, which are some-
times called the classical theories, have a long
history and have proven their power of refin-
ability to accommodate highly system-specific
effects such as unequal reactivity [53], [54], sub-
stitution effects [55], [56], and intramolecular
reactions [18], [19], [57–59], which are impor-
tant in real systems.
One drawback of the statistical theories men-
tioned above is that they assume an equilib-
rium system (i.e., the size distribution is calcu-
lated anew at each time) and they do not con-
sider the kinetic buildup of the system. There-
fore, the classical theories may not be appli-
Figure 6. Molecular mass change and gel growth during cable for kinetically-controlled systems. It has
network formation (functionality f = 3) been shown that although there is no difference
between equilibrium and kinetically-controlled
His basic proposal was that the gel point systems under Flory’s simplifying assump-
is reached when the expectancy of finding the tions, the difference becomes significant as the
next generation in a particular existing molecule conditions deviate further from Flory’s as-
is unity. For the tri-functional monomer units sumptions [60], [61], so that in real systems the
shown in Figure 5, the conversion at the gel kinetic features may be dominant. It has been
point is given by pc = 1/( f − 1) = 0.5, where f is argued that the kinetic buildup can also be ac-
the functionality of a monomer unit. His model counted for by using a statistical approach [62].
was a brilliant development and it provides the Another disadvantage of statistical ap-
starting point for most theories of polymer net- proaches may be the excessive modifications re-
work formation. A few years later Stockmayer quired to generalize them for different reactor
[42–44] further developed Flory’s idea based types (e.g., continuous reactors). The kinetics
on the most-probable size distribution, and their approach was originally shown in the appendix
theory is usually called the Flory – Stockmayer of a paper by Stockmayer [42]. Based on the
theory. Examples of the calculated development chemical kinetics, the reaction rate would be
of the number- and weight-average chain lengths proportional to the product of the number of un-
of the sol fraction and of the weight fraction reacted functional groups in the respective reac-
of gel are shown in Figure 6. Since the gel is tion partner, so that an infinite set of differential
Polymerization Processes 13
equations similar to Equations (2.11) and (2.12) ity. De Gennes wrote in his book [80] that “it
can be set up. This idea has been applied to poly- took more than thirty years to convince exper-
meric systems [60], [63–70]. imentalists that mean-field theory was wrong”.
However, at present the percolation models are
far from simulating actual network formation
quantitatively, because the bonds are too rigid,
the movement of molecules is too suppressed,
and necessary chemical rules of bond formation
are ignored. The percolation theory is essentially
devoted to describing the behavior near the criti-
cal threshold pcr , where the system-specific fea-
tures are not important.
Network polymers are increasingly used as
engineering materials because of their excellent
stability toward elevated temperature and physi-
cal stress. Since the three-dimensional polymers
are neither soluble nor fusible once made, the fi-
nal stage of polymerization is usually carried out
in a mold of the desired shape.
Figure 7. Example of percolation at the gel point in a square 2.2. Chain-Growth Polymerization
lattice (pc = 0.5) [78]
usually has values in the range 0.2 – 1.0 at low Even when the K d ’s for both peroxide groups
monomer conversions, where polymer concen- are the same, both groups on the same peroxide
trations are low. The major cause of low ini- molecule do not decompose at the same time;
tiator efficiency is recombination of the radical thus a significant fraction of the polymer chains
pairs before they diffuse apart, which is called will have a peroxide end group. These terminal
the cage effect [83], [84]. When an initiator de- peroxide groups will later decompose, generat-
•
composes, the primary radicals Rin are near- ing polymer radicals with an initiator fragment
−10 −9 in the backbone. The practical benefits include
est neighbors for about 10 – 10 s. During
this interval they are surrounded by a “cage” of higher molecular masses at the same tempera-
solvent and monomer molecules through which ture or comparable molecular masses at higher
they must diffuse to escape from the cage. Since temperatures. Polymerization at higher temper-
reactions between radicals are extremely fast, atures results in higher productivity. These ben-
there is reasonable probability that reaction bet- efits will only accrue when most of the poly-
ween primary radicals occurs. Direct recombi- mer chains are formed by bimolecular termina-
nation may simply regenerate the original initia- tion of polymer radicals. When chain transfer
tor molecules, but other reactions can also occur to small molecules produces most of the poly-
that consume initiator radicals without forming mer chains, these benefits will no longer exist,
polymer chains. In particular, since azo initiators and since bifunctional initiators are more expen-
decompose with the elimination of a nitrogen sive than monofunctional initiators it is recom-
molecule, recombination of the primary radicals mended that the latter be used.
results in the formation of a stable molecule that The decomposition rates of peroxy and azo
cannot generate radicals, and thus there may be compounds can be increased by irradiation with
a significant decrease in initiator efficiency. Ef- ultraviolet and visible light. Unlike thermal
ficiency decreases with increasing viscosity of decomposition, the activation energy for pho-
the reaction medium [85], [86]. Thus f decreases tochemical initiation is approximately zero, so
during the course of polymerization and may ap- polymerization can be initiated at much lower
proach zero at very high polymer concentrations temperatures. Compounds such as benzoin and
where the diffusion coefficient of primary radi- disulfides, whose bonds are too strong to un-
cals in the “cage” is very small [87], [88]. dergo thermal homolysis, are effective radical
When selecting an initiator type, in general initiators under ultraviolet irradiation. Photo-
one needs to consider the decomposition rate chemical polymerization has been applied in
constant, water and oil solubility, stability of ini- coatings and inks for metal, paper, wood and
tiator fragments on chain ends, and other factors. plastics, in photo-imaging, printing circuits, and
Another important point is the activity of the ini- adhesives, although its use is limited by low pen-
tiator radical center towards the abstraction of etration into the polymerizing mass.
atoms (e.g., hydrogen atoms) from the polymer Another method of lowering the activation
backbone. This can lead to chain scission, long- energy of the peroxide decomposition reaction
chain branching, and possibly cross-linking. is to use redox initiation systems. The addition
Up to this point, only monofunctional ini- of a reducing agent results in radical formation
tiators (initiators with one peroxide or one from an oxidation – reduction reaction between
azo group per molecule) have been consid- the two components. Generally, the reaction is
ered. There are commercially available bifunc- illustrated as follows.
tional initiators (with two peroxide groups per •
molecule) with some potentially useful applica- An+ + ROOR′ −→ A(n+1)+ + R′ O + RO− (2.29)
tions [89–92]. Their function can be illustrated
as follows: where A is a reducing agent and ROOR′ is a per-
oxide. The integer n is two for Fe2+ and zero for
N,N-dimethylaniline. The fate of the free radical
depends on the relative concentration of reduc-
ing agent and monomer. Since the redox initiaton
reactions do not produce a pair of radicals, the
cage effect is not operative. At high monomer
Polymerization Processes 17
concentrations most of the free radicals initi- may be formed, leading to a very complex reac-
ate polymerization, and ordinary second-order tion mixture with the formation of many byprod-
kinetics are obeyed. Redox initiation is usually ucts as well as the formation of long branches
used in the temperature range 0 – 50 ◦ C. and possibly cross-linkages. Since photon ener-
All methods mentioned above employ initia- gies for UV are lower, UV radiation generally
tors. There are, however, other means to initiate gives cleaner polymerizations with the forma-
polymerization. Styrene (and some substituted tion of linear chains, although monomers which
styrenes such as p-methylstyrene) and methyl undergo photolysis by UV radiation are limited.
methacrylate polymerize at elevated tempera-
tures in the absence of a free-radical initiat-
ing system. The accepted mechanism for ther- 2.2.1.2. Propagation
mal initiation of styrene is the Mayo mecha-
nism [93], [94], which involves the formation The propagation reaction (Eq. 2.18) controls
of a Diels – Alder dimer intermediate which re- both the rate of growth and the structure
acts with styrene to produce radicals. The Mayo of the polymer chain. Monomers which un-
mechanism is consistent with an observed initi- dergo free-radical polymerization are com-
ation rate which can vary from second to third monly monosubstituted or 1,1-disubstituted eth-
order in monomer during the course of polymer- ylenes, CH2 =CHX or CH2 =CXY. With 1,1-di-
ization [95–97], and some confirming evidence substituted ethylenes both substituents should
has been reported [98–100]. A serious disadvan- not be large, since propagation would be ster-
tage of the use of thermal initiation for styrene is ically hindered. 1,2-Disubstituted ethylenes are
the formation of undesirable byproducts (cyclic normally considered very difficult to polymer-
dimers and trimers) which are difficult to remove ize since the approach of the propagating rad-
to give a high-quality polystyrene. icals to a monomer is sterically hindered. 1,2-
Irradiation with UV, high-energy electrons, Disubstituted ethylenes can, however, often be
and γ-rays can initiate polymerization with incorporated into copolymers.
or without the presence of initiators. Radia- Due to steric and resonance effects, vinyl
tion initiation has been used almost exclusively monomers predominantly undergo head-to-tail
for polymer modification (chain scission, long- addition:
chain branching, cross-linking, and grafting).
These radiation processes are characterized by
a zero activation energy for radical generation
and as a consequence a low activation energy
for polymerization. Therefore, they are effective
In certain cases when the substituents are
at both low and high temperatures. With radi-
small and do not have large resonance stabiliz-
ation initiation, polymer molecular masses in-
ing effects, head-to-head propagation may oc-
crease with increasing temperature, which is op-
cur. For example, approximately 16 % head-to-
posite to that for chemically initiated free-radical
head placement has been reported for poly(vinyl
polymerizations (the high activation energy for
fluoride) [101].
initiator decomposition is responsible for this).
In free-radical polymerization, chain mi-
Both UV and electrons have small penetration
crostructure is largely independent of initiation
depths and are therefore used for polymeriza-
mechanism and initiator type. Polymers pro-
tions in thin layers. Gamma rays have high
duced by free-radical polymerization are largely
penetration depths but require expensive safety
atactic, since the terminal carbon – carbon bond
installations. Radiation polymerization may be
can rotate freely during chain growth. The con-
initiated by radicals, cations, or anions. The ef-
figuration of a monomer unit in the chain is
fectiveness of a radical center depends on the
not determined during its addition to the rad-
chemistry of the monomer and the polymeriza-
ical center but only when the next monomer
tion conditions. Most radiation polymerizations
molecule adds to it. The slight preference for
are free-radical except at very low temperatures
syndiotactic over isotactic placement is caused
where ionic species are sufficiently stable. With
by steric and/or electrical repulsion between
radiation initiation various active intermediates
18 Polymerization Processes
substituents in the chain, although at high tem- It has long been recognized that some bulk
peratures their effects are progressively dimin- polymerizations stop at well below 100 % con-
ished. For example, the fraction of syndiotactic version [110]. This phenomenon has success-
diads of poly(vinyl chloride) changes from 0.67 fully been explained as due to a glassy-state tran-
to 0.51 as the synthesis temperature increases sition of the polymerizing mass [111]. Although
from − 78 ◦ C to 120 ◦ C [102]. For methyl meth- the polymerization can proceed very slowly in
acrylate, it is 0.86 at − 40 ◦ C and 0.64 at 250 ◦ C the glassy state [109], [112], for practical pur-
[103], [104]. poses it can be assumed that polymerization
For most chain-growth polymerizations stops when the system changes from a viscous
(free-radical or ionic) the propagation reactions liquid to a solid glass. It has been proposed that
are reversible at elevated temperature and the the initiator efficiency f approaches zero when
rate of depropagation is significant [105], [106]. the system reaches a glassy state [87], [113] and
that this is mainly responsible for the cessation
of polymerization.
nation depends on monomer type and polymer- In general, the termination rate constant
ization temperature. Experimental data are not should depend on the size of the polymeric rad-
available for many monomers; however, radicals ical reactants, the concentration and molecular
which undergo termination by combination ap- mass distribution of the accumulated polymer,
pear exclusively to have the structure (1) [114]. solvent type, and temperature. As the concen-
A well-known example is styrene, which experi- tration of entanglement points increases during
ences termination by combination almost exclu- the course of polymerization, the functional de-
sively over a wide range of temperatures [114], pendence of the termination rate constant on
[115]. On the other hand, radicals which undergo the chain lengths of the polymeric radical reac-
disproportionation and combination may have tants should change dramatically. At some high
the structure (2). monomer conversion (high polymer concentra-
tion) when the polymeric radicals are trapped
(diffusion of the center of mass of polymer
chains is essentially zero), radical centers may
continue to move (due to monomer addition
by propagation) and undergo bimolecular ter-
For methyl methacrylate, combination and dis- mination [118]. With this form of termination,
proportionation are both important at low tem- the termination rate constant should be inde-
perature, with disproportionation becoming the pendent of the chain lengths of the polymeric
dominant mode at high temperatures [116–118]. radical reactants. Originally, upon examination
Since bimolecular termination reactions are of the autoacceleration of the conversion – time
intrinsically very fast, these reactions are likely curve, it was believed that the termination reac-
to be diffusion controlled when they involve tion only became diffusion controlled at some
radical centers on polymeric reactants. The monomer conversion greater than zero and that
autoacceleration of polymerization rate that this occurred when the polymer chains were suf-
is a consequence of diffusion-controlled ter- ficiently entangled (with a sufficient number of
mination is usually called the gel effect or physical entanglement points). It has been rec-
Trommsdorff – Norrish effect. Figure 8 illus- ognized that the bimolecular termination reac-
trates the autoacceleration in rate for the poly- tions may be diffusion controlled even at zero
merization of methyl methacrylate [119]. The monomer conversion (zero polymer concentra-
interpretation proposed was that the increase in tion) [114], [120–122]. At low monomer con-
rate is a consequence of a decrease in the rate versions, where polymer chains in a good sol-
of termination, due to the large increase in vis- vent are isolated coils, translational diffusion of
cosity of the reacting medium, thus giving an the center of mass of the chains is sufficiently
increase in radical concentration. rapid, and the limiting step is the so-called seg-
mental diffusion rate of the radical center in the
coil. With limited interpenetration of the coils, a
finite and significant time is required for the rad-
ical centers on the partially penetrating coils to
meet in a suitable reaction volume where bimo-
lecular termination may occur. The probability
of finding the radical centers in a suitable reac-
tion volume near the coil surfaces decreases as
the coil sizes increase, and, therefore, the termi-
nation constant should increase with decreasing
polymer molecular mass, with decreasing good-
Figure 8. Conversion – time histories for the polymeriza- ness of the solvent (which depends on the nature
tion of methyl methacrylate in benzene initiated by benzoyl and concentration of monomer, inert solvent,
peroxide at 50 ◦ C and polymer), and with increasing polymer con-
The different curves are for various concentrations of
monomer in solvent [119] centration (increasing monomer conversion). It
is well known that in dilute solution the poly-
20 Polymerization Processes
mer coil size decreases with increasing polymer where x is the monomer conversion, K t0 is
concentration. the termination rate constant at zero monomer
At somewhat higher conversions, when there conversion (x = 0), and A1 , A2 , A3 are ad-
are a sufficient number of chain entanglement justable parameters. An application is shown
points, the translational diffusion rate of the cen- in Figure 9. The adjustable parameters A1 , A2 ,
ter of mass of polymer coils decreases dramati- A3 are usually estimated by fitting isothermal
cally and bimolecular termination rates become conversion – time curves. The adjustable param-
translationally diffusion controlled. Of course, eters should be functions of temperature and
shorter polymer chains will experience transla- possibly initiator concentration (radical initia-
tional diffusion-controlled termination at higher tion rate). Note that K t estimated by fitting poly-
monomer conversions (higher polymer concen- merization rate and number-average molecular
trations) than longer chains, and clearly the masses is a number-average termination rate
bimolecular termination rate constant will be constant. Although, this termination rate con-
chain-length dependent and the bivariate distri- stant may predict rates of polymerization and
bution K t (r, s) will change its shape dramat- number-average molecular masses adequately,
ically with increasing polymer concentration. its use to calculate higher averages will under-
Finally, when the polymer coils are trapped, estimate weight-average, and Z-average molec-
K t should become independent of chain length ular mass [88].
[118].
Figure 9. Polymerization of acrylamide – rate and molec- Figure 10. Effect of inhibitors and retarders
ular mass development (T = 60 ◦ C, [M]0 = 3.4 mol/L, initi- a) No retarder or inhibitor ; b) With retarder; c) With in-
ated by potassium peroxosulfate [I]0 = 5.2 × 10−4 mol/L) hibitor
– – – = Constant K t ; —- = Use of Equation (2.35) [126]
Kt =Kt0 exp − A1 x + A2 x2 + A3 x3
(2.35)
Polymerization Processes 21
•
When K ′p is approximately zero (i.e., X is a
stable radical) X is called an inhibitor. If K ′p is
smaller than the propagation rate constant K p ,
X is called a retarder. Idealized behavior of in- Termination by disproportionation
hibitors and retarders is shown schematically in
Figure 10. The kinetics of inhibition and retar-
dation can be found elsewhere [127].
For an added agent to be a chain-transfer Termination by combination
agent, K ′p must be approximately equal to K p
(or K p < K ′p , if chain length is large enough).
Therefore, the chain-transfer agent reduces the
molecular masses but does not affect rates of
polymerization. To derive the kinetic rate equations, the fol-
The chain-transfer rate constants for most lowing assumptions are usually made:
monomers are about 104 –105 times smaller than 1) All rate constants are independent of chain
the propagation rate constant (K fm /K p = 10−5 – length.
10−4 ). 2) Chain lengths are sufficiently large that the
The presence of monomer molecules is in- total rate of monomer consumption may be
evitable, so that the value of K fm /K p places an equated to the rate of monomer consump-
upper limit on the polymer molecular mass that tion by the propagation reactions alone [this
can be obtained with a given monomer. Larger is often called the long-chain approximation
K fm values are observed when the propagating (LCA)].
radicals have very high energies (high reactivi- 3) Radicals generated in chain-transfer reac-
ties), such as in the case of ethylene, vinyl ac- tions propagate with monomer rapidly and
etate, and vinyl chloride. thus do not affect the polymerization rate.
4) The stationary-state hypothesis (SSH) is
valid for radical reactions. One can therefore
2.2.1.5. Kinetics of Linear Polymerization assume that both the rates of radical genera-
The elementary reactions involved in linear free- tion and consumption are much greater than
radical polymerization (chains produced are lin- the rate of change of radical concentration
ear with no branches or cross-links) are as fol- with respect to time [128], [129].
lows: Let us first derive an expression for the poly-
Initiation merization rate Rp , applying the above assump-
tions. The balanced equation for polymer radi-
cals with chain length r is given by
∞
1 d V R·l X
= RI +Kfm [M] [R·r ]
V dt r=2
Propagation +Kp′ [T· ] [M] −KfT [R·1 ] [T] −Kp [R·1 ] [M]
− (Ktc +Ktd ) [R·1 ] [R· ] (2.36)
1 d (V [R·r ])
=Kp R·r−1 [M] −Kp [R·r ] [M]
Chain transfer to monomer V dt
−Kfm [R·r ] [M] −KfT [R·r ] [T]
− (Ktc +Ktd ) [R·r ] [R· ] (r ≥ 2) (2.37)
•
Rp = K p [R ] [M]; propagation rate
•
It is worth noting here that Rt = 2 K t [R ]2 is of- Rtd = K td [R ]2 ; rate of termination by dis-
•
ten used in the literature, although Rt = K t [R ]2 proportionation
•
is more widely used in free-radical polymeriza- Rtc = K tc [R ]2 ; rate of termination by com-
tion (e.g., the compilation of kinetic rate con- bination • •
stants in [130]). One must distinguish carefully Rf = K fm [R ] [M] + K fT [R ] [T]; rate of
which type of termination rate constant is being chain transfer.
used when consulting the literature on polymer-
ization kinetics. Since RI = Rtd + Rtc , Equations (2.46) and
From Equation (2.41), the total polymer rad- (2.47) can be simplified as follows:
ical concentration is given by τ +β
[R·1 ] = [R· ] (2.50)
0.5 1 +τ +β
[R ] = (Rl /Kt )
·
(2.43)
1 ·
[Rr· ] = Rr−1 (2.51)
Based on the long-chain approximation, the 1 +τ +β
polymerization rate Rp is given by
Therefore,
1 d (V [M])
Rp = − =Kp [R· ] [M]
V dt [Rr· ] = [R· ] (τ +β) Φr (2.52)
Kp
= 0.5
RI0.5 [M] (2.44) where
Kt
1 d (V [Pr ]) ∞
RFP (r) =
X τ (2 +τ +β) +β (3 +τ +β)
PW = rW (r) =
V dt (τ +β)2
r=1
= (Kfm [M] +KfT [T] +Ktd [R· ]) [R·r ]
2τ + 3β
r−1 ≈ (2.58)
1 X (τ +β)2
+ Ktc [R·s ] R·r−s (2.53)
2 s=1
The instantaneous number-average chain length
•
Substituting for [Rr ] using Equation (2.52) gives PN is given by
1 (1 +τ +β) 1
RFP (r) (2.54) PN = ∞ = ≈ (2.59)
P (τ +β/2) (τ +β/2)
β
W (r) /r
=Kp [R· ] [M] (τ +β) τ + (τ +β) (r − 1) Φr r=1
2
The polydispersity index PDI for polymer pro-
The instantaneous weight chain length distribu- duced instantaneously is given by
tion W (r) is therefore given by
PW (2τ + 3β) (τ +β/2)
rRFP (r) PDI = ≈ (2.60)
W (r) = ∞
PN (τ +β)2
P
rRFP (r)
r=1 If β = 0, i.e., termination by combination does
not occur, the polydispersity index takes on the
n o
(τ +β) τ + β2 (τ +β) (r − 1) rΦr
= maximum value, PDI = 2. On the other hand, if
1 +τ +β
τ = 0, i.e., chain termination is solely by bimo-
β
= (τ +β) τ + (τ +β) (r − 1) rΦr+1 (2.55) lecular termination through combination, PDI
2 takes on the minimum value, 1.5. Figure 11
If β ≪ τ , that is most polymer chains are formed shows the PDI as a function of the fraction of
by chain transfer and/or termination by dispro- chain termination by bimolecular termination by
portionation, Equation (2.55) reduces to combination, β/(τ + β).
r−1 2
1 τ
W (r) =τ 2 rΦr+1 =r (2.56)
1 +τ 1 +τ
Note that (τ + β) has the value of ca. 10−6 – The W (r), PW , PN , and PDI derived here
10−2 for usual free-radical polymerization give the instantaneous properties. In linear free-
[(τ + β) ≪ 1]. radical polymerization the polymer molecules
The weight-average chain length PW for once formed are inert and do not react further.
polymer produced instantaneously is given by
24 Polymerization Processes
In general, since the concentrations of monomer, the effect of temperature can be estimated by
initiator, and chain-transfer agent change with the change in the ratio of three rate constants,
time, the chain length distribution of the ac- K p (K d /K t )0.5 . Since each kinetic rate constant
cumulated polymer is always broader than the is considered to follow the Arrhenius equation,
instantaneous distribution. Particularly, when the activation energy of polymerization E R is
bimolecular termination is strongly diffusion given by
controlled and most of the polymer chains are
Ed Et
produced by bimolecular termination, the accu- ER =Ep + − (2.65)
mulated distribution broadens significantly with 2 2
increasing conversion. The polydispersity index where E p , E d , E t are activation energies for
PDI for commercial polymers is usually larger propagation, initiator decomposition, and bimo-
than two and this is the result of a drift in mo- lecular termination. Typical values for E p , E d ,
lecular mass averages of the instantaneous dis- E t are 30, 120, and 15 kJ/mol, respectively.
tribution. The accumulated distribution and its Therefore, E R is ca. 80 kJ/mol and this is largely
averages can be calculated as follows: due to the very high activation energy for ini-
tiator decomposition. The high activation en-
Zx
1 ergy for polymerization means that the rate of
W̄ (r) = W (r) dx (2.61)
x polymerization increases strongly with increas-
0
Zx
ing temperature. With redox initiation, E d is
1 ca. 40 kJ/mol and therefore E R is considerably
P̄W = PW dx (2.62)
x smaller at ca. 40 kJ/mol. With radiation initia-
0
x tion, E d is close to zero and E R is ca. 20 kJ/mol.
P̄N = (2.63)
Rx 1
Now consider the effect of temperature on the
dx
0
PN molecular mass of polymer obtained. For a sim-
P̄W ple example, consider the case where τ ≪ β, that
PDI = (2.64) is, termination by combination produces most of
P̄N
the polymer chains. Equation (2.58) gives
Superscript bars denote accumulated properties.
These integrals may be replaced with equiva- 1
PW ∝
lent ordinary differential equations which then β
can be solved by using readily available differ- Kp [M] Kp
= ∝ (2.66)
ential equation solvers. The variation of the ki- Ktc (2Kd f [I] /Ktc )0.5 (Ktc Kd )0.5
netic parameters of W (r) with respect to con-
version must be known to calculate the accumu- The activation energy for average chain lengths
lated properties. In a similar manner, accumu- E L is given by
lated molecular mass properties may be calcu- Ed Et
lated for semi-batch and continuous reactors. In EL =Ep − − (2.67)
2 2
a well mixed flow reactor with an ideal residence
time distribution (CSTR), the chain length dis- With initiators E L is about − 40 kJ/mol. The av-
tribution produced is the instantaneous distribu- erage chain lengths decrease significantly with
tion. In batch reactors the distribution is there- increasing temperature when initiators are used
fore broader [131], [132]. Other mathematical and bimolecular termination controls molecular
techniques to derive the distribution functions mass development (most of the polymer chains
can be found elsewhere [29], [32], [33], [133– are produced by bimolecular termination). With
135]. radiation initiation, E L is about 20 kJ/mol and
molecular masses increase moderately with tem-
perature.
2.2.1.6. Effect of Temperature When unimolecular termination (chain trans-
fer to small molecules) dominates in the produc-
In free-radical polymerization initiated by the tion of polymer chains, E L is given by
thermal decomposition of an initiator, the poly-
merization rate is given by Equation (2.45), and EL =Ep −Ef (2.68)
Polymerization Processes 25
where E f is the activation energy for the chain- even near zero conversion and therefore long-
transfer reaction. E f depends on the type of chain branching reactions are more significant
chain-transfer agent, but usually E p − E f < 0, in emulsion than in solution or bulk polymer-
and therefore molecular masses usually decrease ization. Examples of monomers for which long-
with increasing temperature when unimolecular chain branching via chain transfer to polymer is
termination (chain transfer to small molecules) important include ethylene and vinyl acetate.
controls molecular mass development. When long-chain branching is important the
calculation of the full molecular mass distribu-
tion requires excessive computation. However,
2.2.1.7. Branching Reactions the leading moments and molecular mass av-
erages can be readily calculated by using the
For the elementary reactions shown in Sec- method of moments for an infinite set of dif-
tion 2.2.1.4, radical centers are always located ferential equations which describe the chemical
on chain ends, and the dead polymer chains are kinetics [61], [134], [139–147]. The i-th order
chemically inert and are all linear. Branched moment of the polymer distribution can be de-
or cross-linked polymer can be obtained by fined by
chemical treatment of linear chains using pro- ∞
cesses such as vulcanization, radiation, and melt Qi =
X
r i [Pr ] (2.70)
processing with peroxides. This section, how- t=1
ever, is mainly concerned with branching reac-
tions which may occur during polymerization. Therefore, the number- and weight-average
Branched and cross-linked polymers are of sig- chain lengths of the accumulated polymer are
nificant commercial interest, but quantitative in- given by P̄N = Q1 /Q0 and P̄W = Q2 /Q1 , respec-
terpretation has been limited due to a lack of an- tively. For the elementary reactions shown in
alytical techniques for the comprehensive char- Section 2.2.1.4 plus Equation (2.69), some of the
acterization of branched polymers. Some of the lower order moments for batch polymerization
newer analytical techniques are summarized in are given by [61], [145–147]:
[136–138]. 1 d (V Q0 )
=τ +β/2 (2.71)
V0 dx
Chain Transfer to Polymer. Chain transfer
to polymer involves the abstraction of an atom
from the backbone of a polymer chain and re- 1 d (V Q1 )
= 1 (2.72)
sults in the formation of a backbone radical cen- V0 dx
ter. Monomer addition to this radical center pro-
duces a tri-branching point and a long-chain
branch whose average length is equal to that of 1 d (V Q2 ) 2 (1 +Cp2 ) β (1 +Cp2 )2
= + (2.73)
the primary chains produced at the same instant. V0 dx τ +β +Cp1 (τ +β +Cp1 )2
polymer radical center to a double bond on the mixture always has a relatively high polymer
end of a polymer chain are not accounted for in concentration. Comparing long-chain branching
the moment equations above (Eq. 2.71 and 2.73). frequencies in batch and CSTR reactors at the
same monomer conversion levels shows that the
residence time distribution of the CSTR favors
branching [150], [151].
ing. For polyethylene the backbiting reaction ganic packagings used in size exclusion chro-
can be represented as follows matography are lightly cross-linked polymeric
networks. The kinetics of copolymerization of
vinyl and divinyl monomers are discussed in
more detail in Section 2.3.3.
early stages of polymerization before the poly- polar impurities and this often precludes the es-
mer chains have grown much beyond oligomeric tablishment of a stationary state. It is also diffi-
size. In the absence of unimolecular termina- cult to establish what proportion of the initiator
tion a population of polymer chains having the produces growing polymer chains.
same molecular mass can grow. The concentra- Cationic polymerization of vinyl monomers
tion of ionic reactive centers is usually much is essentially limited to those with electron-
larger than that of radical centers. Ionic poly- donating substituents such as 1,1-dialkyl,
merization kinetics are not as well understood alkoxy, phenyl or vinyl groups. Cationic poly-
as those radical-based polymerizations because merization involves initiation, propagation, ter-
of the requirements of extreme purity for the mination, and chain transfer to small molecules
components of the reacting mixture. much as in free-radical polymerization.
Elastomers such as butyl rubber and poly- To initiate cationic polymerization, protonic
isoprene; high-density polyethylene; polypro- acids such as H2 SO4 , HClO4 , and H3 PO4 or
pylene and its copolymers are widely produced Lewis acids such as BF3 , AlCl3 , TiCl4 , and
by ionic polymerization. Polypropylene of high SnCl4 are used. Lewis acids are by far the most
molecular mass cannot be produced by radical important initiators for industrial cationic poly-
polymerization. In addition to carbon – carbon merizations. Initiation with Lewis acids requires
double bonds, carbonyl double bonds [81], [82], the presence of a trace of proton donor such as
alkynes [156], and carbon – nitrogen double water, alcohol, and organic acid or a cation donor
bonds [157] can be polymerized via ionic mech- such as alkyl halide.
anisms. However, the discussion here is limited
to carbon – carbon double bonds.
The apparent propagation rate constant K p can produce polymer with sufficient molecular
depends on the type of initiator and solvent used. mass only at very low temperatures. Figure 13
In general, K p becomes larger as the acidity of shows the Arrhenius plot for the number-average
the initiator and/or the dielectric constant of the chain length [161]. There is a change in the slope
solvent increases. This is due to the fact that the of this plot around − 100 ◦ C. This has been at-
reactivity of free ions in monomer addition is tributed to a change in the chain termination step
much greater than that of ion pairs. from chain transfer to monomer below − 100 ◦ C
A wide variety of reactions may lead to ter- to chain transfer to solvent above − 100 ◦ C.
mination of chain growth in cationic polymer-
Table 1. Effect of counterion on the propagation rate constants (K −
p
ization, but it is usually ambiguous and difficult and K ± ◦
p ) in the anionic polymerization of styrene in THF at 25 C
to distinguish termination reactions from chain-
transfer reactions. Chain transfer to monomer is Counterion K±
p K−
p K × 107
most often responsible for the formation of dead Li+ 160 6.5 × 104 2.2
polymer: Na+ 80 6.5 × 104 1.5
K+ 60 – 80 6.5 × 104 0.8
Rb+ 50 – 80 6.5 × 104 0.1
Cs+ 22 6.5 × 104 0.02
in nonpolar solvents such as benzene, toluene, As shown here, although the concentration of
cyclohexane, and n-hexane is association of var- free ions is only 1.2 % of the total propagating
ious organolithium species. This phenomenon species, approximately 90 % of the monomer is
is important, since the associated species are es- consumed by the free ion.
sentially unreactive in propagation [162], [164]. Since carbanions are relatively stable, anionic
Propagation occurs by the successive inser- polymerization with carefully purified reagents
tion of monomers into the partial bond between may lead to systems in which chain termination
the propagating anion and its cationic counter- is absent. Such polymers are referred to as living
ion. polymers [167], [168].
Let us now develop an expression for the
chain length distribution for living polymer. As-
suming that initiation is instantaneous, the to-
tal number of growing chains N I is constant
throughout the polymerization. Now a monomer
molecule adds to a polymer chain as shown in
Figure 14. The probability that it adds to poly-
mer chain (1) is 1/N I , and that it does not add to
The polymerization rate is fundamentally ex- polymer chain (1) is 1 − 1/N I . Therefore, when
pressed by Rp = K p [M] [M− ], where [M− ] is N M monomer units have been consumed and
the concentration of active species. When non- bound into polymer chains the probability that
polar solvents such as dioxane are used, all active a randomly selected polymer chain possesses r
species may be ion pairs. However, in polar sol- monomer units is given by a binomial distribu-
vents such as THF, the effect of dissociation to tion:
free ions on polymerization rate cannot be ne-
NM
1
r
1 NM −r
glected. Therefore, the propagation rate is given N (r) = 1− (2.92)
r NI NI
by the sum of the rates for free propagating
anions (R− ) and for ion pairs, R− (G+ ). N (r) is also the number chain length distribu-
tion. Since 1/N I ≪ 1 and r is large, the binomial
Rp =Kp− R− [M] +Kp± R− G+ [M]
(2.88) distribution reduces to the Poisson distribution:
K = R− G+ / R− G+
(2.90)
dicate the existence of highly active but short- In this section a very simple example is con-
lived sites. This kind of behavior can be avoided sidered, too approximate to accurately describe
by aging the initiator system prior to addition of real systems, but useful to illustrate a model
monomer. building process. Consider the following poly-
merization scheme [175].
1) Adsorption of monomer (M) on the active
site
1 d V P∗1
=KA [M] [A] 2.3. Copolymerization
V dt
−Kp [M] [P∗1 ] −KD [P∗1 ] (2.105)
Copolymerization permits the synthesis of an al-
1 d (V [P∗r ]) most unlimited number of polymer types and is
=Kp [M] P∗r−1 −Kp [M] [P∗r ]
V dt therefore often used to obtain a better balance of
−KD [P∗r ] (r ≥ 2) (2.106) properties for commercial applications. Copoly-
mers may be synthesized by chain-growth
By application of the SSH for [P∗r ],
and step-growth polymerization. In step-growth
1 polymerization, different monomers with the
[P∗l ] = [A] (2.107)
1 +τ ′ same type of functional group generally show
1 ∗ only minor differences in reactivity. As a result,
[Pr∗ ] = Pr−1 (2.108) most copolymers prepared by step-growth poly-
1 +τ ′
merization contain essentially random place-
where τ ′ = K D /(K p [M]). Therefore, ments of repeat units, with the composition of
r the copolymers essentially the same as those of
[Pr ] =KD [P∗r ] =KD [A] Φ′ (2.109) the original monomer mixture.
′ ′ In contrast, strong selective effects often oc-
where Φ = 1/(1 + τ ).
cur in chain-growth copolymerizations, and the
The number and weight chain length distri-
composition of the copolymer formed may dif-
butions are given by
fer greatly from the composition of the origi-
[Pr ] r−1 nal monomer mixture. This section deals ex-
= 1 −Φ′ Φ′
N (r) = (2.110)
∞
P clusively with chain-growth copolymerization.
[Pr ]
r=1 Chain-growth copolymerization can be carried
r [Pr ] 2 ′ r−1 out with various types of active centers including
W (r) = =r 1 −Φ′ Φ (2.111)
∞
P free-radical, cationic, and anionic species. Free-
r [Pr ]
r=1 radical copolymerization is most commonly
used due to its higher alternating tendencies.
where Φ′ is the probability that a growing poly-
mer chain adds another monomer molecule, and
34 Polymerization Processes
have the same composition. However, since the In this instance, the Stockmayer instantaneous
chain length of a copolymer is finite, the compo- bivariate distribution of chain length and com-
sition and chain lengths of the individual poly- position will be obtained. Another method of
mer molecules cannot all be identical. Therefore, composition control is to use semi-batch oper-
for copolymer chains produced instantaneously ation in which monomers are fed to maintain a
there is a bivariate distribution of composition constant ratio of monomer concentrations in the
and chain length [194–200]. The variance of the reactor [209], [210].
copolymer composition distribution is approxi-
mately inversely proportional to the chain length
and, therefore, for sufficiently long chains it may
be reasonable to neglect the composition distri-
bution. In order to treat oligomeric molecules,
application of discrete mathematics such as the
finite Markov chain theory [184], [201] is nec-
essary.
In batch copolymerization, there is a compo-
sitional drift due to the change in the compo-
sition of the unreacted monomer mixture with
time. The total monomer conversion x is related
to the mole fraction f 1 of unreacted monomer 1
by the following equation [202]:
d f1 f1 −F1
= (2.124)
dx 1 −x
Figure 16. Batch copolymerization of styrene (M1 ) and
f1 =f10 , F1 =F10 at x = 0. methyl methacrylate (M2 ) at 60 ◦ C for f 10 = 0.8, f 20 = 0.2,
r1 = 0.53, r2 = 0.56
Therefore, if the relationship between f 1 and F 1 and F 2 are the accumulated mole fraction of monomer
1 and 2 bound in the copolymers.
F 1 is known, Equation (2.124) can be solved
numerically. If the terminal model is applicable In the terminal model, monomer sequence-
to a binary system (Eq. 2.121 a or b), Equation length distribution depends only on the product
(2.124) can be integrated analytically to obtain of reactivity ratios r 1 r 2 [211], [212]. In free-
the following equation [203–208]: radical copolymerizations r 1 r 2 is generally less
α β γ than unity, indicating a higher alternating ten-
f1 f2 f10 −δ
x= 1− (2.125) dency. The styrene – maleic anhydride system is
f10 f20 f1 −δ
an example of a very highly alternating one with
where both r 1 and r 2 very close to zero. For ionic co-
α = r 2 /(1 − r 2 ), polymerizations, there is a general lack of any
β = r 1 /(1 − r 1 ), tendency towards alternation, and r 1 r 2 is usually
γ = (1 − r 1 r 2 )/{(1 − r 1 ) (1 − r 2 )} close to or greater than unity. Generally, in free-
δ = (1 − r 2 )/(2 − r 1 − r 2 ). radical copolymerization, the reactivity ratios
are relatively insensitive to the reaction medium
Except for copolymerizations at the and temperature. However, in ionic copolymer-
azeotropic point, there will be some composi- ization, temperature and reaction medium can
tional drift. (At the azeotropic point, the compo- significantly affect reactivity ratios.
sition of the instantaneously produced copoly- Traditional methods for estimating reactivity
mer and of the unreacted monomers is the same; ratios [177], [213–215] are based on the trans-
hence in a batch reactor there is no compositional formation of the instantaneous copolymer com-
drift at this point.) An example of compositional position equation into a form that is linear in the
drift during batch polymerization is shown in parameters r 1 and r 2 . While these linearizations
Figure 16 [208]. One method to avoid compo- provide simple techniques for parameter estima-
sitional drift is to use a continuous stirred-tank tion, they are generally statistically invalid be-
reactor with an ideal residence time distribution.
36 Polymerization Processes
Figure 17. A schematic drawing of a cross-linked polymer network synthesized by free-radical copolymerization of vinyl and
divinyl monomer
promise of the same in several other market vinyl monomer increases, the heterogeneity of
areas), cross-linked latex polymers, and other the polymer network (i.e., regions having very
products. Figure 17 shows a schematic of a poly- different M c ) becomes significant [265–268].
mer network synthesized by copolymerization Reactivity ratios for the copolymerization of
of vinyl and divinyl monomers. There may be vinyl and divinyl monomers are rather difficult
many radical centers on the polymer network to determine. If the reactivities of both double
during polymerization since the mobility of rad- bonds on the divinyl monomer are the same and
ical centers chemically bound to the network independent, and cyclization does not occur, the
can be highly restricted. Strong autoacceleration conventional copolymer composition equation
in polymerization rate has been reported during (Eq. 2.121 a or b) is still valid when monomer
network formation by free-radical copolymeri- concentration is replaced by double bond con-
zation [253–260]. The live double bonds located centration and the reactivity ratios defined with
on polymer chains are called pendant double respect to each type of double bond are used
bonds. Kinetic behavior of radical centers on [269]. However, difficulties generally arise due
polymer chains and of pendant double bonds are to the complicated behavior of pendant double
the most important factors influencing the ki- bonds, which may react inter- and intramolec-
netics of network formation during free-radical ularly, and whose reactivity may differ from
polymerization. From the point of view of the that of monomer double bonds. At the moment
mobility of chains, network polymers may be when a divinyl monomer is chemically bound
considered as a heterogeneous reaction system, in a polymer chain, another double bond on the
and the formation of microgels before the gel just-reacted divinyl monomer may be the nearest
point is reached may be a general feature of net- neighbour of the active center, and therefore cy-
work formation in free-radical polymerization clopolymerization may occur under certain con-
[257], [261–265]. The number-average molec- ditions. For example, the free-radical polymer-
ular mass between cross-links M c is important ization of diallyl quaternary ammonium salts
from the point of view of the elastic properties gives soluble, not cross-linked polymers with lit-
of a gel molecule. As the mole fraction of di- tle or no residual unsaturation [270], [271].
Polymerization Processes 39
as residence time distribution (RTD) are usually 3.2. Processes and Reactor Modeling for
not considered by polymer synthesis chemists, Step-Growth Polymerization
although RTD can influence chemical compo-
sition distribution (CCD), molecular mass dis- 3.2.1. Types of Reactors and Reactor
tribution (MWD), long-chain branching (LCD) Modeling
and gel/sol ratios. In the early days of the poly-
mer industry, the chemist played the major role In step-growth polymerization, high molecular
in product and process development and scale- mass polymers are usually not produced until the
up. This has changed, with the process engineer final stage of reactions, so that thermal control
now playing a significant role in all phases of and mixing of the reaction mixture do not present
commercialization of new and improved poly- serious problems in the earlier stages. However,
mer products. His broad experience with pro- since the final stage of polymerization is very im-
cess fundamentals and computer modeling are portant for the production of polymers with high
essential to obtain high-quality products, safely molecular mass, handling of very high viscosi-
and economically. ties and temperatures and high interfacial area
Dynamic reactor models can be used in a to remove small molecules are required. Various
variety of ways. Stability and control of poly- polymerization processes and reactor types, both
mer reactors should be considered at the de- for batch and continuous production, have been
sign stage and control problems minimized then, proposed. Examples of reactors for high viscosi-
rather than take corrective action after the plant is ties are shown in Figures 19 and 20. Careful se-
built. Complex interactions which are involved lection of the polymerization reactor is very im-
in polymerization (highly nonlinear temperature portant to produce high-quality polymers [296],
and concentration effects) preclude optimal de- [297].
sign based on experimentation alone because the
cost would be prohibitive. Models can be used to
identify potential sources of product variability
and strategies to minimize their effects. Models
can be used to store information on process tech-
nology in a concise and readily retrievable and
modifiable form.
Process models can be used to train chemists,
chemical engineers, and plant operators and give
them a feel for the dynamics of the polymeriza-
tion process.
The most expensive aspect of model devel-
opment is experimental estimation of model
parameters; highly instrumented bench-, pilot-
scale, and plant-scale reactors are required. Sta-
tistically designed experiments should be per-
formed to permit efficient parameter estimation
and model development. Modeling is an iterative
process and the very act of developing a deter-
ministic model permits a greater understanding
of the relevant microscopic processes which oc-
cur during polymerization or polymer modifica-
tion. As additional data (plant, pilot-plant, and
bench-scale) become available, model structure
and parameters can be updated.
This section considers recent developments
in polymerization/polymer modification pro- Figure 19. Vertical cone ribbon blade reactor (Mitsubishi
cesses and discusses advances in polymer re- Heavy Industries)
actor modeling, state estimation, and control.
Polymerization Processes 41
loop, and intermediate monomer feed method. neously with those for chemical reactions in a
Some consideration of these reactions in a CSTR rational model for these complex situations.
is given in [311]. Qualitatively, these effects
lower the polydispersity and make the MWD
approach the most probable distribution. This
result seems reasonable, since any MWD ap-
proaches the most probable distribution with
a polydispersity index of two when polymer
chains are severed randomly [312], [313].
Other than the common reactor types dis-
cussed above, other special types of reactor sys-
tem may be applied. For example, in the poly-
merization of urethanes, the reaction rates are
so high that reaction takes place even when the
monomers are being mixed and pumped into
molds. In situ polymerization to form the de-
sired articles directly from monomeric liquids
is known as reaction injection molding (RIM)
[314], [315]. A schematic of the RIM process
is shown in Figure 22. The RIM processing of
polyesters, epoxy resins, polyamides, and dicy-
clopentadienes has also been introduced, al-
though more than 95 % of the total produced by
RIM is polyurethane [315]. In the RIM process,
the reaction is almost complete by the time the Figure 22. Schematic drawing of the RIM process
material fills the mold, and therefore the mix- a) Monomer A; b) Monomer B; c) Polymerizing mixture;
ing and flow equations must be solved simulta- d) Mold; e) Mixer
Polymerization Processes 43
In the finishing stage of nylon 6, nylon 66, and 1) Ring opening of ε-caprolactam by water
PETP polymerizations, higher molecular mass (Eq. 3.1), which produces aminocaproic acid
polymers may be obtained by solid-state poly- (ACA)
merization in which polymerization occurs by 2) Polycondensation of ACA (Eq. 3.2)
heating chips or flakes of a material below its 3) Acid-catalyzed polyaddition (ring-opening
melting point in a stream of hot gases in a flu- polymerization) by nucleophilic attack of the
idized bed or in a drier operated under vacuum amine nitrogen on the lactam (Eq. 3.3)
[316–320]. The monomer, condensation prod-
ucts, and various byproducts diffuse out, and
further reaction takes place inside the solid. The
progress of these types of reaction is affected
significantly by the diffusion of the condensa-
tion products and the morphology of the solid.
Although step-growth polymerization has a
very long history, a systematic kinetic treatment
like that available for free-radical polymeriza-
tion does not exist because of limitations due to
system-specific side reactions and the scarcity
of reliable kinetic data. However, this synthetic
route is becoming more important due to the
development of materials synthesized by step-
growth polymerization such as aramides, PPS, Step-growth polymerization of the amino
PEK, and PES. The production technology of acid (Eq. 3.2) accounts for only a few percent
step-growth polymers seems to have revived as of total polymerization of ε-caprolactam. How-
an attractive research area and is enjoying a Re- ever, step-growth polymerization is important
naissance period. since it usually determines the final degree of
polymerization at equilibrium. The molecular
mass distribution is essentially the most prob-
3.2.2. Specific Processes able distribution, except for the presence of
monomer and cyclic oligomers. Since low mo-
Polyamides (see also → Polyamides) are lecular mass substances lower the polymer qual-
manufactured by two basic routes. One of ity, they are usually removed by leaching or vac-
these is synthesis from cyclic monomers such uum treatment of the polymer melt. The forma-
as lactams. Polymerization of these substances tion of cyclic oligomers is an important side re-
requires ring opening and subsequent chain action [327–329]. For the simulation and opti-
growth. Another class of synthetic polyamides mization of polymerization reactors, only small
is formed from diamines and diacids. ring formation or overall ring formation is con-
The most common types of polyamides are sidered to make the analysis easier [330–333].
nylon 6 and nylon 66. The term nylon is of- Various types of polymerization reactors
ten used for synthetic aliphatic polyamides. One have been proposed both for batch and continu-
number indicates that the product was prepared ous processes. A commonly used industrial reac-
from a single monomer and represents the num- tor for a continuous process is a tubular reactor
ber of carbon atoms in the repeating unit. Two such as the conventional VK column (Verein-
numbers refer to the number of carbon atoms in facht Kontinuierliches Rohr) [321], [322], [334],
the diamine and that in the diacid, respectively. which consists of a vertical tube operating at at-
Nylon 6 is typically produced by the hy- mospheric pressure. The feed enters the top of
drolytic polymerization of ε-caprolactam [321– the column and is heated to ca. 220 – 270 ◦ C.
325], although polymers with higher molecular The simplest model for this type of reactor is a
mass can be produced by ionic polymerization PFR. However, according to impulse response
[321], [323], [326]. The major reactions in the experiments, the flow is approximately laminar
hydrolytic polymerization are rather than plug flow [322], [335], and the reac-
tor should be modeled as a CSTR followed by
44 Polymerization Processes
a tubular reactor when a large quantity of wa- be carried out solely in batch processes. How-
ter is used since a significant convection current ever, complete elimination of oxygen has made it
and mixing is provided by the evaporating water possible to carry out continuous polymerization.
[322]. An example of a continuous melt polymeriza-
Nylon 66 is manufactured by polycondensa- tion process is shown in Figure 23. The aqueous
tion of hexamethylenediamine and adipic acid nylon salt solution is heated to above 200 ◦ C at
[336], usually in a multistage process. First, ny- > 17 bar in an oxygen-free atmosphere. There-
lon salt (hexamethylenediammonium adipate) is after, the pressure is reduced to atmospheric and
prepared from stoichiometric quantities of hexa- vapor is separated from polymer to promote
methylenediamine and adipic acid in water. The polymerization to the desired high molecular
salt can easily be separated by precipitation with mass. It has also become possible to polymerize
methanol. molten hexamethylenediamine and adipic acid
directly [330], [336]. Polymerization can also
be completed in the solid state.
Several kinetic studies on the synthesis of ny-
lon 66 have been published [337–341]. How-
ever, more information is necessary for detailed
simulation and optimization of nylon 66 reac-
tors.
Figure 25. Continuous polymerization process of PETP via direct esterification route
tion method has been gaining in importance. The comonomer systems under a variety of operat-
process is claimed to give polyesters with supe- ing conditions. Bulk (suspension) and solution
rior quality due to their low content of carboxyl polymerizations are considered first; extensions
end groups and diglycol linkages [351]. In the required for multiphase systems (emulsion, in-
modeling of this process, aside from the diffi- verse emulsion, suspension, dispersion, and gas-
culties caused by the various reactions and mass phase processes) may be found elsewhere [355].
balances involved, it is necessary to take account Special cases where spatial variations in temper-
of the heterogenity of the reactions due to the low ature and concentrations are important (e.g., in
solubility of TPA in EG. Simulation and control tubular reactors or packed beds) are also consid-
of the direct esterification reactors is reported ered.
in [343], [350], [352–354]. Figure 25 shows a
flow diagram of a continuous process for PETP Bulk, solution, and suspension polymer-
production by direct esterification. ization systems are characterized by the fact that
all of the reactions proceed in a single phase
with no spatial variations in temperature and
3.3. Processes and Reactor Modeling for concentration. A model for a reactor carrying
Chain-Growth Polymerization out such polymerizations would consist of a set
of material balances giving the rates of accu-
3.3.1. Material Balance Equations for Batch, mulation, inflow, outflow and a reaction source
Semi-Batch, and Continuous Reactors (sink) term for the various monomers, initiators,
chain-transfer agents, and polymer in the reac-
The following material balance equations ap- tor. These balance equations are now given in
ply for multicomponent polymerization, accom- general form
modate operation of a well-stirred reactor (no Monomer balances:
spatial variations in temperature and concentra-
tions), and may be used to simulate different dNi /dt =Fi, in − (Ni /V ) Vout −Rpi V (3.7)
Polymerization Processes 47
both begin to fall dramatically, and these ef- Long-Chain Branching and Cross-
fects should be properly accounted for. These ef- Linking. The production of long branches and
fects will also be considered in detail later when cross-links requires that so-called dead polymer
MMA polymerization is discussed. The mod- chains take part in branching reactions to pro-
eling of diffusion-controlled bimolecular termi- duce tri- and tetrafunctional branch points via
nation, propagation, and the cage effect on ini- transfer to polymer and by addition of polymer
tiator efficiency is not entirely clear, and much radical centers to polymer double bonds. The
research must be done before these topics may mechanisms of anionic, cationic, and anionic
be considered standard engineering practice. coordination polymerization invariably produce
The polymerization rates for individual linear polymer chains. There may be a few ex-
monomer type j can be calculated from ceptions, but these will not be considered.
Pseudo-kinetic rate constants for transfer to
n
! "
Rpj =
X
Kpij ϕ∗i fj [M] [P∗ ] (3.14e)
polymer and polymer radical addition to pendant
i=1
double bonds may be defined as [355], [357],
[363–365]
with j = 1, . . . n.
n
The mole fraction of monomer of type j in X
Kfp = Kfpij ϕi F̄j (3.15)
copolymer produced instantaneously is given by ij
n
X
Fj =Rpj /Rp (3.14f) Kp∗ = Kp∗ij ϕi F̄j (3.16)
ij
Monomer sequence length distributions may be
calculated by using equations given in [356]. when the terminal model is valid; where F̄j
is the mole fraction of monomer j chemically
bound in the accumulated polymer. When a sig-
3.3.1.2. Molecular Masses, Long-Chain nificant number of labile atoms have been ab-
Branching, and Cross-Linking stracted and when a significant number of dou-
ble bonds have been consumed, Equations (3.15)
Linear Copolymer Chains. For chain and (3.16) should be modified to account for this
lengths greater than about 50 and when the [363], [364].
terminal model for copolymerization is valid, When polymer chains that are normally inert
Stockmayer’s bivariate weight chain length to further reaction undergo long-chain branch-
distribution may be used to calculate the com- ing reactions, the instantaneous MWD is no
position and chain length of binary copolymer longer a permanent quantity. Therefore, the
produced instantaneously [356], [362]. The bi- method of moments should be used to calculate
variate distribution of the accumulated polymer the molecular mass averages. For details on the
is readily calculated by integrating the instan- use of the method of moments for the calcula-
taneous distribution using weighting factors tion of sol molecular mass averages before and
based on instantaneous rates of polymer pro- after the gelation point and other methods for
duction. Unfortunately, an analytical function calculating sol – gel fraction and cross-linking
for a multidimensional distribution (involving density, see [363–365].
three or more monomer types) has yet to be
derived. However, part of this problem has al-
ready been solved. In the limit of large chain 3.3.2. Examples of Free-Radical
lengths, the copolymer composition of chains Polymerization
produced instantaneously may be assumed to
3.3.2.1. Homopolymerization – Linear
be independent of chain length, and therefore,
Chains
the instantaneous bivariate weight chain length
distribution is that given by the same expres- The modeling techniques described in Section
sion as for homopolymerization with all of the 3.3.1 are illustrated with actual monomer sys-
chains having the same composition Fi . For tems and experimental kinetic data. The sim-
more details, see Section 2.3.1 and [356]. plest modeling examples (homopolymerization
50 Polymerization Processes
producing linear chains) are considered first, be- a wide range of reactor type and operational con-
ginning with the thermal bulk polymerization of ditions. These include:
styrene, which is relatively easy to model and the
modeling has been most successful in a variety 1) Wu et al. [374] used the model for a theo-
of applications. retical/experimental optimization study em-
ploying temperature programming in a batch
reactor with highly successful results.
Bulk Thermal Polymerization of Styrene 2) Kirchner et al. [375] applied the model to
(T > 100 ◦ C). This system is comparatively a CSTR and obtained accurate predictions.
easy to model for the following reasons: 3) Tien et al. [375] applied the model to a tubu-
lar reactor with internal mixers.
1) The Mayo mechanism for thermal initiation 4) DIERS [376], [377] (Design Institute for
of radicals is valid [366–368] Emergency Relief Systems) a consortium of
2) The polystyrene chains are linear chemical and insurance companies financed
3) The Trommsdorff – Norrish effect (see Sec- the design and construction of a unique
tion 2.2.1.2), although significantly affecting adiabatic reactor system (see Fig. 26) for
the polymerization rate, has at most a minor the measurement of temperature and pres-
effect on molecular mass development be- sure/time variations during adiabatic run-
cause most of the polymer chains are pro- away exothermic reactions. They measured
duced by chain transfer to the Diels – Alder responses for the adiabatic thermal poly-
intermediate [366]. merization of styrene (Fig. 27 and 28) and
compared them with those predicted by
The size of the polymeric radicals (radical
the Hui – Hamielec polystyrene model and
centers are exclusively on chain ends) depends
found excellent agreement.
on temperature and monomer concentration (or
conversion), and the molecular mass distribu-
tion of the accumulated polymer differs little
from that of the polymeric radicals. In general,
the self-diffusion coefficients of polymer radi-
cals should depend on the size of the macrorad-
ical, the concentration and MWD of the accu-
mulated polymer, and temperature. The size of
the macroradical is of greater importance than
the MWD of the accumulated polymer [369],
[370].
An empirical correlation of the bimolecular
termination constant with polymerization tem-
perature and monomer conversion should pro-
vide a model which is applicable over a range
of process conditions (batch and continuous re-
actor operation, temperature programming, etc).
Another important factor, revealed in the work of
Kirchner and Riederle [367], is that reactions
involved in thermal initiation do not become
diffusion controlled at monomer conversions as
high as 97 %. The first effective model for the
bulk thermal polymerization of styrene was de-
veloped by Hui and Hamielec [371] and later Figure 26. DIERS VSP (adiabatic batch reactor)–monitors
extended to higher temperatures (T < 230 ◦ C) temperature and pressure changes during runaway of highly
exothermic reactions [377]
[372] and shown to be valid for a continuous a) Containment vessel (ca. 4 L); b) Test cell; c) Outer can;
stirred-tank reactor up to 280 ◦ C [373]. This d) Guard heater; e) Inner heater; f) Insulation; g) Exhaust
model has been evaluated by many workers over and supply; h) Bypass; i) Fill
Polymerization Processes 51
Figure 27. VSP self-heat rate response for the adiabatic ther-
mal polymerization of styrene (80 wt % styrene and 20 wt % Figure 29. Thermal polymerization of p-methylstyrene:
ethylbenzene) compared with the predictions of the H–H molecular mass development followed by GPC and light
polystyrene model [377]
scattering (LALLS). Deviation for M W between GPC and
– – – Constant heat of reaction (− 700 kJ/kg); —- Temper-
LALLS suggests that LCB frequency is increasing with
ature-dependent heat of reaction; • Experimental data
monomer conversion. Solid curves are model predictions
neglecting chain transfer to polymer [378].
pletely separated from the old polymer by GPC. length-dependent model for bimolecular termi-
If the GPC response for the added polymer shifts nation. This work has been summarized in a
towards larger radii of gyration (hydrodynamic recent article by Adams et al. [393]. The first
volume) this is evidence for long-chain branch- important models [381–383] for MMA poly-
ing [379]. merization were carefully evaluated [384] using
comprehensive rate and molecular mass data in-
Bulk polymerization of methyl methacry- volving three different initiator types measured
late (MMA) with free-radical initiator is the by Röhm. The Marten – Hamielec model was
model monomer system for the investigation found to better satisfy the specifications for a
of diffusion-controlled bimolecular termination polymer reactor model that can be used to op-
and propagation and the decrease in initiator ef- timize commercial production systems. It was
ficiency at high monomer conversions (cage ef- pointed out however, that further work should
fect). It has the largest Trommsdorff – Norrish be done to investigate the applicability of the
effect because most of the polymer chains are model to systems that have been prepolymerized
produced by bimolecular termination and the and also polymerized nonisothermally (perhaps
higher average molecular masses (M̄ W , M̄ Z , with temperature programming or adiabatically)
M̄ Z+1 ) increase dramatically in the absence of a and for systems with mixed initiators. Panke
chain-transfer agent. The MWD shifts to higher [394] has more recently shown that when us-
molecular masses and sometimes becomes bi- ing prepolymer, simulations are better when the
modal [380]. GPC detector responses, multi- parameter n is changed from 1.75 to 0.5 in the
plied by monomer conversion so that the total M–H model. From a fundamental point of view
area under the detector response is proportional the M–H model has several weaknesses which
to the amount of polymer in the batch reactor, are should be pointed out. Chain-length dependence
shown in Figure 30. At the monomer conversion of bimolecular termination is accounted for in an
where the number of physical chain entangle- overly simplified manner. The weight-average
ment points becomes significant a spike of high molecular mass of the accumulated polymer
molecular mass polymer is produced. There- does reflect the change in the size of the macro-
after, polymer with lower molecular masses is no radicals but in a dampened fashion. For example,
longer produced. The instantaneous MWD has a sudden change in the size of the macroradi-
clearly shifted towards higher molecular mass cals would not be felt soon enough, particularly
(higher molecular mass polymer has a lower when a substantial amount of dead polymer has
GPC retention volume or retention time). MMA accumulated. This model effectively uses one
is generally polymerized below the glass transi- termination constant (the number-average ter-
tion temperature of PMMA (ca. 110 ◦ C) and as mination constant [358]). It can therefore predict
a consequence the initiator efficiency and prop- polymerization rate and number-average molec-
agation constant decrease dramatically at high ular mass, but invariably underestimates M̄ W
monomer conversions (∼ 80 %) due to restric- and higher molecular mass averages. The M–
tions on diffusion rates during the glassy-state H model as well as most others have assumed
transition because of appreciable loss in free vol- that K p becomes diffusion controlled while the
ume. There is also evidence that during the rapid initiator efficiency f remains constant. It has
autoacceleration in polymerization rate (due to long been known that the initiator efficiency falls
large increase in polymer radical concentration at high conversions [395–398]. To separate the
[360]) radicals become frozen in the glassy-state 1
product f 2 K p which appears in the rate expres-
[358]. Radical pairs which form in the cage sion, accurate molecular mass data at high con-
may become frozen after a few monomer addi- versions are required. This has not been possible
tions because of monomer starvation. This ho- to date, because of the difficulty of measuring
mopolymerization is difficult to model. Never- M̄ N and M̄ W for the very high molecular mass
theless, there have been many serious attempts PMMA produced during the autoacceleration of
to model this system [381–392]. More recent reaction rate. For all of the models for which
research has focused on predicting the fall in f was taken to be independent of monomer con-
initiator efficiency and propagation constant at version, the observed decrease in K p is actually
high conversion and on the use of a simple chain-
Polymerization Processes 53
1
the decrease in f 2 K p . The change in K p at very copolymers synthesized with vinyl monomers
high monomer conversions can be measured by having a wide variety of structures and range
ESR [360], [399] and of course this would per- of reactivities. The terminal model has not been
1
mit the estimate f from the product f 2 K p . An- as successful in the prediction of comonomer
other factor which has been completely over- sequence length distributions [405], [406] and
looked is that during the autoacceleration when the propagation rate [407–413]. Model discrim-
approaching the glassy-state transition, the ac- ination has been based on the use of mea-
tual volume of the polymerizing mixture may surement techniques which provide estimates
be significantly greater than the local equilib- of the elementary overall (or pseudo-kinetic)
rium volume. This is largely responsible for the rate constants K p and K̄ tN . These include ro-
fact that the limiting conversion depends on the tating sector [407–409], spatially intermittent
initiator concentration at high initiator and rad- polymerization (SIP) reactor [414], and pulsed-
ical concentration levels [400–402]. laser techniques [411–413]. ESR measurements
[410] have also been used to show the ex-
istence of penultimate effects. Most of these
studies considered the binary copolymerization
of styrene and methyl methacrylate; however,
other monomer pairs have been investigated in-
cluding: styrene – acrylonitrile [408] and styrene
with a series of alkyl methacrylates [408], [415].
The use of the pulsed-laser technique has a se-
rious limitation when applied to copolymeriza-
tion. One must measure the MWD by GPC and
the potential errors are several and potentially
serious. For example, there is inevitable statis-
tical broadening of composition distribution for
short chains and the uncertainty that the con-
cept of universal molecular mass calibration is
valid. Nonuniform composition of chains in the
detector cell makes the conversion of detector
Figure 30. GPC chromatograms showing molecular mass response to polymer solute concentration uncer-
development due to the Trommsdorff–Norrish effect for the tain and in addition the errors due to deviation
isothermal bulk free-radical polymerization of methyl meth- from the universal calibration curve may be sig-
acrylate in a batch reactor
Parameter x denotes monomer conversion (T = 70 ◦ C, nificant.
[AIBN] = 0.3 wt %) [380] Most of the serious attempts to model binary
copolymerizations from an industrial perspec-
During the autoacceleration in polymer- tive (accounting for diffusion-controlled bimo-
ization rate which accompanies diffusion- lecular termination and propagation and for
controlled bimolecular termination, it is dif- the fall in initiator efficiency at high conver-
ficult to maintain isothermal conditions. The sions) have employed the terminal model and
use of large ampoule reactors with inadequate the pseudo-kinetic rate constant method [355],
surface-to-volume ratios for heat transfer has [357], [416–423]. There have been some recent
been recently criticized [403], [404]. The use attempts to employ the penultimate model in this
of ampoule reactors (3 – 5 mm diameter) is rec- regard [424], [425]. It should be stressed that
ommended for kinetic investigations of the whether terminal or penultimate models are used
Trommsdorf – Norrish effect [404]. appropriate pseudo-kinetic rate constants can be
defined for calculating rates of polymerization
and molecular mass distribution [356].
3.3.2.2. Copolymerization – Linear Chains
3.3.2.3. Copolymerization – Long-Chain ratios for reactors are usually < 2 to achieve
Branching acceptable mixing. When jacket cooling is no
longer sufficient to maintain isothermal poly-
The few serious attempts to model polymer- merization, additional modes of heat transfer
ization rate and molecular mass development must be used, as shown in Figure 31. Internal
have employed the pseudo-kinetic rate con- cooling coils are often not practical because they
stant method with the method of moments tend to interfere with stirring. External tubular
[355], [357], [363–365], [418], [419], [422]. The coolers can, in principle, provide a very large
method of instantaneous MWD, which is such a heat-transfer area, but they may have very large
powerful method for calculating the full MWD pumping requirements in the case of highly
for linear multicomponent polymers is not use- viscous solutions. Reflux cooling removes the
ful when dead polymer chains can be reactivated heat of polymerization by evaporation of solvent
during formation of long-chain branches. The and/or monomer; the condensed vapor is recy-
instantaneous MWD is no longer a permanent cled to the reacting mass. Condensers may be as
quantity but loses some of its chains, which be- large as necessary, with the limiting factor usu-
come branched during the course of polymer- ally the amount of vapor that can be treated with-
ization. It should be noted here that the pseudo- out causing intense foaming or spattering of the
kinetic rate constant method is equally valid for polymer solution. Remixing of the condensed
the modeling of linear and branched copoly- liquid with the more viscous reacting mass may
mer chain synthesis. The most common ana- also be difficult.
lytical technique for the measurement of long-
chain branching frequency (average number of
branches per polymer molecule or per 1000 3.3.3.1.2. Addition of a Solvent in which
backbone carbon atoms) is GPC with a dual de- both Monomer and Polymer are Miscible
tector system (mass concentration detector plus
either a viscometer or light scattering photome- The addition of a solvent in which both monomer
ter as detector in series) or GPC with off-line and polymer are miscible lowers the viscosity
viscometry [426]. of the reacting mass, thereby improving its flow
and heat-transfer characteristics. As a result, and
depending upon the nature and con-centration
3.3.3. Polymerization Processes of the solvent, the Trommsdorff – Norrish effect
can be either completely suppressed or signifi-
3.3.3.1. Solution Polymerization cantly reduced. Use of solvent can be especially
beneficial when evaporative cooling is used. In
3.3.3.1.1. Polymer Soluble in Monomer choosing a solvent, it is important to take into ac-
count the possibility of chain transfer to solvent
Kinetics. A polymerization in which the with a concomitant reduction in polymer mo-
polymer being synthesized is soluble in its lecular mass. Removal of solvent and residual
monomer may be called a bulk or mass as well as (unreacted) monomer from the highly viscous
a solution polymerization. A full description of polymer solution requires very high surface ar-
the polymerization kinetics and modeling tech- eas to permit rapid devolatilization at the mod-
niques can be found in Section 2.2.1 and Section erate temperatures required to minimize poly-
3.3.2. merization and degradation of chains during de-
volatilization to reduce off-spec polymer. Fig-
Polymerization Processes. The main tech- ure 32 illustrates possible designs of devolatiliz-
nical problems associated with solution poly- ers. One of these, the vacuum degasser, incorpo-
merization are heat removal, recovery of resid- rating a type of spray device [427], operates adia-
ual monomer and solvent, and the manipula- batically, which means that the heat for evapo-
tion of highly viscous solutions and melts. It is ration is supplied by the solution itself. In con-
well known that the ratio of cooling surface area trast, a degasser in series with a tubular heat ex-
to volume of reacting mixture decreases as the changer causes some of the monomer/solvent to
reactor volume increases. Length-to-diameter
Polymerization Processes 55
Figure 31. Alternative methods of heat removal for polymerization conducted in a stirred reactor
A) Internal cooling coils; B) External cooler; C) Reflux cooling
evaporate during passage through the heat ex- [435]: dilution with solvent and, in most cases,
changer. This evaporation accelerates the flow of an increase in temperature increases the compat-
product, thereby increasing the heat-transfer rate ibility; increasing the molecular masses of the
[428]. Twin-screw extruders with one or more polymers has the opposite effect. Except in the
vapor outlets that can be connected to a vac- case of high dilution, incompatibility in solution
uum source are also utilized for the removal of is the rule for pairs of polymers, even when the
monomer and solvent [429], [430]. Intermesh- solvent is a good solvent for both polymer types.
ing and self-cleaning screws provide continuous Systems such as polymer A – polymer B –
renewal of the evaporating surface. The use of block or graft copolymer AB can be re-
thin-film evaporators with rotating wiper blades garded as a polymeric oil-in-oil emulsion in
has also been suggested [431]. which the copolymer functions as an emul-
Given stable operation of the devolatilizer, sifying agent [436–439]. Such systems arise,
solution polymerization can be carried out in for example, in the manufacture of high-
a continuous stirred-tank reactor [432], [433]. impact polystyrene (HIPS), or in the prepara-
Conversion is normally lower than with tower tion of ABS (acrylonitrile – butadiene – styrene)
processes, however, requiring large amounts of by solution polymerization. In the simplest
monomer/solvent to be recovered and recycled case, ca. 5 – 10 % polybutadiene is dissolved in
to the reactor. Special attention must therefore be monomeric styrene to give a homogeneous so-
paid to the buildup of impurities (e.g., inhibitors, lution suitable for polymerization. The poly-
chain-transfer agents) over time by using appro- styrene synthesized is incompatible with the
priate purge streams. Problems with processes polybutadiene present, causing phase separa-
involving step-growth polymerization are dis- tion even at very low monomer conversion
cussed in Section 3.2. and producing a polybutadiene – styrene con-
tinuous phase and a polystyrene – styrene dis-
perse phase. Simultaneously, graft polymeriza-
3.3.3.1.3. Polymer – Polymer Demixing tion produces polystyrene branches on polybu-
during Polymerization tadiene backbone. The graft copolymer serves
Polymer – polymer demixing is especially im- as an emulsifier, accumulating at the interface
portant in the production of thermoplastics and stabilizing the oil-in-oil emulsion.
whose application characteristics are enhanced With increasing conversion, the volume frac-
by the presence of dispersed domains containing tion of the polystyrene phase (which is initially
an elastomer. Generally, the thermodynamics small) increases considerably due to formation
are unfavorable for complete miscibility bet- of additional polystyrene which absorbs styrene
ween different types of polymers. For a system monomer. Finally, often at a phase-volume ra-
polymer A – polymer B – solvent, the follow- tio of about unity, a phase reversal occurs, with
ing generalizations are usually applicable [434], the rubber phase now the disperse phase, and the
56 Polymerization Processes
polystyrene phase the continuous phase. Agita- tures, since the other morphologies shown gen-
tion is essential for the completion of phase re- erally provide lower impact strength.
versal, since rapid approach to equilibrium with
respect to transfer of monomer/polymer must be
attained in a highly viscous medium. A common 3.3.3.2. Precipitation Polymerization
result of inadequate agitation is the interpenetra-
tion of two continuous phases [438], [440–442]. The term precipitation polymerization refers to
Phase reversal can also lead to various processes in which the initial ingredients of
types of emulsions; e.g., polystyrene – styrene a recipe are soluble, giving a homogeneous
droplets can be occluded within the rubber par- solution, but the synthesized polymer precipi-
ticles of the disperse phase. This is actually de- tates during the course of polymerization. The
sirable as it increases the volume fraction of the precipitated polymer is generally swollen with
disperse rubber phase. A reinforcing effect is monomer and with nonsolvent if present. To
observed, with the resulting HIPS having higher ensure convenient handling the disperse phase
impact strength for a given mass of rubber in must be finely divided. This is achieved by ef-
comparison with materials prepared by emul- fective agitation, and a protective colloid (steric
sion grafting, in which occluded polystyrene is stabilizer) is often used. The associated prob-
not formed [443], [444]. Rather than rely on in lems are similar to those with HIPS manufac-
situ formation of grafted rubber, it is also possi- ture.
ble from the outset to utilize block copolymers
of styrene and butadiene as an additive in the
recipe. The desired particle size distribution and 3.3.3.2.1. Polymer Insoluble in its Monomer
morphology of the rubber particles in HIPS is
then achieved by varying the intensity of agita- Polymers that are insoluble in their monomers
tion, the viscosities of the disperse and continu- include poly(vinyl chloride) and other polymers
ous phases, the graft activity of the primary rad- derived from halo or pseudohalo-substituted
icals of the initiator, the molecular mass of the ethylenes such as vinyl bromide, vinylidene
continuous phase, and the mass fraction and mo- chloride, trifluoroethylene, and acrylonitrile.
lecular mass of the blocks in the diblock copoly- Polyethylene also falls into this category, at least
mer [445–454]. when produced under moderately high pressure.
Figure 33 provides examples of the morphol- For the system vinyl chloride – poly(vinyl chlo-
ogy of these rubber-modified polystyrene sys- ride), for example, virtually no polymer dis-
tems. Morphologies of commercial significance solves in the monomer in the temperature range
are essentially limited to cell and capsule struc- 30 – 60 ◦ C. Solubility of the monomer in the
polymer is described well by the simplified
Polymerization Processes 57
Figure 33. Possible morphologies for rubber particles in impact resistant polystyrene [454]
Length of the scale bar: 1 µm
Flory – Huggins equation (3.17) [435, p. 511], grows at the expense of the monomer-rich phase
[455–457]: with increasing monomer conversion. This ex-
plains the autoacceleration in rate as monomer
p
ln = ln (1 −ϕP ) +ϕP +χϕ2p (3.17) conversion increases.
p0
where
p0 is the vapor pressure of pure vinyl chloride
p is the partial pressure of vinyl chloride
ϕp is the volume fraction of poly(vinyl chlo-
ride)
χ is the polymer – solvent interaction param-
eter.
According to [457], deviations from Equa-
tion (3.17) are expected at low vapor pressures.
The conversion – time curves for the bulk poly-
merization of such monomer – polymer systems
all display rate increases with increasing con-
version. This phenomenon has been especially Figure 34. Time – conversion curve for the bulk polymer-
thoroughly investigated for the bulk polymer- ization of vinyl chloride [459]
ization of vinyl chloride. Its cause may be in- Polymerization temperature 50 ◦ C, initiator lauryl perox-
terpreted as follows: even at very low conver- ide, theoretical curves dashed
[I]: • 0.78 × 10−3 ; 1.57 × 10−3 ; △ 3.38 ×10−3 ; ×
sion, poly(vinyl chloride) precipitates, forming 5.50 × 10−3 mol/mol vinyl chloride
a monomer-swollen polymer-rich phase. Initia-
tor is partitioned between the phases, and thus Talamini has suggested that such a reac-
radical generation and polymerization occur in tion may be described in terms of two homo-
both phases. The bimolecular termination rate geneous polymerizations occurring in parallel,
is diffusion controlled in the polymer-rich phase with rapid monomer transfer from the monomer-
and hence the concentration of radicals is higher rich to the polymer-rich phase [458], [459]. As-
in this phase. Even though the monomer con- suming that the monomer/polymer mass ratio in
centration is lower in the polymer-rich phase, the polymer-rich phase is independent of con-
the specific polymerization rate Rp is higher. In version or time, and that the ratio of the spe-
addition, the volume of the polymer-rich phase cific polymerization rates in the two phases re-
58 Polymerization Processes
mains constant (Talamini suggests a ratio of ca. to which a continuous supply of monomer flows
19 at 50 ◦ C), then the observed conversion – time from the gaseous phase. Commercial examples
curve can be described well up to ca. 70 % con- of gas-phase processes include the Union Car-
version, as shown in Figure 34. However, Ta- bide Unipol process [473–476] and the BASF
lamini’s model fails at higher conversions be- process [477–481] for low-pressure polymeriza-
cause the monomer-rich phase disappears, and tion of ethylene and propylene (→ Polyolefins,
polymerization now occurs only in the remain- Chap. 1.5.3., → Polyolefins, Chap. 2.5.6.). Fig-
ing polymer-rich phase, with a monomer con- ure 35 shows a schematic of the Unipol process
centration which decreases with increasing re- in which polyethylene powder is produced us-
action time. Several authors have offered exten- ing ethylene as a fluidizing gas in a fluidized-
sions and modifications of the original Talamini bed reactor that contains a modified chromium
model [460–468]. catalyst. A high-density polyethylene (HDPE)
which has a very broad molecular mass distri-
bution and linear chains is produced. Copoly-
merization of ethylene with propene, 1-butene,
and 1-hexene gives products with a controlled
amount of short-chain branching and lower
polymer density (LLDPE) [482]. The densities
of LLDPE are between those of HDPE and
LDPE made in the high-pressure free-radical
processes.
based on ethylene – propene (EPM) and ethyl- A similar process is used by Exxon for the
ene – propene – diene (EPDM) mixtures. Acry- synthesis of butyl rubber [489]. In this case, iso-
lonitrile, sometimes together with a comonomer, prene serves as the comonomer and methyl chlo-
can be polymerized in aqueous phase using ride takes the place of ethylene. Polymerization
a redox system such as K2 S2 O8 –Na2 S2 O5 or is carried out in a continuous stirred-tank reac-
H2 O2 –Fe2+ [487]. The polymer precipitates as tor. Residual monomer and diluent are removed
a fine powder, which is then filtered, washed, from the resulting polymer suspension by strip-
and dried. Dissolution of the polymer powder ping with hot water.
in dimethylformamide produces a spinning so-
lution that can be used to produce polyacryloni-
trile fibers. This process has been conducted in a 3.3.3.2.2. Monomer Functioning as Solvent
continuous manner [488]. One of the first com- for the Polymer
mercial precipitation polymerizations was the
belt conveyor process for polyisobutylene devel- The Polymer – Monomer – Precipitant
oped by BASF (Fig. 37; see also → Polyolefins, System. If the polymer is soluble in its
Chap. 4.2.4.). Equal amounts of isobutene and monomer, precipitation polymerization requires
ethylene are first mixed and then deposited in the addition of a precipitant that is miscible with
the liquid state on a circulating steel belt. A sec- the monomer. Polymerization then begins in a
ond inlet is used to add a solution of BF3 in solvent – nonsolvent mixture and it ends in a
ethylene. Cationic polymerization occurs very phase consisting only of pure precipitant once
rapidly, and the heat of polymerization is dissi- conversion of the monomer is complete. Thus,
pated by the evaporation of ethylene. Thus, eth- the solubility relationships change during the
ylene functions here not only as a precipitant but course of the polymerization, and polymeriza-
also as a medium for evaporative cooling. The tion may initially occur in a homogeneous man-
resulting gaseous ethylene is purified, liquefied, ner prior to the onset of precipitation, induced by
and recycled. the enrichment in precipitant that accompanies
the consumption of monomer.
60 Polymerization Processes
Figure 37. Schematic diagram of the BASF process for manufacturing polyisobutylene [433]
a) Storage vessel for liquid isobutene; b) Storage vessel for liquid ethylene; c) Refrigerating condenser; d) Storage vessel
for ethylene containing 0.03 % boron trifluoride; e) Conveyor belt reactor; f) Heated degassing screw; g) Gaseous ethylene;
h) Purification with calcium oxide ; i) Gasometer; j) Compressor
∗
γprec =
volume of precipitant
(3.18)
volume of precipitant + volume of solvent
Figure 41. Schematic diagram of dispersion and polymerization in a suspension bead polymerization
A) Monomer emulsion in the absence of dispersant, or a polymerization mixture that has not yet reached the identity point;
B) Polymerizing mixture after passing the identity point
A polymerizing bead with a diameter For what has already been said about the
d = 10−2 cm contains ca. 108 growing polymeric course of suspension polymerization, together
radicals. The effects of subdivision due to parti- with various results from the literature [507],
cle breakup in suspension polymerization are not [510], [513], [518], [519], it is possible to estab-
anticipated to occur at the levels found in emul- lish a number of special factors – apart from
sion polymerization (polymer particles are sub- those common to all free-radical polymeriza-
micron in size) where radical contents of 0.5 or tions – that exert an important influence on par-
lower per particle occur [511], [512]. Each bead ticle size and size distribution:
may be regarded as a small, isolated reactor. For 1) Geometric factors of the reactor: profile, type
this reason, the observed polymerization kinet- of stirrer, stirrer diameter D relative to the
ics correspond directly to those for bulk poly- reactor dimensions, bottom clearance of the
merization [506], [513], [514]. Here again the stirrer, and internal fittings
Trommsdorff – Norrish and glass effects must be 2) Operating parameters: stirrer velocity N,
taken into account, as must the effects associated stirring and polymerization time, phase vol-
with demixing when the polymer is insoluble in ume ratio ϕ, fill level of reactor, and temper-
its monomer [459], [460], [462], [515]. Indeed, ature T
the process is sometimes referred to as a water- 3) Substance parameters: dynamic viscosities
cooled bulk polymerization. To ensure that con- η c and η d and densities ̺c and ̺d of the con-
version is as complete as possible, it is common tinuous and disperse phases, and interfacial
to employ mixtures of initiator types with dif- the tension σ.
ferent half-lifes, and to allow the polymeriza-
tion temperature to increase in the final stages During monomer fragmentation, in colli-
of conversion [516], [517]. With many industri- sions leading to agglomeration, and in de-
ally important suspension polymerizations, sim- agglomeration of clusters, the most important
ply preparing a polymeric material is not suffi- consideration is the energy introduced into the
cient. Often a particular particle-size distribu- reaction mixture per unit time. This can be ex-
tion and morphology must be achieved, as in pressed in terms of the mean rate of energy dis-
the manufacture of expandable polystyrene, or sipation per unit mass ε. In the case of a stirred
poly(vinyl chloride), whose particles must later reactor containing baffles and operated with a
absorb substantial quantities of plasticizer for high Reynolds number, the following equation
some applications. is applicable [520]:
ε̄ =KN 3 D2 cm2 s−3 or W kg−1
(3.19)
Polymerization Processes 65
where K is a dimensionless constant that de- tially hydrolyzed poly(vinyl alcohol), the resid-
pends on the type of stirrer. Increasing the stirrer ual acetate groups act as hydrophobic points of
speed N causes a decrease in particle size. attachment, while the OH groups are directed
The concentration of dispersant [S] deter- into the continuous aqueous phase. The most
mines the maximum particle surface area that important factor in dispersant effectiveness is
can be stabilized and influences the interfacial an appropriate balance between hydrophilic and
tension. Increasing [S] leads to a decrease in hydrophobic groups [521]; molecular mass is of
particle diameter, as does lowering the interfa- considerably less significance. The wettability
cial tension. Increased disperse phase viscosity of a polymer can be varied by the addition of
reduces particle breakup and thus leads to larger trace amounts of a low molecular mass surfac-
particles. tant.
Higher concentrations of protective colloid
may cause a bead polymer to be contami-
nated by a small amount of a much more
finely divided emulsion polymer. This should be
avoided because it results in polymer loss dur-
ing workup. The chance of encountering such
a problem is enhanced by increased solubility
of the monomer and initiator in the continu-
ous phase. However, emulsion polymerization
via homogeneous nucleation in the continuous
phase can be suppressed by addition of a water-
soluble inhibitor such as NH4 SCN or a copper
salt [513], [522].
from equilibrium between three interfacial ten- water-in-oil emulsion and the polymer forms a
sions: block that contains water-filled voids [507]. It is
clear that the limiting cases C and G are inap-
σSW +σWG · cosα =σSG (3.20) propriate for suspension polymerization. A good
Pickering dispersant must possess amphiphatic
characteristics, thus leading to one of the cases
D – F. Many pure inorganic substances are com-
pletely wetted by water, the chief reason why
modulation is so important in practice as a means
of inducing the transition from C to D.
to convert Equation (3.22) to the following where C ′3 and C 3 are empirical constants,
form: g is the acceleration due to gravity, ϕ
is the volume ratio (disperse phase vol-
−3/8 ume/continuous phase volume), and f (ϕ) is
dmin =C1′ ̺c A (h)−3/8 N −3/4 D−1/2 (3.23)
an empirical function.
If d < d min , drops will coalesce until a diam- According to [524–526], turbulence stabi-
eter d min has been reached. If energy dissipa- lization is only possible if the drop diameter is
tion in the stirred reactor is not uniform (e.g., larger than d min as given by Equation (3.23),
if only near the stirrer blades is it sufficient to and smaller than both d max from Equation (3.25)
break up drop clusters), then material circu- and d max from Equation (3.27). It is reasonable
lation within the vessel must be sufficiently to assume that the Sauter mean diameter given
rapid to ensure that each cluster approaches by
the stirrer blades at least once during the crit-
ical coalescence time. Σ ηi d3i
d32 = (3.28)
2) The dissipated stirring energy must not be Σ ηi d2i
so large as to cause significant breakup of
individual drops, that is, the critical Weber is proportional to the maximum diameter d max .
number W e (crit) or a maximum drop diam- Figure 44 illustrates these relationships. Stabil-
eter d max must not be exceeded: ity is achieved only in the shaded region bet-
ween the lines defined by Equations (3.23),
(3.25), and (3.27). If ε < εmin , then d min (co-
5/3
W e (crit) =C2′ dmax ̺c σ −1 ε̄2/3 (3.24) alescence) > d max (demixing) and the emulsion
will separate into two phases. On the other hand,
which is transformed by using Equation
if ε > εmax , then d min (coalescence) > d max
(3.19) into:
(breakup) and the emulsion will be unstable
because the energy necessary for separating a
−3/5 3/5
dmax =C2 ̺c σ N −6/5 D−4/5 (3.25) droplet pair is sufficient to breakup the droplets
themselves.
where C ′2 and C 2 are empirical constants and
σ is the interfacial tension. Equation (3.25)
is only applicable if the viscosity ratio η d /η c
is not too large. Otherwise, the stable drop
diameter increases with increasing values of
η d /η c , because turbulent oscillations in the
disperse phase are damped (viscosity stabi-
lization of drop size).
3) A density difference between the phases re-
sults in a tendency towards settling, and this
increases with increasing drop size. Stirring
energy must be sufficient to counteract this
tendency. The maximum drop diameter d max
that can be sustained in an emulsion at a par-
ticular rate of energy dissipation ε is given
Figure 44. Theoretical relationship governing the frag-
by: mentation (Eqs. 3.22 and 3.23), coalescence (Eqs. 3.24 and
3.25), and demixing (Eqs. 3.26 and 3.27) of droplets in a
3 stirred reactor. Only in the shaded region can a turbulence-
̺c 1
dmax =C3′ f (ϕ) ε̄2 (3.26) stabilized emulsion form [525]
̺d −̺c g3
A prerequisite for the validity of Equa-
and using Equation (3.19) one obtains tions (3.22) – (3.27) is the applicability of Kol-
mogoroff ’s theory of local isotropy [527–529].
3
The characteristic length L of the energy-con-
̺c 1
dmax =C3 f (ϕ) N 6 D4 (3.27)
̺d −̺c g3 taining large eddies (L ≈ 0.08 D, according to
68 Polymerization Processes
[244]) must be larger, and the characteristic in stirring speed has no influence on particle
length l of the energy-dissipating small ed- size. Apparently, a turbulence-stabilized state
dies [l = (γ 3c /ε)1/4 ], where γ c is the kinematic is reached at the very onset of polymerization.
viscosity of the continuous phase] must be Evaluation with respect to particle size is partic-
much smaller than the drop diameter d (i.e., ularly straightforward in this case, since changes
L ≫ d ≫ l). Equations (3.24) and (3.25) [531– in the above-mentioned parameters during poly-
534] as well as (3.22) and (3.23) [525], [526], merization are irrelevant.
[535] have been verified experimentally. Nev- A series of experiments in geometrically sim-
ertheless, they apply only for very small phase ilar reactors (see Fig. 45) coupled with dimen-
ratios ϕ < 0.015, which are unrealistic for indus- sional analysis, permitted derivation of the fol-
trial suspension polymerizations. The polymer- lowing dimensionless equation in the case of this
izing system is also subject to nonnegligible ef- especially simple system:
fects of the viscosity ratio η d /η c . In [536], for ex- 0.1
ample, this has been taken into account by intro- d50 ηd
=kRe0.5 W e−0.9 F r −0.1 ϕ0 (3.30)
duction of the viscosity group η d (̺d σ d)−1/2 , D ηc
which depends only on the physical properties where d 50 is the bead diameter below which
of the disperse phase. At higher phase ratios, 50 wt % of the particles pass through the sieve
both d 32 and d max increase with increasing dis- (in other words 50 wt % of the particles have a
tance from the stirrer [534], [537], [538]. Various diameter less than d 50 ), D is the stirrer diameter,
corrections [531], [534], [539], [540] have been which throughout the experiments was kept in a
suggested for Equation (3.25), all of which take constant ratio to the reactor diameter, and k is a
the form: numerical constant.
d32
=A (1 +Bϕ) W e−3/5 (3.29)
D
where A and B are numerical constants. For
phase relationships such as those applicable on
an industrial scale it is therefore not possible to
assume a homogeneous energy-dissipation rate
ε; instead, it must be anticipated that ε is large
in the vicinity of the stirrer, becoming smaller
in more remote circulation zones. A simulation
program has been described [541–543] that ap-
proaches this problem by dividing the reactor
into various stirring and circulation zones and
then applying Monte Carlo methods.
D 2 N ̺c
d
Re = = ratio of inertial/viscous forces =kW e−0.6 Eu−1.0 (3.31)
ηc D
DN 2 or
Fr= =
g
ratio of inertial/gravitational forces (3.30a) d ∼D−0.8 N −1.2 (3.32)
styrene/acrylonitrile and permits bulk polymer- tained. This point marks the beginning of the
ization to occur under stirring until phase rever- so-called “sticky-stage” at which point the co-
sal or inversion has occurred. Water and disper- alescence rate begins to increase, causing the
sant are then added and the polymerization is beads to grow from a mean particle diameter
completed in suspension [558], [559]. of about 0.2 mm to the desired size, depending
Expandable polystyrene is prepared by sus- on the original stabilizer formulation, for the fi-
pension polymerization in the presence of a nal application of the resin product. During this
blowing agent, such as pentane [560], [561]. It stage of the process, particle size is monitored
is also possible to introduce the blowing agent in by periodic sampling of particle size growth
a second step after polymerization, allowing it rate. Additional stabilizer may be added if the
to diffuse into the beads [562], [563]. Warming growth rate is too large. At 65 – 68 % conver-
to 80 – 110 ◦ C, generally with steam, causes the sion of monomer, the identity point is reached.
beads to expand by foaming, their volume in- At this point the particle viscosity is sufficiently
creasing by a factor of ca. 30 – 50. Particle size large that collisions between particles are elas-
and size distributions both play important roles. tic and particle size growth ceases. In addition,
For example, if thin-walled objects are to be the density of dispersed and continuous phases
made from expandable polystyrene, especially are almost identical, and the suspension is very
small polymer particles are required. The un- stable. Autoacceleration of the polymerization
foamed product is fractionated by sieving prior rate becomes appreciable at the identity point
to drying. Figure 46 shows a schematic of a typ- and increases until ca. 95 % conversion where a
ical EPS production facility. glassy-state transition occurs and the beads be-
come hard. Once the beads are hard the reac-
tion mixture is heated to a temperature above
the glass transition temperature of the polysty-
rene (T g ≈ 100 ◦ C). During heating, the reactor
is pressurized with a blowing agent (5 – 8 % with
respect to polymer), a low-boiling hydrocarbon
(C4 – C7 ). The reactor is then pressurized with
nitrogen at 700 – 950 kPa and the so-called im-
pregnation stage starts and proceeds for 3 – 8 h.
During impregnation the blowing agent diffuses
into the beads. At the same time, the free vol-
ume increases, and the finishing initiator rapidly
Figure 46. Schematic representation of the manufacture of
Styropor by batch suspension polymerization generates radicals, causing a relatively rapid in-
a) Mixing tank; b) Stirred reactor; c) Puffer tank; d) Cen- crease to a monomer conversion of ca. 99.9 %.
trifuge; e) Sieving; f) Drying; g) Silo; h) Packaging The impregnation time should be sufficient to
allow the blowing agent to reach the core of the
The required amount of deionized water is particle and to cause the breakup of hydrocarbon
loaded into the reactor at ambient temperature domains within the polymer matrix, giving a uni-
and agitation is started. Styrene and the initiator form distribution. At the end of the impregnation
pair, AIBN or benzoyl peroxide plus a finishing stage the suspension is cooled to 20 – 30 ◦ C, de-
initiator such as di-tert-butyl peroxide or tert- pending on the blowing agent type, to freeze in
butyl peroxybenzoate are pumped into the reac- the ingredients and prevent bead expansion dur-
tor at a constant rate, while the stabilizer, either ing handling. Some typical properties of an EPS
an inorganic, insoluble, finely divided powder or grade are:
a polymeric steric stabilizer is added. The reac-
tor is closed and the heating cycle starts. Droplet Monomer conversion > 99.9 %
size development occurs during the heating cy- M̄ W × 10−3 200 – 300
Polydispersity 2.2 – 2.4
cle. When the polymerization temperature is Mean particle diameter d̄ 0.4 – 1.5 mm
reached, between 75 ◦ C and 95 ◦ C depending on PSD breadth σ/d̄ 0.20 – 0.25
the initiator type, the polymerization proceeds Blowing agent concentration 5.0 – 8.0 %
until a conversion in the range 32 – 35 % is ob-
Polymerization Processes 71
Table 3 lists required properties of the bead observed that no further breakup occurs beyond
for different applications. 50 % monomer conversion when the particle vis-
cosity is about 104 cP. Addition of stabilizer is
Table 3. EPS bead properties and applications
used to obtain the desired d̄ at the identity point.
d̄, mm σ/d̄ Density, kg/m3 Use At the identity point both breakup and coales-
cence rates are zero. At the end of stage II, the
1.5 0.20 8 – 16 construction
(insulation) PSD has been established except for some minor
1.0 0.15 12 – 20 packaging shrinkage in the third stage due to density dif-
0.4 0.10 50 – 70 coffee cups ferences between monomer and polymer. Fig-
ure 47 shows a typical growth path for EPS
beads with d̄ = 0.425 mm. Since d̄ continually
increases during stage II, the variance of the PSD
also increases significantly. Figure 48 shows the
broadening of the PSD with conversion observed
by Konno et al. [565].
and bead porosity has been made [573]. Ion- sizes up to 200 m3 . Their construction presents
exchange resins are almost always made by sus- numerous engineering problems [554], [584–
pension polymerization giving spherical beads 588]. The most effective stirring in large reac-
in the size range ca. 0.3 – 1.2 mm. Most prod- tors is achieved with impellers driven from be-
ucts use polystyrene cross-linked with divinyl- low. The patent literature describes a wide va-
benzene to which functional groups are subse- riety of approaches for continuous suspension
quently attached (e.g., – SO3 groups by treat- polymerization. Apparently to date there are no
ment with sulfuric acid, chlorosulfonic acid, or continuous suspension polymerizations carried
SO3 ). Weakly acidic cation exchangers are pre- out commercially. The main problems relate to
pared by copolymerization of divinylbenzene the fact that, on the one hand, it is important to
with methacrylic acid, acrylate esters of lower assure the most uniform shear gradients possible
alcohols, or acrylonitrile. In this case the func- (i.e., total back-mixing) to establish the desired
tional groups are incorporated during polymer- particle size distribution and to prevent coagula-
ization, or they result from subsequent hydroly- tion and clumping in dead spaces. On the other
sis. Macroporosity is achieved by addition of an hand, maximum conversion is also desirable,
inert liquid which is a solvent for the monomer and this is only possible in a continuous process
but a nonsolvent for the polymer and which can with a narrow residence time distribution. Diffu-
readily be removed after polymerization is com- sion of monomer through the continuous phase
plete [574]. may not be sufficiently rapid to ensure that con-
With water-soluble monomers, especially ac- version is the same in all particles, independent
rylamide and comonomers (e.g., acrylic acid, of their residence time in the reactor. A particle
dimethylaminoethyl acrylate) it is common to that has a long residence may have a very low
use “inverse microsuspension polymerization” monomer concentration with concomitant high
in which a concentrated aqueous solution of the level of branching, cross-linking, and gel.
monomer is emulsified in an oily continuous
phase, usually a hydrocarbon, and then polymer-
ized with either an oil- or water-soluble initiator. 3.3.3.4. Emulsion Polymerization
When an oil-soluble initiator is used with an aro-
matic continuous phase, the kinetics have been Emulsion polymerization is probably the most
shown to resemble those of emulsion polymer- versatile of the polymerization techniques, ap-
ization [575–577]. The resulting polymer parti- plicable with many monomer types in batch,
cles are much smaller than the original monomer semi-batch (semicontinuous), and continuous
droplets, and the number of radicals per polymer processes. The product is a finely divided (par-
particle is small (< 1). However, when paraffinic ticle diameters ca. 0.05 – 0.3 µm) aqueous poly-
oil continuous phases are used, as is most com- mer dispersion (latex) containing up to 60 wt %
mon commercially, the locus of polymerization solids, which can either be used in latex form
is in the monomer droplets. This has been ver- or first coagulated and dried. Particle size dis-
ified by dynamic light scattering measurements tribution may play an important role in the fi-
which failed to detect inverse micelles and indi- nal application, as with emulsion PVC paste
cated a constant particle morphology with in- products. However, with some polymers (e.g.,
creasing conversion [578–580]. The polymer- styrene – butadiene rubber), the latex particles
ization therefore physically and kinetically re- are coagulated during work up to rubber bales
sembles a suspension polymerization and the and so their size is irrelevant, except perhaps in
prefix “micro” is added because average poly- the coagulation stage of the process.
mer particle diameter is nominally 1 µm, well Suspension and emulsion polymerization
below the usual size range for suspension poly- are both begun in an aqueous emulsion of a
merization. Suitable dispersants include Picker- monomer with low water solubility. In emul-
ing emulsifiers, polymers bearing hydrophilic sion polymerization, however, the locus of poly-
groups, or block or graft copolymers whose merization is in latex particles and not monomer
components differ in solubility [581–583]. droplets, the latex particles being much smaller
Stirred batch reactors are by far the most com- and having a much larger total interfacial area
mon for suspension polymerization, reaching [589]. Various theories exist for the mechanism
Polymerization Processes 73
of latex particle formation, differing primar- ous phase. Initiator decomposes in the water
ily with respect to the effect of the degree of phase to generate primary radicals, which prop-
monomer solubility in water. The polymeriza- agate with monomer dissolved in water to form
tion process in the latex particles is also quite dif- oligomeric radicals. When an oligomeric radical
ferent from that in monomer – polymer droplets enters a micelle it propagates rapidly with sol-
in suspension polymerization, because the pri- ubilized monomer to form a polymer particle.
mary radicals generally form in the aqueous con- In a typical emulsion polymerization there are
tinuous phase and migrate from there into the about 1013 monomer droplets per liter of emul-
latex particles. The most obvious difference in sion, with an average droplet size of about 3 µm.
the kinetics compared to solution or suspension This compares with ca. 1018 micelles, each con-
polymerization is the fact that polymerization sisting of ca. 100 emulsifier molecules with a
rate and molecular mass of the polymer pro- diameter of about 5 – 10 nm. The total interfa-
duced may be increased simultaneously in emul- cial area of the micelles is about three orders-
sion polymerization. Various explanations have of-magnitude larger than that of the monomer
been offered for the observed kinetic behavior. droplets. Consequently, oligomeric radicals in
The differences relate primarily to the question the aqueous phase are much more likely to dif-
of whether or not radicals, once they have en- fuse into a micelle swollen with monomer than
tered a latex particle, are then capable of leav- into a monomer droplet. Polymerization thus oc-
ing again and entering other particles. The de- curs almost exclusively in the micelles and poly-
cisive factors are the prevalence of chain trans- mer particles which are later formed, consum-
fer to small molecules (e.g., monomer) and the ing monomer that arrives by diffusion through
water solubility of the monomer. Finally, the the aqueous phase from the monomer droplets.
Trommsdorff – Norrish effect also plays an im- Micelles are thus gradually transformed into
portant role but with some modified features. polymer (latex) particles with a diameter of ca.
It should also be noted that polymer particles 0.1 µm and a concentration of ca. 1017 particles
in emulsion polymerization have a rather high per liter. As polymerization proceeds a form of
polymer concentration even at their birthtime. subdivision occurs, with monomer being trans-
Several reviews discuss kinetics and mecha- ferred from large monomer droplets with a con-
nisms [590–602] as well as mathematical mod- comitant increase in total interfacial area. As a
els [357], [603] applicable to emulsion polymer- consequence, micelles are consumed by being
ization. Proceedings from various symposia on “stung” with an oligomeric radical from the wa-
emulsion polymerization and related topics have ter phase and by being adsorbed on new inter-
also been published [604–611]. facial area which is continuously being formed.
When all the micelles are consumed and the con-
centration of emulsifier in the aqueous phase is
3.3.3.4.1. Theories of Emulsion just about to fall below the CMC, polymer parti-
Polymerization cle nucleation (via micellar nucleation) ceases.
The interval from the start of the generation of
Qualitative Theory. The qualitative theory oligomeric radicals in the aqueous phase to the
of batch emulsion polymerization is due pri- point where micelles have been consumed is
marily to the groups of Fikentscher [589], called Stage I in the emulsion polymerization
[612–614] and Harkins [615–618]. It is based process. At the end of Stage I, as illustrated in
on a system consisting of water, a monomer Figure 50, there is a rapid drop in the free emul-
with low water solubility, an emulsifier, and a sifier concentration (which throughout Stage I
water-soluble initiator that decomposes to pro- is equal to the CMC due to equilibrium with
duce radicals in the aqueous phase (see Fig. 49). micelles) and the surface tension (head-space
The emulsifier concentration is above the criti- gas/latex) rises rapidly from its previously sta-
cal micelle concentration (CMC) and thus mi- tionary value. Because the fractional coverage
celles form. The hydrophobic interior of the of the surface of polymer particles falls after the
micelles contains solubilized monomer, which end of Stage I problems with particle stability
is apportioned by diffusion out of the emul- and coagulation may occur.
sified monomer drops and through the aque-
74 Polymerization Processes
where N p = N 0 + N 1 .
Since water-phase termination affects Ri by
the same factor (on both sides of the equation)
its magnitude is irrelevant. Radical scavengers in
the water phase will for the same reasons have
The formation rate of particles with n radicals no effect on n̄. Radical scavengers in the poly-
equals the disappearance rate of particles with n mer particles would, however, lower N 1 and n̄
radicals. to values below 1/2.
where Ri is the rate of radical entry (radical Case 3) Rate of exit ≪ rate of entry ≥ rate of
cm−3 s−1 ); K 0 is the rate constant for radical exit termination
(cm/s); S is the particle surface area (cm2 ); K tp is
the rate constant for bimolecular termination in K0 S Ri Ktp
≪ ≥ (3.40)
the polymer particles (cm3 radical−1 s−1 ); and v Np v
v is the particle volume. Here the latex particles are effectively flooded
Smith and Ewart have derived expressions with radicals, so that n̄ ≫ 1, and it can be shown
for several limiting cases [623]: that the kinetics in the polymer particles corre-
Case 1) Rate of radical exit ≫ rate of radical spond to those in bulk polymerization. During
entry the buildup of radicals in the particles with time,
76 Polymerization Processes
radical entry rate will exceed the bimolecular ter- Gardon has described a series of investi-
mination rate; however, a stationary-state with gations in which the assumption dN n /dt = 0 in
respect to radical concentration will be reached Equation (3.35) was not made [620], [628]. Re-
as with bulk polymerization. alistic parameters when used in the nonstation-
A general solution to Equation (3.35) has ary form of Equation (3.35) led to the conclu-
been provided by Stockmayer [624] with mi- sion that negligible errors were introduced in
nor corrections by O’Toole [625]. After multi- Equation (3.35) by neglecting the transient ac-
plication by v/K tp and the substitutions cumulation term [597, pp. 566, 602 ff], [629].
vRi K0 S One possible exception is a system subject to
α= , m= , a = (8α)1/2 a very large Trommsdorff–Norrish effect and
Np Ktp Ktp
where K tp ≫ K p is no longer valid. In princi-
Equation (3.35) is transformed into: ple, Equations (3.41) and (3.42) may be used
Nn+2 (n + 2) (n + 1) +Nn+1 (n + 1) m +Nn−1 α = to estimate the magnitude of the Trommsdorff–
Nn [n (n − 1) +m n +α]
Norrish effect in emulsion polymerization.
Using an appropriate relationship for the ter-
Solutions to this equation follow: mination constant K tp and its dependence on
a I0 (a) polymer concentration or monomer conversion
n̄ = for m = 0 (3.41a)
4 I1 (a) in Stage III, one can calculate n̄ versus conver-
a Im (a) sion as shown in Figure 52 for styrene emul-
n̄ = for 0<m < 1 (3.41b) sion polymerization. Figure 53 shows calculated
4 Im−1 (a)
(m − 1) a Im−2 (a)
conversion – time curves for several monomer
n̄ = + for m ≥ 1 (3.41c) systems using appropriate expressions for K tp
2 4 Im−1 (a)
as a function of conversion. It is clear that the
Here the expressions Im (a) = i−m Jm (ia) are Trommsdorff–Norrish effect is of greater impor-
first-order Bessel functions, tabulated in [626], tance in emulsion polymerization when Case 2
[627]. An approximate solution to the Bessel kinetics are obeyed and when the polymer par-
functions is available in [597, pp. 556, 602 ff]. ticles are larger (vinyl acetate is clearly a Case
Figure 51 shows the dependence of n̄ on a and 1 system).
m. Knowledge of n̄ allows calculation of Rp us-
ing the relationship:
Rp =Kp [M]p n̄Np /NA (3.42)
where N A is Avogadro’s number.
ical formed in the aqueous phase. Particle for- Surfactant ∼ [S]3/5 ∼ [S]3/5 ∼ [S]3/5
mation would then continue until the total sur- concentration
[S]
face area of the latex particles Ap corresponds
Initiator ∼ [I]2/5 ∼ [I]2/5 ∼ [I]−3/5
exactly to the interface-covering capacity of the concentration
emulsifier as · [S] minus the area of monomer [I]
droplets. A correction for emulsifier dissolved in Temperature E N = ER = 3/5 (E P − E d )
2/5 (E d − E P ) EP + EN
the water should also be made. In this expression
∗ Ignoring chain transfer
[S] is the emulsifier concentration and as is the
emulsifier covering capacity per unit of emulsi-
fier (per mole or gram). Based on this assump- Table 4 illustrates the interdependency of the
tion, two limiting cases can be described, in each number of particles N p , the rate of polymeriza-
of which it is further assumed that n̄ = constant tion Rp , and the degree of polymerization PN
and [M]p = constant, and that the polymer par- based on Equations (3.42) and (3.47) or (3.49)
ticles grow with a constant volumetric growth [612]. The relationships have been confirmed
rate, dv/ dt = µ = constant. experimentally over wide ranges of the rele-
Model 1) All of the radicals formed in the vant variables for such relatively water-insoluble
water phase by initiator decomposition enter mi- monomers as styrene, butadiene, isoprene, and
celles, so that the rate of formation of polymer chloroprene [651–658]. By contrast, other rela-
particles equals the rate of generation of radicals. tionships are found to apply in certain situations,
80 Polymerization Processes
especially in the case of more soluble monomers Smith – Ewart kinetics are applicable in the form
with large transfer-to-monomer rate constants, of Equation (3.47).
including vinyl acetate and vinyl chloride [640], On the other hand, in the case where
[642], [659–664]. Even in the case of styrene it ε N p /[S] ≫ 1, there is a somewhat differ-
is not possible to explain all the experimental ent dependency, with N p ∼ (Ri, w )2/7 and
results on the basis of the Smith – Ewart theory. N p ∼ [S]5/7 . To obtain agreement between cal-
If particle formation were to conform to Model culated and experimental N p , it is necessary to
1, then at the end of Stage I, each latex par- introduce the values ε = 1.3 × 105 for styrene
ticle would contain precisely one radical, i.e., [666] and ε = 1.2 × 107 for vinyl acetate [667].
n̄ = 1 [665]. In addition the molecular mass of the This is explained by assuming that radicals exit
polymer chain in a particle nucleated near t = 0 very rapidly from very small latex particles as
would be extremely large at the end of Stage I. well as micelles – so rapidly that they do not have
For Model 2, n̄ = 0.67 at the end of Stage I [628]. sufficient time to propagate to the extent required
Since n̄ = 0.5 during Stage II, Rp must peak at for insolubility in the water phase. Hansen and
the end of Stage I. However, no such maximum Ugelstad [597, p. 556, 602 ff], [668] have ap-
has been observed with styrene. Moreover, N p plied Danckwerts theory of diffusion with ho-
calculated by using Equations (3.47) or (3.49) mogeneous reaction [669] to this problem. The
often exceeds observed values by a factor of rate of absorption by latex particles that already
2 – 3. These discrepancies can be rationalized by contain a radical is significantly larger than that
assuming that latex particles are more efficient of latex particles and micelles containing no rad-
at capturing radicals than micelles [665], [666]. icals, because the rate of termination between
Some particle coagulation would also reduce the two radicals is much higher than the rate of prop-
discrepancy. If radicals formed in the aqueous agation. Termination by combination with a sec-
phase can enter either micelles or latex particles, ond radical normally leads to molecules that are
the condition for radical balance assures that no longer able to desorb due to having exceeded
d [R· ] the critical degree of polymerization Pcr .
=Ri, w −K1 [Mi ] [R· ] −K2 Np [R· ] (3.50) In the derivation of Equations (3.47) and
dt
where [Mi ] is the micelle concentration. Assum- (3.49) the volumetric growth rate µ of a latex
ing a stationary state is valid, one obtains particle, given by
Ri, w dv Kp ϕ m ̺m
[R· ] = (3.51) µ= = · ·n̄ (3.54)
K1 [Mi ] +K2 Np dt NA (1 +ϕm ) ̺p
Particle formation should only occur after the was considered constant since n̄ was taken to be
entry of a radical into a micelle, so a constant, independent of the latex particle age.
dNp This assumption is no longer valid when Case
=K1 [Mi ] [R· ] (3.52) 1 kinetics apply, and n̄ increases with particle
dt
growth. Reference [643] has therefore adopted
Substitution of Equation (3.51) into (3.52) gives
the following general relationship for the rate of
dNp K1 [Mi ] Ri, w Ri, w particle formation:
= =
dt K1 [Mi ] +K2 Np 1 + K2 Np
K [M ] 1 i dNp δNM rχ
M
Ri, w =Ri · (3.55)
= (3.53) dt δNM rχ χ
M +NM rp
εNp
1+ [S]
where N M is the number of micelles, r M is the
where [S]/[Mi ] = M m is the aggregation number micelle radius, and r p is the particle radius, χ
for emulsifier molecules in micelles (in many (= 1, 2, 3) is the exponent that characterizes the
cases, M m ≈ 100); K 2 N p /K 1 [M i ] = ε N p /[S] is dependence of the capture rate on the radii of the
the ratio of the rate of entry into latex particles micelles and polymer particles, and δ is an effi-
versus micelles, and ε = (K 2 /K 1 )M m character- ciency factor for the capture of radicals by mi-
izes the radical capture efficiency of latex parti- celles relative to polymer particles. This in turn
cles relative to micelles. For ε N p /[S] ≪ 1, Equa- is a function of the factor ε in Equation (3.56):
tion (3.53) is equivalent to Equation (3.45) and
Polymerization Processes 81
Zts
Np = Ri, w − vc dt (3.61)
0
vc =Ri, w Np πr 2 L
(3.62)
[HSO− 3 ] = 1.14 × 10 −3 ; T = 30 ◦ C
ilar results have been obtained with ethyl acry- Song and Poehlein [688–690] have devel-
late [679]. Electron micrographs of the resulting oped new approaches to modeling homogeneous
polyacrylate latex particles after etching with O2 nucleation for monomers having a range of water
clearly show that they were formed by coagula- solubility. They account for the variation of the
tion of a large number of smaller primary parti- critical chain length for precipitation with con-
cles. centration, and for sparingly soluble monomers
If limited coagulation (or flocculation) oc- suggest that oligomers generated in the water
curs, it is necessary to also take into account phase form micelles which are then stung by a
the rate of flocculation vf , transforming Equa- radical to generate polymer particles. They also
tion (3.60) into showed that the number of polymer particles N p
increases slowly with emulsifier concentration
dNp [S] below the CMC, where homogeneous nu-
=Ri, w − vc − vf (3.64)
dt cleation is dominant, but rapidly increases above
The Smoluchowski theory [680] can be used to the CMC due to micellar nucleation. Others have
calculate the flocculation rate vf [674]. concluded that micellar nucleation is dominant
If to an anionic or cationic emulsifier there is even for monomer with appreciable water solu-
added a small amount of a straight-chain alco- bility [691].
hol whose chain length corresponds at least to Radical scavengers (e.g., O2 and monomer
that of the emulsifier, then emulsification leads inhibitors such as tert-butyl catechol) can have
to an especially stable emulsion consisting of interesting effects on the number of polymer par-
many very small monomer droplets. Polymeri- ticles formed and n̄. Radical scavengers have
zation of such an emulsion with an oil- or water- been classified as water soluble and monomer
soluble initiator can, in an appropriate formula- (organic) soluble [692], [693]. Oxygen, which
tion, lead to almost total adsorption of the emul- dissolves in water, monomer droplets, micelles,
sifier on the surface of the monomer droplets. and polymer particles, mainly influences the ini-
Since the number of micelles is no longer large tiation of particle nucleation. Oxygen dissolved
compared to the number of monomer droplets, in the aqueous phase reacts rapidly with primary
polymerization occurs partially or even princi- radicals, preventing particle nucleation. This re-
pally within the monomer droplets. The conse- sults in an induction period in which no poly-
quence is a bimodal distribution of polymer par- merization occurs. The induction period ends
ticle sizes, where small particles formed in the when the oxygen content of the aqueous phase
aqueous phase are accompanied by large parti- has been reduced to an almost indetectable level.
cles whose origin is in the monomer droplets. In After the induction period, apart from usually a
the limiting case, the size distribution of the la- minor loss of initiator, the polymerization takes
tex particles corresponds almost exactly to that its normal course. However, in the presence of,
of the original monomer droplet size distribution say, tert-butyl catechol (an oil-soluble inhibitor)
[681], [682]. These relatively large latex parti- in the micelles and polymer particles, polymer
cles may contain considerably more than one particles are nucleated, but n̄ can be very low
radical and the observed polymerization kinetics due to radicals reacting with inhibitor. This re-
are similar to those for homogeneous bulk poly- duces the volumetric growth rate µ and hence
merization [683], [684]. This therefore repre- a larger number of polymer particles are nu-
sents a transition toward suspension bead poly- cleated (refer to Equations (3.47), (3.49), and
merization. (3.54). Once the organic-soluble inhibitor has
An emulsion polymerization in which poly- been consumed, the polymerization rate recov-
merization occurs in both latex particles (formed ers but to a rate higher than originally expected
from micellar or homogeneous nucleation) and in the absence of the inhibitor. This phenomenon
monomer droplets is called miniemulsion poly- can cause low-frequency oscillations in reactor
merization (a term coined by the Lehigh Uni- trains when inhibitor contents in monomer recy-
versity Group). For such systems bimodal PSD cle streams vary and potential safety problems
as well as polymerization rates have been both for all reactor types (heat generation rate may be
measured and predicted [685–687]. excessive).
84 Polymerization Processes
3.3.3.4.2. Physicochemical Parameters of masses depend on radical entry rate per parti-
Dispersions cle, which in turn is some unknown function of
particle size and number. For the special case
This section treats some properties of disper- of a monodisperse latex the radical entry rate
sions that can be unambiguously described in is known, however, and this case can be easily
terms of physiochemical quantities. In addition treated when termination is instantaneous (rate
to these, applications technology makes use of of radical entry is much smaller than the rate of
a number of other characteristics, primarily em- termination in the polymer particle; or in other
pirical quantities and tests, [694], [695]. words two radicals cannot coexist in a poly-
mer particle). This is true for Case 2 kinetics
Molecular Mass Distribution of Linear (n̄ = 1/2). An expression is now derived which
Homopolymer Chains. In emulsion polymer- describes molecular mass development for this
ization, chain transfer to monomer is more im- special case. Transfer to monomer and to chain-
portant than in homogeneous bulk polymeriza- transfer agent are included in the analysis.
tion because bimolecular termination rates for a Consider an oligomeric radical in a polymer
given polymerization rate are generally lower for particle. The probability that this radical adds r
emulsion polymerization. This is why it is pos- monomer molecules and then terminates either
sible to obtain high molecular mass at high poly- by chain transfer to monomer or chain-transfer
merization rates in these systems. When transfer agent T or by instantaneous termination with a
to monomer is dominant in controlling molec- new oligomeric radical which enters the particle
ular mass development, the process type is ir- from the aqueous phase is given by ϕr (1 − ϕ),
relevant and molecular masses of linear chains where
depend solely on polymerization temperature. Kp [M]p
Therefore, equations developed in Section 2.2 ϕ= R
i, w
Kp [M]p + Kfm [M]p +KfT [T]p + NA
for bulk and solution polymerization in homoge- Np
and long-chain branching and cross-linking) by Gianetti [699] in a theoretical study of the
application of the pseudo-kinetic rate constant evolution of PSD in Stage 2 has reviewed the
method [417], [649], [710] and properly ac- more important theoretical studies and discussed
counting for changes in chemical and physical their limitations. The results obtained represent
properties during the course of polymerization a generalization of previous theories in that
[711–713]. 1) A comprehensive description for monomer
Copolymer composition is usually control- systems which conform to zero – one kinet-
ling semi-batch operation [357], [405], [714], ics has been made
[715]. The composition of polymer particles de- 2) The contribution of latex particles having
pends on the thermodynamic compatibility of more than one growing radical has been
polymer chains and is not always spatially uni- properly accounted for
form. Core/shell morphology, which is often 3) Bimolecular termination has been explicitly
the planned particle morphology for specialty included in the model (at least where mutual
products, can be effected by grafting and cross- annihilation of two growing chains is not the
linking reactions as well as compositional drift main termination reaction)
[715–718]. Special end use properties can be ob- 4) General expressions for the time evolution
tained by controlling morphology [719], [720]. of the cumulants of the PSDs (both in the
The morphology of latex particles is also a func- transient and nontransient case) have been
tion of the mechanism of particle formation. determined
Limited coagulation (flocculation) leads to latex
particles composed of a number of not entirely Gianetti’s solutions not only revise theoret-
fused smaller primary particles. Such particles ical misinterpretations which appeared in the lit-
are often not smooth and spherical, displaying a erature, but also allow rate coefficients to be ex-
rather rough surface and an irregular lumpy or tracted with more precision from reliable experi-
“potato-like” shape [721]. mental data. In this connection it has been shown
that rate coefficients obtained from experimen-
Polymer Particle Size Distribution. In tal PSD data are in good agreement with val-
general, the PSD is narrower the lower the ues found by using dilatometry to measure rates
conversion at the end of Stage 1 is relative of polymerization. Recent interest in analyzing
to the final conversion at the end of the poly- the experimental time evolution of PSD is due
merization. In the limiting case of stepwise seed mainly to the possibility of determining kinetic
polymerization, no new polymer particles are rate constants with a small confidence interval
produced, even though a very high monomer [602], [723]. According to Gianetti’s solutions
conversion is reached, resulting in larger latex PSD and kinetic data are not independent of each
particles that are nearly monodisperse in PSD other at steady state (in other words, if a certain
[676], [677]. A semiquantitative calculation volume dependence for the entry rate constant is
[590, p. 275 ff] based on Smith – Ewart Case 2 assumed, from the analysis of an experimental
kinetics shows that PSD narrows with increasing PSD one must find the same volume dependence
monomer/water ratio, as well as with increasing for the exit rate constant). Apparently, PSDs for
temperature, increasing initiator concentration systems with n̄ ≤ 1/2 are insensitive to assump-
in the aqueous phase, and decreasing emul- tions about the mechanisms of radical entry and
sifier concentration [S]. Experiments involving exit. In this connection, a new approach based on
styrene have confirmed these predictions. Quan- the effect of PSD on MDW has been proposed
titative calculations are also in good agreement [724]. In fact, a similar approach was proposed
with experiment [606, pp. 153 – 161] for styrene much earlier by DeGraff and Poehlein [725].
emulsion polymerization. A more comprehen- A CSTR was used to obtain a broad PSD for
sive population balance model which accounts styrene emulsion polymerization, and assuming
for coagulation in the seeded emulsion poly- that radical capture was according to the colli-
merization of vinyl chloride has been developed sion theory (capture rate ∼ r 2 ), a polydispersity
[722]. The predicted bimodal distributions of of 4.84 was calculated for the MWD, DeGraff
particle size are in good agreement with experi- and Poehlein’s MWD measurements showed
mental data. that the molecular mass averages M̄ N and M̄ W
Polymerization Processes 87
were independent of mean residence time and a dispersion can be converted into an integral
that the polydispersity was ca. 3. The discrep- film on a surface by evaporation of the water.
ancy between theory and experiment may be due This normally corresponds approximately to the
to any number of possibilities, including: glass transition temperature T g of the polymer
and is one of the most important application pa-
1) Perhaps the collision model is not valid (try
rameters of a polymer dispersion. Copolymer-
the diffusion model)
ization of monomers whose homopolymers have
2) Larger latex particles may not obey Case 2
a range of glass transition temperatures makes
kinetics
it possible to achieve desired values for both
3) Transfer to monomer may not be insignifi-
the glass temperature and the minimum film-
cant
forming temperature. The glass transition tem-
Similar experimental data were found for perature [T g ] of the copolymer can be calculated
continuous emulsion polymerization of styrene by using the equation
in a CSTR [726]. Simultaneous growth of la-
W1 Tg1 +K W2 Tg2 ∆α1
tex particles by polymerization and coagulation Tg = with K = (3.70)
W1 +K W2 ∆α2
may occur at various stages in emulsion poly-
merization [688–690], [723], [727–730]. For the where W 1 and W 2 are mass fractions of
calculation of PSD in the emulsion polymeriza- monomers 1 and 2 in the copolymer, T g1 and T g2
tion of vinyl chloride, it may be necessary to are the glass transition temperatures of the cor-
account for coagulation [731], [732]. responding homopolymers, and ∆α1 and ∆α2
are the differences between the thermal expan-
The extent of coverage of the particle sur- sion coefficients above and below T g (melt and
faces by emulsifier is an important factor in the glass) for the two homopolymers.
stability of a dispersion. For example, this cover-
age should not be too large if the polymer is to be
later recovered by controlled coagulation. The 3.3.3.4.3. Inverse Emulsion Polymerization
surface coverage is evaluated in a detergent titra-
tion [733], [734], in which the amount of emul- In inverse emulsion polymerization, a hy-
sifier that must be added to give total monomo- drophilic monomer is dissolved in water, emulsi-
lecular coverage of the surface is measured. To- fied in a continuous hydrophobic oil phase with
tal coverage is indicated, for example, by the a water-in-oil emulsifier, and polymerized by us-
point where additional emulsifier no longer low- ing an oil- or water-soluble initiator. The product
ers the surface tension (surface tension remains is a latex consisting of very small polymer par-
constant after micelles are formed). If the sur- ticles, swollen with water and suspended in an
face coverage required for particle stability is oil continuous phase. The emulsified monomer
known, emulsifier can be added during Stage II droplets are also very small, and they may serve
to maintain stability but not form new micelles as the source of some of the latex particles
with the danger of nucleating a second family of (a form of miniemulsion polymerization). The
particles. More is involved here than simply the overall rate of polymerization is significantly
adsorption of an emulsifier on the particle sur- higher here than in the corresponding solution
faces, however. The majority of the hydrophilic polymerization. This observation strongly sup-
end groups on polymer molecules also tend to ports the idea that what is occurring is a true
migrate to the interface (e.g., – OH, – SO4 , – inverse emulsion polymerization rather than an
COOH), thereby contributing to stabilization of inverse suspension polymerization. When oil-
the polymer particles. A comparable effect is soluble initiators are used with aromatic con-
achieved by the addition of small amounts of tinuous phases the kinetics have been shown
hydrophilic comonomers (e.g., acrylic or meth- to resemble those of emulsion polymerization
acrylic acid), which polymerize preferentially at [576], [577], [735] with the locus of nucleation
the particle surface [721]. of particles in inverse micelles. However, when
paraffinic oil continuous phases are used, as is
The minimum film-forming temperature most common commercially, the locus of par-
of a polymer is the lowest temperature at which ticle nucleation and polymerization is in the
88 Polymerization Processes
monomer droplets and the process is properly cesses. A monomer-feed process based on a
called inverse suspension polymerization (the very large starter mix resembles more batch pro-
term microsuspension is often used because the cesses, whereas an emulsion semi-batch process
monomer droplets are nominally 1 µm in diam- involving a small initial charge with most of the
eter) [575]. This has been verified by dynamic monomers being fed in during the semi-batch
light scattering measurements which failed to period is more similar to continuous processes.
detect inverse micelles and indicated a con- These two semi-batch methods are often men-
stant particle size throughout the polymeriza- tioned in the patent literature [745]. Their advan-
tion [578–580]. Reviews of polymerization in tages include better control of polymerization
inverse emulsions and microemulsions are avail- and heat-generation rates by appropriate manip-
able [736–738]. Inverse microsuspension poly- ulation of feed rates. Moreover, the concentra-
merization has been used to study the kinetics tion of unreacted monomer can be minimized
of polymerization of acrylamide with cationic (offering a safer process which is less prone to
comonomers (quaternary ammonium cationic runaway) and cold feed can give higher produc-
monomers) [739]. tivity (less demand for jacket or condenser cool-
Water-in-oil emulsions of high molecular ing, for example). In the case of copolymeriza-
mass polyacrylamide and acrylamide copoly- tions, it is possible to manipulate monomer feeds
mers (anionic and cationic) are particularly use- to control copolymer composition [746–751]. In
ful as flocculating agents in sewage treatment particular, such methods are often exploited for
and as retention aids in papermaking. At the the purpose of reaching a specific degree of poly-
present time inverse emulsion and microsuspen- merization, particle size, or particle size distri-
sion polymerization is the only technology for bution without changing the overall composition
the large-scale production of very high molec- of the copolymer in the latex particles. Adjust-
ular mass polymers in a liquid-like form that ment of the process parameters can also have
affords a convenient suspension viscosity, high an influence, for example, on the stability of an
solids content, and easy phase inversion during acrylate dispersion [752–755].
application [740–742]. Kinetic studies [756], [757] have shown that,
provided the feed rate is not too large, both
types of semi-batch polymerization experience
3.3.3.4.4. Semi-Batch Emulsion a quasi-steady state in which the polymeriza-
Polymerization tion rate and feed rate of monomer remain com-
parable. During the semi-batch feeding period,
In semi-batch polymerizations, water, the concentration of monomer [M]p is rela-
monomers, initiators, and emulsifiers may be tively constant and it stays below the satura-
added to a reactor over a time period which tion concentration predicted by Equation (3.34).
is comparable to the total polymerization time The resulting conversion – time curves are lin-
(usually over several hours). Several feed poli- ear over a wide range of monomer feed times.
cies have been employed. For example, a starting Increasing the monomer feed rate causes an in-
mixture of water, emulsifier, and initiator is first crease in [M]p and according to Equation (3.42)
prepared, usually also containing a portion of this also leads to increases in both Rp and PN .
the monomer; the remaining monomer (often to- Slower feed rates prolong the steady state pe-
gether with initiator) is added during the course riod, and this should result in a narrower MWD
of polymerization (monomer feed) [743]. With for the polymeric product [757], [758]. Prolong-
another procedure, the polymerization is begun ing the monomer feed period lowers [M]p and
in a portion of the total batch, the rest being raises polymer concentration. For certain types
fed into the reactor gradually after the onset of of monomer this can lead to greater long-chain
polymerization in the form of a monomer emul- branching and cross-linking [355], [357].
sion (emulsion feed), although the composition When every ingredient except a reserve por-
of the feed may well differ somewhat from the tion of the monomer is initially charged to the
material used to initiate the process [744]. reactor, the phase ratio of monomer/water differs
Semi-batch processes are intermediate bet- from the corresponding batch process, but this
ween batch and continuous polymerization pro- has no effect on the number of particles nucle-
Polymerization Processes 89
ated. On the other hand, when polymerization is to slow monomer feed, for example) then the
initiated in a portion of the complete recipe, the rate of polymerization will equal the monomer
number of polymer particles nucleated per unit feed rate. The rate of polymerization and heat-
volume of emulsion may not be the same as for generation rate will increase with increasing
a batch process. Clearly the number of particles monomer feed rate. The polymerization temper-
nucleated in the initial charge will be much less. ature can therefore be controlled by manipulat-
If the onset of addition is delayed until some ing the monomer feed rate.
time after polymerization has begun, then Stage For the control of copolymer composition
I (the nucleation stage) for the initial charge may distribution, various monomer feed policies may
have been completed. If no further particles are be used and equations have been developed to
nucleated during the semi-batch feed period, the determine the appropriate time-dependent feed
feed will be entirely directed towards the growth rates required [356], [357], [405]. Consideration
and stabilization of the existing polymer parti- of molecular mass, long-chain branching, and
cles. The number of polymer particles is then cross-linking is also possible [357].
fewer and their size at the end of the polymer-
ization is larger. Based on the same total recipe,
the two semi-batch processes just described can 3.3.3.4.5. Continuous Emulsion
be compared and contrasted as follows: Polymerization
When the initial charge and the semi-batch
feed have the same recipe (composition), fewer Continuous emulsion polymerization is used
(hence larger) latex particles are produced than particularly where the latex is to be coagu-
for the batch process or the semi-batch process lated and the solid polymer recovered. Im-
with just monomer fed to the reactor over time. portant examples include the manufacture of
If particle formation is avoided during the semi- styrene – butadiene rubber (cold SBR) [760–
batch period, then the initial rate of polymeriza- 762], acrylonitrile – butadiene rubber (NBR)
tion Rp, o and the number of particles nucleated [763], polychloroprene [764], [765], SAN and
N p will be proportional to the size of the initial ABS polymers [766–769], and poly(vinyl chlo-
charge. ride) [733], [770]. For products used in latex
Assuming particle formation does not oc- form, most manufacturers prefer the flexibility
cur during the semi-batch feed period, emulsion associated with batch and semi-batch processes,
feed provides a narrower PSD than monomer especially with product lines that are subject to
feed or batch polymerization. If particle for- frequent change. Apparently, however, there is
mation does occur during emulsion feed, then also a certain amount of large-scale polymer dis-
the PSD becomes broader, and in extreme cases persion manufacture by the continuous process.
it can be even broader than with the other Systematic investigations have been carried
processes. Particle formation during semi-batch out on the kinetics and mechanisms of par-
feed can be suppressed by using a larger amount ticle formation in continuous stirred-tank or
of initial charge and prolonging the time period stirred-cascade reactors for styrene [771–781],
before semi-batch feed is initiated (i.e., more styrene – butadiene [782], [418], [419], ethylene
polymer particles are nucleated and grow larger [783], vinyl chloride [733], [784], [785], vinyl
before semi-batch feed is initiated). Taking the acetate [786–791], methyl methacrylate [786],
increasing surface area into account also makes and methyl acrylate [776]. A tubular reactor has
it possible to adjust the emulsifier feed so that also been analyzed [780] and review articles are
new polymer particles are not nucleated and no available [792], [793] on the general subject of
coagulation occurs [759]. continuous emulsion polymerization.
As long as the rate of addition of monomer is The most important elements of the theory
sufficiently large to keep the polymer particles of emulsion polymerization in a stirred reac-
saturated, then the rate and degree of polymer- tor or stirred reactor cascade have been pre-
ization for both semi-batch processes are inde- sented by Gerhsberg and Longfield [771].
pendent of feed rate. They began with the Smith – Ewart assumption
If the monomer concentration falls below its that latex particles originate with the entry of
saturation value in the polymer particles (due an oligomeric radical into a micelle, and that
90 Polymerization Processes
radicals enter both latex particles and micelles be towards older and larger polymer particles)
according to their surface areas (collision the- and n̄ = 0.5 and combination with Equations
ory, with no distinction between micelles and (3.72) and (3.74) then gives
polymer particles). The following equation then
Ri,w τ
describes the steady state with particle formation Np = (3.76)
Kl Ri,w τ Kp τ [M]p
rate equal particle outflow rate (Case 2 kinetics 1+ a [s] l−K [M]
s 2 p
apply)
As can be seen the comparison of Equations
dNp Ri, w Am Np
= − = 0 (3.71) (3.74) and (3.76), the second term in the de-
dt Am +Ap τ
nominator of Equation (3.76) is analogous to the
where Am and Ap are the surface areas per unit quantity Ap /Am . At low concentrations of emul-
volume of latex for micelles and polymer parti- sifier [S] and high values of Ri, w and τ , it can
cles and τ is the mean residence time of a single be assumed that Ap /Am ≫ 1, so Equation (3.76)
CSTR. The residence-time distribution for latex takes on the simplified form
particles in a CSTR is given by !2/3
as [S] 1 −K2 [M]p
dNp 1 Np = (3.77)
E (t) dt = = exp (− t/τ ) dt (3.72) K1 (Kp τ )2/3 [M]p
Np τ
where E (t) dt is the fraction of latex particles in Substitution into Equation (3.42) then gives
the exit stream with age t. Because latex particles 1/3
!2/3
as [S] Kp 1 −K2 [M]p
are very small and have a density close to that of Rp =K3 [M]p (3.78)
τ 2/3 [M]p
water, the continuous phase, it is reasonable to
assume that the residence-time distribution of la- Here the constants K 1 –K 3 are functions of the
tex particles and the aqueous phase are the same specific volumes V m and V p of monomer and
(latex particles follow streamlines). polymer as well as of the molecular masses of
It is further assumed that the role of molecu- the monomers; K 1 and K 3 contain in addition the
larly dissolved emulsifier in the aqueous phase assumed constant n̄ = 0.5 within the latex parti-
can be neglected relative to the amount of emul- cles [771].
sifier in micelles and adsorbed on latex particles. In order to compare exprimental data ob-
Additional assumptions are that [S] ≫ CMC and tained over a wide range of conditions, it is con-
that venient to rewrite Equation (3.76) in dimension-
less form [772]:
as [S] NA =Am +Ap (3.73)
!2/3
Ri, w τ Ri, w τ τ Kp [M]p
The number of particles is then given by = 1 +K1 (3.79)
Np as [S] 1 −K2 [M]p
Ri, w τ
Np = (3.74) or
(1 +Ap /Am )
Figures 58 A and 58 B. In Figure 58 A, essen- though it had earlier been predicted on theoret-
tially all of the points lie above the 45◦ line; ical grounds for autocatalytic processes in gen-
that is, fewer latex particles are formed than eral [795–806]. Autocatalytic acceleration here
predicted by theory. By contrast, the experi- is a consequence of the Trommsdorff –Norrish
mental values for Rp in Figure 58 B, which are effect. The mass balance for monomer at steady
more precise, correspond well to the theoretical state is given by
straight line. Overall, one may conclude that in
the case of styrene the theory is well substanti- v̇ [M]0 − v̇ [M] −Rp V = 0 (3.81)
ated. The Gershberg – Longfield theory has been where υ̇ is the volumetric flow rate to and from
extended and modified a number of times. Thus the reactor, [M]o is the monomer concentration
DeGraff and Poehlein dropped the assump- in the feed, [M] is the monomer concentration
tion that n̄ = 0.5 and instead calculated n̄ using in the reactor and exit stream, V is the volume of
the Stockmayer – O’Toole solution for different the reacting mass in the reactor, and Rp is the rate
particle sizes (Eq. 3.41) [772]. This accounts for of polymerization in the reactor. Furthermore,
the possibility of more than one radical per par-
ticle for the larger particles. Nomura et al. [773] 1"
[M]0 − [M] =Rp (3.82)
also applied Equation (3.53), according to which τ
radicals are absorbed more rapidly into latex par- where τ = V /υ̇ is the mean residence time in the
ticles than into micelles, to continuous emulsion reactor.
polymerization and obtained a prediction that is Figure 59 shows a graphical solution of Equa-
in better agreement with experiment (as com- tion (3.82) and Rp versus monomer concen-
pared to that in Fig. 58 A). Brooks [794] dis- tration, in which data have been plotted as a
cusses various equations for the entry of rad- function of both monomer concentration [M]
icals into latex particles and micelles, assum- and conversion X. At low values of mean res-
ing among other things that micelles disintegrate idence time τ , there is one intersection (one so-
only slowly under subsaturation conditions, and lution) between experimental Rp = f ([M]) and
that even in the presence of micelles the surface the straight line (Eq. 3.82) which implies a single
of the latex particle may not be saturated with stable operating point at low conversion. By con-
emulsifier. trast, longer residence times lead to three points
of intersection, with stable operating points at
both low and high conversions and an unsta-
ble operating point at an intermediate conver-
sion. For a train or cascade of n stirred reactors
there may be as many as n + n (n + 1)/2 stable
operating points and n unstable operating points
for the individual reactors as well as n + 1 sta-
ble states for the entire cascade. Oscillations in
the number of particles, the polymerization rate,
and the interfacial tension have attracted consid-
erable theoretical attention. These are attributed
Figure 58. A) Number of particles according to Equation to bursts of particle formation that accompany
(3.79), and B) Overall rate of polymerization according to swings between states of supersaturation of the
Equation (3.80) for the continuous emulsion polymeriza- latex particle surfaces, indicating large amounts
tion of styrene (dimensionless representation) [772]
2 from [772] of free emulsifier (and micelles), and states char-
H from [771] acterized by undersaturation, in which particle
◦ from [776] formation almost ceases. This phenomenon has
• calculated from values for Rp with the assumption that long been recognized in industrial-scale con-
n̄ = 1/2
tinuous emulsion polymerization [733] and has
The existence of multiple steady states for now been thoroughly investigated in the case of
the isothermal operation of a CSTR was first styrene [771], [778], methyl methacrylate [786],
demonstrated in the case of continuous emulsion [807], [808], and vinyl acetate [786], [798],
polymerization by Gerrens et al. [776–778], al- [799], [809].
92 Polymerization Processes
has received a great deal of attention [818–836]. It is particularly effective for chemical modi-
These models are notable for the detailed kinet- fication of high molecular mass, solvent-free,
ics, which include transfer to polymer, backbit- commodity polymers to tailor-made products
ing, and β-scission in an attempt to calculate to meet the growing diversity in polymer ap-
both short- and long-chain branching frequen- plications. The extruder reactor provides short
cies. The polymerizations are almost adiabatic, and controlled residence times; efficient mix-
with large temperature increases, and phase sep- ing, particularly for reactants at low concentra-
aration between ethylene and polyethylene may tions; and good heat transfer. Multistage reac-
occur in autoclave reactors. The tubular reactor tion, with sequential feeding of reactants and
is considered to be in plug flow, while mixing removal of byproducts, is possible. There are
in the autoclave is rather complex and various certain advantages of twin-screw over single-
mixing models have been considered. A com- screw extruders [839]. These include: intense
prehensive copolymerization model for ethylene shear mixing (with better surface renewal rates)
and comonomers in a high-pressure continuous giving molecular-level mixing (micromixing),
tubular reactor has been developed [836]. improved heat transfer, multistage feeding, vent-
A comprehensive tubular reactor model for ing of volatile byproducts, and screw speed can
the solution polymerization of vinyl acetate has be changed without changing the throughput.
been developed by Hamer and Ray [837]. The These attributes of the twin-screw extruders are
kinetics employed account for transfer to poly- ideal for chemical modification where a small
mer and reaction with terminal double bonds amount of the low molecular mass compound to
(trifunctional branching frequencies are calcu- be grafted on the polymer chains must be ho-
lated). The model solves the equations of mo- mogeneously mixed with a highly viscous base
tion for both axial and radial velocity profiles. polymer.
Experimental validation of the model has been Chemical modifications are often carried out
carried out. using free-radical reactions in the temperature
The bulk and solution polymerization of range 170 ◦ C – 350 ◦ C. When a polymer con-
styrene in tubular reactors has also been exten- taining a peroxide and a compound to be grafted
sively studied both theoretically and experimen- is melt processed, chain scission, long-chain
tally [375], [838]. Spatial distributions of veloc- branching, cross-linking, and grafting reactions
ity, temperature, and concentration were mod- may occur simultaneously. To optimize product
eled [838] and it was shown that for tube diame- properties, the rates of these reactions must be
ters > 2 cm, thermal runaway may occur. Inter- controlled.
nal mixers were used in larger diameter tubes Chain Scission. Polymer chain scission oc-
to give better radial mixing and this technique curs when chemical bonds (usually C – C) along
appears to give polystyrenes with high molecu- the backbone break. Since a higher molecu-
lar mass at a productivity of commercial interest lar mass chain has a greater number of such
[375]. References to other important studies on bonds, it experiences chain scission preferen-
styrene production in tubular reactors may be tially (for polypropylene, scission seems to be
found elsewhere [375], [838]. random with respect to the position of the bond
along the chain backbone [840], [841]). There-
Chemical Modification of Polymers in Ex- fore, the broad MWDs, usually found for poly-
truders The commercial incentive for the chem- olefins narrow as the average molecular mass
ical modification of polymers by chain scission, falls. With random scission occurring exclu-
long-chain branching, cross-linking, and graft- sively, the limiting polydispersity for all initial
ing is the enhancement of the physical and chem- MWDs is two and the limiting MWD is Flory’s
ical properties of polymers and polymer mix- most-probable distribution. A reduction in mo-
tures (alloys, blends, additives) and/or improve- lecular mass improves processability. The out-
ment of their processability. In many cases, the standing commercial example of the use of con-
extruder has been found to be an effective chem- trolled chain scission of polypropylene (PP) is in
ical reactor in which chemical modification of the production of controlled-rheology PP used
high molecular mass polymers in the melt can for fiber manufacture, film-extrusion, and for
be done economically for low-volume products. fast molding applications [842].
94 Polymerization Processes
properties. Residence-time distribution (RTD) The gas-phase UNIPOL process has become
and micromixing can significantly affect the one of the most successful commercial processes
properties of the chemically modified polymer. for the production of polyolefins [858]. In this
One of the important advantages of twin-screw process, homo- and copolymerizations of ethyl-
over single-screw extruders is the greater control ene with α-olefin comonomers are carried out
they allow over RTD and mixing. The modeling in a fluidized-bed reactor using heterogeneous
of conventional or physical extrusion processes Ziegler – Natta or Philips supported metal oxide
has been well documented in the literature, par- catalysts [859].
ticularly for single-screw extruders. Details of Modeling of these processes can be classified
the modeling of extruders may be found in the re- into three categories [857], [860]:
view article by Tzoganakis [839]. Tzoganakis
et al. [855] developed a comprehensive rheoki- 1) Microscale kinetic phenomena: coordina-
netic model for the random scission of isotactic tion kinetic mechanism, multiple active site
polypropylene in a single-screw extruder. Finite- types, stereoregularity, copolymer composi-
element or finite-difference methods will play tion and molecular mass distributions, and
an important role in the solution of the three- catalyst deactivation kinetics
dimensional flow equations for both single and 2) Mesoscale particle phenomena: fracture of
twin-screw extruders [856]. catalyst particles, heat generation in parti-
cles, mass transfer, and growth and influence
of changing properties of reaction environ-
3.3.5. Ionic Polymerization Modeling ment
3) Macroscale reactor phenomena: overall
3.3.5.1. Introduction mass and energy balances, gas – liquid
mass transfer effects, influence of reaction
The most powerful processes for the control of medium, effects of particle motion, and heat
MWD of linear chains are living anionic and transfer limitations and influence of reactor
cationic polymerizations. These processes are type
interesting from the point of view of process en-
gineering because the MWD of the product can Similar modeling categories could be con-
be varied widely by changing the RTD of the sidered for the manufacture of PVC and EPS by
process or by oscillating the process in a con- free-radical suspension polymerization, where
trolled manner. These living ionic processes will particle morphology and foamed cell structure
be considered from this perspective in Section are important considerations.
3.3.6.1. One of the major challenges in modeling het-
erogeneous coordination polymerizations has
been to rationalize the very broad MWDs
3.3.5.2. Heterogeneous Coordination and copolymer composition distributions (CCD)
Polymerization that are often observed. There have been two
The commercially important anionic coordina- schools of thought. Ray and coworkers have
tion processes (heterogeneous ZN polymeriza- until recently attempted to explain the broad
tion) are now discussed. Seppala and Auer MWDs in terms of diffusional resistances for
have published an excellent review of much reactants, which increase as the catalyst parti-
of the relevant subject matter [857]. Third- cles are enveloped by a growing shell of poly-
and fourth-generation catalysts have already mer. An additional resistance may result from
been commercialized for slurry polymeriza- the crystallization of polymer chains. Others
tions. These newer catalysts possess high and have attempted to explain the broad MWDs and
stable activity, high stereospecificity indepen- CCDs as due to multiple sites of different ac-
dent of polymerization time, and increase in ac- tivity. These sites have different compositions.
tivity with increasing temperature up to about To model a binary copolymerization it can be
80 ◦ C. Electron donors may be used to regulate assumed that each site type produces a poly-
isotacticity. Catalysts may also be designed to mer with Stockmayer’s bivariate distribution
control the size and shape of polymer particles. [861], [862]. The more difficult problem is, of
96 Polymerization Processes
course, to determine the number of active site all polymers. It is thus important to know the
types and the concentration of each. Two active- distribution functions that correspond to vari-
site-type models have been used [862], [863] ous polymerization mechanisms and how these
as well as site-type distribution functions [864]. distributions change with reactor type and con-
Among the diffusion-limited models, the multi- figuration. Another way of expressing this is to
grain model is the most comprehensive. It is as- note that these molecular properties are strong
sumed that fragmentation of the original cata- functions of the residence-time distribution of
lyst particle is complete before appreciable poly- the polymerizing mass and that once an optimal
mer has been produced [865], [866]. Thus, the residence-time distribution has been established,
large macroparticle is composed of many cata- one can choose reactor types and manipulate re-
lyst fragments encapsulated by polymer [865], actor configuration to obtain this residence-time
[867–869]. Both macroparticle and microparti- distribution in a practical manner. Most devia-
cle mass transfer can be important for large cat- tions of predicted and measured molecular prop-
alyst particles of high activity [857]. Ray et al. erties are likely to be due to assumptions about
[868] found that the maximum possible temper- levels of micromixing and segregated flow and
ature rise in both micro and macroparticles is the comparison of predicted instantaneous mo-
negligible in slurry polymerization of propyl- lecular properties with measurements of these
ene. However, in gas-phase processes the tem- properties on accumulated polymer (e.g., instan-
perature inside the polymer particle could reach taneous properties can change with time in a
its melting point under some conditions [866]. batch reactor as, say, [M] decreases and hence
Near the beginning of polymerization, the poly- the distributions for molecular properties for
mer particles may heat up because of the high the accumulated polymer will have larger vari-
catalyst activity and polymerization rate. In sum- ances). From an industrial standpoint, however,
mary, it can be said that the very broad MWDs any process of interest involves high – if not
and CCDs can be explained by invoking mul- complete – conversion, and a wide variety of
tiple site types. However, under certain condi- batch and continuous reactors is utilized. The
tions, mass- and heat-transfer resistances may relationships between reactor types and config-
also play a significant role. The development urations and the various polymerization mecha-
of more realistic models for copolymerization nisms are often quite complex, and it will only
on heterogeneous coordination catalysts will re- be possible within the confines of this article to
quire the measurement of the bivariate distri- treat certain simple ideal reactors and reaction
bution of molecular mass and composition by types.
a combination of analytical techniques such as Figure 61 shows four ideal reactors, char-
TREF/GPC and TREF/NMR to observe the de- acterizing them on the basis of residence-time
tailed microstructure of the copolymer chains distribution and the temporal and spatial course
[870]. of chemical reaction. Batch reactors (BR), con-
tinuous plug flow reactors (CPFR), and homo-
geneous continuous stirred-tank reactors (HC-
3.3.6. Process Variables, Reactor Dynamics/ STR) are treated in the article Stirred –Tank and
Stability, On-Line Monitoring and Control Loop Reactors. With a homogeneous continu-
3.3.6.1. Influence of Reactor Type and ous stirred-tank reactor, perfect mixing down to
Configuration on Molecular Mass and the molecular level is assumed, and for a CSTR
Copolymer Composition Distributions, and with an ideal residence-time distribution, there
on Long-Chain Branching and are by definition no spatial variations in tempera-
Cross-Linking ture and concentrations. Mixing at the molecular
level is often called “micromixing”. This condi-
Survey of Idealized Reactor Types and tion is often not achieved in practice, however,
Simple Polymerization Reactions. Molecular and for this reason a fourth ideal reactor type
mass and copolymer composition distributions, is introduced, the segregated continuous stirred-
long-chain branching, and cross-linking can ex- tank reactor (SCSTR) [801–803]. Here the fluid
ert a significant influence on the properties of phase is regarded as subdivided into many small
Polymerization Processes 97
Figure 61. Schematic illustration of the course of reaction in various types of reactors
E/E 0 = mass fraction of the material throughput traversing the reactor with a residence time between t and t + dt; C A = concen-
tration of component A; t = time; τ = mean residence time; x = spatial coordinate; L = reactor length; n = order of the reaction
Figure 62. Cumulative degree of polymerization P̄N as a Under the assumption that R1 = constant (con-
function of conversion for various polymerization reactions stant radical generation rate; half-life t 1/2 of
a) Monomer coupling with termination; b) Monomer cou- the initiator ≫ residence time τ of reactor con-
pling without termination; c) Polymer coupling tents) and [M] = constant (small conversion in-
crement), the instantaneous degree of polymer-
Polymerization Processes 99
Table 5. Molecular mass distribution for polymerization reactions in various types of reactors
where
kp [M]
ϕ=
kp [M] + (Ktd RI )1/2
frequency distribution decreases with increasing chain-transfer agents) is negligible can cause
conversion. However, since σ 2 = P2N (PDI − 1), dramatic increases of molecular mass with con-
σ 2 continuously decreases as PN decreases with version. See, for example, data for the change of
conversion, except in the case of a monodisperse molecular mass distribution with conversion for
MWD with PDI = 1. For this reason, one of the the bulk homogeneous polymerization of methyl
quantities PDI or U is preferred for expressing methacrylate [380]. On the other hand, when
distribution breadth. chain transfer to monomer (as in vinyl chloride
polymerization) or to chain-transfer agent pro-
duces most of the polymer chains, the Tromms-
dorff effect has no influence on molecular mass
development. In particular, when chain trans-
fer to monomer produces most of the polymer
chains, molecular mass development will de-
pend on temperature and be independent of pro-
cess type and reactor type [889].
with a polydispersity
1
PDI =PW /PN = 1 + (3.93)
η
Thus the distribution becomes narrower as large number of molecules with equal residence
the contribution from statistical broadening de- times. The molecular mass distribution is there-
creases with chain growth (increase in η) (cf. fore subject to less broadening relative to a batch
the bottom curve in Fig. 71). A comparison of reactor than in the case of the HCSTR. At very
Equations (3.87) and (3.93), or inspection of Fig- low conversion, it is possible to assume constant
ure 70 indicates that Poisson distribution is sig- monomer concentration, so the distributions in
nificantly narrower than the Schulz – Flory dis- the three reactor types are almost identical. At
tribution. high conversion the effect of the residence-time
distribution diminishes. At complete conversion
the lifetime of the active species must be signifi-
cantly shorter than the mean residence time, and
the molecular mass distribution becomes equiv-
alent to that in a batch reactor. Figure 70 shows
the transition from a Schulz – Flory to a Pois-
son distribution with increasing conversion. Fig-
ure 71 is a plot of polydispersity PDI as a func-
tion of PN and x. The bottom curve (for x = 1.0)
corresponds to Equation (3.93) for a batch reac-
tor.
pp. 336 – 339], [873], [882], [883], [902], [905– polymerization the Schulz – Flory distribution
908]. always has a PDI = 2 because ϕ, the probabil-
ity of propagation, is almost always very close
to unity. This is not so for polycondensations,
where p can vary from 0 to 1, and thus PDI varies
from 1 to 2.
Figure 75. Composition of the copolymer produced in a batch reactor (BR) as a function of monomer composition of the
charge as well as conversion
First column: instantaneous composition; second column: instantaneous compositions, starting with monomer ratios
[M1 ] : [M2 ] = 1 : 3, 1 : 1, and 3 : 1; third column: cumulative compositions based on the same starting ratios
Figure 76. Ternary copolymerization in the system styrene (M 1 ), 2,5-dichlorostyrene (M2 ), and acrylonitrile (M3 ) [912]
A) Instantaneous copolymer composition (arrow point) as a function of composition of the monomer mixture (origin of the
arrow); B) Partial azeotropes, where arrows outside the diagram indicate the positions of binary azeotropes
STR and SCSTR systems would therefore ap- more than two comonomers. Figure 76 shows a
pear inappropriate (extreme viscosities would three-fold combination represented in terms of
be inappropriate for a CSTR). On the other triangular coordinates. The compositions of var-
hand, many polycondensations and polyaddi- ious comonomer mixtures are indicated by the
tions are accompanied by rearrangements at origins of arrows, with the corresponding arrow
the heteroatoms, including transesterifications points showing the instantaneous compositions
or transamidations. This means that polymer of the resulting polymers. The length of an ar-
with a Schulz – Flory distribution would be ob- row is thus a measure of the deviation between
tained even in an HCSTR [435, pp. 336 – 339], compositions of free monomer and copolymer.
[911]. Such an arrow degenerates to a point in the case
of an azeotropic composition. A phenomenon
known as “partial azeotropy” is of interest in the
3.3.6.1.4. Copolymerization context of multicomponent systems, with only
The theory of copolymerization kinetics is co- one of the monomers represented by an identical
vered in Section 2.3. However, the performance mole fraction in both copolymer and monomer
of the three reactor types (CPFR/BR, HCSTR, mixture. Thus, for ternary copolymerization
and SCSTR) were not compared and therefore m1 [M1 ]
this topic is considered here. = (3.101)
m1 +m2 +m3 [M1 ] + [M2 ] + [M3 ]
Figure 77. Copolymer composition distributions (CCDs) for the monomer pairs of Figure 75. CCDs of completely polymer-
ized batches with molar ratios [M1 ] : [M2 ] = 1 : 3 (first column), 1 : 1 (second column), and 3 : 1 (third column)
The mean composition of the copolymer corresponds to that in the batch. The height of each block represents that fraction of
the overall copolymer that has a composition within the block width of 0.05
Experimental data and calculated values as a function of f 1 ; 60 ◦ C, [I] = 1 g/L azobisisobutyronitrile
statistical distribution about a mean [913], [914], composition. The only other situation in which
although at high degrees of polymerization this the composition of the copolymer corresponds
variation is minor in comparison to the hetero- precisely to the composition of the monomer
geneity that results from progressive changes in mixture in the feed is the technically unrealis-
the composition of the monomer mixture with tic limit of complete conversion, which would
conversion. require impractically long residence times. The
instantaneous copolymer equation, of course,
Copolymerization in an HCSTR. In an can always be used when monomer composi-
HCSTR operating at steady state the tempera- tion in the exit stream is used (as opposed to
ture and concentration are constant in both space inlet stream) [915], [916]. Figure 78 shows the
and time. The result is therefore a chemically change in steady-state copolymer composition
uniform copolymer. In the limiting case of very for the system styrene/acrylonitrile (40/60) as
low conversion, the copolymer composition cor- a function of conversion. Thus, a copolymer
responds to the predictions of Equation (2.121) with a particular composition can be made in
and Figure 75 when concentrations of monomer practice (at least approximately) either by estab-
in the inlet stream are used to calculate monomer lishing in advance a preferred composition for
108 Polymerization Processes
the monomer feed and then varying the extent of again producing a uniform CCD. The amount
conversion, or by varying the feed composition of homopolymer produced is, of course, greater
at a fixed conversion. at 73 % than at 35 % conversion.
Figure 81 shows predicted versus measured be valid for low-viscosity solution processes;
heterogeneity index (polydispersity index or however, in bulk polymerization, the viscosity
M W /M N ), covering the range from that obtained can increase by several orders of magnitude and,
in a PFR or batch reactor to that obtained in a therefore, all 3 assumptions are questionable.
single CSTR. Figure 82 shows the polydisper- Henderson again points out that a thermal run-
sity for 2 CSTRs of equal volume in series with away can occur when:
equal conversion of monomer in each, giving the
lowest value of polydispersity, 1.5. 1) The process side heat-transfer coefficient de-
creases significantly
2) The agitator provides insufficient mixing of
3.3.6.2. Reactor Dynamics and Stability the reaction mass, allowing hot spots to de-
velop
Reichert and Moritz [918] discuss reactor sta- 3) The agitator is putting more mechanical
bility and safety under the subtopics thermal and work into the system than designed for
concentration stability. The strong nonlinear de-
pendence of polymerization rate (or heat pro- Ray et al. [788–791], [936–945] have made
duction rate) on temperature is due to the Ar- the most significant contributions to the under-
rhenius dependence of rate on temperature and standing of polymer reactor dynamics and sta-
to the large activation energy and heat of poly- bility. Comprehensive reactor models were de-
merization. The dynamic behavior of polymer veloped for a range of polymerization processes
reactors is therefore greatly affected by temper- and reactor types: nonisothermal solution homo-
ature. The influence of the nonlinear dependence and copolymerization in a CSTR [931], [939],
of polymerization rate on monomer concentra- [940]; batch and continuous emulsion polymer-
tion, on reactor dynamics is much smaller than ization reactors [788–791], [941], [942]; hetero-
that for thermal effects. Both static and dynamic geneous coordination polymerization for both
instabilities may occur when stability limits are liquid and gas dispersion reactors [943–945].
crossed. The reactor is statically unstable if tem- The contributions by Ray et al. are notable not
perature and conversion rapidly move from one only for the comprehensive mathematical mod-
state to another as if alternately experiencing “ig- els but also for attempts at experimental verifi-
nition” and “extinction”. Dynamic instabilities cation. In this regard, the experimental investi-
give rise to periodic changes in temperature and gation of the effect of chain-transfer agents on
monomer conversion with certain phase shifts the stability of continuous latex reactors is very
observed [931], [932]. Thermal instabilities may revealing. Whereas under most operation con-
occur in various reactor types (CSTR, PFR, non- ditions the continuous emulsion polymerization
ideal reactors) [933], [934]. Henderson [935] of styrene is stable, the addition of a chain-trans-
points out that for all prior publications on mul- fer agent to the recipe can lead to sustained os-
tiple steady states and instability for free radical cillations. Some of Ray’s general conclusions
polymerization in a CSTR, three basic assump- include:
tions were made: 1) Bifurcation analysis reveals a parame-
1) The heat-transfer coefficient of the vessel ter space rich in dynamic phenomena. It
wall does not change with monomer conver- confirms limit cycle behavior (in which
sion monomer conversion does not smoothly ap-
2) The viscous dissipation term for the agitation proach a constant steady-state value, but
is negligible rather oscillates with constant frequency and
3) Perfect mixing (ideal RTD and micromixing) amplitude indefinitely) and analyzes the sta-
bility of periodic branches in detail providing
Mechanical work of the agitator can be a sig- useful guidelines for experimental design.
nificant factor in the energy balance for a pilot- 2) Full-scale reactors exhibit dynamic behavior
scale reactor (perhaps for solution and bulk poly- of high complexity.
merization, but not for suspension and emulsion 3) Semi-batch reactors can be operated under
polymerization), while it is almost negligible for conditions that insure a fast approach to a
commercial scale. Assumptions (2) and (3) may
Polymerization Processes 111
steady-state operating value, hence permit- time require measurements and parameter up-
ting almost perfect control. The possibility of dating to track and control the process. The need
oscillatory behavior was, however, demon- for monitoring the polymerization is clear and
strated. to be most effective in controlling the process,
4) Multiplicity (multiple steady states) oc- on-line monitoring is highly desirable. A survey
curs under isothermal conditions due to the of on-line sensors for polymerization reactors
Trommsdorff – Norrish effect and there ap- was made by Chien and Penlidis [947]. Al-
pears to be no relationship between phenom- though considerable advances have been made
ena causing multiplicity and reactor oscilla- in polymer reaction engineering over the past
tions. two decades, sensor technology for on-line mon-
5) The PSD plays a major role in latex reac- itoring is still in its infancy. The major problem
tor stability. Models which calculate only a has been the on-line measurement of polymer
mean diameter d (and not the full PSD) can- and particle properties (copolymer composition,
not predict oscillations under any operating molecular mass averages, long-chain branching,
conditions. as well as cross-linked gel content and poly-
6) Polymer particle multiplicity, which leads to mer particle size distribution in suspension and
polymer melting and sticking (in gas-phase emulsion polymerization). Sensors in the reac-
heterogeneous coordination polymerization, tion mixture are readily fouled by sticky polymer
such as UNIPOL) can cause a thermal run- and polymer particles. Another factor to explain
away of the reactor (UNIPOL is open-loop the lack of progress is the fact that sensor devel-
unstable). Multiplicity and Hopf bifurcation opment is a multidisciplinary task with exper-
of the fluidized-bed reactor can lead to run- tise required in statistics, mathematical model-
away and long periods of slowly damped os- ing, process understanding, reactor design, ad-
cillations. The reactor is prone to runaway vanced control concepts, electronics, and in-
even under feedback control because of cool- strumentation engineering [947]. Even the mea-
ing limitations and nonlinear sensitivity to surement of polymer properties off-line is diffi-
process disturbances. cult (e.g., measurement of molecular mass aver-
Lu and Brooks [946] have confirmed that la- ages and long-chain-branching frequencies for
tex reactor startup policy can have a significant heterogeneous copolymers [870]). Chien and
effect on reactor stability. Penlidis [947] classify sensors as those which
It is clear, based on these studies of reactor monitor reactor operation [by measuring tem-
stability, that a comprehensive dynamic model perature, pressure, flows and level (of reaction
of the polymerization reactor is required to prop- mixture in the reactor)], and those that moni-
erly design a continuous manufacturing process tor polymer properties (e.g., by measuring den-
(process stability, control, and startup proce- sity, viscosity, concentrations, copolymer com-
dures should be considered at the design stage). position, particle size, using densitometers, vis-
The interactions are too complex to permit an ef- cometers, gas and liquid chromatographs, IR and
fective design based on costly experimentation UV spectrophotometers, light scattering, ultra-
alone. sonics, fiber-optic techniques, robotics, reactor
energy balances, and state estimation/filtering
techniques). Most of the commercial applica-
3.3.6.3. On-Line Monitoring and Control tions of on-line monitoring involve those which
monitor reactor operation, although reactor en-
The goals in commercial polymerizations are ergy balances are commonly used to monitor
consistent polymer properties, high productiv- monomer conversion. The main problem with
ity, and safe operation achieved in the most eco- the successful use of reactor energy balances lies
nomic manner possible. Polymerizations (par- in the evaluation of the transient accumulation
ticularly ionic and free-radical) are very sensi- terms (time derivatives of temperature) and in
tive to temperature and impurities (radical scav- accounting for the propagation of measurement
engers and poisons at ppm levels) and, therefore, errors (temperature and flow rate) into the cal-
adjustments may have to be made during poly- culated heat release term. Acceptable results are
merization. Process models when applied in real
112 Polymerization Processes
often obtained through rapid sampling and then timating these properties on-line by using fun-
averaging or filtering all the measurements at damental mathematical models have been pro-
regular short intervals [949]. posed. State estimators such as the Kalman Filter
Two promising on-line monitoring tech- [952], [953] and recursive parameter estimators
niques are based on the use of ultrasound and [954] have been advocated to update model pa-
NIRS (near infrared spectroscopy) [948]. Ul- rameters and predict polymer properties.
trasonic velocity and attenuation measurements Feedback control over measured or inferred
have been used for monitoring high-temperature properties in continuous reactors has been ac-
composition in extruders and melt-transfer lines; complished by using empirical models [955],
high-temperature imaging studies in extruders; [956].
and for ultrasonic spectroscopy of dispersions. However, in spite of the many advances that
NIRS is an older technique which has been im- have been made in the methodology for the ad-
proved by newly available computing power. vanced control of polymerization reactors, there
It is the most promising process spectroscopy are still few industrial applications.
available at present because of its process com-
patability and ability to analyze multicomponent
mixtures. NIRS has been applied as an on-line
monitoring technique for both extruders used for
chemical modification and polymer reactors.
The on-line monitoring and control of poly-
mer and polymer particle properties should pro-
vide a major improvement in product consis-
tency and productivity.
There have been a number of excellent re-
views on control of polymerization reactors
[947], [949], [950]. Most industrial control prac-
tice to date has centered around batch reactor
sequencing and the control of process variables
such as temperature, pressure, and viscosity. Re- Figure 83. Continuous emulsion polymerization in a reac-
actor energy balances, as mentioned earlier, have tor train with a split feed (small polymer particle nucleating
also been used to infer polymer production rates reactor followed by one or more larger finishing reactors)
[956]
and monomer conversion. a) Small seeding reactor; b) First large reactor in train
Much of the academic literature has focused
on the computation of optimal operating poli- To again emphasize the point that control
cies for batch reactors by using nonlinear pro- problems should be considered at the design
gramming or the maximum principle [374]. stage of a polymer manufacturing process, ref-
These policies are open-loop in that they provide erence is made to the well-known stability prob-
optimal feed and temperature policies versus lems that are experienced with continuous emul-
time. Kozub and MacGregor [951] presented sion polymerization (in a single CSTR) involv-
a much simpler solution to the optimal trajec- ing monomer(s) that experience Case I kinetics
tory problems based on an “instantaneous prop- (e.g., vinyl acetate and vinyl chloride). Modern
erty” approach. This latter approach is applica- control theory did not provide suitable control
ble only to chain-growth polymerizations (see methodology for the single CSTR. It was de-
Section 2.2 for details of instantaneous property cided, therefore to go back to the design stage,
calculations), but it allows for the feedback im- redesign the process by using a dynamic reac-
plementation of these optimal policies via non- tor model and minimize control problems at the
linear control. design stage. The new design which is shown
Due to the lack of sufficient on-line sen- in Figure 83 has almost trivial control problems
sors to monitor polymer properties of interest or [949], [956]. Experimental verification of the in-
because some property measurements are only crease in stability of this new design may be seen
available infrequently from quality control lab- in Figure 84. The initial response (conversion
oratories, various methods for inferring or es-
Polymerization Processes 113
Figure 84. Conversion responses to CSTR reactor system shown in Figure 83 for continuous emulsion polymerization of vinyl
acetate
Part A: operation with a single CSTR (shows sustained oscillations)
Part B: switching over to seed reactor followed by one finishing reactor (responses for both reactors are shown, with very
stable response for downstream reactor and minor disturbance for seed reactor) [611]
versus time) is for a single CSTR. The follow- 9. R. W. Lenz: Organic Chemistry of Synthetic
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