8289gda

Mathematical Modeling of Multicomponent Chain-Growth
Polymerizations in Batch, Semibatch, and Continuous Reactors: A

Review
Marc A. Dube
Department of Chemical Engineering, University of Ottawa, Ottawa, Ontario, Canada K1N 6N5
Joa o B. P. Soares and Alexander Penlidis*
Department of Chemical Engineering, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1
Archie E. Hamielec
McMaster Institute for Polymer Production Technology, Department of Chemical Engineering,
McMaster University, Hamilton, Ontario, Canada L8S 4L7
A practical methodology for the computer modeling of multicomponent chain-growth polymeriza-
tions, namely, free-radical and ionic systems, has been developed. This is an extension of a
paper by Hamielec, MacGregor, and Penlidis (Multicomponent free-radical polymerization in
batch, semi-batch and continuous reactors. Makromol. Chem., Macromol. Symp. 1987, 10/11,
521). The approach is general, providing a common model framework which is applicable to
many multicomponent systems. Model calculations include conversion of the monomers,
multivariable distributions of concentrations of monomers bound in the polymer chains and
molecular weights, long- and short-chain branching frequencies, chain microstructure, and cross-
linked gel content when applicable. Diffusion-controlled termination, propagation, and initiation
reactions are accounted for using the free-volume theory. When necessary, chain-length-
dependent diffusion-controlled termination may be employed. Various comonomer systems are
used to illustrate the development of practical semibatch and continuous reactor operational
policies for the manufacture of copolymers with high quality and productivity. These
comprehensive polymerization models may be used by scientists and engineers to reduce the
time required to develop new polymer products and advanced production processes for their
manufacture as well as to optimize existing processes.
1. Introduction
Mathematical models and their role in science/
engineering are points of constant debate, especially
when models are employed in an industrial environ-
ment. The role of a mathematical model is often
misinterpreted; as a result, we frequently blame the
model, instead of blaming our own lack of understand-
ing about a process as well as our reluctance to experi-
ment with a process in a meaningful and systematic
way.
Why, then, are models useful?
1. Models enhance our process understanding since
they direct further experimentation. They act as the
reservoir of ones knowledge about a process, and hence
they may reveal interactions in a process that may be
difficult, if not impossible, to visualize/predict solely
from memory or experience, especially when many
factors vary simultaneously. Since a model is a concise,
compact form of process knowledge, models enhance
transferability of knowledge; they may act eventually
as an inference engine, closely resembling the train
of thought of an experienced human. In a sense,
mathematical modeling is the best way to find out what
one does not know about a process!
2. Models are useful for process design, parameter
estimation, sensitivity analysis, and process simulation.
The significance of these is quite obvious. A valid model
allows one to test deviations from process trajectories
using a simulator in lieu of running experiments. Cost
effectiveness implications are also obvious.
3. Models are useful for process optimization, espe-
cially when dealing with highly nonlinear problems such
as grade changes/switchovers in batch, semibatch, and
continuous reactors. Extensions to recipe modifications
and design are another application.
4. Models are useful for safety/venting consider-
ations. It is very useful to be able to extrapolate to
different operating conditions and anticipate worst-case
scenarios or investigate the possible effects of process
factors. In this case one may be better prepared to
tackle situations that might not always be apparent
from the outset.
5. Models are useful for optimal sensor selection and
testing, sensor location, filtering and inference of un-
measured properties, and process control. The trends
nowadays in process control are toward model-based
control, and as the term signifies, application of ad-
vanced control techniques may not be possible without
a model.
6. Finally, since a model contains process knowledge
and is transferable, interactive models are extremely
useful for the education and training of new (and old)
personnel.
In this paper, a practical methodology for the com-
puter modeling of multicomponent chain-growth poly-
merizations, namely, free-radical and ionic systems, is
developed. This is an extension of the paper by Hamielec
* To whom correspondence should be addressed. Phone:
(519) 888-4567. Fax: (519) 746-4979. E-mail: penlidis@
cape.uwaterloo.ca.
E-mail: dube@genie.uottawa.ca.
966 Ind. Eng. Chem. Res. 1997, 36, 966-1015
S0888-5885(96)00481-2 CCC: $14.00 1997 American Chemical Society
et al. (1987). The approach is general, providing a
common model framework which is applicable to many
multicomponent systems. Various comonomer systems
are used to illustrate the development of practical
reactor operational policies for the manufacture of
polymers with high quality and productivity.
Thorough general reviews of polymerization reactor
modeling have recently been published (Penlidis et al.,
1985b; Hamielec et al., 1987; Rawlings and Ray, 1988).
The model developed in this paper employs the pseudo-
kinetic rate constant method (Hamielec et al., 1987;
Tobita and Hamielec, 1991; Xie and Hamielec, 1993a,b).
Our development uses many techniques and ideas
similar to those contained in Hoffman (1981), Broad-
head et al. (1985), Penlidis et al. (1986), Hamielec et al.
(1987), Mead and Poehlein (1988, 1989a), Rawlings and
Ray (1988), Maxwell et al. (1992b), Fontenot and Schork
(1992-93a,b), Xie and Hamielec (1993a,b), Casey et al.
(1994), and Urretabizkaia and Asua (1994).
2. Model Development: Free-Radical
Polymerizations
The objective of this section is to define the equations
which form a mechanistic model to simulate bulk (or
suspension), solution, and emulsion free-radical homo-
polymerization, copolymerization, and multicomponent
polymerization (three or more monomer types) in well-
stirred batch, semibatch, and continuous modes. The
equations presented in this section are valid for the
general case of an unsteady-state CSTR. For a CSTR
operating at steady state, the accumulation derivative
terms can be set equal to zero to give a set of algebraic
equations. For a semibatch reactor, the outflow terms
should be eliminated, and for a strictly batch reactor,
all inflow and outflow terms should be eliminated.
However, it is usually advantageous to consider com-
plete equations since one has the flexibility of handling
all these reactor situations with a single model.
The model is comprised of a set of mathematical
expressions which describe the physical and chemical
phenomena of polymerization. It consists of a set of
differential equations that describe material and energy
balances on the reaction mixture. For computational
purposes, the model is split into two categories. The
first category consists of bulk, suspension, and solution
polymerization, while the other describes the emulsion
case. In the model development, we shall examine both
categories in parallel.
Bulk, suspension, and solution polymerizations are
characterized by the fact that all of the reaction steps
proceed in a single phase. A model for a reactor
carrying out such polymerizations would consist of a set
of material balances describing the rates of accumula-
tion, inflow, outflow, and disappearance by reaction of
the various monomers, initiators, polymers, and other
ingredients in the reactor. These polymerizations con-
sist of initiation, propagation, termination, and transfer
reactions occurring simultaneously through the full
conversion range. Conventional emulsion polymeriza-
tions usually occur in three stages and are comprised
of more than one phase (reactor head-space; the mono-
mer droplets, which act as a monomer reservoir; the
(continuous) aqueous phase, which can act as a locus of
polymerization as well as a species transport medium;
and the polymer particle phase, the main locus of
polymerization). The first of the three common polym-
erization stages involves the nucleation (birth) of poly-
mer particles. This can occur by either micellar or
homogeneous (coagulative) nucleation. The second
stage involves the growth of the particles until the
monomer droplets disappear. The third stage begins
with the disappearance of the monomer droplets and
continues until the end of the reaction.
The emulsion polymerization model can be briefly
described as follows. First, the initiation can be ac-
complished via a redox mechanism or via thermal
decomposition of an initiator. The fate of radicals
(initiator, monomeric, and oligomeric) in the water
phase is propagation with dissolved monomers in the
water phase, reaction with water-soluble impurities
(WSI), termination in the water phase, possible recom-
bination of initiator fragments, reaction with monomer
droplets, desorption from polymer particles, reabsorp-
tion of desorbed radicals into polymer particles, capture
by emulsifier micelles, and capture by polymer particles.
The birth of particles can be accomplished by homoge-
neous (aqueous phase) nucleation, micellar nucleation,
and particle coalescence. Once captured by particles (or
micelles or droplets), the radicals may propagate, mutu-
ally terminate, react with monomer-soluble impurities
(MSI), react with chain-transfer agent (CTA), undergo
chain transfer to monomer, undergo chain transfer to
polymer, and participate in internal and terminal
double-bond polymerizations. The average number of
radicals per particle is followed by accounting for entry/
absorption of radicals from the water phase, radical-
radical termination, radical-MSI termination, and
desorption of radicals into the water phase. The par-
titioning of monomer, monomer-soluble impurities, and
CTA into the various phases is another important factor.
For both the bulk/suspension/solution and emulsion
models, material balances on the various components
of the polymerization are used to calculate the conver-
sion, composition, molecular weight, and, in the case of
emulsion polymerizations, particle size and number.
Other, not necessarily measurable, polymer properties
can also be calculated or inferred. Finally, molecular
weight averages dependent on termination, branching,
and transfer reactions are estimated.
The various symbols, subscripts and superscripts, and
variables are shown in the Nomenclature section. The
units of the variables are also shown therein.
2.1. Initiation. The first step in a polymerization
involves the creation of highly reactive free radicals.
This is accomplished in the initiation stage. Bulk,
suspension, and solution polymerizations involve organic-
soluble initiators such as 2,2!-azobis(isobutyronitrile)
(AIBN). The initiator is decomposed into free radicals
by thermal or photochemical (ultraviolet light) means.
In emulsion polymerizations, there are two commonly
used initiation methods. The first, redox initiation, is
used for low-temperature polymerizations, while initia-
tion by thermal decomposition is used for the higher
temperature range.
Andersen and Proctor (1965) suggested the following
mechanism for the redox system persulfate (PS)/sodium
formaldehyde sulfoxylate (SFS)/iron (Fe).
(Symbols not explained in the text are given in the
S
2
O
8
2-
+ Fe
2+
98
k
1
SO
4
-
+ Fe
3+
+ SO
4
2-
(1)
Fe
3+
+ RA 98
k
2
Fe
2+
+ X (2)
SO
4
-
+ M
j
98
k
pIj
R
1,j
(3)
Ind. Eng. Chem. Res., Vol. 36, No. 4, 1997 967
detailed Nomenclature section.) In the above mecha-
nism, M
j
refers to monomer of type j; S
2
O
8
2-
represents
the persulfate initiator, I; RA is the reducing agent (in
this case SFS), often referred to as activator; SO
4
-
is
the initiator fragment that reacts with monomer, M
j
,
to produce primary radicals R
1,j
, i.e., radicals of chain

length 1 ending in monomer j. k
1
is the rate constant
for the oxidation reaction, k
2
is the rate constant for the
reduction reaction, and k
pIj
is the propagation rate
constant for the addition of monomer j to an initiator
fragment. Radicals are generated in the water phase
by the reaction between the initiator (PS) and a complex
of Fe
2+
and ethylenediamine tetrasodiumacetate (EDTA)
(see eq [REF:eqn:ini1]). The complexation of iron and
EDTA reduces the effective concentration of Fe
2+
and
prevents undesirable side reactions. Thus, the initiator
is reduced to a negatively charged free radical, while
the Fe
2+
is oxidized to Fe
3+
(see eq 1). The SFS then
reduces Fe
3+
to Fe
2+
(see eq 2). The free radical, SO
4
-
,
reacts with monomer j to form radicals of chain-length
unity (see eq 3). Broadhead et al. (1985) used a similar
scheme to describe redox initiation for styrene/butadiene
(SBR) polymerization.
Performing material balances for the initiator (I or
PS) and the reducing agent (RA) gives
where N
i
is the number of moles of component i, F
i,in
is
the inflow of component i into the reactor in mol min
-1
,
V
w
is the volume of the water phase, V
T
is the total
volume of the reaction mixture, and v
out
is the volumet-
ric flow out of the reactor. The time dependence of all
terms involved in the equations is not shown for the
sake of brevity. One should note that k
1
and k
2
are
effective rate constants, since other (unknown) el-
ementary reaction steps may be occurring but have been
assumed to have a negligible contribution to the overall
initiation rate. This will simplify our set of equations.
Further simplification occurs when we apply the reactor
stationary-state hypothesis to ferrous and ferric ions to
provide the ion concentrations in terms of total iron
concentration as follows:
where
and
For the case of thermal decomposition of a persulfate
initiator, the commonly accepted mechanism is (Sarkar
et al., 1988)
where k
d
is the initiator decomposition rate constant.
This mechanism results in the following material bal-
ance for the moles of initiator:
Finally, the overall rate of initiation, R
I
, is
where [I] is the initiator concentration and f is the
initiator efficiency factor. Equation 12 is implemented
into the computer model as shown above and includes
the rate of initiation by redox means and thermal
means. However, when one of the methods is activated,
the term representing the other option becomes negli-
gible.
The acceleration of the decomposition of potassium
persulfate (KPS) by free sodium dodecyl sulfate emul-
sifier has been reported by Okubo et al. (1991). Sarkar
et al. (1990) reported the acceleration of KPS decompo-
sition due to the addition of vinyl acetate (VAc) mono-
mer, but no emulsifier effect was detected. Consider-
ations such as these may be responsible for some
discrepancies between model predictions and experi-
mental data.
Often, the initiator efficiency is considered to be
constant. However, in a high-viscosity regime the
initiator efficiency may decrease significantly (Garcia-
Rubio and Mehta, 1986; Russell et al., 1988b; Zhu et
al., 1990a). Since initiator decomposition occurs in the
water phase for conventional emulsion polymerizations,
it is likely that initiator fragments are not subject to a
high-viscosity environment and the initiator efficiency
is thus held constant (Adams et al., 1990). One can then
argue that, if the initiator efficiency changes, this
represents water-soluble impurity effects. For bulk
and solution polymerizations, however, the following
semiempirical equation is used to describe the changing
initiator efficiency when the free volume of the reaction
mixture (V
F
) becomes less than a critical free volume,
V
Fcrif
:
where f
o
is the initial initiator efficiency and C is a
parameter which modifies the rate of change of the
efficiency. The critical free volume, V
Fcrif
, is dependent
on temperature and initiator type. The initiator ef-
ficiency typically becomes diffusion-controlled at very
high conversions (>80 wt %). The calculation of the free
volume, V
F
, will be discussed later.
In the model, therefore, eqs 4-7 and 11-13 are used
directly to describe the initiation step.
2.2. Water Phase Reactions. The discussion in this
section is restricted to emulsion polymerizations. Once
the radicals are generated in the water phase, they can
then go on to propagate with monomer, react with
various other species in the reaction mixture, and
nucleate particles. Two approaches for particle nucle-
ation are commonly employed nowadays: homogeneous
(coagulative or aqueous phase) nucleation and hetero-
geneous (micellar) nucleation. Several representative
articles dealing with these mechanisms follow: Fitch
dN
I
dt
) F
I,in
-
N
I
V
T
v
out
-
k
1
N
I
N
Fe
2+
V
w
(4)
dN
RA
dt
) F
RA,in
-
N
RA
V
T
v
out
-
k
2
N
RA
N
Fe
3+
V
w
(5)
N
Fe
2+
)
k
2
N
Fe
N
RA
k
1
N
I
+ k
2
N
RA
(6)
N
Fe
) N
Fe
2+
+ N
Fe
3+
(7)
dN
Fe
dt
) F
Fe,in
-
N
Fe
V
T
v
out
(8)
S
2
O
8
2-
98
k
d
2SO
4
-
(9)
SO
4
-
+ M
j
98
k
pIj
R
1,j
(10)
dN
I
dt
) F
I,in
-
N
I
V
T
v
out
- k
d
N
I
(11)
R
I
) k
1
N
Fe
2+
V
w
[I] + 2fk
d
[I] (12)
f ) f
o
exp(-C(1/V
F
- 1/V
Fcrif
)) (13)
968 Ind. Eng. Chem. Res., Vol. 36, No. 4, 1997
and Tsai (1970, 1971), Hansen and Ugelstad (1978,
1982), Poehlein et al. (1986), Maxwell et al. (1991,
1992b), and Casey et al. (1994). Another interesting,
slightly different nucleation case has recently been
described by Lepizzera and Hamielec (1994).
We now examine the fate of the radical species in the
water phase:
1. The radicals may react with monomers in the
water phase:
where the rate constants of propagation are used to
define reactivity ratios as follows:
R
n,i
represents a radical of chain length n ending in

monomer i. Equation 14 represents the reaction be-
tween initiator fragments and monomers to form pri-
mary radicals. Equation 15 represents propagation.
Equation 15 describes the addition of monomer j to a
growing radical chain of length n ending in monomer i.
The reaction, proceeding with a rate constant of k
pij
,
results in a radical chain of length n + 1 ending in
monomer j. For the case of a terpolymerization, there
are nine different propagation reactions and six sepa-
rate reactivity ratios. In principle, k
pii
in eq 16 may be
obtained from homopolymerization data for each mono-
mer type, while the six reactivity ratios may be calcu-
lated fromthe three binary copolymerizations involved
in the terpolymerization. Copolymerization is described
using four propagation reactions and two reactivity
ratios.
The propagation reactions shown above represent
terminal model kinetics. That is, the reactivity of a
radical center is assumed to depend only upon the
monomer unit bound in the polymer chain on which it
is located. Other alternative models could also be
considered and are discussed later.
2. The radicals may react with water-soluble impuri-
ties:
where P(WSI) is a dead molecule and k
zj
is the rate
constant for reaction of water-soluble impurity, j, with
a monomer i-ended radical. The use of k
zj
as an overall
rate constant, regardless of which monomer radical the
impurity is reacting with, is a simplification to our
model. It is assumed that the rate of reaction of WSIs
does not depend on the radical type. Water-soluble
impurities may cause an induction period by consuming
large amounts of free radicals. Typical examples of such
impurities are oxygen and other commonly used mono-
mer inhibitors with a considerable water solubility at
the conditions of the polymerization (e.g., hydroqui-
nones). The effects of impurities on polymerization rate
and quality are poorly understood, yet they are one of
the most important sources of variation in an industrial
setting (Huo et al., 1988; Penlidis et al., 1988; Chien and
Penlidis, 1994a,b; Dube and Penlidis, 1997).
3. The radicals may terminate upon encountering
another radical:
where P
m+n
is a dead polymer molecule of chain length
m + n. Note that in eq 18 termination may occur either
by combination of the radical chains or by dispropor-
tionation. k
tw
is often considered to be negligible
(Urretabizkaia et al., 1992; Urretabizkaia and Asua,
1994); however, in systems containing highly water-
soluble monomers (Sarkar et al., 1988), or depending
on the emulsifier concentration (Song and Poehlein,
1988b), water-phase termination may be significant.
4. The initiator fragments may recombine. This
phenomenon is taken into account by use of the ef-
ficiency factor, f, for the initiation step or by the use of
an effective initiator decomposition rate constant.
5. The radicals may be captured by monomer drop-
lets. Most modeling efforts ignore this phenomenon due
to the fact that the surface area of the polymer particles
and micelles is far greater than that of the monomer
droplets. Thus, the likelihood of a radical species
entering the monomer droplets is minimal. This as-
sumption can be tested by the use of electron microscopy
to determine if any abnormally large particles exist and,
if so, how many. Droplet nucleation may occur should
extremely high shear rates be used during mixing along
with the appropriate emulsifier concentration. Also,
this phenomenon usually occurs in the presence of
alcohol groups with ionic emulsifiers. The rate of
radical capture by monomer droplets can be defined as
where [R
TOT
]
wdrop
is the total concentration of radicals
able to enter a micelle, a particle, and/or a droplet (the
calculation of this quantity would be similar to that for
[R
TOT
]
wmic
and [R
TOT
]
wpar
in eqs 30 and 31, respec-
tively), and [drops] is the concentration of droplets. In
the examples cited later in this paper, the rate constant
for the capture of radicals by monomer droplets, k
cmd
,
is set to zero. For the interested reader, the case of
monomer droplet polymerization has been described by
Ugelstad et al. (1973, 1974), Hansen and Ugelstad
(1979), Song and Poehlein (1988a,b), and Fontenot and
Schork (1992-93a,b).
6. Radicals may desorb from polymer particles at the
following rate:
where N
p
is the number of polymer particles per liter
of water, nj is the average number of radicals per
particle, N
A
is Avogadros number, and V
w
is the total
volume of water. Several authors have reported expres-
sions for the desorption rate constant, k
des
, all of which
are based on the same principle. Information may be
found in Nomura et al. (1971a), Ugelstad and Hansen
(1976), Nomura and Harada (1981), Rawlings and Ray
(1988), Mead and Poehlein (1989b), Asua et al. (1989),
and Casey et al. (1994). Desorption is a phenomenon
restricted to small molecules, usually as a result of chain
transfer to monomer or monomer-soluble impurity or
chain-transfer agent. However, the use of relatively
large CTA molecules (e.g., n-dodecylmercaptan) in many
polymerizations would obviate the need to include the
chain transfer to CTA in the desorption equation. The
desorption rate constant is discussed in detail later.
R
n,i
+ R
m,j
98
k
tw
P
m+n
or P
m
+ P
n
(18)
R
cmd
) k
cmd
[R
TOT
]
wdrop
[drops] (19)
F
des
)
k
des
N
p
nj
N
A
V
w
(20)
R
I
+ M
j
98
k
pIj
R
1,j
(14)
R
n,i
+ M
j
98
k
pij
R
n+1,j
(15)
r
ij
)
k
pii
k
pij
(16)
R
n,i
+ WSI 98
k
zj
P(WSI) (17)
7. Desorbed radicals may reabsorb into the polymer
particles. Expressions for the reabsorption of previously
desorbed radicals back into the particles have been put
forth by Poehlein et al. (1986). This phenomenon, while
not included in the desorption equation itself, is included
in the water-phase radical balances shown later.
8. Radicals may be captured by micelles according
to
where k
cm
is the rate constant of capture by micelles
and A
m
is the total free micellar area. The radical
concentration [R
TOT
]
wmic
is the concentration of radi-
cals in the water phase which can enter micelles; it does
not include those radicals which, due to their size,
electric charge, and hydrophilicity, cannot be captured
by micelles. The derivation of [R
TOT
]
wmic
is shown
later; it is defined in eq 30. Equation 38 gives the rate
of particle nucleation by the micellar mechanism.
9. Radicals may be captured by particles at the
following rate:
where k
cp
is the rate constant for capture by polymer
particles and A
p
is the total surface area of the polymer
particles. The radical concentration [R
TOT
]
wpar
is the
concentration of radicals in the water phase which can
enter particles. The same arguments explained for
micellar capture of radicals in the water phase apply
here as well. [R
TOT
]
wpar
is defined later in eq 31.
2.3. Particle Nucleation. The aspect of emulsion
polymerization that generates the most discussion and
conflict is the debate regarding the nature of particle
nucleation (Richards et al., 1989; Dunn, 1992; Hansen,
1992, 1993). In this model, both micellar and homoge-
neous particle nucleation mechanisms are accounted for.
The assumption that particle sizes are monodisperse is
also employed in the following discussion; accounting
for a distribution of particle sizes is discussed in the next
section.
Reviews of the polymer particle formation mecha-
nisms may be found in Ugelstad and Hansen (1976) and
Hansen and Ugelstad (1982). Micellar and homoge-
neous nucleation can both play a significant role in
particle formation (Fitch and Tsai, 1971; Fitch, 1981).
The relative importance of homogeneous nucleation
increases with the solubility of monomer in the water
phase, while at high emulsifier levels, micellar nucle-
ation dominates due to the high surface areas and rapid
radical absorption rates fromthe water phase. Particle-
particle coalescence has been neglected in modeling by
most workers. Notable exceptions include Min and Ray
(1974), Hansen and Ugelstad (1978), Morbidelli et al.
(1983), and Song and Poehlein (1988a,b). It has been
difficult to develop a general model for radical absorp-
tion into micelles and polymer particles and desorption
from polymer particles (Hansen and Ugelstad, 1982;
Nomura, 1982).
We now proceed to form the expression for homoge-
neous particle nucleation. In this paper, a combination
of two methods, along with modifications to allow for
multicomponent polymerizations and inhibitors, was
implemented into the model. The first method, origi-
nally proposed by Hansen and Ugelstad (1978), is more
rigorous but requires knowledge of parameters that are
not readily known for all polymer systems. The second
method, that of Fitch and Tsai (1970, 1971), involves
the use of grouped parameters, thus simplifying the
structure of the equations but not necessarily rewarding
us with less uncertainty.
According to the first method:
where N is the total number of monomers in the system
and N
z
is the total number of WSIs in the system. The
above expression equates the rate of radical generation
to the rate of radical disappearance. In other words,
we are invoking a steady-state hypothesis. On the left-
hand side of eq 23 we have the overall rate of initiation
(see R
I
of eq 12). The right-hand side of eq 23 shows
the disappearance of the initiator radicals by propaga-
tion with monomer j in the water phase (see k
pIj
[M
j
]
w
)
and by reaction with water-soluble impurities (see k
zi
-
[WSI]
i
). [R
I
] is the concentration of initiator radicals

in the water phase. [M
j
]
w
is the concentration of
monomer j in the water phase. We are making the
assumption that initiator radicals will not terminate
(this is accounted for by initiator efficiency) and the
visualization that radicals of this size will not enter
particles nor micelles nor monomer droplets due to
electrostatic forces and the hydrophilicity of such radi-
cals.
Next, we perform balances on radicals of chain length
1, ending in monomer i:
The above equation nowincludes termination with other
radicals in the water phase (see k
tw
[R
TOT
]
w
in eq 24).
The creation of radicals of chain length 1 by desorption
is not included in the above balance. The desorbed
radicals are of a different nature compared to primary
radicals or oligomers in that they are a result of transfer
to monomer and transfer to chain-transfer agent reac-
tions inside the polymer particles. Hence, desorbed
radicals have an electric charge different fromthe other
radicals in the water phase and can be recaptured by
the particles. In fact, the desorbed radicals will not
move far beyond the particle from which they desorbed.
That is, it can be argued that the desorbed radicals will
not necessarily enter the bulk of the water phase but
will stay in the vicinity of the particle surface. However,
if there is a large amount of desorption, a significant
amount of desorbed radicals may stray from the par-
ticles.
We now perform balances on radicals of chain length
k (2 e k e (jcr/2)), ending in monomer i. jcr/2 is the
critical chain length at which oligomers may be captured
by micelles, particles, and/or droplets.
Now a balance is performed on radicals of chain
length k (jcr/2 + 1 e k e (jcr - 1)), ending in monomer
R
cm
) k
cm
[R
TOT
]
wmic
A
m
/V
w
(21)
R
cp
) k
cp
[R
TOT
]
wpar
A
p
/V
w
(22)
R
I
) [R
I
](
"
j)1
N
k
pIj
[M
j
]
w
+
"
i)1
N
z
k
zi
[WSI]
i
) (23)
k
pIi
[M
i
]
w
[R
I
] ) [R
1,i
](
"
j)1
N
k
pij
[M
j
]
w
+
"
i)1
N
z
k
zi
[WSI]
i
+
k
tw
[R
TOT
]
w
) (24)
(
"
j)1
N
k
pji
[R
k-1,j
])[M
i
]
w
) [R
k,i
](
"
j)1
N
k
pij
[M
j
]
w
+
"
i)1
N
z
k
zi
[WSI]
i
+ k
tw
[R
TOT
]
w
) (25)
i. jcr is the critical chain length at which oligomers will
precipitate and form a polymer particle (homogeneous
nucleation) given that there is remaining free emulsi-
fier. We also see that all capture mechanisms (micellar,
particle, droplet) have now been included (see the terms
k
cm
A
m
/V
w
, k
cp
A
p
/V
w
, and k
cmd
[drops], respectively, in eq
26). The inclusion of the capture mechanisms reflects
the visualization that the oligomeric radicals have now
grown enough so that there are no repulsion barriers
(i.e., the charge at the end of the oligomer is no longer
strong enough to create a repulsion from micelles,
particles, or droplets).
Equations 23-26 represent a reasonable and practical
way to handle differing monomer solubilities in water.
Our visualization that the capture of radicals by micelles
and particles begins at about a length of jcr/2 units has
been independently supported by Poehlein (1990), Max-
well et al. (1991, 1992b), and Kshirsagar and Poehlein
(1994).
jcr is calculated as a weighted function of the instan-
taneous composition of the polymer formed in the water
phase (F
jw
):
F
jw
is described later in eqs 132-134 as F
j
.
The concentration of radicals of chain length jcr
ending in monomer i is
A balance on the total amount of radicals in the water
phase (excluding initiator radicals) gives
Recall that radicals of chain length jcr/2 + 1 to jcr
can be captured by micelles, particles, and droplets.
Also, radicals of chain length jcr can undergo homoge-
neous nucleation. Droplet nucleation is neglected as a
simplification to our model. Thus, a balance on the
concentration of radicals in the water phase able to be
captured (radicals of chain length > jcr/2) yields the
following equations. First, the concentration of radicals
in the water phase that may be captured by micelles is
given by
Next, the concentration of radicals in the water phase
that may be captured by particles is given by
Finally, the concentration of radicals in the water phase
that may undergo homogeneous nucleation is defined
by
A
m
represents the total free micellar surface area, that
is, the surface area created by the emulsifier remaining
after the coverage of droplets and particles. A
m
is given
by
[S]
t
is the total concentration of emulsifier in the reactor,
[S]
CMC
is the critical micelle concentration, S
a
is the area
occupied by an emulsifier molecule, A
d
is the area of
monomer droplets, and A
p
is the total surface area of
polymer particles. As the reaction proceeds, the total
surface area of polymer particles quickly becomes very
much greater than the total surface area of monomer
droplets, so A
d
is neglected as a simplification to our
model. In eq 34, V
p
is the total volume of polymer
particles. Equation 34 is based on the assumption that
the polymer particles are spherical. S
a
(see eq 33) is
affected by the polarity of the adsorbing surface and is
therefore affected by persulfate initiators (Ali and
Zollars, 1985).
k
h
is the homogeneous nucleation rate constant
defined by Fitch and Tsai (1971) as
L in the above expression represents the critical radical
diffusion length and is given by Einsteins diffusion law:
M
wsat
is the saturation concentration of monomer in the
water phase.
The rate of change of the number of particles is
described by the following equation:
F
Np,in
is the inflow of particles (i.e., in the case of a
seeded emulsion polymerization), while the second term
on the right-hand side of eq 37 (N
p
(V
w
/V
T
)
out
) represents
the outflow of particles from the reactor. The rates of
homogeneous and micellar particle generation are de-
scribed by the third and fourth terms on the right-hand
(
"
j)1
N
k
pji
[R
k-1,j
])[M
i
]
w
) [R
k,i
](
"
j)1
N
k
pij
[M
j
]
w
+
"
i)1
N
z
k
zi
[WSI]
i
+ k
tw
[R
TOT
]
w
+ k
cm
A
m
/V
w
+ k
cp
A
p
/V
w
+
k
cmd
[drops]) (26)
jcr )
"
j)1
N
jcr
j
F
jw
(27)
[R
jcr,i
] )
(
"
j)1
N
k
pji
[R
jcr-1,j
])[M
i
]
w
(k
cm
A
m
/V
w
+ k
cp
A
p
/V
w
+ k
cmd
[drops])
(28)
[R
TOT
]
w
)
"
i)1
N
"
k)1
jcr-1
[R
k,i
] (29)
[R
TOT
]
wmic
)
"
i)1
N
"
k)(jcr/2)+1
jcr-1
[R
k,i
]
k
cm
A
m
/V
w
k
cm
A
m
/V
w
+ k
cp
A
p
/V
w
+
"
i)1
N
[R
jcr,i
]
k
cm
A
m
/V
w
k
cm
A
m
/V
w
+ k
cp
A
p
/V
w
+ k
h
(30)
[R
TOT
]
wpar
)
"
i)1
N
"
k)(jcr/2)+1
jcr-1
[R
k,i
]
k
cp
A
p
/V
w
k
cm
A
m
/V
w
+ k
cp
A
p
/V
w
+
"
i)1
N
[R
jcr,i
]
k
cp
A
p
/V
w
k
cm
A
m
/V
w
+ k
cp
A
p
/V
w
+ k
h
(31)
[R
TOT
]
whom
)
"
i)1
N
[R
jcr,i
]
k
h
k
cm
A
m
/V
w
+ k
cp
A
p
/V
w
+ k
h
(32)
A
m
) ([S]
t
- [S]
CMC
)V
w
S
a
N
A
- A
p
- A
d
(33)
A
p
) (N
p
)
1/3
(6V
p
)
2/3
(34)
k
h
) k
ho
(
1 -
LA
p
4V
w
)
(35)
L )
(
2D
w
jcr
k
p
M
wsat
)
1/2
(36)
dN
p
V
w
dt
) F
N
p
,in
- N
p
V
w
V
T
v
out
+
dN
hom
dt
V
w
+
dN
mic
dt
V
w
-
k
F
N
p
2
V
w
(37)
side of eq 37, respectively. k
F
N
p
2
V
w
represents a crude
attempt to take particle coalescence into account (Ugel-
stad and Hansen, 1976; Hansen and Ugelstad, 1978,
1979). Song and Poehlein (1988a,b), Fontenot and
Schork (1992-93a), and Chern and Kuo (1996) discuss
particle coagulation in more detail. This is a difficult
subject, still under investigation, and hence, especially
due to lack of specific data, we decided to neglect the
term in further simulations with the model.
The rate of micellar nucleation, dN
mic
/dt, is given by
As can be seen from eq 30, when the surface area of
free micelles, A
m
, goes to zero, micellar nucleation is
halted.
The expression for the rate of generation of particles
by homogeneous nucleation becomes
The homogeneous nucleation rate constant, k
h
, tends
toward zero as the area of polymer particles, A
p
,
increases (see eq 35). This is because there is a higher
probability for an oligomer to be captured by a preexist-
ing particle rather than form a new particle by homo-
geneous nucleation.
2.3.1. Emulsion Particle Size Distribution (PSD)
Calculation. If one wishes to relax the assumption of
a monodisperse particle size distribution, it is necessary
to account for different classes or ages of particles as
shown below. In the first instance, it is assumed that
statistical broadening can be neglected and, thus,
polymer particles born at time with volume V
0
will
all have the same volume (V(t,)) at some later time t
(at least for those particles which have not left the
reactor in the case of a CSTR). Calculation of PSD with
exact correction for statistical broadening requires the
solution of a large number of partial differential equa-
tions (Behnken et al., 1963; Sundberg, 1979; Kiparis-
sides and Ponnuswamy, 1981; Rawlings and Ray, 1988;
Storti et al., 1989), and this appears to be impractical
at the present time except for special cases (the number
of polymer particles containing three or more radicals
is zero).
The consumption rate of monomer in the reactor R
p
-
(t) is given by
where R
p
(t,) is the consumption rate of monomer at
time t in polymer particles born at time . N
p
(t,) d is
the number of polymer particles in the reactor at time
t which were born at time .
The total polymerization rate, R
p
(t,) in these particles
may be expressed as
where k
p
is defined in eqs 47 and 84, [M]
p
is the
concentration of monomer in the polymer particles, and
nj is the average number of radicals per particle.
The rates of polymerization for the individual species
R
pj
(t,) may be found using R
p
(t,) and reactivity ratios
(see eq 126).
The volumetric growth rate of polymer in a polymer
particle is given by
where V
jmp
(t,) is the volume of monomer j in the
particle born at time and
i
is the mole fraction of
radicals in the particles ending in monomer i (see eq
48). Equation 44 is defined by eqs 126 and 86 but with
the dependence on t and shown in the variables.
The following algebraic relationship may be used to
calculate the volumetric growth rate for polymer par-
ticles born at times > 0.
In this manner, one can calculate the full particle size
distribution.
2.4. Organic Phase Reactions. This section de-
scribes reactions in bulk and solution polymerization
as well as those reactions occurring in the bulk phase
in emulsion polymerization once the radicals have been
captured by particles (or micelles or monomer droplets).
1. The radicals may propagate (as shown in eq 15):
For multicomponent polymerizations (e.g., in this case,
terpolymerization), the overall propagation pseudo-
kinetic rate constant can be defined as (Hamielec et al.,
1987; Tobita and Hamielec, 1991; Xie and Hamielec,
1993a,b)
where
i
is the mole fraction of radicals in the particles
ending in monomer i and f
j
is the mole fraction of
monomer j in the particle or bulk phase. The
i
s are
calculated as above by invoking the quasi-steady-state
assumption (QSSA) for the radicals. The QSSA is not
valid at high conversion levels, but the conversion and
Mh
n
(number-average molecular weight) results will not
be significantly affected and the Mh
w
(weight-average
dN
mic
dt
) N
A
k
cm
[R
TOT
]
wmic
/r
mic
(38)
dN
hom
dt
) N
A
k
h
[R
TOT
]
whom
V
w
(39)
R
p
(t) )
0
t
R
p
(t,) V(t,) N
p
(t,) d (40)
R
p
(t,) )
k
p
[M]
p
(t) nj(t,)
N
A
V(t,)
(41)
dV
p
(t,)
dt
) (
"
j)1
N
MW
j
R
pj
(t,))
V(t,)
F
p
(t)
(42)
V(t,) ) V
p
(t,) +
"
j)1
N
V
jmp
(t,) (43)
R
pj
(t,) )
f
j
(t) (
"
i)1
N
k
pij
i
(t))[M]
p
(t) nj(t,)
N
A
V(t,)
(44)
dV
p
(t,)
dt
)
nj(t,)
nj(t,0)
dV
p
(t,0)
dt
(45)
R
n,i
+ M
j
98
k
pij
R
n+1,j
(46)
k
po
)
"
i)1
N
"
j)1
N
k
pij
i
f
j
(47)
1
) (k
p21
k
p31
f
1
2
+ k
p21
k
p32
f
1
f
2
+ k
p23
k
p31
f
1
f
3
)/ (48)
2
) (k
p12
k
p31
f
1
f
2
+ k
p12
k
p32
f
2
2
+ k
p13
k
p32
f
2
f
3
)/ (49)
3
) 1 -
1
-
2
(50)
) (k
p12
k
p31
f
1
2
+ k
p21
k
p32
f
1
f
2
+ k
p23
k
p31
f
1
f
3
+
k
p12
k
p31
f
1
f
2
+ k
p12
k
p32
f
2
2
+ k
p13
k
p32
f
2
f
3
+
k
p12
k
p23
f
2
f
3
+ k
p13
k
p21
f
1
f
3
+ k
p13
k
p23
f
3
2
) (51)
molecular weight) predictions will be affected only
slightly (Achilias and Kiparissides, 1994). The pseudo-
kinetic rate constants for multicomponent polymeriza-
tion described throughout this paper are in the context
of terminal kinetics. Tobita and Hamielec (1991) have
derived equivalent expressions for pseudo-kinetic rate
constants in the context of the penultimate copolymer-
ization model. The pseudo-kinetic rate constant method
is perhaps the only practical way of handling complex
multicomponent polymerization modeling.
Equations 48-51, as shown above, have been devel-
oped for the terpolymerization case. The reduction of
eqs 48-51 to copolymerization and homopolymerization
and their extensions to higher multicomponent systems
should be clear.
2. The radicals may mutually terminate:
Equation 52 represents termination by combination,
whereas eq 53 represents termination by disproportion-
ation. The two termination rate constants are defined
by the overall termination rate constant, k
t
, and , the
ratio of termination by disproportionation to the overall
termination:
Describing an overall termination pseudo-kinetic rate
constant in multicomponent polymerizations has been
a source of constant debate. In this study, several
different methods were attempted, but each method had
limitations. The overall termination pseudo-kinetic rate
constant was calculated as
For the bulk/solution case, the cross-termination rate
constants were defined as
where F
i
, the instantaneous polymer composition, is
defined later in eqs 132-134. The cross-termination
rate constants in the emulsion case were defined as
There has been little agreement as to how the cross-
termination rate constants should be defined. There-
fore, both eqs 57 and 58 were implemented for future
comparison.
An overall was calculated using a weighted average
of the homopolymerization s based on the instanta-
neous polymer composition.
3. The radicals may react with monomer-soluble
impurities such as hydroquinone and tert-butylcatechol
(TBC), which are commonly added to the fresh monomer
by the suppliers due to their radical scavenging proper-
ties:
where P(MSI) is a dead polymer molecule. k
fmsi
is the
rate constant for the reaction of monomer-soluble
impurities with radicals ending in monomer j. The use
of k
fmsi
as an overall rate constant, regardless of which
monomer the impurity is reacting with, is a simplifica-
tion to our model. It is assumed that the rate of reaction
of MSIs does not depend on the monomer type. In
emulsion polymerizations, MSIs are transferred into the
particles with monomer(s) during monomer diffusion.
In the bulk/solution case, the MSIs are in the same
phase as the initiator, thus causing an induction time.
The effect of monomer-soluble impurities, usually ig-
nored or at least poorly understood, can be quite
pronounced on the overall reaction rate, eventually
affecting particle growth (in emulsions), particle nucle-
ation (in emulsions), and molecular weight (Huo et al.,
1988; Penlidis et al., 1988; Chien and Penlidis, 1994a,b;
Dube and Penlidis, 1997).
The impurity effect on particle growth can be de-
scribed as follows. If a MSI partitions into the growing
polymer particles, it scavenges the free radicals. Thus,
the particle growth rate is slowed down considerably.
This leads to a prolonged particle nucleation stage
because the micellar emulsifier, which is used to sta-
bilize the particles, is consumed more slowly. Therefore,
the average lifetime of a micelle is extended and more
particles are nucleated. Since the rate of polymerization
is proportional to the number of particles, a significant
increase in the rate may result (Dube and Penlidis,
1997).
4. The radicals may react with a chain-transfer agent
such as a mercaptan:
where RSH represents the chain-transfer agent which
loses a labile hydrogen to the growing radical chain. k
fctaj
is the rate constant for transfer to a CTA molecule for
the monomer j-ended radical type. The product of the
above reaction, RS
, continues propagating with mono-

mer(s), thus lowering the average molecular weight. The
importance of these reactions is stressed by the findings
of Broadhead et al. (1985), who showed that transfer to
CTA dominated the SBR polymerization.
In the case of multicomponent polymerization, an
overall chain transfer to CTA pseudo-kinetic rate con-
stant (k
fcta
) is defined as
5. The radicals may undergo chain transfer to
monomer:
In this case, the active radical center is transferred to
a monomer molecule which may propagate further, thus
lowering the overall molecular weight.
Chain transfer to monomer is an important reaction.
It greatly affects the molecular weight and is a precursor
to terminal double-bond reactions and desorption. For
example, the transfer reaction to VAc results in a stable
radical which reinitiates slowly; thus, desorption from
polymer particles is possible (Litt, 1993).
As previously with k
fcta
, an overall pseudo-kinetic rate
constant for chain transfer to monomer (k
fm
) is defined
R
n,i
+ R
m,j
98
k
tc
P
m+n
(52)
R
n,i
+ R
m,j
98
k
td
P
m
+ P
n
(53)
) k
td
/k
t
(54)
k
t
) k
tc
+ k
td
(55)
k
to
)
"
i)1
N
"
j)1
N
k
toij
j
(56)
k
toij
) k
toi
F
i
+ k
toj
F
j
(57)
k
toij
) (k
toi
k
toj
)
1/2
(58)
R
n,j
+ MSI 98
k
fmsi
P(MSI) (59)
R
n,j
+ RSH 98
k
fctaj
HP
n,j
+ RS
(60)
k
fcta
)
"
j)1
N
k
fctaj
j
(61)
R
n,i
+ M
j
98
k
fmij
P
n,i
+ M
j
(62)
as
6. The radicals may undergo chain transfer to
polymer:
Transfer to polymer does not necessarily occur at the
end of a dead polymer molecule. Thus, the species type
at the end of the radical chain is not important. The
presence of chain transfer to polymer reactions has been
reported for BA and VAc polymerizations (Scott and
Senogles, 1970, 1974; Friis et al., 1974; Hamielec, 1981;
El-Aasser et al., 1981, 1983; Penlidis et al., 1985a; Dube
et al., 1991b; Lovell et al., 1991, 1992). Lovell et al.
(1991, 1992) reported that the transfer to polymer
reaction for BA occurred by the abstraction of a tertiary
hydrogen from a BA unit in the polymer chain. Friis et
al. (1974) reported that transfer to polymer and transfer
to monomer reactions dominate the VAc polymerization.
The chain transfer to polymer occurs at the methyl
hydrogen of VAc.
The overall pseudo-kinetic rate constant for transfer
to polymer (k
fp
) is
The cumulative polymer composition, Fh
j
, is defined later
in eq 135.
In a batch reactor when there is significant compo-
sitional drift, the use of the above equation is not strictly
valid and one would have to resort to the cumbersome
method of moments for the complete set of chemical
equations for polymerization. In many practical cir-
cumstances compositional drift is either small or main-
tained small (batch reactors and reactivity ratio pairs
which give small compositional drift, semibatch reactors
where compositional drift is controlled to low levels and
well-mixed continuous stirred-tank reactors with mi-
cromixing where only statistical spreading of composi-
tion occurs).
7. The radicals may undergo reactions with internal
and terminal double bonds. Once again, an effective
rate constant will be used. The rate constant for
terminal double-bond reactions is k*
p
and that for
internal double-bond reactions is k*
p
*.
Terminal double-bond reactions yield trifunctional branch
points, whereas internal double-bond reactions yield
tetrafunctional branch points. Hence, an overall pseudo-
kinetic rate constant for terminal (k*
p
) and internal
double-bond (k*
p
*) reactions are defined as
The importance of the terminal double-bond reaction
has been documented for the BA and VAc polymeriza-
tions (Scott and Senogles, 1970, 1974; Friis et al., 1974;
Hamielec, 1981; El-Aasser et al., 1981, 1983; Penlidis
et al., 1985a; Dube et al., 1991b; Lovell et al., 1991,
1992).
As in the case for transfer to polymer, the validity of
the above pseudo-kinetic rate constant equations comes
into question in the presence of strong compositional
drift.
2.5. Diffusion-Controlled Rate Constants. When
discussing the various reactions taking place in a
polymerization, many of the parameters were referred
to as rate constants. This is somewhat of a misnomer
as these so-called rate constants (e.g., k
p
, k
t
) vary with
the viscosity of the reaction medium. Thus, in a bulk
system, the viscosity increases due to the increase in
polymer concentration and, hence, affects the rate of
propagation and termination. In the emulsion case, the
viscosity in the main locus of polymerization (i.e., the
particles) is high from the onset of the reaction due to
the high polymer concentration. Thus, the rates of
termination and propagation may be diffusion-controlled
even at low conversion levels.
The general chemical equations for diffusion-con-
trolled termination were expressed earlier in eqs 52 and
53. The termination constants k
tc
and k
td
can be
redefined as k
tc
(n,m) and k
td
(n,m), respectively. This
illustrates their dependence, in general, on the chain
lengths n and m of the polymer radicals, R
n,i
and R
m,j
(see eqs 52 and 53) but not on the polymeric radical type
(i and j denote the monomer type on which the radical
center is located on the end of the polymer chain). One
might expect that two backbone radical centers would
mutually terminate at a significantly lower rate. The
dependence of this rate on the position of the radical
centers in the polymer backbone is not clear and the
modeling of this effect is beyond the scope of this
investigation. In other words, we limit the treatment
of polymer radical/polymer radical termination to linear
chain systems where termination rates are controlled
by radical centers on chain ends. The termination rate
constants for linear chain systems also depend on the
mass concentration, molecular weight distribution of the
accumulated dead polymer, and polymerization tem-
perature. When most of the dead polymer chains
(chains without a radical center) are made via chain
transfer to a small molecule (such as chain-transfer
agent, monomer, etc.) chain-length dependence of the
termination rate constant may not be an important
issue (accurate MWDs of the dead polymer may be
calculated without a knowledge of this chain-length
dependence).
The calculation of the total polymer radical concen-
tration and then the rate of polymerization would
require at most a single number-average termination
constant (kh
tN
). However, when a significant number of
dead polymer chains are made via polymer radical/
polymer radical termination, then to calculate the full
MWD or higher molecular weight averages (Mh
w
, Mh
z
,
etc.), one must account for chain-length dependence
when it is operative. When calculating MWD and its
averages, chain-length dependence can be accounted for
in different ways. One can use an approximate expres-
sion to account for the dependence of k
t
(n,m) on chain
k*
p
* )
"
i)1
N
"
j)1
N
k*
p
*
ij
i
Fh
j
(69)
k
fm
)
"
i)1
N
"
j)1
N
k
fmij
i
f
j
(63)
R
n,i
+ R
m,j
98
k
fpij
P
n,i
+ P
m,j
(64)
k
fp
)
"
i)1
N
"
j)1
N
k
fpij
i
Fh
j
(65)
R
n,i
+ P
m
98
k*
p
R
m+n,i
(66)
R
n,i
+ P
m
98
k*
p
*
R
m+n,i
(67)
k*
p
)
"
i)1
N
"
j)1
N
k*
pij
i
Fh
j
(68)
lengths n and m (k
t
(n,m) ) k
tc
(n,m) + k
td
(n,m)). Some
of the earlier studies to use this approach include
Benson and North (1962), Duerksen and Hamielec
(1967), Duerksen (1968), and others and more recent
studies by Cardenas and ODriscoll (1976), Ito (1980,
1981), Soh and Sundberg (1982a), Coyle et al. (1985),
Russell et al. (1992), and OShaughnessy and Yu
(1994a,b). These attempts to find a general and effec-
tive expression for k
t
(n,m) based on theoretical and
experimental considerations are to be lauded even
though to date an expression for k
t
(n,m) which can be
considered effective and useful for commercial polymer
reactor modeling is not available. In the meantime, it
is recommended that a less general approach using
averages of k
t
(n,m) be used (Boots, 1982; Olaj et al.,
1987; Zhu and Hamielec, 1989) for reactor modeling.
The use of k
t
(n,m) averages permits one to calculate the
rate of polymerization, Mh
n
, Mh
w
, and possibly Mh
z
of both
accumulated dead polymer and dead polymer produced
instantaneously. Individual empirical correlations for
kh
tN
, kh
tW
, and kh
tZ
versus polymer concentration, temper-
ature, and other significant variables as shown by Zhu
and Hamielec (1989) are required. Methods based on
averages have yet to be comprehensively evaluated
although Vivald-Lima et al. (1994a) have recently
compared the effectiveness of the CCS (Chiu et al., 1983)
and MH (Marten and Hamielec, 1979) models.
The number-average termination constant is given by
and the termination rate of polymeric radicals, R
t
, by
where
n
is the mole fraction of polymeric radicals of

chain length n. The use of kh
tN
to calculate Mh
w
, Mh
z
, and
higher molecular weight averages will give estimates
that are smaller than the true values when chain-length
dependence is significant. For the correct calculation
of higher molecular weight averages one should use kh
tw
,
kh
tz
, etc. Examples are given in Zhu and Hamielec
(1989).
Anseth et al. (1994a) have made a comprehensive
experimental investigation of the effect of volume
relaxation on free-radical cross-linking kinetics. This
phenomenon may explain observations made by Stickler
(1983) of the effect of initiator level on limiting conver-
sions for polymerization of methyl methacrylate in the
absence of cross-linking monomers. At higher polym-
erization rates, the actual volume is greater than the
equilibrium volume, permitting higher limiting conver-
sions to be reached. Anseth et al. (1994b) have also
recently shown dominance of termination by reaction
diffusion in highly cross-linked systems. Recent papers
by Vivaldo-Lima et al. (1994b) and Hutchinson (1992-
3) have accounted for diffusion-controlled termination
as affected by cross-linking.
The validity of the stationary-state hypothesis (SSH)
was tested by direct experimentation for the homopo-
lymerization of methyl methacrylate and for the copo-
lymerization of methyl methacrylate and cross-linker
ethylene glycol dimethacrylate using ESR for the first
time (Zhu et al., 1990b). The SSHwas shown to be valid
for homopolymerization of methyl methacrylate and for
low levels of cross-linking. For high levels of cross-
linking, however, the SSH is clearly not valid.
For chemically-controlled termination, k
t
equals kh
t
,
and these are given by equations such as eq 56. For
isothermal polymerization and small compositional
drift, k
t
can be treated as a constant. The instantaneous
number-average molecular weight is given by
where R
pi
is the rate of polymerization of monomer i
and R
tc
and R
td
are rates of termination by combination
and disproportionation, respectively. As mentioned
earlier, the modeling to be discussed herein will use kh
t
exclusively, with chain-length dependence neglected in
calculating Mh
w
, Mh
z
, etc.
Under diffusion-controlled termination a single ter-
mination rate constant can be employed to model the
rate of multicomponent polymerization and molecular
weight development. In other words, the monomer type
on which the radical center is located is unimportant.
However, when dealing with polymer radicals with long
branches, the self-diffusion coefficient of the polymer
molecule will depend not only upon chain length or the
number of monomer units in the chain but also upon
the number of long branches, branch lengths, and their
location on the polymer molecule. The position of the
radical center (on the chain end or somewhere on the
backbone) should also affect the termination rate.
Termination under these conditions is clearly very
complex, and a good deal of empiricism is required to
model termination reactions for polymer radicals with
long branches. The self-diffusion coefficient should also
depend upon the distribution of monomer types in the
polymer chains. This is another complicating factor
when compositional drift is important.
Diffusion-controlled rate constants are modeled in this
paper using the free-volume approach (Marten and
Hamielec, 1979; Soh and Sundberg, 1982a-c; Hamielec
et al., 1987). In order for the termination reaction to
occur, two macroradical chains must approach each
other via translational diffusion. Next, the diffusion of
the chain segments containing the active centers toward
each other occurs. This is termed segmental diffusion.
Finally, the termination reaction takes place. Thus,
three diffusion-control intervals can be described.
In the early stages of an isothermal, batch multicom-
ponent polymerization (typically at conversions less
than about 10% in bulk polymerization), where termi-
nation might be chemically controlled, compositional
drift is usually small and hence a single constant
termination constant, k
t
(k
t
) k
tc
+ k
td
), may be used to
model the rate of polymerization and molecular weight
development to the conversion where termination be-
comes diffusion-controlled. However, when relatively
high molecular weight polymers are being produced at
low monomer conversions, the termination rate may be
controlled by segmental diffusion. Bhattacharya and
Hamielec (1986), Jones et al. (1986), and Yaraskavitch
et al. (1987) have applied a model for segmental diffu-
sion-controlled termination after Mahabadi and ODriscoll
(1977). The rate constant for termination controlled by
segmental diffusion is given by
where k
to
is given by eq 56 shown earlier, is a
parameter dependent on the molecular weight of the
polymer radicals as well as solvent quality (monomers
kh
tN
)
"
n)1
#
"
m)1
#
kh
t
(n,m)
n
(70)
R
t
) kh
tN
Y
o
2
(71)
Mh
n
)
"
i)1
N
MW
i
R
pi
(R
tc
/2 + R
td
)
(72)
k
tseg
) k
to
(1 + c) (73)
plus solvent if present), and c is the mass concentration
of accumulated polymer in the reaction mixture. As the
polymer concentration increases in a good solvent, the
coil size of polymer chains decreases, increasing the
gradient of concentration of the radical center across
the coil and thus the diffusion rate of the radical center.
The consequence of this is that the termination rate
constant increases with monomer conversion to the
point where translational diffusion of the center of mass
of the polymer radical coils controls the termination rate
and then k
t
begins to fall very rapidly. The contribution
of c is rather small in many cases (Bhattacharya and
Hamielec, 1986; Jones et al., 1986; Hamielec et al., 1987;
Yaraskavitch et al., 1987) and could be neglected in most
reactor calculations.
The next interval, translational diffusion control,
occurs up to high polymer concentrations (85-90%
conversion in bulk). It is in this stage that the gel effect
or autoacceleration occurs. Using the free-volume ap-
proach, the point at which the reaction becomes trans-
lational diffusion-controlled is identified by a temper-
ature-dependent term, K
3
, defined by Marten and
Hamielec (1979, 1982) as
where A and mare adjustable parameters but hopefully
independent of temperature, radical initiation rate, and
monomer and polymer concentrations over wide ranges
of these polymerization conditions. This has been
proven so for both homo- and copolymerization by
Stickler et al. (1984) and others (Bhattacharya and
Hamielec, 1986; Jones et al., 1986; Yaraskavitch et al.,
1987). Mh
wcrit
is the accumulated weight-average mo-
lecular weight at the monomer conversion at which the
termination rate is translational diffusion-controlled.
Mh
wcrit
= M
wcrit
, the instantaneous weight-average mo-
lecular weight, and thus there is a direct connection
with the size of the polymer radicals. V
Fcrit
is the critical
free volume corresponding to that conversion. K
3
was
found to have an Arrhenius temperature dependence
for both homo- and copolymerization (Stickler et al.,
1984; Bhattacharya and Hamielec, 1986; Jones et al.,
1986; Yaraskavitch et al., 1987). The frequency factor
had a small dependence on chain composition for the
p-methylstyrene/acrylonitrile system (Yaraskavitch et
al., 1987).
In multicomponent polymerizations, the free volume
is given by
where i represents the monomer, polymer, and solvent.
R
i
is the difference in the thermal expansion coefficients
for species i above and below its glass transition
temperature, T
gi
. T is the polymerization temperature,
V
i
is the volume of each species, and V
T
is the total
volume of the reaction mixture.
The translational diffusion-controlled termination
rate parameter, k
T
, is given by
where k
tcrit
is the value of k
t
when eq 74 is satisfied. n
is an adjustable parameter.
For the modeling of homopolymerizations and copo-
lymerizations, the adjustable parameters have been
arbitrarily set equal to 0.5 for mand 1.75 for n (Marten
and Hamielec, 1979, 1982; Garcia-Rubio et al., 1985;
Bhattacharya and Hamielec, 1986; Jones et al., 1986;
Yaraskavitch et al., 1987). Panke (1986) has shown that
setting m ) n ) 0.5 gives an equally good fit to rate
and molecular weight data for the homopolymerization
of methyl methacrylate. These values for m and n also
give the correct response when methyl methacrylate is
polymerized in a batch reactor with a high molecular
weight heel.
Finally, in extremely viscous environments, the reac-
tion diffusion-control termination rate constant, k
trd
,
becomes significant. Two methods of describing this
regime were employed in the model. The first (Stickler
method) uses an expression by Stickler et al. (1984) and
is given by
where
and N
A
is Avogadros number, is the reaction radius,
D is the reaction diffusion coefficient, V
m
is the molar
volume, n
s
is the number of monomer units in one
polymer chain segment, and l
o
is the length of the
monomer unit.
The second method (RNG method) involves what is
termed residual termination. Russell et al. (1988a)
defined upper and lower bounds for the residual termi-
nation rate parameter as
and
where a is the root-mean-square end-to-end distance per
square root of the number of monomer units, is the
Lennard-Jones diameter, and j
c
is the entanglement
spacing of pure polymer, measured in monomer units.
When attempting to model multicomponent polymeriza-
tions, options to use residual monomer mole fraction
weighted averages or overall values for a, , and j
c
were
made available. The lower limits of the RNG method
and the Stickler method give similar results. The upper
and lower bounds are handled in the model with the
following expression:
where x is the conversion.
As will be discussed later, the reaction diffusion (or
residual termination) concept may not be perfectly
correct. Recent ideas regarding trapped radicals may
have to be incorporated into future modeling efforts (Zhu
et al., 1990a).
K
3
) Mh
wcrit
m
exp(A/V
Fcrit
) (74)
V
F
)
"
i)1
N
(0.025 + R
i
(T - T
gi
))
V
i
V
T
(75)
k
T
) k
tcrit
(
Mh
wcrit
Mh
w
)
n
exp
(
-A
(
1
V
F
-
1
V
Fcrit
))
(76)
k
trd
)
8N
A
D
1000
(77)
)
(
6V
m
N
A
)
1/3
(78)
D )
n
s
l
o
2
6
k
p
[M] (79)
k
tres,min
)
4
3
k
p
[M]a
2
(80)
k
tres,max
)
8
3
k
p
[M]a
3
j
c
1/2
(81)
k
trd
) k
tres,min
x + k
tres,max
(1 - x) (82)
The point at which the reaction changes from trans-
lational diffusion control to reaction diffusion control can
be somewhat ambiguous. Thus, the following overall
k
t
is defined to circumvent this problem:
Equation 83 has been previously employed to handle
the various diffusion-control equations for k
t
by Marten
and Hamielec (1979) and Soh and Sundberg (1982a-
c). Vivaldo-Lima et al. (1994a) showed that this ap-
proach (which they termed as a serial approach)
resulted in as good, if not better, prediction of various
polymerization data compared to the parallel approach
such as that used by Russell (1994). The parallel
approach involves summing the reciprocals of each k
t
expression from each diffusion-control interval. This is
discussed further by Gao and Penlidis (1996).
As will be discussed later, the prediction of the
termination rate is still under investigation. Recent
publications by Zhu et al. (1990a), Tobita and Hamielec
(1991), Achilias and Kiparissides (1992), Maxwell and
Russell (1993), Buback et al. (1994), Russell (1994), and
Tobita (1994a,b) have shown some insight into solving
this problem while at the same time demonstrating a
wide variety of approaches.
For free-radical polymerizations below the glass tran-
sition temperature of the polymer being synthesized,
reaction mechanisms at very high monomer conversions
can be very complex due to the decrease in the diffusion
coefficients of small molecules: primary radicals and
monomer. These decreases in mobility will have one
or more of the following consequences: (1) decrease of
the initiation efficiency; (2) the propagation reaction
becomes diffusion-controlled; (3) radical pair formation
(Zhu and Hamielec, 1989). An experimental observation
for such polymerizations is the reduction in conversion
rate to almost zero, even though appreciable concentra-
tions of monomer and initiator exist in the polymeriza-
tion mixture. Most polymerization models permit the
propagation constant to fall with monomer conversion
while fixing the initiator efficiency at a constant value.
This is in effect equivalent to letting the product f
1/2
k
p
fall with monomer conversion to fit the rate of polym-
erization. There are practical reasons for doing this
because it is very difficult to measure f and k
p
separately
without the use of electron spin resonance spectroscopy
(ESR). The use of data for polymerization rate and for
molecular weights of accumulated polymer can, in
principle, permit one to estimate f and k
p
separately as
has been done before (Hui and Hamielec, 1968; Duerk-
sen and Hamielec, 1968). However, for the bulk po-
lymerization of methyl methacrylate with the very
pronounced diffusion-controlled termination followed by
a glassy effect and the associated broad MWD with both
low and high molecular weight tails on the distribution,
accurate molecular weight measurements are extremely
difficult if not impossible to obtain. ESR is the preferred
method of measuring both f and k
p
at high monomer
conversions for bulk polymerization of monomers such
as methyl methacrylate. Zhu and Hamielec (1989) did
ESR/rate of polymerization measurements and found
that f and k
p
fall significantly with conversion at about
thesame monomer conversion, while Ballard et al.
(1986) observed that for the same monomer (methyl
methacrylate) but with emulsion polymerization, k
p
became diffusion-controlled at higher monomer conver-
sions. This interesting result may be due to the swelling
of surface layers of polymer particles by water in
emulsion polymerization. Sulfate groups dragged into
the interior of polymer particles may be responsible for
this. In the event that f falls sooner than k
p
, the dead
polymer produced in the time interval between the fall
in f and k
p
would have very high molecular weights. This
should affect high-order molecular weight averages.
This, however, has not been confirmed experimentally
for MMA bulk polymerization. Molecular weights are
difficult to measure as already mentioned, and there is
the possibility that chain transfer to monomer might
intervene to put a cap on molecular weights generated.
For a discussion of phenomena such as radical pair
formation and heterogeneous effects during glassy-state
transition, one should refer to the original paper by Zhu
and Hamielec (1989).
In order to model diffusion-controlled propagation, i.e.,
when the polymerization temperature is less than the
glass transition temperature of the polymer being
synthesized, the propagation rate constants are then
given by
where i is the radical type where the active center is
located, j is the monomer type being added to the
polymer chain, B is an adjustable parameter which
should depend on monomer molecule type, and V
Fpcrit
is the critical free volume where the propagation reac-
tion of monomer j adding to a polymer chain ending in
monomer i becomes diffusion-controlled. One might
expect these critical free volumes to depend on polymer
radical type as well as monomer type with propagation
rates which are greater, becoming diffusion-controlled
at lower monomer conversions. It is also reasonable to
expect that diffusion-controlled propagation rate con-
stants for the same monomer are equal (k
pij
) k
pji
). This
can be used to reduce the number of adjustable param-
eters.
When dealing with multicomponent polymerizations,
the diffusion-control expressions shown above were
simplified somewhat by taking weighted averages of
many of the parameters. The parameter from the
segmental diffusion-controlled termination rate expres-
sion (see eq 73) was averaged by the cumulative polymer
composition. A weighted average of the parameter A
from eq 74 by the instantaneous polymer composition
(F
i
) was included as an option in the simulation package.
As well, the sum of the K
3
parameters of each monomer
was included as an option. The option for the V
Fpcrit
parameter in the diffusion-controlled propagation rate
expression (see eq 84) was a weighted average based
on the residual monomer mole fraction. Alternatively,
overall values for A, K
3
, and V
Fpcrit
were input. Although
several parameters were mentioned above as being
adjustable, only the latter three (A, K
3
, V
Fpcrit
) were
adjusted to fit the data. As will be discussed later, they
were not adjusted for each experiment.
2.6. Free-Radical Concentrations. In order to
calculate the reaction rates, one must also know the
concentration of free radicals in the reactor. For the
bulk, suspension, and solution case, one may use the
overall concentration of free radicals in the reactor, but
for the emulsion case, one requires an average number
of radicals per particle.
2.6.1. Bulk/Suspension/Solution Case. The con-
centration of free radicals in the bulk, suspension, and
solution cases is given by
k
t
) k
tseg
+ k
T
+ k
trd
(83)
k
pij
) k
pijo
exp
(
-B
(
1
V
F
-
1
V
Fpcrit
))
(84)
Equation 85 describes the initiation of radicals by
initiator decomposition and the consumption of free
radicals by reaction with impurities.
2.6.2. Emulsion Case. In the emulsion case the
overall concentration of free radicals in the particle
phase is
where nj is the average number of radicals per polymer
particle. There have been several methods proposed to
estimate nj (Stockmayer, 1957; OToole, 1965; Ugelstad
et al., 1967; Ballard et al., 1981a; Huo et al., 1988; Li
and Brooks, 1993). One can, in principle, write a
balance around a polymer particle assuming a steady
state, where the disappearance of radicals from the
particle is equal to the entry of radicals into the particle.
The phenomena to be accounted for in the balance are
radical entry (absorption, capture) from the aqueous
phase, radical-radical termination in the particle, reac-
tion of the radical with monomer-soluble impurities in
the particle, and desorption of radicals into the water
phase. The balance is performed for N
n
, the number of
particles with n radicals:
where [R
TOT
]
des
is the concentration of desorbed radi-
cals in the water phase given by
v
p
in eq 87 is the average volume of a particle or V
p
/N
p
.
(Also note that N
n
and N
p
in eqs 87, 90, and 91 represent
the number of particles, not the number of particles per
liter of water.) The first term (on the left-hand side) in
eq 87 represents the capture of free radicals (including
desorbed radicals) fromthe water phase (see also eq 31).
The second term describes termination in the particles,
while the third term represents radical desorption and
reaction with monomer-soluble impurities. The solution
of the above recursive equation was originally proposed
as a modified Bessel function; Ugelstad et al. (1967)
proposed the following partial fraction expansion as an
approximation:
where
and
Equation 89 requires approximately 10 levels of frac-
tions to obtain a converged value for the average
number of radicals per particle.
More recently, Li and Brooks (1993) presented a more
universal model (does not assume a steady state) for
estimating nj. An investigation of the Li and Brooks
(1993) approach is recommended in future modeling
efforts. In the computer implementation, we decided
to adopt the method of Ugelstad et al. (1967) due to its
simple form and reduced amount of computational
effort.
2.7. Radical Desorption. We will now look at the
rate of free-radical desorption fromthe polymer particles
(restricted to the emulsion polymerization case). In the
most general case, desorption occurs when a small
radical traverses fromthe particle to the aqueous phase.
The desorbed radical is usually assumed to be no more
than 1 monomer unit in length. The formation of these
monomeric radicals in the particles is a result of chain
transfer to monomer, to impurity, or to chain-transfer
agent. In our case, radicals formed as a result of chain
transfer to chain-transfer agent will be assumed not to
desorb since typical CTAs are relatively large and
insoluble molecules (e.g., n-dodecylmercaptan) (Nomura
et al., 1982).
It is commonly accepted that desorbed radicals will
not move far beyond the particle from which they
desorbed. That is, it can be argued that the desorbed
radicals will not necessarily enter the bulk of the water
phase but will rather stay in the vicinity of the particle
surface. However, if there is a large amount of desorp-
tion, a significant amount of desorbed radicals may stray
from the particles. Thus, while the following model
equations are rigorous, there are certain underlying
assumptions that should always be checked with specific
process data, in order to explain possible discrepancies.
Expressions describing desorption rate constants
continue to be developed and reported in the literature.
For large particles, desorption may be negligible; how-
ever, in the early stages of a reaction (i.e., when the
particles are small) or when the rate of absorption of
radicals by the particles is slow, desorption may be
important. In the following equations, any reactions
with monomer soluble impurities were assumed to yield
nonreactive products.
Several groups have developed expressions for the
desorption rate constant. Their expressions attempted
to give the desorption rate constant as a function of
particle diameter. Mead and Poehlein (1989b) derived
particle-size-independent expressions for k
des
. They also
rederived the equations put forth by other research
groups while incorporating particle-size independence.
The notion of a nonuniform distribution of radicals in
the particles is applicable to large particles and in cases
where chain-transfer reactions do not dominate (Chern
and Poehlein, 1990). It is due to the hydrophilicity of
end groups (initiator fragments) on the oligomers being
captured. de la Cal et al. (1990) also discussed the
nonuniform distribution of radicals. As a simplification
Y
o
)
(
"
i)1
N
z
k
zi
2
[MSI]
i
2
+ 4k
t
R
I
)
1/2
-
"
i)1
N
z
k
zi
[MSI]
i
2k
t
(85)
Y
o
)
njN
p
V
p
N
A
(86)
k
cp
([R
TOT
]
wpar
+ [R
TOT
]
des
)[N
n
] +
k
t
(n) (n - 1)[N
n
]/v
p
+ (k
des
+ k
fmsi
[MSI]
p
)n[N
n
] )
k
cp
([R
TOT
]
wpar
+ [R
TOT
]
des
)[N
n-1
] +
k
t
(n + 2)(n + 1)[N
n+2
]/v
p
+ (k
des
+
k
fmsi
[MSI]
p
)(n + 1)[N
n+1
] (87)
[R
TOT
]
des
)
F
des
V
w
k
cp
A
p
(88)
nj )
R
m +
2R
m + 1 +
2R
m + 2 +
2R
m + 3 + ...
(89)
R )
k
cp
A
p
([R
TOT
]
wpar
+ [R
TOT
]
des
)V
p
N
A
2
N
p
2
k
t
(90)
m )
(k
des
+ k
fmsi
[MSI]
p
)V
p
N
A
N
p
k
t
(91)
to our model, particle-size-independent expressions were
not used. Recently, Fontenot and Schork (1992-93a)
used the model developed by Nomura et al. (1976) and
incorporated ideas by Mead and Poehlein (1989a,b) to
account for nonuniform monomeric radical concentra-
tions in particles. Fontenot and Schork (1992-93a)
were dealing with large particles and droplet nucleation.
The first desorption expression that we will examine
is that of Ugelstad and Hansen (1976):
In eq 92, k
fm
is the transfer to monomer rate constant,
k
p
! is the rate constant for reinitiation of oligomeric
radicals from desorbed monomeric radicals, D
w
is the
diffusivity of monomer radicals in the aqueous phase,
a is the partition coefficient for monomer radicals
between the aqueous and particle phases, D
p
is the
diffusivity of monomeric radicals in the particles, and
d
p
is the particle diameter.
Harada et al. (1971) and Nomura et al. (1971a) have
theoretically derived an expression for the desorption
rate coefficient, k
des
, using a stochastic approach and
have successfully applied it to vinyl acetate emulsion
polymerization. Their result is the following:
In eq 93, m
d
is the partition coefficient for monomeric
radicals (same as Ugelstad and Hansens a and
equivalent to 1/K
jwp
in eq 110), d
p
is the average particle
diameter, D
w
is the diffusivity of monomer radicals in
the aqueous phase, k
fm
is the transfer to monomer rate
constant, and
where D
p
is the diffusivity of monomeric radicals in the
particles. In eq 93, the term R
I
(1 - nj)/N
p
k
p
[M]
p
nj
represents desorption of initiator radicals. In our model
development, it was assumed that initiator radicals
would not be captured by the particles due to their
hydrophilic nature and electric charge; hence, this term
may be safely neglected. As discussed above, radicals
formed as a result of chain transfer to CTA will not
desorb due to the size of the CTA assumed in this case.
Thus, k
fcta
[CTA]
p
/k
p
[M]
p
in eq 93 can be neglected.
Equation 93 can then be written as
Nomura and Harada (1981) derived exactly the same
expression as in eq 95 using a deterministic approach.
If nj is much less than 0.1 during the whole range of
conversions (which is not always the case), then the
following expression may be used:
The parameter (see eq 94) can be described as a
lumped coefficient or, alternatively, as the ratio of film
mass-transfer resistance to overall mass-transfer resis-
tance (Nomura and Harada, 1981). At the start of the
polymerization, D
w
and D
p
are of the same order of
magnitude because the particles are saturated with
monomer. Thus, assumes a value close to unity. As
the conversion and, hence, the viscosity inside of the
particles increases, D
p
decreases markedly and, hence,
k
des
decreases. An empirical model of the decrease in
D
p
was used in the model (Friis and Hamielec, 1977):
Previous efforts in the literature to simulate emulsion
polymerizations (Harada et al., 1971; Nomura et al.,
1971b; Friis and Nyhagen, 1973; Nomura et al., 1976)
made use of eq 96 and assumed an average constant
value for throughout the conversion range. Thus, in
our case, eqs 94 and 95 were used. This approach is
identical to the one used by Penlidis (1986) to model
vinyl acetate and vinyl chloride emulsion polymeriza-
tions. Furthermore, in order to accommodate the mul-
ticomponent aspect of the polymerization, the param-
eters D
w
and m
d
were calculated as weighted functions
of the mole fraction of monomer in the particles.
Rawlings and Ray (1988) presented an expression
that included chain transfer to CTA. However, their
use of an overall chain-transfer rate constant would
enable one to modify other groups equations similarly.
where
and
k
trt
is the chain transfer to CTA rate constant, [CTA]
p
is the concentration of CTA in the particle, k
trm
is the
chain transfer to monomer rate constant, d
m
is the
monomer density, is the monomer volume fraction in
the particle, M
wt
is the monomer molecular weight, and
r is the particle radius.
Asua et al. (1989) offered the following expression:
where
and
D
p
) D
po((
1 - x
1 - 0.19x
)
2
+ 0.0017x
)
(97)
k
des
)
3D
m
k
tr
k
p
3D
m
M
wt
d
m
k
p
+ r
2
(98)
D
m
)
D
p
D
w
m
d
D
p
+ D
w
(99)
k
tr
) k
trm
(
1 +
k
trt
[CTA]
p
k
trm
[M]
p
)
(100)
k
des
) k
fm
[M]
p
K
o
K
o
+ k
p
[M]
p
(101)
K
o
)
12D
w
/m
d
d
p
2
1 + 2D
w
/m
d
D
p
(102)
k
des
)
k
fm
k
p
! [
12D
w
(a + D
w
/D
p
)d
p
2
]
(92)
k
des
)
(
nj +
k
p
[M]
p
m
d
d
p
2
12D
w
)
-1
(
k
fm
k
p
+
k
fcta
[CTA]
p
k
p
[M]
p
+
R
I
(1 - nj)
N
p
k
p
[M]
p
nj
)
k
p
[M]
p
(93)
)
(
1 +
6D
w
m
d
D
p
)
-1
(94)
k
des
)
(
nj +
k
p
[M]
p
m
d
d
p
2
12D
w
)
-1
k
fm
[M]
p
(95)
k
des
)
(
12D
w
m
d
d
p
2
)
k
fm
k
p
(96)
k
tw
is the rate constant for termination in the water
phase, [M]
w
is the concentration of monomer in the
water phase, k
a
is the radical absorption (by particles)
rate coefficient, N
T
is the total number of particles per
unit volume of aqueous phase,
w
w
is the volume frac-
tion of water in the continuous phase, and N
A
is
Avogadros number.
Finally, the particle-size-independent expression de-
rived by Mead and Poehlein (1989b) is shown below:
where
R, in the above equations, is the radius of a monomer-
swollen particle and r is the radial position within the
monomer-swollen particle.
Both the Nomura group and the Poehlein group
present expressions for the desorption rate constant for
copolymerization. The extension to the copolymer case
from the homopolymerization equations shown above
is quite straightforward. If one so desires, one may use
a weighted average of two homopolymer equations.
Also, one should check whether one of the comonomers
is insoluble. This could lead to further simplifications
and modifications to the copolymer equations.
After careful evaluation of the methods presented
above, we performed some tests with representative
numbers and found very little difference between the
various methods. Hence, we have employed the expres-
sion for k
des
of Nomura and Harada (1981) (see eq 96).
As an example, consider the monomers in the BA/
MMA/VAc system. VAc is known to exhibit significant
radical desorption (Nomura et al., 1971a; Friis and
Nyhagen, 1973; Penlidis, 1986), while MMA desorbs to
a lesser extent (Ballard et al., 1981b) and the desorption
for BA is considered negligible (Mallya and Plamthot-
tam, 1989). Urretabizkaia et al. (1992) and Urretabi-
zkaia and Asua (1994) reported that desorption was
negligible for the seeded semibatch emulsion polymer-
ization of BA/MMA/VAc. Considering the dominance
of the acrylic monomers at lower conversions (<60 wt
%, see Dube and Penlidis, 1995a-c), it is likely that
desorption will not play a role in the BA/MMA/VAc
emulsion polymerizations.
2.8. Species Concentrations in the Different
Phases. We shall now look at defining the concentra-
tion of monomers and of various other components that
may partition between different phases (i.e., water
phase, monomer droplet phase, particle phase). Under
equilibrium conditions, the concentrations of monomers
in the particles are determined by the balance between
the gain in interfacial free energy caused by an increase
in surface area upon swelling and the loss in free energy
caused by dissolving the monomer in the polymer. A
knowledge of interfacial tension and the Flory-Huggins
interaction parameters would permit one to make
reasonable estimates of these concentrations.
There are several methods available to define parti-
tioning of species between several phases: a rigorous
thermodynamic approach, an experimental approach
(based on x
c
, the conversion at which the monomer
droplets disappear), an empirical approach, and the use
of partition coefficients.
Several groups in the literature employ the following
equation (Dougherty, 1986):
where a
2
is an adjustable parameter that has a value
less than 1 for a water-soluble monomer and is equal
to 1 otherwise. F
m
and F
p
are the densities of monomer
and polymer, respectively. x
c
is the critical conversion
at which the monomer droplets disappear. After the
conversion has reached x
c
, one can replace x
c
in the
above equation with the conversion level x.
The thermodynamic approach presented by Guillot
(1985) is as follows:
Equation 107 represents the chemical potential of
species i in the monomer droplets.
i
is the volume
fraction of component i, m is a coefficient related to
volume characteristics, and
ij
is the Flory-Huggins
interaction parameter. In the water phase:
and for the particle phase a similar expression can be
written. Asua et al. (1989), Dimitratos et al. (1989),
Mead and Poehlein (1989b), Urquiola et al. (1991), Noel
et al. (1994), and Schoonbrood et al. (1994) have also
used this thermodynamic approach successfully. It is
evident from eqs 107 and 108 that several parameters
(e.g., the Flory-Huggins interaction parameter,
ij
; the
volume coefficients, m
i
and m
w
) must be known. The
uncertainties around these parameters make use of the
thermodynamic approach less practical compared to the
one described below, which is based on defining parti-
tion coefficients. Noel et al. (1994) recently published
a simplification to the thermodynamic approach which
was extended for the case of multiple monomers by
Schoonbrood et al. (1994). While the thermodynamic
approach is rigorous, partitioning may also be a function
of emulsifier concentration and monomer feed (f
i
) (Guil-
lot, 1985; Emelie et al., 1991).
According to the empirical approach, one tries to
correlate the points where the monomer droplets disap-
pear with the weight fraction of monomer in the initial
charge. This approach involves a good deal of experi-
mentation and will, of course, be practical only when
narrow ranges of reactor operation are of interest.
Finally, the method of partition coefficients based on
that proposed by Omi et al. (1987) was adopted in the
current model with ideas from Maxwell et al. (1992a)
and Urretabizkaia and Asua (1994). Recent updates of
these ideas are also available (Armitage et al., 1994;
Gugliotta et al., 1995a). This general and valid ap-
proach for modeling uses partition coefficients between
the monomer/water phases and the water/polymer
phases combined with the overall material balances on
)
k
p
[M]
w
+ k
tw
[R
]
w
k
p
[M]
w
+ k
tw
[R
]
w
+ k
a
N
T
w
w
/N
A
(103)
k
des
! )
k
fm
k
p
!
12D
w
(/6)
2/3
(
a +
D
w
[sinh()(1 + 3/
2
) - 3 cosh()/]
k
p
![M]
p
R
2
[cosh()/ - sinh()/
2
]
)
(104)
) r
[
k
p
![M]
p
D
p
]
1/2
(105)
[M]
psat
)
a
2
F
m
M
wt
1 - x
c
1 - x
c
(1 - F
m
/F
p
)
(106)
i
)
o,i
+ RT(ln
i
+ (1 - m)
j
+
ij
j
2
) (107)
i
w
)
o,i
w
+ RT(ln
i
+ (1 - m
i
/m
w
)
w
+ m
i
w
2
)
(108)
the monomers, the polymer, and the water. Partition
coefficients for monomer j between the monomer droplet
phase and the water phase (K
jmw
) and for monomer j
between the water phase and the particle phase (K
jwp
)
are defined as
where V
jmd
, V
jmw
, and V
jmp
are the volumes of monomer
j in the droplets, aqueous phase, and particles, respec-
tively. V
md
is the volume of the monomer droplets, V
aq
is the volume of the aqueous phase, and V
p
is the volume
of particles.
The total volume of monomer j, V
mj
, is given by
where V
jmd
and V
jmw
are derived from eqs 109 and 110,
respectively, as follows:
Combining eqs 111-113 gives
The algorithm used to calculate the partitioning of
the monomers into the different phases is as follows.
Initially, when there are no particles present, the
volumes of monomer j in the droplet and water phases
are calculated by guessing values for V
aq
(using mono-
mer solubilities) and V
md
and iterating over the follow-
ing equations:
When particles are generated, the volume of particles,
V
p
, is calculated using the differential equations shown
later in eqs 141 and 142. The volume of the aqueous
phase, V
aq
, is calculated from the moles of monomer in
the aqueous phase (see eq 125). The volume of the
monomer droplet phase, V
md
, is calculated by the
difference between the total monomer in the reactor and
the sum of the monomer in the particle and water
phases. Then, eq 114 is calculated followed by eqs 112
and 113. The concentrations of the monomers in the
various phases can then be calculated. The above
method has a rigorous thermodynamic basis as shown
in Mead and Poehlein (1988); at the same time, the
approach is quite practical and amenable to experimen-
tal confirmations.
In order to obtain the concentration of the monomer-
soluble impurities and the chain-transfer agent in the
particles, partition coefficients were also used as shown
below:
where
Equations 119 and 120 both assume that monomer-
soluble impurities and chain-transfer agents are not
considerably soluble in water. N
msi
and N
cta
represent
the total number of moles of MSI and CTA in the
reactor, respectively.
2.9. Material and Population Balances: Pro-
ductivity and Quality. We now present the various
material balances for all of the species involved (save
the initiating system which was presented earlier) and
the rate equations to which they are related. For the
emulsion case, the terms with subscripts p and w
represent the particle and water phases, respectively.
In the bulk, suspension and solution cases, recalling
that the reaction steps proceed in only one phase, the
terms with the subscript w should be ignored, while
those with subscript p represent the bulk reaction
phase. Note that terms for semibatch and continuous
reactors which allow for the inflow and outflow of the
various species have been included here. In this section,
the inflow of species i is designated by F
i,in
and v
out
represents the volumetric flow out of the reactor.
The balances for the monomers comprise the inflow
and outflow of monomers and their depletion by polym-
erization in the organic (or particle) phase as well as in
the aqueous phase (for the emulsion case):
The inflow of monomer increases the rate of accumula-
tion of the number of moles of monomer j (dN
mj
/dt) in
the reactor. The outflow (second term on the right-hand
side of eq 123) and the reaction of monomer (third and
fourth terms on the right-hand side of eq 123) result in
a decrease in dN
mj
/dt. The reaction takes place in the
particles, hence the term R
pjp
V
p
in eq 123, and in the
water phase, hence the term R
pjw
V
w
in the same
equation.
Similarly, the balances for the monomers bound in
the polymer involve accumulation of bound monomer
by polymerization in both the particles and the water
phase. In a batch reactor, where there is no inflow or
outflow of a polymer fromthe reactor, the total amount
of polymer formed and its composition can be obtained
from the monomer material balances directly by con-
sidering the net change in moles of each monomer j.
K
jmw
)
V
jmd
/V
md
V
jmw
/V
aq
(109)
K
jwp
)
V
jmw
/V
aq
V
jmp
/V
p
(110)
V
mj
) V
jmd
+ V
jmw
+ V
jmp
(111)
V
jmd
)
V
md
V
jmp
K
jmw
K
jwp
V
p
(112)
V
jmw
)
V
aq
V
jmp
K
jwp
V
p
(113)
V
jmp
)
V
mj
1 +
V
md
K
jmw
K
jwp
V
p
+
V
aq
K
jwp
V
p
(114)
V
jmd
) V
mj
(
1 +
V
aq
V
md
K
jmw
)
(115)
V
jmw
) V
mj
- V
jmd
(116)
V
md
)
"
j)1
N
V
jmd
(117)
V
aq
) V
w"
j)1
N
V
jmw
(118)
[MSI]
p
)
N
msi
V
p
+ V
m
K
msi
(119)
[CTA]
p
)
N
cta
V
p
+ V
m
K
cta
(120)
K
msi
) K
MSIwp
K
MSImw
(121)
K
cta
) K
CTAwp
K
CTAmw
(122)
dN
mj
dt
) F
mj,in
-
N
j
V
T
v
out
- R
pjp
V
p
- R
pjw
V
w
(123)
However, in a semibatch or continuous-flowreactor with
inflow and outflow of polymer and monomer, additional
balances are needed for the moles of each monomer j in
the reactor that are bound as polymer, i.e.
The moles of monomer j bound in the polymer (N
polj
)
are a result of polymerization in the particles (R
pjp
V
p
)
and in the water phase (R
pjw
V
w
) as well as inflow (F
pj,in
)
and outflow ((N
polj
/V
T
)v
out
). Polymerization in the mono-
mer droplets is neglected for the reasons presented
earlier.
A separate balance on the number of moles of mono-
mer j in the water phase is used to calculate the volume
of monomers in the water phase. During the interval
when monomer droplets exist, the number of moles of
monomers in the water phase is held constant fromthe
initial values based on the partitioning equations shown
earlier (see eq 116). When the droplets are depleted,
the monomer in the water phase is calculated by:
The polymerization rates are defined as
where [R
TOT
]
w
is the total concentration of radicals in
the water phase (see eq 29).
From the above balances, a number of variables of
interest can be calculated directly. For example, the
total mass conversion of monomers to polymer can be
calculated by
The instantaneous polymer composition (F
j
) in the
particles can now be calculated as:
Expressions for the instantaneous polymer composition
based solely on the reactivity ratios (defined earlier in
eq 16) and the monomer feed mole fractions were
derived from the Alfrey-Goldfinger equations for ter-
polymers (Alfrey and Goldfinger, 1944). The Alfrey-
Goldfinger equations are shown below:
After some algebraic manipulation, one may obtain
where num(F
i
/F
j
) refers to the numerator of the equa-
tions for F
i
/F
j
(see eqs 130 and 131) and den refers to
their denominator. Equations 132-134 may be reduced
to the homo- or copolymerization case by setting the
reactivity ratios, which include the missing monomer,
equal to 1.
The cumulative polymer composition (Fh
j
) is calculated
as
The instantaneous polymer composition is calculated
mainly for its use as a weighting function for the various
parameters in the model and is calculated for two
separate cases. One is based on the polymer being
formed in the particles and the other on that being
formed in the water phase. On the other hand, the
cumulative polymer composition takes into account the
polymer formed in both phases, i.e., the total polymer
formed in the reactor. The cumulative polymer com-
position includes both water phase and particle phase
polymerizations in order to account for the contribution
to the composition due to the capture of oligomeric
radicals from the water phase by the particles.
A balance is now performed on the solvent, which is
in the emulsion case, water, comprising of inflow and
outflow:
Similarly, a balance for the emulsifiers results in
Note that the emulsifier can be located in four areas:
dN
polj
dt
) F
pj,in
-
N
polj
V
T
v
out
+ R
pjp
V
p
+ R
pjw
V
w
(124)
dN
mjw
dt
) -R
pjw
V
w
(125)
R
pjp
) Y
o
[M]
p
f
j"
i)1
N
k
pij
i
(126)
R
pjw
) [R
TOT
]
w
[M]
w
f
jw"
i)1
N
k
pij
iw
(127)
x )
"
j)1
N
(N
polj
MW
j
)
"
j)1
N
((N
mj
+ N
polj
)MW
j
)
(128)
F
j
)
R
pjp
"
j)1
N
R
pjp
(129)
F
1
F
3
)
f
1
(f
1
r
23
r
32
+ f
2
r
23
r
31
+ f
3
r
21
r
32
)(f
1
r
12
r
13
+ f
2
r
13
+ f
3
r
12
)
f
3
(f
1
r
12
r
23
+ f
2
r
13
r
21
+ f
3
r
12
r
21
)(f
1
r
32
+ f
2
r
31
+ f
3
r
31
r
32
)
(130)
F
2
F
3
)
f
2
(f
1
r
13
r
32
+ f
2
r
13
r
31
+ f
3
r
12
r
31
)(f
1
r
23
+ f
2
r
21
r
23
+ f
3
r
21
)
f
3
(f
1
r
12
r
23
+ f
2
r
13
r
21
+ f
3
r
12
r
21
)(f
1
r
32
+ f
2
r
31
+ f
3
r
31
r
32
)
(131)
F
1
)
num(F
1
/F
3
) - 2num(F
2
/F
3
) - 2den
num(F
1
/F
3
) - num(F
2
/F
3
) - den
(132)
F
2
)
num(F
2
/F
3
)
num(F
1
/F
3
) - num(F
2
/F
3
) - den
(133)
F
3
)
den
num(F
1
/F
3
) - num(F
2
/F
3
) - den
(134)
Fh
j
)
N
polj
"
j)1
N
N
polj
(135)
dN
s
dt
) F
s,in
-
N
S
V
T
v
out
(136)
dN
em
dt
) F
em,in
-
N
em
V
T
v
out
(137)
as micelles, stabilizing monomer droplets, and stabiliz-
ing particles and dissolved in the aqueous phase.
Now, balances for the water-soluble (z
1
, z
2
) and
monomer-soluble impurities (MSI) are performed:
Water-soluble impurities such as oxygen and hydro-
quinones can enter the reaction via various feed streams
and consume radicals in the water phase. Monomer-
soluble impurities can arise from the feed streams and
recycle streams.
A balance for the consumption of chain-transfer agent
(CTA) is
The volume of polymer particles is defined in two
separate regimes: when monomer droplets exist and
when there are no longer any droplets. The balances
respectively are
where
p
is the volume fraction of polymer in the
particles, F
mj
is the density of monomer j, and F
p
is the
density of the polymer. F
p
is calculated using the
individual polymer densities weighted by the mole
fractions of each polymer in the particles. For the case
of seeded emulsion polymerizations or a series of
constant stirred-tank reactors (CSTRs), a term describ-
ing the inflow of polymer particles can be added to the
equations. Note that one may be required to include
an outflow term to describe the flow of polymer out of
the reactor. Since the outflow term, v
out
, includes both
the organic (monomer and polymer) and aqueous phases,
it should be multiplied by the percentage of polymer in
the reactor. In any case, one must satisfy the mass
balances. The first term in eq 141 describes the
increasing volume of the particles due to the saturation
of the particles by monomer. In other words, as polym-
erization within the particles proceeds, monomer is
consumed and replaced by monomer from the droplets
in amounts required to maintain a constant monomer
concentration in the particles. R
pjw
V
w
takes into account
the growth of the particles by capture of oligomeric
radicals formed in the aqueous phase. Equation 141 is
active while the monomer droplets exist. Equation 142
represents the stage of the emulsion polymerization
when the monomer droplets disappear as a separate
phase. At this stage, the volume of the particles can
increase only by capture of radicals from the water
phase. This growth is counteracted by shrinkage due
to the density differences between the monomers and
the polymer. What results is a net decrease in the total
volume of particles.
The particle diameter of the swollen particles, under
the monodispersed approximation, is defined as
The particle diameter of the unswollen particles (the
quantity measured using a disc centrifuge), under the
monodispersed approximation, is defined as
The volume of the monomer droplets can be calculated
by the difference between the volume of the organic
phase and the sum of the volume of polymer particles
and the volume of monomer in the aqueous phase. The
balance for the volume of the organic phase is
The volume of the organic phase changes due to the
inflow of monomer and polymer, the outflow of monomer
and polymer, and volume shrinkage during the polym-
erization. V
o
corresponds to the total volume in a bulk
polymerization. Recall that v
out
can be included in the
equation to describe the outflow of monomer and
polymer.
2.10. Molecular Weight, Long-Chain Branching,
and Cross-Linking Development. 2.10.1. Linear
Copolymer Chains. With linear copolymer chains,
polymer molecules once formed are inert and do not take
part in reactions such as transfer to polymer and
reaction with internal double bonds bound in polymer
chains, and, therefore, the method of instantaneous
molecular weight distribution can profitably be em-
ployed for homo-, co-, and, in general, multicomponent
polymerizations. This approach, shown below, was first
introduced for binary copolymerization by Stockmayer
(1945), who derived the instantaneous bivariate distri-
bution for linear copolymer chains, assuming that both
monomer types have the same molecular weight. A
correction factor to account for differing monomer
molecular weights was recently derived by Tacx et al.
(1988) and is given by eq 210 shown later.
where W(r,y) dr dy is the weight fraction of copolymer
of chain length in the range r to r + dr and composition
deviation in the range y to y + dy for copolymer
produced instantaneously (in the time interval t to t +
dt in a batch reactor).
dN
zi
dt
) F
zi,in
-
N
zi
V
T
v
out
- k
zi
N
zi
[R
TOT
]
w
(138)
dN
msi
dt
) F
msi,in
-
N
msi
V
T
v
out
- k
fmsi
[MSI]
p
Y
o
V
p
(139)
dN
cta
dt
) F
cta,in
-
N
cta
V
T
v
out
- k
fcta
[CTA]
p
Y
o
V
p
(140)
dV
p
dt
)
"
j)1
N
MW
mj
(R
pjp
V
p
+ R
pjw
V
w
)
p
F
p
(141)
dV
p
dt
)
"
j)1
N
MW
mj
R
pjw
V
w
F
p
-
"
j)1
N
MW
mj
R
pjp
V
p
(1/F
mj
- 1/F
p
)
(142)
d
p
)
(
A
p
N
p
)
1/2
(143)
d
p
)
(
6V
p
p
N
p
)
1/3
(144)
dV
o
dt
)
"
j)1
N
F
mj,in
MW
mj
F
mj
-
"
j)1
N
MW
mj
(R
pjp
V
p
+ R
pjw
V
w
)
(
1
F
mj
-
1
F
p
)
(145)
W(r,y) ) ( + )( + /2( + )r)r exp(-( +
)r(1/2
2
)
1/2
exp(-y
2
/2
2
) (146)
y ) y
1
- F
1
(147)
2
) F
1
(1 - F
1
)K/r (148)
where y
1
is the mole fraction of monomer 1 in the
copolymer and F
1
is the overall mole fraction of mono-
mer 1 in the copolymer and was given earlier in eq 129
and
The pseudo-kinetic rate constants for multicomponent
polymerization were given earlier by eqs 61 (for transfer
to CTA), 63 (for transfer to monomer), 83 (for diffusion-
controlled termination), and 84 (for diffusion-controlled
propagation).
The instantaneous molecular weight distribution of
the copolymer is given by
For long polymer chains, one can assume with small
error that all chains produced instantaneously have the
same composition F
1
, F
2
, .... These overall compositions
can be found using eq 129.
The bivariate distribution for polymer accumulated
in a batch or semibatch reactor may be found by
integration of eq 146 as follows:
Instantaneous number- and weight-average chain lengths
are given by
Number- and weight-average chain lengths of the
accumulated polymer in batch or semibatch reactors are
given by
Tobita and Hamielec (1991) generalized Stockmayers
bivariate distribution to account for chain-length de-
pendence of polymer radical/polymer radical termina-
tion. Expressions equivalent to eqs 155 and 156 when
chain-length-dependent termination is significant may
be found in Zhu and Hamielec (1989).
2.10.2. Polymers with Long Branches. The
method of instantaneous molecular weight distribution
which is such a powerful method for the calculation of
molecular weight distribution of linear polymer chains
must be modified when long-chain branching reactions
such as transfer to polymer and reaction with internal
or terminal double bonds are significant. In this case,
dead polymer chains are no longer inert and can react
with polymeric radicals (and other radical types) and
now the instantaneous molecular weight distribution is
no longer a permanent quantity but changes with time
as its chains react. One must keep track of these chains
in order to predict the MWD of the accumulated linear
chains. In principle, this can be done for chains having
1, 2, or more long branches (Soares and Hamielec,
1996c). Alternatively, one can use Monte Carlo simula-
tions to calculate the full MWD for chains with long
branches as illustrated by Tobita (1995a,b).
Teymour and Campbell (1994) developed a novel
method coined numerical fractionation to calculate the
full MWD of sol before and after the gelation point
without the normal discontinuity that plagued earlier
methods using the method of moments. This method
is presently being comprehensively evaluated by various
research groups, and we await the results of these
studies. Of course, when the full MWD is not essential
and average molecular weights will do, it is recom-
mended that the method of moments be used. The use
of the pseudo-kinetic rate constant method for copolym-
erization with long-chain branching has been illustrated
by Xie and Hamielec (1993b,c).
Using the method of moments, the leading moments
of the distribution (Q
0
, Q
1
, Q
2
) can be calculated as
follows. Invoking the stationary-state hypothesis for
radicals, one can readily derive the following moment
equations (Ray, 1972; Broadhead et al., 1985; Hamielec
et al., 1987; Xie and Hamielec, 1993a,b).
where
K ) (1 - 4F
1
(1 - F
1
)(1 - r
1
r
2
)) (149)
)
k
td
Y
o
k
p
[M]
p
+ C
fm
+
C
fcta
[CTA]
p
[M]
p
+
C
fmsi
[MSI]
p
[M]
p
(150)
)
k
tc
Y
o
k
p
[M]
p
(151)
W(r) )
-#
#
W(r,y) dy ) ( + )( + /2( + )r)r
exp(-( + )r) (152)
Wh (r,y) )
0
t
W(r,y) R
pW
(t) V(t) dt
0
t
R
pW
(t) V(t) dt
(153)
R
pW
(t) )
"
i)1
N
R
pi
MW
i
(154)
r
N
)
1
+ /2
(155)
r
W
)
2 + 3
( + )
2
(156)
rj
N
)

0
t
R
pW
(t) V(t) dt
0
t
(1/r
N
)R
pW
(t) V(t) dt
(157)
rj
W
)
0
t
r
W
R
pW
(t) V(t) dt
0
t
R
pW
(t) V(t) dt
(158)
dV
p
Q
0
dt
)
(
+ /2 -
C
k
Q
1
[M]
p
-
KQ
0
[M]
p
)
k
p
[M]
p
Y
o
V
p
(159)
dV
p
Q
1
dt
)
(
1 + C
fm
+
C
fcta
[CTA]
p
[M]
p
-
C
fmsi
[MSI]
p
[M]
p
)
k
p
[M]
p
Y
o
V
p
(160)
dV
p
Q
2
dt
)
(
factor + 2
(
1 +
KQ
1
+ C
k
Q
2
[M]
p
)
bracket
denom
+
(
bracket
denom
)
2
)
k
p
[M]
p
Y
o
V
p
(161)
)
k
td
Y
o
k
p
[M]
p
+ C
fm
+
C
fcta
[CTA]
p
[M]
p
+
C
fmsi
[MSI]
p
[M]
p
(162)
)
k
tc
Y
o
k
p
[M]
p
(163)
C
fm
, C
fcta
, and C
fmsi
are the constants for transfer to
monomer, to chain-transfer agent, and to monomer-
soluble impurities, respectively. They are defined as
C
fp
, C
k
, and K are the constants for transfer to polymer,
internal double-bond, and terminal double-bond reac-
tions, respectively. They are defined as
The accumulated number- and weight-average mo-
lecular weights are then defined as
The effective molecular weight, M
weff
, is calculated by
summing the individual monomer molecular weights
and weighting them by the cumulative polymer com-
position.
To calculate instantaneous number- and weight-
average chain lengths, one can simply divide eq 160 by
eq 159 and then eq 161 by eq 160, respectively. Setting
C
fp
, C
k
, and K to zero should then give the average chain
lengths for linear polymer chains (see eqs 155 and 156).
The branching frequencies for both trifunctional and
tetrafunctional branching are calculated as follows:
2.10.3. Cross-Linking and Gelation. Reaction
with internal double bonds may rapidly lead to a three-
dimensional network and the onset of gelation. In the
context of the present kinetic models, the onset of
gelation occurs when Q
2
(or the weight-average molec-
ular weight) goes to infinity. In other words, the first
cross-linked gel particle of infinite molecular weight
forms in the polymerizing mixture. To illustrate the use
of eq 161 to calculate the onset of gel formation, a
limiting form of this equation will be used. It is
assumed that transfer to monomer and reaction with
internal double bonds control molecular weight develop-
ment, with an insignificant number of polymer chains
produced by termination reactions. In addition, it is
assumed that, in the batch reactor, the volume of the
reacting mixture is constant. Equation 161 thus re-
duces to
Introducing monomer conversion, eq 177 can be
rearranged to give
where
and
Equation 178 can be solved analytically to give
where x
c
is the monomer conversion at the point of
gelation.
The solution (eq 181) applies for a homopolymeriza-
tion of a divinyl monomer whose double bonds have
equal reactivity. For the copolymerization of a divinyl
monomer with a vinyl monomer, one must redefine
as follows:
where F
1
is the mole fraction of divinyl monomer in the
copolymer chains.
The physical interpretation of these results is straight-
forward. The more active the double bonds bound in
the copolymer chains (larger k*
p
*) and the greater the
number of these double bonds (larger F
1
), onset of
gelation occurs at lower monomer conversions. The
more transfer to a small molecule such as monomer or
chain transfer agent (larger k
fm
), the further in conver-
sion is the onset of gelation delayed.
Models which can be used to calculate the quantity
of gel and details of gel structure are under development
(Tobita and Hamielec, 1989, 1992; Tobita, 1992, 1993a,b;
Charmot and Guillot, 1992; Teymour and Campbell,
1994).
2.11. Energy Balance Equations. Two energy
balances, one around the reactor contents and the other
around the reactor cooling jacket, will enable one to
investigate nonisothermal operation, variable heat-
transfer coefficients, reactor runaways, and temperature
controller design). For heat transfer through the reactor
walls (reactor jacket) and with the jacket full of perfectly
mixed heat-transfer fluid, the two heat balance equa-
tions may be written as follows for a well-mixed vessel:
factor ) 1 + C
fm
+
C
fcta
[CTA]
p
[M]
p
+
C
fmsi
[MSI]
p
[M]
p
(164)
denom ) + +
C
fp
Q
1
[M]
p
(165)
bracket ) 1 + C
fm
+
(C
fp
+ C
k
)Q
2
[M]
p
+
KQ
1
[M]
p
+
C
fcta
[CTA]
p
[M]
p
+
C
fmsi
[MSI]
p
[M]
p
(166)
C
fm
) k
fm
/k
p
(167)
C
fcta
) k
fcta
/k
p
(168)
C
fmsi
) k
fmsi
/k
p
(169)
C
fp
) k
fp
/k
p
(170)
C
k
) k*
p
*/k
p
(171)
K ) k*
p
/k
p
(172)
Mh
w
) Q
1
/Q
0
M
weff
(173)
Mh
w
) Q
2
/Q
1
M
weff
(174)
dV
p
Q
0
B
N3
dt
) k
p
Y
o
V
p
(C
fp
Q
1
+ KQ
0
) (175)
dV
p
Q
0
B
N4
dt
) k
p
Y
o
V
p
C
k
Q
1
(176)
dQ
2
dt
)
(
2
C
fm
(1 + Q
2
C
k
/[M]
p
)
2
)
k
p
[M]
p
Y
o
(177)
dQh
2
dx
) 2
(
1 +
Qh
2
1 - x
)
2
(178)
Qh
2
) k*
p
*Q
2
/k
p
[M]
p
(179)
) k*
p
*/k
fm
(180)
Qh
2
)
4(1 - x)(1 - (1 - x)
1+8
)
(1 + 4 - 1 + 8)
[(
1 - x
1 - x
c
)
1+8
- 1
]
(181)
: 0 0.1 0.2 0.3 0.4 0.5 1.0 5.0
x
c
:
1 0.943 0.835 0.778 0.647 0.577 0.370 0.094
) F
1
k*
p
*/k
fm
(182)
Controller Equation. Reactor temperature can be
controlled by manipulating the temperature of the
cooling jacket water feed. The temperature adjustment
of the cooling jacket water feed is assumed to be
instantaneous. A proportional-integral controller can
be simulated as follows:
where the error e is the difference between the desired
and actual reactor temperature.
The integral term of the controller can be simulated
with the following differential equation
where
The control action is implemented through the following
equation:
where T
j,in
represents the control action and T
c
a
steady-state or bias term.
The controller gain, K
c
, and integral time,
I
, can be
tuned using a linearized process model and stability
analysis. U and A
j
are the overall heat-transfer coef-
ficient and jacket heat-transfer area, respectively. Q
R
and Q
j
are uncontrolled heat losses for reactor and
jacket.
3. Model Development: Olefin Polymerization
with Homogeneous and Heterogeneous
Ziegler-Natta Catalysts
Polyolefins are very important commodity polymers.
Polyethylene and polypropylene are today the major
tonnage plastic materials worldwide, accounting for 44%
of all U.S. plastic sales in 1988 and reaching a capacity
of about 45 million tons in 1990 (Elias, 1992; Whiteley
et al., 1992).
Most industrial processes for the production of poly-
olefins utilize heterogeneous Ziegler-Natta catalysts.
Conventional soluble Ziegler-Natta catalysts have not
found widespread industrial applications, mainly be-
cause of insufficient catalytic stability and stereochem-
ical control. This picture, however, will likely change
in the near future with the advent of metallocene-based
catalyst systems. Metallocene catalysts with aluminox-
ane and other cocatalysts are able to produce polyolefins
at a very high productivity with a degree of microstruc-
tural control not possible to achieve using conventional
Ziegler-Natta catalysts (Hamielec and Soares, 1996;
Huang and Rempel, 1995; Soares and Hamielec, 1995a).
Ziegler-Natta catalysts are formed by a transition
metal salt of metals of groups IV-VIII and a metal alkyl
of a base metal of groups I-III (known as cocatalyst or
activator). However, not all combinations are equally
efficient and can be used for all monomers. From the
industrial point of view, most heterogeneous catalysts
are based on titanium salts and aluminum alkyls.
Most types of heterogeneous Ziegler-Natta catalysts
have a common intriguing characteristic: they yield
polymer with broad molecular weight distribution (MWD)
and, in the case of copolymerization, broad chemical
composition distribution (CCD). There is now a general
agreement that heterogeneous Ziegler-Natta catalysts
possess more than one type of active site, each one with
distinct ratios of chain transfer to propagation rates,
comonomer reactivity ratios, and stereoselectivities.
Each site type makes polymer chains that have different
average chain lengths, comonomer compositions, comono-
mer sequence lengths, and, in the case of asymmetric
monomers, different degrees of stereoregularity. Con-
sequently, heterogeneous Ziegler-Natta catalysts pro-
duce a mixture, at the molecular level, of polymer chains
having dissimilar average properties. These dissimilar
average properties are reflected in broad MWDs and
CCDs. Additionally, intraparticle heat- and mass-
transfer resistances during the polymerization may
somewhat broaden these distributions even further.
On the other hand, polyolefins made with most
soluble Ziegler-Natta catalysts, including several met-
allocene systems, have narrow MWD, and copolymers
also have narrow CCD. This behavior supports the
multiple-site-type hypothesis for heterogeneous cata-
lysts. Soluble Ziegler-Natta catalysts consist of rea-
sonably well-defined, single catalytic species, probably
not subject to significant heat- and mass-transfer re-
sistances during polymerization.
The complexity of MWDs and CCDs of polyolefins
made with Ziegler-Natta catalysts constitutes a chal-
lenging problem for polymer quality control. Most
properties of polyolefins are routinely measured only as
average values. Measurements of melt flow index (as
an estimator for a molecular weight average), melt flow
index ratio (as an estimator of polydispersity), and bulk
density (as an estimator of copolymer composition or
degree of short-chain branching) are common practice
in industry. However, macroscopic properties of poly-
mers, in general, and polyolefins, in particular, cannot
be uniquely determined by average values, since poly-
mers that have some average properties in common can
possess other properties that differ markedly. Even a
knowledge of the full molecular weight distribution for
polypropylene may not be sufficient for many practical
applications, due to differences in stereoregularity of the
chains. In the same way, determining average composi-
tions of copolymers or average degrees of branching will
not entirely define the polymer in question. The whole
distribution of composition in addition to chain length
is necessary to accomplish this task. This issue becomes
very complex with polyolefins made with heterogeneous
Reactor Balance
d(
"
j
M
i
C
pi
(T - T
ref
))
dt
)
"
i
F
i,in
C
pi
(T
in
- T
ref
) -
"
i
F
i,out
C
pi
(T - T
ref
) +
"
i
R
pi
(-H
pi
)V
p
- UA
j
(T -
T
j
) - Q
R
(183)
Cooling Jacket Balance
dT
j
dt
)
(F
jw
C
pw
(T
j,in
- T
j
) + UA
j
(T - T
j
) - Q
j
)
F
w
V
j
C
pw
(184)
T
j,in
) K
c
e (
K
c
0
t
e dt (185)
e ) T - T
set
(186)
dI/dt ) T - T
set
(187)
I )
0
t
e dt (188)
T
j,in
) T
c
+ T
j,in
(189)
Ziegler-Natta catalysts because polymers with broad
and sometimes multimodal MWDs and CCDs can be
produced.
The concern about the breadth of MWD and CCD of
polyolefins is far from academic. Those distributions
affect the final mechanical and rheological properties
of polyolefins and ultimately determine their applica-
tions. Polyethylenes with broad MWD are easier to
process because of greater flowability in the molten state
at high shear rate, while polyethylenes with narrow
MWDhave greater dimensional stability, higher impact
resistance, greater toughness at low temperatures, and
higher resistance to environmental stress cracking. For
polypropylene, narrow MWD is required for rapid mold-
ing of products with good mechanical properties. Nar-
row MWD and especially narrow CCD are required for
the production of elastomers. Polymers with broad CCD
might have some chains containing long sequences of
one monomer type, increasing the crystallinity of the
polymer, which is highly undesirable for elastomers.
3.1. Mathematical Models. It is convenient to
classify mathematical models for polymerization pro-
cesses in three levels: microscale, mesoscale, and mac-
roscale (Ray, 1988). Microscale models define the
kinetics of polymerization and the types of active sites
on the catalyst. Mesoscale models define interparticle
and intraparticle mass- and heat-transfer resistances
in the polymer particle. Macroscale models describe the
macroscopic behavior of the polymerization reactor, such
as imperfect mixing, residence time distribution, gas-
liquid mass transfer, and removal of heat of polymeri-
zation. The final application of the model determines
the degree of complexity required in each modeling level.
Figure 1 shows schematically these three levels of
mathematical modeling.
Knowledge of the kinetics of polymerization is evi-
dently fundamental for the mathematical modeling of
Ziegler-Natta polymerization reactors. The kinetics of
polymerization with heterogeneous and homogeneous
Ziegler-Natta catalysts has been the subject of detailed
study and will not be covered in this review. Good
reviews on polymerization kinetics are available in the
literature for both heterogeneous (Keii, 1972; Cooper,
1976; Bohm, 1978; Boor, 1979; Tait and Watkins, 1989)
and homogeneous (Hamielec and Soares, 1996; Huang
and Rempel, 1995; Soares and Hamielec, 1995a) Zie-
gler-Natta catalysts.
Mathematical models that can predict MWDand CCD
of polymer chains will be reviewed in the next sections.
3.1.1. Heterogeneous Catalysts. Heterogeneous
Ziegler-Natta catalysts are porous secondary particles,
formed by loosely aggregated primary particles (Tait,
1989, Noristi et al., 1994). During polymerization, the
growing polymer chains fragment these secondary
particles, forming an expanding particle containing
primary particles and living and dead polymer chains
(Figure 2). This catalyst fragmentation mechanismhas
been documented for several types of heterogeneous
Ziegler-Natta catalysts (Hock, 1966; Buls and Higgins,
1970; Wilchinsky et al., 1973; Boor, 1979; Kakugo et al.,
1989; Noristi et al., 1994). One of its consequences is
the well-known replication phenomenon: the particle-
size distribution of the polymer particles at the end of
batch or semibatch polymerization closely approximates
the particle-size distribution of the catalyst at the
beginning of polymerization (Simonazzi et al., 1991).
Good replication is supposed to occur when there is an
adequate balance between the mechanical strength of
the particle and catalytic activity. Replication factors
of 40-50 (ratio of average polymer particle diameter to
average catalyst particle diameter) are obtained with
third generation Ziegler-Natta catalysts (Galli and
Haylock, 1992). For the case of continuous reactors,
residence time distribution can significantly affect this
particle size distribution (Soares and Hamielec, 1995d;
Choi et al., 1994).
Based on this well-known experimental evidence,
some researchers advocate that, due to diffusion resis-
tances, catalyst fragments in different radial positions
are exposed to different concentrations of monomer and
Figure 1. Levels of mathematical modeling.
chain-transfer agent (generally hydrogen) and conse-
quently produce polymer with chain-length averages
that differ spatially inside the polymeric particle. For
copolymerization, monomers with different effective
diffusivities and reactivities may be responsible for
spatial compositional heterogeneity in the polymeric
particle. In addition, if there is appreciable heat-
transfer resistance, hot spots can occur inside the
polymer particle, altering reaction rates and further
broadening MWD and CCD (Figure 3). Models based
on this approach are generally called physical models
(Schmeal and Street, 1971, 1972; Singh and Merrill,
1971; Crabtree et al., 1973; Nagel et al., 1980; Taylor et
al., 1983; Floyd et al., 1986a-c; Galvan and Tirrell,
1986a; Hutchinson and Ray, 1988; Skomorokhov et al.,
1989; Sarkar and Gupta, 1991, Soares and Hamielec,
1995b).
A second category of mathematical models neglects
heat- and mass-transfer resistances in the polymer
particle. In these models, multiple types of catalytic
sites are responsible for the production of polymer with
broad MWDs and CCDs ( chemical models). Each site
type has its own kinetic constants and produces polymer
with often very different MWDs, CCDs, and stereoregu-
larities, as shown in Figure 4 for a three-site-type
catalyst (Tait and Wang, 1988; de Carvalho et al., 1989;
Rincon-Rubio et al., 1990; McAuley et al., 1990; Loren-
zini et al., 1991; Vela-Estrada and Hamielec, 1994; Lee
et al., 1994; Soares and Hamielec, 1995b). There is vast
experimental evidence supporting the existence of mul-
tiple site types on heterogeneous Ziegler-Natta cata-
lysts (Cozewith and VerStrate, 1971; Boor, 1979; Keii,
1982; Zucchini and Cecchin, 1983; Keii et al., 1984;
Chien et al., 1985; Usami et al., 1986; Spitz, 1987; Cheng
and Kakugo, 1991; Soares and Hamielec, 1996a,b).
The effects of transfer resistances and of multiple site
types on MWD and CCD broadening are evidently not
exclusive; the heterogeneity caused by the presence of
multiple site types can be increased by transfer resis-
tances during the polymerization. Some models com-
bining these two effects have been proposed recently and
seemto be highly successful in predicting the qualitative
behavior of polymerization with Ziegler-Natta cata-
lysts. These models will be called hybrid models since
they combine the two previous modeling strategies
(Galvan and Tirrell, 1986b; Floyd et al., 1988; Ray, 1988;
Hutchinson et al., 1992; Sau and Gupta, 1993; Soares
and Hamielec, 1995b).
Physical Models. Different mathematical models
have been proposed to describe interparticle and intra-
particle mass and heat transfer during polymerization
with heterogeneous Ziegler-Natta catalysts. Some are
very simplified pictures of the polymerization process
and are only useful as a reference point for comparison
with more sophisticated models. Among those, the most
Figure 2. Fragmentation of heterogeneous Ziegler-Natta catalyst (secondary) particles during polymerization. The growing polymer
chains break the secondary catalyst particles into primary particles, forming an expanding particle made of catalyst fragments surrounded
by dead and living polymer chains. This behavior is responsible for the replication phenomenon observed in heterogeneous Ziegler-
Natta catalysis.
Figure 3. Generic representation of physical models. T )
temperature; [M] ) monomer concentration; %M1 ) percent of
comonomer type 1 in the polymer; Mn )number-average molecular
weight. In physical models, intraparticle mass- and heat-transfer
resistances are responsible for MWD and CCD broadening.
representative for this review are the solid core model
and the polymeric core model (Figure 5).
The solid core model does not model the breakup of
the catalyst particle. The polymer is considered to grow
around a solid catalyst core containing all active sites
on its surface. This model using a single type of catalyst
site cannot predict broad MWDs (Schmeal and Street,
1971, 1972; Nagel et al., 1980). This result should not
come as a surprise since the polymerization takes place
only at the surface of the catalyst. For a given polym-
erization time, the monomer concentration is constant
at the surface of the catalyst and therefore all polymer
chains are produced with the same average properties.
Only if the concentration of monomer at the surface of
the catalysts changed significantly in time (because of
increasing transfer resistance caused by the growth of
polymer around the catalytic particle) would the solid
core model predict significant broadening of MWD.
Additionally, the solid core model is clearly in contradic-
tion with experimental data on catalyst breakup. De-
spite of these limitations, Brockmeier and Rogan (1976)
adjusted the solid core model to data collected in a
semibatch reactor and used this model to predict the
behavior of a continuous reactor. The predictions were
accurate for polymer yield, but no molecular weight
results were shown.
With the polymeric core model, polymer grows around
a nonexpanding polymeric core formed by polymer and
catalyst particles (Figure 5). Although this model is an
improvement over the first one, it still is not able to
account for broad MWDs (Schmeal and Street, 1971,
1972; Singh and Merrill, 1971). It shows, however, the
importance of a core of polymer-catalyst fragments in
the explanation of broad MWD.
The models that best represent the polymerization in
this category of single-site-type, transfer-controlled
models are the so-called expansion models. Expansion
models consider the fragmentation of the catalyst
particle and the formation of an expanding particle of
polymer and catalyst fragments.
Growing polymer chains and catalyst fragments form
a continuum in the polymeric flow model (Schmeal and
Street, 1971, 1972; Singh and Merrill, 1971; Galvan and
Tirrell, 1986a). Diffusion of reagents as well as heat
transfer occurs in this polymeric particle. If the reaction
is diffusion-controlled, the radial profiles of monomer
and chain-transfer agent in the particle may cause
MWD and CCD broadening. The effective mass- and
heat-transfer parameters in the polymeric particle have
to be estimated to use this model (Figure 6). The
polymeric flow model can predict significant broadening
of MWD using reasonable physical parameters.
The multigrain model (Crabtree et al., 1973; Nagel et
al., 1980) considers two levels of mass- and heat-transfer
resistances. The polymeric particle ( macroparticle or
secondary particle) is formed by an agglomerate of
microparticles or primary particles. Each microparticle
consists of a fragment of the original catalyst particle,
with all active sites on its surface, surrounded by dead
Figure 4. Generic representation of chemical models. 1, 2, and 3 indicate sites of different types; open and shaded circles indicate different
types of monomers. In chemical models, multiplicity of active site types is responsible for MWD and CCD broadening.
Figure 5. Schematic representation of the solid core model and
of the polymeric core model.
and living polymer (the solid core model describes the
behavior of the microparticles). Monomer diffuses
through the pores of the macroparticle and through the
layer of polymer surrounding the catalyst fragment in
the microparticle. Polymerization occurs on the surface
of the catalyst fragment. Electron microscopy studies
confirm the formation of primary and secondary struc-
tures in polymerizations with Ziegler-Natta catalysts
(Hock, 1966; Buls and Higgins, 1970; Kakugo et al.,
1989; Noristi et al., 1994). It is necessary to estimate
the number of microparticles and the transfer param-
eters in the microparticle and macroparticle to use the
multigrain model (Figure 6).
The multigrain model is probably the most studied
expansion model for polymerization of olefins with
heterogeneous Ziegler-Natta catalysts. It has been
extensively used to study heat- and mass-transfer
resistances for the homopolymerization of ethylene and
propylene in slurry and gas-phase reactors. Some
important conclusions obtained with the multigrain
model are as follows: (1) In most cases, intraparticle
temperature gradients are negligible. (2) Concentration
gradients in the macroparticles are likely to be more
important in slurry reactors. For gas-phase reactors,
these gradients may be significant in the microparticles.
(3) Interparticle mass- and heat-transfer resistances are
negligible except for high activity catalysts. (4) For
slurry reactors, gas-liquid mass-transfer resistances
are generally negligible for sparged reactors but can be
important for unsparged reactors (Nagel et al., 1980;
Taylor et al., 1983; Floyd et al., 1986a-c). Most mass-
and heat-transfer resistances are only significant at
early stages of polymerization as suggested by detailed
mathematical modeling of catalyst particle fragmenta-
tion (Laurence and Chiovetta, 1983; Ferrero and Chio-
vetta, 1987a,b, 1991).
Hutchinson and Ray (1988) used the multigrain model
to analyze the influence of monomer adsorption on the
surface of the microparticle. In the multigrain model,
before diffusing into the microparticle, adsorption of the
monomer on the outer surface of the microparticle has
to take place. Rate enhancement in copolymerization
and differences between slurry and vapor-phase reac-
tions were explained based on differences of solubilities
in each case, since more crystalline polymer layers have
lower monomer solubility and effective diffusivity.
Hutchinson et al. (1992) further expanded the multi-
grain model to describe copolymerization and particle
morphology.
Modeling equations for intraparticle radial profiles of
monomer concentration and temperature for all expan-
sion models are very similar. The radial profile of
monomer concentration in the secondary particle is
described by the well-known diffusion-reaction equation
in spherical coordinates:
where D
s
)effective diffusivity of monomer in secondary
particle (cm
2
s
-1
), k
s
) mass-transfer coefficient in an
external film (cm s
-1
), M
b
) monomer concentration in
the reactor (mol cm
-3
), M
s
) monomer concentration
in the secondary particle (mol cm
-3
), M
s0
) initial
monomer concentration in the secondary particle (mol
cm
-3
), r
v
) volumetric rate of polymerization is the
secondary particle (mol cm
-3
s
-1
), r
s
) radial position
in the secondary particle (cm), R
s
) radius of the
secondary particle (cm), and t ) polymerization time (s).
Notice that r
v
is the average rate of polymerization
at a given radial position in the secondary particle. In
the multigrain model, the polymerization is supposed
to only take place on the surface of the catalyst fragment
in the primary particle. Mathematically, it is intro-
duced as a boundary condition for the mass balance
equation of the primary particles.
The radial profile of monomer concentration in the
primary particles is given by the equations for the solid
core model:
where D
p
) effective diffusivity of monomer in the
primary particle (cm
2
s
-1
), M
eq
) equilibrium concentra-
tion of monomer in the interface between the primary
and secondary particles (mol cm
-3
), M
p
) monomer
concentration in the primary particle (mol cm
-3
), M
p0
) initial monomer concentration in the primary particle
(mol cm
-3
), r
c
) rate of polymerization on the surface
of the catalyst fragment (mol cm
-3
s
-1
), R
c
) radius of
the catalyst fragment in the primary particle (cm), r
p
)
radial position in the primary particle (cm), and R
p
)
radius of the primary particle (cm).
The rate of polymerization on the surface of the
catalyst fragment is generally given by
where k
p
) average rate constant for monomer propaga-
tion (cm
3
mol
-1
s
-1
), C* ) concentration of active sites
on the catalyst surface (mol cm
-3
), and M
c
) monomer
concentration on the catalyst surface (mol cm
-3
).
Figure 6. Schematic representation of the polymeric flow model
and of the multigrain model.
M
s
t
)
1
r
s
2
r
s
(
D
s
r
s
2
M
s
r
s
)
- r
v
(190)
M
s
r
s
(r
s
)0,t) ) 0 (191)
D
s
M
s
r
s
(r
s
)R
s
,t) ) k
s
(M
b
- M
s
) (192)
M
s
(r
s
,t)0) ) M
s0
(193)
M
p
t
)
1
r
p
2
r
p
(
D
p
r
p
2
M
p
r
p
)
(194)
4R
c
2
D
p
M
p
r
p
(r
p
)R
c
,t) )
4
3
R
c
3
r
c
(195)
M
p
(r
p
)R
p
,t) ) M
eq
e M
s
(196)
M
p
(r
p
,t)0) ) M
p0
(197)
r
c
) k
p
C*M
c
(198)
The effective diffusivity in the secondary particle can
be estimated as usually done for heterogeneous catalytic
reactions (Froment and Bischoff, 1990), using the value
of monomer diffusivity in the reaction medium, D
b
:
where and are the porosity and tortuosity of the
secondary particle, respectively.
For the primary particles, one has to correct the
diffusivity of monomer in amorphous polymer, D
a
,
according to the equation:
where R and are correction factors to account for
polymer crystallinity and chain immobilization of the
amorphous fraction (Floyd et al., 1986b).
Analogous equations can be used for the radial
temperature profiles. For the secondary particle:
where C
p
) heat capacity of the secondary particle (cal
mol
-1
K
-1
), h ) film heat-transfer coefficient (cal cm
-2
s
-1
K
-1
), H
p
) heat of polymerization (cal mol
-1
), k
e
) effective heat conductivity in the secondary particle
(cal cm
-1
s
-1
K
-1
), T
b
) reactor temperature (K), T
s
)
temperature in the secondary particle (K), T
s0
) initial
temperature in the secondary particle (K), and F
p
)
density of the polymer particle (mol cm
-3
).
Similarly, for the primary particles the temperature
profile is given by
where T
p0
is the initial temperature in the primary
particle.
Equations for intraparticle monomer concentration
and temperature radial profiles for the polymeric flow
and related models are similar to the ones for the
secondary particles of the multigrain model. The reac-
tion term in eqs 190 and 201 are calculated using the
average concentrations of monomer, Mh , and catalytic
sites, Ch *, in the secondary particle:
Equations for the moments of the molecular weight
distribution and copolymer composition have then to be
solved simultaneously with the intraparticle mass- and
heat-transfer equations for each radial position in order
to calculate the molecular weight and composition
averages in the polymeric particle.
The existence of yet another level of mass transfer is
suggested by Skomorokhov et al. (1989). In their model,
microparticles (described by the solid core model) ag-
glomerate to form subparticles. The polymer particle
(macroparticle) results fromthe agglomeration of these
subparticles. Growing polymer rapidly fills the pores
of the subparticles, and therefore the monomer diffusion
in the subparticle is in the order of magnitude of
diffusion in pure polymer. This model evidently predicts
higher diffusion resistances than that predicted by the
multigrain model, since the effective diffusion in the
larger subparticles is of the same magnitude as that in
the microparticles. These transfer resistances can, in
some polymerization conditions, decrease polymer yield.
Unfortunately, no predictions of MWD or CCD were
reported. Some experimental results on particle mor-
phology seem to support this model (Bukatov et al.,
1982; Skomorokhov et al., 1987, Kakugo et al., 1989).
Some mathematical models combine the approaches
of the polymeric flow model and the multigrain model.
In the polymeric multigrain model (Sarkar and Gupta,
1991), catalyst fragments are assumed to be in a
continuum of polymer with only one level of diffusional
resistance for the monomer. This model can predict
higher values of polydispersity than the multigrain
model.
In the polymeric multilayer model (Soares and
Hamielec, 1995b), the polymeric particle is divided into
concentric spherical layers as in the multigrain model
but microparticles are not considered. Therefore, the
intraparticle radial profiles of monomer concentration
and temperature for the multilayer model are the same
as those of the polymeric flow model; i.e., mass- and
heat-transfer processes that take place in the primary
particles are not explicitly considered in the model. Prior
to polymerization all layers have the same concentration
of active sites as the whole catalyst particle; i.e., there
is no radial profile of active sites. This assumption is
supported by some recent electron microscopy studies
of heterogeneous Ziegler-Natta catalysts (Noristi et al.,
1994). Population balances for each active species are
calculated inside each layer. The volume of each
concentric layer is updated using average monomer
concentrations and temperature after a given integra-
tion interval. The population balances derived for each
layer are the same as those for a model with no transfer
resistances. If transfer resistances are found to be of
little importance, the same equations can still be used
with the bulk monomer concentration and polymeriza-
tion temperature.
Additionally, the polymeric multilayer model esti-
mates the distributions of molecular weight and chemi-
cal composition in each model layer and whole polymer
using a theoretically sound equation, Stockmayers
bivariate distribution (Stockmayer, 1945), as shown in
Figure 7. The former expansion models could only
estimate averages of molecular weight and composition.
The instantaneous chain length and composition
distribution proposed by Stockmayer and corrected for
differing monomer molecular weights is given by
D
s
) D
b
/ (199)
D
p
) D
a
/R (200)
F
p
C
p
T
s
t
)
1
r
s
2
r
s
(
k
e
r
s
2
T
s
r
s
)
+ (-H
p
)r
v
(201)
T
s
r
s
(r
s
)0,t) ) 0 (202)
k
e
T
s
r
s
(t
s
)R
s
,t) ) h(T
b
- T
s
) (203)
T
s
(r
s
,t)0) ) T
s0
(204)
F
p
C
p
T
p
t
)
1
r
p
2
r
p
(
k
e
r
p
2
T
p
r
p
)
(205)
-4R
c
2
k
e
T
p
r
p
(r
p
)R
c
,t) ) (-H
p
)
4
3
R
c
3
r
c
(206)
T
p
(r
p
)R
p
,t) ) T
s
(207)
T
p
(r
p
,t)0) ) T
p0
(208)
r
v
(polymeric flow) ) k
p
Ch *Mh (209)
w(r,y) ) (1 + y)
2
r exp(-r) dr
1
2/r
exp(-y
2
r/2) dy (210)
where
and Fh
1
) average mole fraction of monomer type 1 on
copolymer, M
1
, M
2
) molecular weights of monomer
types 1 and 2, respectively, r ) chain length, r
1
, r
2
)
reactivity ratios, and y ) deviation from average
copolymer composition.
For single-site catalysts, the principal conclusions of
the polymeric multilayer model confirm and comple-
ment the conclusions obtained with the polymeric flow
model and the multigrain model: (1) Mass-transfer
resistances can reduce the polymerization rate, decrease
molecular weight averages, and affect copolymer com-
position for large, highly active catalysts. (2) Particu-
larly important for supported catalysts, the concentra-
tion of highly active sites can increase mass-transfer
resistances and have undesirable results in catalyst
performance and product quality. (3) Mass-transfer
resistances may also be a source of copolymer composi-
tion heterogeneity for highly active and large catalyst
particles, if the comonomers have reactivities that differ
significantly. (4) Temperature gradients in the poly-
meric particle are not expected to be a significant factor
for reactions carried out in slurry reactors.
The conclusions obtained with single-site-type expan-
sion models are especially important for the technology
of supported metallocene catalysts, where single-site,
highly active catalytic species may be subjected to
significant mass- and heat-transfer resistances (Soares
and Hamielec, 1995a,b).
Chemical Models. It is generally accepted that,
under most polymerization conditions, the effect of
multiple-site types on polymer properties is far more
important than mass- and heat-transfer resistances
(Ray, 1988; Soares and Hamielec, 1995b). Under these
conditions, each site type instantaneously produces
polymer that has Florys most probable MWD. There-
fore, the instantaneous MWD of accumulated polymer
made with heterogeneous Ziegler-Natta catalysts can
be considered an average of that produced by the
individual site types, weighted by the weight fraction
of polymer produced by each site type, as shown in
Figure 8 (Soares and Hamielec, 1995c).
The same treatment can be extended to copolymers
by using Stockmayers bivariate distribution to describe
the instantaneous bivariate distribution of chain length
and composition. Therefore, if one assumes that each
site type produces copolymer that obeys distinct bivari-
ate distributions of chain length and copolymer compo-
sition, the bivariate distribution of the accumulated
copolymer can be considered an average of that pro-
duced by the individual site types, as shown in Figure
9 (Soares and Hamielec, 1995e).
If these hypotheses are valid, broad MWDs and CCDs
result fromthe superposition of narrower distributions
produced on each site type. Additionally, from the
knowledge of the global MWDs and CCDs, one can use
Figure 7. Prediction of the bivariate distribution of chemical
composition and chain length with the polymeric multilayer model.
r ) chain length; W(r) dr ) chain-length distribution; y )deviation
from copolymer average composition; W(y) dy ) composition
distribution; s1, s2, s3 site types; l1, l2, ..., l9 ) model layers; l1 is
the innermost layer; l9 is the outermost layer.
) Fh
1
(1 - Fh
1
)K (211)
K ) [1 + 4Fh
1
(1 - Fh
1
)(r
1
r
2
- 1)]
0.5
(212)
)
1 - M
2
/M
1
M
2
/M
1
+ Fh
1
(1 - M
2
/M
1
)
(213)
Figure 8. Instantaneous chain-length distribution (CLD) of a
polyolefin made with a multiple-site-type catalyst as a superposi-
tion of four individual Florys most probable weight chain-length
distributions (solid line indicates CLD of whole polymer, and
dotted lines represent CLD of polymer made on distinct active site
types).
Figure 9. Instantaneous chemical composition distribution (CCD)
of a binary olefin copolymer made with a multiple-site-type
catalyst as a superposition of five individual Stockmayers CCDs
considering all chain lengths (solid line indicates CCD of whole
polymer, and dotted lines represent CCDs of polymer made on
distinct active sites).
mathematical models to infer the number of active site
types present on the catalyst (Vickroy et al., 1993;
Soares and Hamielec, 1995c,e). Multiple-site-type mod-
els without heat- and mass-transfer resistances have
achieved considerable success in simulating polymeriza-
tions using heterogeneous catalysts in slurry reactors
(Rincon-Rubio et al., 1990; Lee et al., 1994), series of
slurry reactors (de Carvalho et al., 1989, 1990; Soares,
1994), gas-phase reactors (McAuley et al., 1990; Xie et
al., 1994), and high-pressure-high-temperature tubular
reactors (Lorenzini et al., 1991).
Hybrid Models. Hybrid models provide the most
complete description of polymerization with heteroge-
neous Ziegler-Natta catalysts since they account for
multiple-site types and transfer resistances simulta-
neously. Although multiple-site types are probably the
main explanation for the characteristic behavior of
heterogeneous Ziegler-Natta catalysts, transfer resis-
tances may have a secondary effect on these properties
in certain polymerization conditions (Ray, 1988; Soares
and Hamielec, 1995b).
Several of the expansion models described above have
been modified to include the presence of more than one
type of active site: the polymeric flow model (Galvan
and Tirrell, 1986b), the multigrain model (Ray, 1988),
the polymeric multilayer model (Soares and Hamielec,
1995b), and the polymeric multigrain model (Sau and
Gupta, 1993). All these models indicate that the pres-
ence of more than one type of active site is mainly
responsible for the broad MWDs and CCDs observed in
polymer produced with heterogeneous Ziegler-Natta
catalysts. In general, mass- and heat-transfer resis-
tances are regarded as secondary effects. However,
under certain polymerization conditions with large,
highly active catalyst particles, mass-transfer resis-
tances can have an important role in further broadening
the MWD and CCD of polymers made with heteroge-
neous Ziegler-Natta catalysts.
The polymeric multilayer model uses Stockmayers
bivariate distribution to predict MWDs and CCDs of
polymer chains per site type in each concentric layer of
the model. These distributions are averaged over all
particles to obtain the MWD and CCD of the whole
polymer. Figure 10 shows the CCDs per site type of an
ethylene-propylene copolymer made with a three-site-
type catalyst averaged over all model layers. Figure 11
shows the CCDs of the same copolymer per layer
averaged over all site types. Finally, Figure 12 shows
the MWDs per site type for the same polymer averaged
over all model layers (Soares and Hamielec, 1995b).
Among the expansion models, only the polymeric mul-
tilayer model can predict complete distributions of
molecular weight and copolymer chemical composition.
3.1.2. Homogeneous Catalysts. Soluble Ziegler-
Natta catalysts, including metallocene catalysts, can
make polymer with narrow MWD and CCD (Kaminsky,
1986a, 1991). This behavior supports the multiple-site-
type hypothesis for heterogeneous catalysts since these
catalysts consist of reasonably well-defined, single
catalytic species and should produce polymer that has
narrow MWD and CCD.
Some metallocenes, however, can synthesize polymer
with broad MWD and CCD. This behavior has been
linked to the presence of different site types (Kaminsky,
1986b). In fact, a combination of different types of
metallocene catalysts can be used to produce polymer
with broad MWD and CCD (Welborn, 1987, 1991, 1992,
1993), which is in good agreement with the chemical
models presented above.
In most processes using homogeneous Ziegler-Natta
catalysts, in general, and metallocenes, in particular,
the polymer is not soluble in the reaction medium and
precipitates after a critical chain length is achieved. If
after chain termination the active site returns to the
Figure 10. CCDs for each site type over all model layers for
propylene-ethylene copolymerization (Soares and Hamielec, 1995b).
Figure 11. CCDs considering all site types in different polymer
layers for propylene-ethylene copolymerization. Layer 1 is the
innermost layer, and layer 9 is the outermost layer (Soares and
Hamielec, 1995b).
Figure 12. Chain-length distribution for each site type over all
layers for propylene-ethylene copolymerization (Soares and
Hamielec, 1995b).
solution, then interparticle mass and heat transfer
should not influence the polymerization. In this case,
chemical models would be adequate to describe the
polymerization. However, if the active sites are trapped
inside polymer particles, interparticle mass- and heat-
transfer resistances could become significant. A math-
ematical model for particle growth during polymeriza-
tions catalyzed with metallocenes has been proposed
recently (Herrmann and Bohm, 1991). It is possible
that, as the polymer particles grow by agglomeration,
some active sites will remain inside the polymer par-
ticles. This is especially more likely in processes where
the active sites are exposed to high concentrations of
monomer, as in liquid monomer polymerizations. In
this case, due to the high activity of metallocene
catalysts, transfer resistances may play a role in
broadening MWD and CCD.
Very few mathematical models have been proposed
to describe polymerization using homogeneous Ziegler-
Natta catalysts. Soares and Hamielec (1995b) proposed
that the polymeric multilayer model could be used to
simulate polymerization with homogeneous Ziegler-
Natta catalysts if one neglects mass- and heat-transfer
resistances in the polymeric particle. This would be
rigorously valid only if active sites are not trapped inside
polymer particles during polymerization. Vela-Estrada
and Hamielec (1994) were the first to model the polym-
erization of ethylene with bis(cyclopentadienyl)zirco-
niumdichloride and methylaluminoxane. Experimental
polymerization rates and MWD results could be well
represented by a two-site-type model. This was the first
study to use size-exclusion chromatography to establish
the number of active site types quantitatively for
polymers synthesized with homogeneous Ziegler-Natta
catalysts. In fact, a bimodal distribution gave a poly-
dispersity index of 2 for each mode. This result is in
excellent agreement with the model proposed in Figure
8.
Supported metallocenes have also been studied ex-
tensively. Among the several incentives for supporting
metallocenes are the use of already existing polymeri-
zation reactors for heterogeneous catalysts, the enhance-
ment of stereochemical and regiochemical control, de-
crease in the methylaluminoxane/catalyst ratio, and
production of polymer with better particle properties.
The models described before for heterogeneous Ziegler-
Natta catalysts can also be applied to this class of
catalysts (Soares and Hamielec, 1995b). In this case,
in the presence of only one active site type on the
catalyst, transfer resistances and statistical broadening
would be the only factors causing broadening of MWD
and CCD.
Hoel et al. (1994) developed a simplified flow model,
with no MWD prediction capabilities, and used it to
interpret their experimental data on ethylene-pro-
pylene polymerization using two silica-supported met-
allocene catalysts in a liquid-propylene slurry reactor.
Both catalysts produced polymer with narrow MWD at
a constant rate of polymerization. However, one cata-
lyst produced polymer with narrow CCD and the other
produced polymer with broad CCD and decreasing
amount of ethylene in the copolymer as a function of
polymerization time (unfortunately, the catalyst types
were not specified). The radial copolymer composition
was measured by FTIR-microscope analysis for micro-
tomed 250-750 m particles, and it was found to be
richer in propylene in the center than in the exterior
layers of the particle, which is also in good agreement
with the multilayer model predictions for single-site-
type catalyst (Soares and Hamielec, 1995b), as shown
in Figure 13. Although their model could qualitatively
predict the radial profile of chemical composition, it
could not account for the decrease in ethylene content
during the polymerization. In reality, their model
predicted an increase in ethylene content with polym-
erization time, and so would any other physical model
published in the literature, since the concentration of
active sites in the polymeric particle decreases during
the polymerization, therefore decreasing the effect of
intraparticle mass-transfer resistances. The observed
decrease in ethylene content in the copolymer was
tentatively attributed to variations in monomer diffu-
sivity and particle porosity during the polymerization.
Recently, Bonini et al. (1995) applied a modified form
of the multigrain model to the polymerization of pro-
pylene with silica-supported Me
2
Si(Ind)
2
ZrCl
2
/MAO.
Their model takes into account the mechanism of
catalyst fragmentation by the growing polymer chains
to explain the observed induction period when the
supported metallocene is used. In their model, the
catalyst particle is fragmented by the growing polymer
in successive concentric shells, fromthe external surface
to the center of the particle, as proposed by Ferrero and
Chiovetta (1991). Their model agreed well with experi-
mental rates of polymerization, including the induction
period and number-average molecular weight, but could
not predict the relatively broad MWD (polydispersities
from 2.4 to 3.8). The simulated polydispersities were
always less than 2.1, surprisingly low values.
3.1.3. Modeling of Long-Chain Branching. Con-
strained geometry metallocene catalysts can be used to
synthesize polyolefins with narrow molecular weight
distributions and significant degrees of long-chain
branching. These polymers have excellent mechanical
properties combined with good processability (good
shear thinning, delayed melt fracture, and improved
melt strength) (Hamielec and Soares, 1996).
The most suitable catalyst types for long-chain branch
formation appear to be those with an open metal active
center, such as the Dow Chemical constrained geometry
catalysts. The active center of these catalysts is based
on group IV transition metals that are covalently
bonded to a monocyclopentadienyl ring and bridged with
Figure 13. CCDs in different polymer layers for propylene-
ethylene copolymerization made on a single-site-type catalyst.
Layer 1 is the innermost layer, and layer 10 is the outermost layer
(Soares and Hamielec, 1995b).
a heteroatom, forming a constrained cyclic structure
with the transition-metal center. Strong Lewis acids
are used to activate the catalyst to a highly effective
cationic form. This geometry allows the titaniumcenter
to be more open to the addition of ethylene and higher
R-olefins but also for the addition of vinyl-terminated
polymer molecules (Lai et al., 1993a,b).
The most likely long-chain branch formation mecha-
nism with metallocene catalyst systems is terminal
branching, a mechanism which has been known in the
free-radical polymerization literature for many years.
In free-radical polymerization, macromonomers are
generated via termination by disproportionation and via
chain transfer to monomer. With metallocene catalyst
systems, the facile -hydride elimination reaction ap-
pears to be responsible for in-situ macromonomer
formation. Other reaction types, such as -methyl
elimination and trans, may also generate dead polymer
chains with terminal unsaturation (Resconi et al., 1992).
-Methyl elimination can actually be the most important
transfer mechanism in propylene polymerization when
(Me
5
Cp)
2
Ti, (Me
5
Cp)
2
Zr, and (Me
5
Cp)
2
Hf complexes are
used (Huang and Rempel, 1995). Therefore, these
catalytic systems have the potential of producing poly-
propylene with long-chain branches.
The chain-length distribution of polymer chains pro-
duced with metallocene catalysts that permit long-chain
branch formation via the terminal double-bond mech-
anism can be described analytically for each population
containing a different number of long-chain branches
per polymer molecule (Soares and Hamielec, 1996c). The
polymerization kinetic model involves the following
steps:
where P
r,i
is a living polymer molecule of chain length
r containing i long-chain branches, D
q,j
d
is a dead
polymer molecule of chain length q containing j long-
chain branches and having terminal vinyl unsaturation,
D
q,j
is a dead polymer molecule of chain length q
containing j long-chain branches and a saturated chain
end, M is the monomer, CTA is a chain-transfer agent,
k
p
is the propagation rate constant for monomer, k
pLCB
is the propagation rate constant for dead polymer with
terminal vinyl unsaturation, k
CTA
is the rate constant
for transfer to chain-transfer agent, and k
is the rate
constant for -hydride elimination. Chain initiation is
assumed to be instantaneous.
Dead polymer chains having terminal vinyl unsat-
uration, D
q,j
d
, can coordinate to the catalytic active site
and insert in the growing chain, forming a trifunctional
long-chain branch. Dead polymer chains with saturated
chain ends, D
q,j
, cannot polymerize again. Observe that
by examining the mechanism of chain formation, one
can conclude that the instantaneous molecular weight
distributions of live polymer, dead polymer with vinyl
chain-end unsaturation, and dead polymer with satu-
rated chain ends will be the same. However, the
relative amount of dead polymer with and without
terminal vinyl unsaturation is proportional to the rates
of -hydride elimination (producing dead polymer chains
with terminal vinyl unsaturation) and transfer to chain-
transfer agent (commonly to hydrogen, producing dead
polymer chains with saturated chain ends).
The frequency distribution of chain length for polymer
populations with n long-chain branches per chain is
given by (Soares and Hamielec, 1996c):
where r represents chain length, n represents the
number of long-chain branches per polymer molecule,
and is given by
where R
is the rate of -hydride elimination, R

p
is the
rate of monomer propagation, R
CTA
is the rate of
transfer to chain-transfer agent, and R
LCB
is the rate
of macromonomer propagation or long-chain branch
formation.
The chain-length averages of the polymer populations
with different numbers of long-chain branches per chain
are related by the simple relationships:
where i indicates the number of long-chain branches per
chain, and rj
n,i
, rj
w,i
, rj
z,i
, and pdi
i
are the number, weight,
and z-average chain lengths and polydispersity, respec-
tively.
Parts a and b of Figure 14 show the predicted weight
chain-length distributions for a polyolefin produced in
a CSTR for a given value of . Figure 15 shows the
effect of varying the rate of long-chain branch incorpo-
ration in the chain-length distribution. The chain-
length distribution becomes broader as the long-chain
branching level increases, but the distribution is still
very narrow as compared with the ones for polyolefins
made with heterogeneous Ziegler-Natta catalysts.
The analytical solution for the chain-length distribu-
tion of homopolymer with long-chain branches (eq 218)
is also valid for copolymerization when appropriate
pseudo-kinetic rate constants are used to calculate .
Additionally, for the case of binary copolymerization,
Stockmayers distribution can be used to obtain the
chemical composition distribution of the copolymer. This
is possible because the branched chains are formed by
linear copolymer chains which follow Stockmayers
bivariate distribution (Soares and Hamielec, 1996c).
4. Determination of Binary Reactivity Ratios
The determination of reactivity ratios (terminal model)
with small confidence intervals requires sensitive ana-
lytical techniques, carefully planned experiments, and
the use of statistically valid methods of estimation.
Unfortunately, most of the binary reactivity ratio data
published to date were not found using statistically valid
P
r,i
+ M98
k
p
P
r+1,i
(214)
P
r,i
+ D
q,j
d
98
k
pLCB
P
r+q,i+j
(215)
P
r,i
+ CTA 98
k
CTA
D
r,i
+ P
0,0
(216)
P
r,i
98
k
D
r,i
d
+ P
0,0
(217)
f(r,n) )
1
(2n)!
r
2n
2n+1
exp(-r) (218)
)
R
R
p
+
R
CTA
R
p
+
R
LCB
R
p
(219)
rj
n,i
) (1 + 2i)rj
n,0
(220)
rj
w,i
) (1 + i)rj
w,0
(221)
rj
z,i
) (1 + 2i/3)rj
z,0
(222)
pdi
i
)
(
1 + i
1 + 2i
)
pdi
0
(223)
methods and confidence intervals were usually not
given. The reactivity ratios are highly correlated with
major disagreement in values measured in different
laboratories (ODriscoll and Reilly, 1987; Dube et al.,
1991a; Burke et al., 1993; Rossignoli and Duever, 1995).
4.1. Statistically Valid Methods for Estimation
of Reactivity Ratios. Traditional methods for esti-
mating reactivity ratios (Mayo and Lewis, 1944; Fine-
man and Ross, 1950; Braun et al., 1973; Kelen and
Tu dos, 1975) are based on first transforming the in-
stantaneous copolymer composition equation into a
linear form in the parameters r
1
and r
2
, for example
and then estimating the reactivity ratios by graphical
plotting or by linear least squares. However, these
approaches, aside fromrequiring that the instantaneous
copolymer composition equation be valid, are statisti-
cally unsound because the independent variable
a
b
Figure 14. Weight chain-length distribution for polymer populations containing different numbers of long-chain branches per polymer
chain: (a) weight chain-length distribution normalized with respect to the weight of individual populations; (b) weight chain-length
distribution normalized with respect to the total weight of the whole polymer. The global distribution (overall polymer populations) is
indicated by the bold line. The table in the top right corner indicates number and weight fractions of each population.
(f
1
/f
2
)(F
2
/F
1
- 1) ) -r
2
+ r
1
(f
1
/f
2
)
2
(F
2
/F
1
) (224)
(f
1
/f
2
)
2
(F
2
/F
1
) has error, and the dependent variable
(f
1
/f
2
)(F
2
/F
1
- 1) does not have constant variance. Both
of the latter assumptions are necessary for linear least
squares to be a statistically valid estimation method.
As a result, they have been shown often to lead to very
poor estimates with misleading confidence intervals
(Tidwell and Mortimer, 1965, 1970). The common use
of these statistically invalid estimation procedures in
the past is one of the reasons for the wide variation in
reactivity ratios reported by different researchers.
It should be mentioned here that the Kelen and Tu dos
(1975) method, although statistically invalid, can be
used to at least obtain good initial r
1
and r
2
estimates,
provided the experiments have been suitably designed.
More details are given in McFarlane et al. (1980) and
Laurier et al. (1985).
Reactivity ratios are nowadays most usually esti-
mated using procedures based on the statistically valid
error-in-variables model (EVM) or on its modifications
(Box, 1970; Britt and Luecke, 1973; Sutton and MacGre-
gor, 1977; Garcia-Rubio et al., 1985; Yamada et al., 1978;
Van der Meer et al., 1978; Patino-Leal et al., 1980;
Patino-Leal and Reilly, 1981; Dube et al., 1991a; Burke
et al., 1993; Rossignoli and Duever, 1995). Extension
of these EVM methods to the estimation of reactivity
ratios in terpolymerizations has been discussed in
Duever et al. (1983). These methods allow one to take
properly into account all the sources of experimental
error. No groups of variables are considered to be
independent and free of error or dependent with
constant error. All measured variables (e.g., [M
j
]
m
, j
) 1,2 comonomers) are considered on an equal basis and
represented as coming from some true (but unknown)
value [M
j
]
t
which is contaminated with measurement
error, that is
The estimates obtained by these EVM approaches are
superior to those obtained by arbitrary graphical or
arbitrary least-squares procedures.
Although EVM procedures require more information
than arbitrary least-squares procedures, namely, the
measurement error variances and covariances, the point
estimates of the reactivity ratios obtained by these
procedures have been shown to be very insensitive to
changes in these covariance values. The great improve-
ment provided by the EVM estimation methods comes
from simply accounting correctly for the major sources
of error.
4.2. Design of Experiments. For any experimental
investigation, an optimal experimental design is of great
importance since it enables one to performthe minimum
number of experiments and obtain the most precise
parameter estimates. In copolymerizations, such a
design is that using the Tidwell-Mortimer (1965)
criterion. The criterion employs the Mayo-Lewis model
(e.g., see ODriscoll and Reilly (1987) or Hamielec et al.
(1989)) and is based on the sensitivity of the reactivity
ratio estimates to the errors encountered in the deter-
mination of copolymer composition. Tidwell and Mor-
timer (1965) recommended running several replicates
at two different monomer feed compositions, f !
1o
and f !!
1o
,
defined by the following equations:
It is evident from eqs 226 and 227 that preliminary
estimates of the two reactivity ratios, r
1
and r
2
, are
needed. These estimates can be obtained from the
literature (e.g., Polymer Handbook, 1989), a set of
Figure 15. Effect of varying macromonomer addition rate on weight chain-length distribution.
[M
j
]
i
m
) [M
j
]
i
t
+
i
(225)
f !
1o
)
2
2 + r
1
(226)
f !!
1o
)
r
2
2 + r
2
(227)
preliminary experiments, a calculated guess using the
Q-E scheme, etc. (ODriscoll and Reilly, 1987). In
addition, the copolymerizations should be carried out
to a conversion low enough that composition drift (i.e.,
a change in the monomer feed composition, f
10
) is
negligible (e.g., conversion <5-8%).
5. Alternative Copolymerization Kinetic Models
Deviations from the terminal model have been noted
for various comonomer pairs and for various polymer-
ization systems including free-radical, anionic, and
heterogeneous Ziegler-Natta. In order to explain some
deviations from the terminal model in free-radical
polymerization, several alternative models have been
proposed to describe copolymerization kinetics (Har-
wood, 1987). A model first formulated by Merz et al.
(1946), the penultimate unit effect model has received
much attention over the last decade. This model
describes how the reactivity of a radical center may
depend on the type of monomer unit bound in the chain
end adjacent to the radical center. Much of the recent
interest in the penultimate model is due to the work of
Fukuda et al. (1985, 1987, 1989, 1991). Using the
pseudo-kinetic rate constant modeling approach de-
scribed earlier, extension of these alternative models to
multicomponent systems is straightforward.
With the existence of several alternatives to describe
the polymerization mechanism, it is then left to distin-
guish between the models to find which gives the best
description of experimental data. Early model discrimi-
nation attempts were geared toward fitting models to
measurements of copolymer composition and diad and
triad fractions (Hill et al., 1982, 1984, 1989; Brown et
al., 1993). Some researchers have proposed that co-
polymer composition data can usually be adequately
represented by terminal model kinetics since differences
between model predictions are typically small (Fukuda
et al., 1987). On the other hand, results by Burke et al.
(1994a) have indicated that, with the use of statistical
experimental design techniques, these data may be
more useful in discriminating between copolymer mod-
els than previously thought. However, sequence dis-
tribution and copolymer composition data do not provide
enough information to estimate all of the parameters
contained in some models (e.g., the penultimate model).
Thus, in recent attempts to discriminate between com-
peting copolymerization models, polymerization rate
data were used to gain additional information on model
adequacy (Fukuda et al., 1985; Davis et al., 1989).
Typical attempts at identifying the best model have
involved spreading experiments over the entire range
of feed compositions. This may not be optimal for either
model discrimination or parameter estimation (Burke
et al., 1994a). Rather, the use of statistical model
discrimination methods which include the design of
experiments and the measurement of copolymer com-
position, triad fractions, and copolymerization rate is
preferred (Burke et al., 1994a,b, 1995, 1996). The
results of Burke et al., which were verified experimen-
tally, showed that the use of model discrimination
techniques should improve our ability to discriminate
between proposed copolymerization kinetic models.
6. Semibatch Monomer Feed Policies
In the absence of an azeotrope and when one mono-
mer is more reactive than the other in a binary, batch
copolymerization (say r
1
> 1 and r
2
< 1), the instanta-
neous copolymer composition will decrease in monomer
1 with an increase in monomer conversion. The extent
of compositional drift which leads to a copolymer
heterogeneous in composition depends on the ratio of
reactivity ratios r
1
/r
2
(increase with an increase in
r
1
/r
2
), the initial monomer composition (f
10
), and the
monomer conversion (x). A copolymer which is hetero-
geneous in composition usually has inferior properties,
and therefore industrial semibatch processes have been
developed to reduce composition hetereogeneity. There
are, however, certain semibatch emulsion polymeriza-
tion processes where heterogeneous copolymers are
produced in the latex particles to achieve certain
property improvements (Bassett and Hamielec, 1981).
There are two basic monomer feed policies, originally
shown in Hamielec et al. (1987), which may be used in
semibatch copolymerization to minimize compositional
drift. Effective commercial processes are usually based
on one or a combination of these feed policies. Some
additional promising derivations of these policies have
been presented (Arzamendi and Asua, 1989, 1990, 1991;
Arzamendi et al., 1991, 1992; van Doremaele et al., 1992;
Leiza et al., 1993; Schoonbrood et al., 1993, 1996;
Canegallo et al., 1994; Canu et al., 1994; Urretabizkaia
et al., 1994a; de la Cal et al., 1995; Echevarria et al.,
1995). These feed policies (Policy I and Policy II) are
described below using binary copolymerization as an
example.
Policy I. All of the slower monomer and sufficient
enough of the faster monomer (to give the desired
composition F
1
) are added to the reactor at time zero.
Thereafter, the faster monomer is fed to the reactor with
a time-varying feed rate to maintain N
1
/N
2
(the ratio of
the number of moles of monomer 1 to that of monomer
2 in the reactor) and F
1
constant with time or grams of
copolymer produced.
Policy II. A heel of monomers 1 and 2 at the desired
concentration levels (to give the desired F
1
) is added to
the reactor at time zero. Thereafter, monomers 1 and
2 are fed to the reactor with time-varying feed rates to
maintain [M
1
], [M
2
] and F
1
constant with time or grams
of copolymer produced.
The equations to be solved to determine the required
feed rates to produce a homogeneous binary copolymer
in a semibatch process are given by eqs 228-233.
dN
1
dt
) -N
1
(k
11
1
+ k
21
2
)[P
] + F
1,in
(228)
dN
2
dt
) -N
2
(k
12
1
+ k
22
2
)[P
] + F
2,in
(229)
dV
dt
)
F
1,in
MW
1
F
m1
+
F
2,in
MW
2
F
m2
-
[
R
p1
MW
1
(
1
F
m1
-
1
F
p
)
+
R
p2
MW
2
(
1
F
m2
-
1
F
p
)]
V (230)
Initial Conditions
t ) 0, N
1
) N
1o
, N
2
) N
2o
, V ) V
o
(231)
Conditions
Policy I:
F
2,in
) 0 and
d(N
1
/N
2
)
dt
) 0 (232)
Policy II:
d[M
1
]
dt
)
d[M
2
]
dt
) 0 (233)
Since f
1
and F
1
are constant,
1
is also constant.
Given the time variation of the total polymer radical
concentration, [P
], one can readily solve for F

1,in
and
F
2,in
, the time-varying monomer feed rates, using the
above equations.
We will now investigate Policies I and II with respect
to cross-linking using the criterion of onset of gelation
already discussed. Monomer 1 is the cross-linker (di-
vinyl monomer) and a chain-transfer agent (CTA) is
used to delay the onset of gelation.
6.1. Policy I. For constant [P
] and F
2,in
) 0, eq 229
may be solved analytically for N
2
to give
where
For constant N
2
/N
1
, N
1
is given by
One may now solve eq 228 for F
1,in
to get
Assuming that the densities of monomers and copolymer
are the same (F
m1
) F
m2
) F
p
), one can integrate eq 230
analytically to get
The total monomer concentration in the reactor is
therefore given by
where
We will now investigate gelation for a binary copo-
lymerization of vinyl and divinyl monomers. The divin-
yl monomer is considered the more reactive monomer,
and therefore, with Policy I, it is fed into the reactor
over time. Low levels of the cross-linking monomer are
to be used and therefore to simplify the analysis, one
can assume that the volume of the reacting mixture, V,
is constant and equal to the initial volume, V
0
. We now
apply eq 161 for constant V, ) C
p1
) C
p2
) 0 and )
k
fCTA
[CTA]/(k
p
[M]) with Policy I to give
with Qh
2
at t ) 0 where
and
Q
2
goes to infinity at the gelation point t ) t
c
and t
c
is
given approximately by
We employ the following set of kinetic parameters: k
fCTA
) 10
2
L mol
-1
s
-1
, [CTA] ) 0.1 mol L
-1
, a constant k*
p
*
) 10
2
L mol
-1
s
-1
, F
1
) 0.01, k
p
) 10
3
L mol
-1
s
-1
, Y
0
)
10
-7
mol L
-1
, [M]
0
) 10 mol L
-1
, and t
c
) 5000 s (1.4
h).
Employing eqs 159, 160, and 176 for this example of
Policy I, it can readily be shown that, at the gelation
point (t ) t
c
), Bh
N4
=
1
/
3
. In other words, at the gelation
point one polymer molecule in three on the average has
a tetrafunctional long-chain branch point.
6.2. Policy II. To simplify the analysis, we assume
that the densities of monomers and copolymer are the
same and that the molecular weight of the monomers
are the same, in addition to constant [P
]. Equation 229
may be solved analytically to give the following:
where
Since the ratio F
1,in
/F
2,in
is independent of time, the two
monomers may be premixed and fed to the reactor in
the same stream.
We will now investigate gelation for a binary copo-
lymerization of a vinyl and divinyl monomer. To
simplify the analysis, it is assumed that the concentra-
tion of chain-transfer agent, [CTA], is maintained
constant. We now apply eq 161 under the following
conditions: ) C
p1
) C
p2
) 0 and ) k
fCTA
[CTA]/
(k
p
[M]) constant with time in the context of Policy II.
with Qh
2
) 0 and t ) 0. The definitions of Qh
2
and are
the same as those used with eq 241. Equation 251 can
be solved numerically (setting ) 4.54 10
-4
s
-1
and
R ) 1.515 10
-4
s
-1
) to give
N
2
) N
2o
e
-
2
t
(234)
2
) (k
12
1
+ k
22
2
)[P
] (235)
N
1
) N
1o
e
-
2
t
(236)
F
1,in
) N
1o
(
1
-
2
)e
-
2
t
(237)
V ) V
o
+
(
N
1o
MW
1
F
m1
(
1
-
2
2
))
(1 - e
-
2
t
) (238)
[M] )
N
1
+ N
2
V
)
(N
1o
+ N
2o
)e
-
2
t
V
o
+ R(1 - e
-
2
t
)
(239)
R ) N
1o
MW
1
1
-
2
2
/F
m1
(240)
dQh
2
/dt ) (1 + Qh
2
)
2
e
-
2
t
(241)
Qh
2
)
k*
p
*Q
2
k
p
[M]
(242)
)
2F
1
k*
p
*k
p
[M]
0
Y
o
k
fCTA
[CTA]
(243)
t
c
) 1/ )
k
fCTA
[CTA]
2F
1
k*
p
*k
p
[M]
0
Y
o
(244)
N
1
) N
1o
e
Rt
(245)
N
2
) N
2o
e
Rt
(246)
F
1,in
) (R +
1
)N
1o
e
Rt
(247)
F
2,in
) (R +
2
)N
2o
e
Rt
(248)
R )
f
1o
1
+ f
2o
2
V
o
F
m
(MW(N
1o
+ N
2o
) - 1) (249)
V ) V
o
e
Rt
(250)
dQ
2
/dt ) (1 + Qh
2
)
2
- RQh
2
(251)
t (s) 0 100 200 300 400 500 700 900
Qh 2 0 0.0472 0.0983 0.154 0.215 0.282 0.438 0.636
t (s) 1100 1300 1500 1700 1900 2100 2150 2200
Qh
2 0.894 1.249 1.769 2.61 4.22 8.57 11.13 15.60
t (s) 2250 2300 2310 2320 2330
Qh
2 25.4 64.0 91.1 157.0 556.0
Neglecting RQh
2
in eq 251, one gets an analytical solution
for Qh
2
and
Using eq 253, one finds t
c
) 2203 s. RQh
2
in eq 251
accounts for the volume increase due to monomer fed
and has the effect of delaying the onset of gelation. The
following set of kinetic parameters has been used to
calculate and R and will be used to calculate the
number- and weight-average molecular weights and
branching frequency (Bh
N4
) with Policy II.
In the context of Policy II, one can solve eqs 159, 160,
and 176 analytically to give
Employing the above kinetic parameters in eqs 254, 255,
and 256 and eqs 155 and 156, one can calculate rj
N
, and
rj
W
, and Bh
N4
versus time of polymerization to give
At this point of gelation, t ) t
c
) 2350 s, rj
N
) 1513, rj
W
) #, and Bh
N4
) 0.333.
6.3. Beyond the Point of GelationsGel Growth
and Structure. Beyond this critical point, the calcula-
tion of Q
2
and rj
W
is no longer possible as they are both
infinite; however, one can continue to calculate rj
N
and
Bh
N4
beyond the point of gelation. Experimental data
clearly show that once gel is formed, it grows very
rapidly at the expense of the sol. The gel acts like a
great sponge, sucking in the polymer from the sol.
Radical centers located on polymer chains in the gel are
longer lived because of their greatly reduced mobility.
These radical centers are terminated by reaction diffu-
sion (these radical centers move in the gel by the act of
monomer addition or propagation). The greatly reduced
termination rates of radical centers located on chains
in the gel result in a very high concentration of these
radical centers, and this in part is the cause of the rapid
growth of the gel at the expense of the sol. One can
identify the following reactions as responsible for the
growth of the gel.
1. k*
p
*Y
1,b
[R
s
] consumption rate of polymer radicals

in the sol by addition to double bonds bound in polymer
chains in the gel (Y
1,b
equals the concentration of
monomer bound in the gel and [R
s
] is the concentration
at radical centers on the gel).
2. k
p
[M][R
b
] consumption rate of monomer by radical

centers located on polymer chains in the gel.
3. k*
p
*Q
1,s
[R
b
] addition rate of polymer chains from

the sol to radical centers located on the chains in the
gel (Q
1,s
is the concentration of monomer bound in the
polymer chains in the sol).
4. k
tsb
[R
s
][R
b
] termination rate of polymer radicals

in the sol with those on the gel.
Termination of radical centers on the gel may result
from the following reactions in addition to number 4
above:
k
trd
[R
b
]
2
termination rate of radical centers on chains
in the gel by reaction diffusion (this reaction type
produces intramolecular cross-links and leads to a
denser gel with lower absorbency and higher gel
strength).
As soon as gel is formed, it grows rapidly at the
expense of the sol with the above reactions playing a
major role in its rapid growth.
7. Some Recent Case Studies
7.1. Introduction. In the previous review by
Hamielec et al. (1987), an evaluation of the free-volume
theory for the modeling of diffusion-controlled termina-
tion and propagation in binary copolymerization as well
as the pseudo-kinetic rate constant method was pre-
sented. Several case studies involving the implementa-
tion of these ideas are summarized in Table 1. Early
application of the pseudo-kinetic rate constant method
was made for the batch, semibatch, and continuous
emulsion polymerization of styrene/butadiene rubber by
Broadhead et al. (1985). Four other comonomer systems
(styrene/acrylonitrile, styrene/p-methylstyrene, p-me-
thylstyrene/acrylonitrile, and p-methylstyrene/methyl
methacrylate), modeled using the free-volume theory to
account for diffusion-controlled termination and propa-
gation in batch reactors (Garcia-Rubio et al., 1985;
Bhattacharya and Hamielec, 1986; Jones et al., 1986;
Yaraskavitch et al., 1987), were discussed in detail in
Hamielec et al. (1987). Since then, Storti et al. (1988,
1989) employed the pseudo-kinetic rate constant method
to model the emulsion copolymerization of styrene/
acrylonitrile and acrylonitrile/methyl methacrylate as
well as the emulsion terpolymerization of styrene/
acrylonitrile/methyl methacrylate. Xie and Hamielec
(1993c) modeled solution polymerizations with added
Qh
2
)
t
1 - t
(252)
t
c
) 1/ (253)
r
1
) 2, r
2
) 0.5
(monomer 1 is the divinyl monomer), F
1
) 0.2
k
11
) k
22
) 2 10
3
L mol
-1
s
-1
) 0.333, f
1
) 0.1111,
1
) 3.33 10
-4
,
2
) 1.667 10
-4
s
-1
F
m
) F
m1
) F
m2
) F
p
) 1000 g L
-1
MW) MW
1
) MW
2
) 100
V
o
) 1 L, N
1o
) 0.5 mol, N
2o
) 4 mol
[M
1
] ) 0.5 mol L
-1
, [M
2
] ) 4 mol L
-1
k
p
) 2.52 10
3
L mol
-1
s
-1
, k*
p
* ) 10 L mol
-1
s
-1
k
fCTA
) 10
2
L mol
-1
s
-1
, [CTA] ) 0.1 mol L
-1
,
Y
o
) 10
-7
mol L
-1
R ) 1.515 10
-4
s
-1
, ) 4.54 10
-4
s
-1
VQ
0
) (F
1
k*
p
*[M]Y
o
2
V
o
/R)[t - (1/R)(e
Rt
- 1)] +
(1/R)(k
fCTA
[CTA]Y
o
V
o
)(e
Rt
- 1) (254)
VQ
1
) (k
p
[M]Y
o
V
o
/R)(e
Rt
- 1) (255)
Bh
N4
)
(F
1
k*
p
*[M]Y
o
2
V
o
/R)[(1/R)(e
Rt
- 1) - t]
VQ
0
(256)
t (s) 0 100 500 1000 2000 2500
rjN 1134 1147 1201 1274 1445 1544
rjW 2270 2380 2930 4070 16 650 #
Bh N4 0 0.0113 0.0592 0.1242 0.274 0.362
cross-linker (styrene/ethylene dimethacrylate, styrene/
divinylbenzene) using similar techniques.
Further applications of the free-volume theory were
demonstrated by Xie et al. (1991) for the suspension
polymerization of vinyl chloride and by Penlidis et al.
(1992) for the solution polymerization of MMA. The
latter showed howto simplify the general model (similar
to the one described herein) for a particular case. Of
most significant note, however, is the work by Gao and
Penlidis (1996) which demonstrated the general ap-
plicability of the modeling techniques presented herein.
They modeled bulk and solution polymerizations of
several monomers as well as some suspension polym-
erization cases (see Table 1). The most convincing
aspects of that work were the good model predictions
of data from a large number of research groups and
widely varying reaction conditions.
7.2. Styrene/Ethyl Acrylate Model Prediction
Case Study. An experimental study of the bulk free-
radical copolymerization of styrene (Sty)/ethyl acrylate
(EA) was carried out by McManus and Penlidis (1996).
This thorough kinetic study included conversion, com-
position, and molecular weight data for reactions at a
variety of feed compositions, initiator concentrations,
and temperatures, with and without added chain-
transfer agent. The model described herein was applied
to these data, and some representative results are
shown below.
In Figures 16 and 17 are shown model predictions
which correctly predict the conversion vs time data for
three different monomer feed compositions at 50 and
60 C, respectively, for a given initiator concentration.
The cumulative copolymer composition is plotted against
conversion in Figure 18 for three different monomer feed
compositions at 60 C. These results are representative
of all of the composition plots. The good agreement
between the composition data and the model predictions
Table 1. Some Examples of Practical Applications of Copolymerization Models
Broadhead et al., 1985 batch, semibatch, and continuous emulsion styrene (Sty)/butadiene
Garcia-Rubio et al., 1985 bulk Sty/acrylonitrile (AN)
Bhattacharya and Hamielec, 1986 bulk Sty/p-methylstyrene
Jones et al., 1986 bulk p-methylstyrene/MMA
Yaraskavitch et al., 1987 bulk p-methylstyrene/AN
Storti et al., 1988 emulsion Sty/AN, AN/MMA, Sty/AN/MMA
Penlidis et al., 1989 solution MMA
Storti et al., 1989 emulsion AN/Sty/MMA
Xie et al., 1991 suspension VC
Xie and Hamielec, 1993c solution Sty/ethylene dimethacrylate, Sty/divinylbenzene
Gao and Penlidis, 1996 bulk and solution MMA, Sty, AN, BA, ethyl acrylate, methyl acrylate,
VAc, p-methylstyrene, carboxylic acid
Figure 16. Bulk Sty/EA: model predictions of conversion vs time
data from McManus and Penlidis (1996) for [AIBN] 0.05 M at 50
C.
Figure 17. Bulk Sty/EA: model predictions of conversion vs time
data from McManus and Penlidis (1996) for [AIBN] 0.05 M at 60
C.
Figure 18. Bulk Sty/EA: model predictions of copolymer com-
position vs conversion data from McManus and Penlidis (1996)
for [AIBN] 0.05 M at 60 C.
is not surprising since the reactivity ratios used in this
study were estimated using the statistically valid
methods outlined earlier.
Finally, representative plots of number- and weight-
average molecular weight vs conversion are shown in
Figures 19 and 20 for two different initiator concentra-
tions at 60 C. The model correctly predicts the trend
of increased molecular weight as a result of an increase
in the initiator concentration. The important point to
consider in this case study is that only one set of
database parameters was used to predict the data over
a wide variety of reaction conditions.
7.3. BA/MMA/VAc Model Prediction Case Study.
A comprehensive study of the butyl acrylate (BA)/methyl
methacrylate (MMA)/vinyl acetate (VAc) terpolymer
system was recently reported in Dube (1994) and Dube
and Penlidis (1995a-c, 1997). While the eventual
objective of the work was to develop an understanding
of the emulsion terpolymerization system, bulk, solu-
tion, and emulsion homo- and copolymerization data
were also collected. The model described herein was
applied to these systems, and some representative
results are discussed below. The parameter values used
in the model are found in Dube, 1994.
As an example of a bulk homopolymerization, the
prediction of bulk BA data from Dube et al. (1991b), is
shown in Figure 21. From these data, values for the
propagation and termination rate constants (k
p
and k
t
,
respectively) were estimated using only one set of data,
hence, more accurate values of these rate constants are
required (see Dube, 1994). Updated values of these rate
constants are now available from pulsed-laser polym-
erization studies (Buback et al., 1989, 1994; Buback and
Degener, 1993; Lyons et al., 1996). Values for the free-
volume parameters A and V
Fpcrit
were fit to the data at
one set of reaction conditions. For the BA system, rate
constants for transfer to polymer and terminal double-
bond reactions are unknown, thus necessitating the
acquisition of molecular weight data. This is particu-
larly difficult due to the presence of significant amounts
of gel in the samples (Dube et al., 1991b). Although no
molecular weight plots are shown for these data, it was
noted that Mh
n
and Mh
w
are extremely sensitive to the
value of k
fm
. As mentioned earlier, a thorough inves-
tigation of bulk and solution modeling showing a large
set of examples (including BA, MMA, and VAc bulk
homopolymerization) is found in Gao and Penlidis
(1996).
Bulk copolymerization data reported in Dube and
Penlidis (1995a) (the reaction conditions can be found
therein) are plotted along with model predictions in
Figures 22-25. Conversion vs time data for bulk BA/
MMA runs are plotted in Figure 22. The free-volume
parameters A, K
3
, and V
Fpcrit
were fit to data at one set
of reaction conditions. The reader is referred to Dube
and Penlidis, 1995a, for the model prediction of copoly-
mer composition. Molecular weight data are shown in
Figure 23. No parameter fitting to the molecular weight
data was attempted. As was the case for the bulk
homopolymerization modeling of BA, the molecular
weight predictions were quite sensitive to the value for
the transfer to monomer constant, k
fm
, for BA. Results
from a bulk BA/VAc and a bulk MMA/VAc run are
Figure 19. Bulk Sty/EA: model predictions of number- and
weight-average molecular weight vs conversion data from Mc-
Manus and Penlidis (1996) for [AIBN] 0.05 M at 60 C.
Figure 20. Bulk Sty/EA: model predictions of number- and
weight-average molecular weight vs conversion data from Mc-
Manus and Penlidis (1996) for [AIBN] 0.10 M at 60 C.
Figure 21. Bulk BA: model predictions of conversion vs time data
from Dube et al. (1991b) at 60 C.
shown with model predictions in Figures 24 and 25,
respectively. As was the case for the BA/MMA runs,
the free-volume parameters A, K
3
, and V
Fpcrit
were fit
to the data. The prediction of the composition data for
both BA/VAc and MMA/VAc are reported in Dube and
Penlidis, 1995a.
Values for the free-volume parameters A, K
3
, and
V
Fpcrit
were fit to the BA/MMA/VAc conversion data from
Dube and Penlidis, 1995b, for one set of reaction
conditions. Conversion vs time data and model predic-
tions for the bulk terpolymerizations are plotted in
Figures 26 and 27. The prediction of the composition
data is plotted in Figure 28. The predictions of the
terpolymer composition data were achieved through the
use of copolymerization reactivity ratios estimated using
the optimal methods described earlier. Molecular weight
predictions also followed similar trends (see Dube,
1994).
In the prediction of emulsion polymerizations, a larger
number of physical constants and rate parameters were
required. It was not possible to obtain all of the
constants from the open literature, nor was it possible
to obtain empirical estimates of the parameters. There-
fore, many of the parameters used in the prediction of
the emulsion polymerization data were arrived at by
way of calculated guesses. In several cases, unknown
parameters were given values previously reported for
other monomers (see Dube, 1994). Prediction of conver-
sion for the BA emulsion polymerization run described
in Dube and Penlidis (1995c) is plotted in Figure 29.
Despite the uncertainty in the various rate parameters
for BA, the model prediction was quite good. Emulsion
terpolymerization composition vs conversion data are
shown in Figures 30 and 31. This is yet another
confirmation of the accuracy of the reactivity ratios as
well as the partition coefficients used in the model
(Dube, 1994).
Figure 22. Bulk BA/MMA: model predictions of conversion vs
time data from Dube and Penlidis (1995a) for f10 ) 0.439 at 60
C.
Figure 23. Bulk BA/MMA: model predictions of molecular weight
vs conversion data from Dube and Penlidis (1995a) for f10 ) 0.439,
[AIBN] ) 0.005 mol/L at 60 C.
Figure 24. Bulk BA/VAc: model prediction of conversion vs time
data from Dube and Penlidis (1995a) for f10 ) 0.8, [AIBN] )
0.00054 mol/L at 60 C.
Figure 25. Bulk MMA/VAc: model prediction of conversion vs
time data from Dube and Penlidis (1995a) for f10 ) 0.3, [AIBN] )
0.01 mol/L at 60 C.
7.4. Semibatch Production of Multicomponent
Polymers. The practical implementation of monomer
feed policies requires the use of on-line (or possibly off-
line) measurements to permit one to adjust for uncon-
trolled variations in recipe impurities such as O
2
(which
is a radical scavenger at temperatures below about 100
C) and other impurities in the recipe components which
can affect radical concentration. An extensive review
of on-line sensors for polymerization reactors was
published by Chien and Penlidis (1990). Examples of
on-line calorimetry, gas chromatography, and densito-
metry are discussed below.
7.4.1. Calorimetric Control of Monomer Feed in
a Copolymerization. The instantaneous heat genera-
tion due to polymerization (VQ) is given by
where V is the volume of polymerizing mixture, Q is
the instantaneous heat generation rate due to polym-
erization in cal L
-1
s
-1
, -H
1
is the heat of polymeri-
zation when monomer 1 adds to either polymer radical
type and similarly for -H
2
.
The feed rate of M
1
, F
1,in
, is given by
for any monomer feed policy, where
Dividing eq 257 by eq 258 and thus eliminating the total
polymer radical concentration, one obtains
Figure 26. Bulk BA/MMA/VAc (30/30/40 wt %): model predic-
tions of conversion vs time data from Dube and Penlidis (1995b)
at 50 C.
tions of conversion vs time data from Dube and Penlidis (1995b)
at 70 C.
tions of terpolymer composition vs conversion data from Dube and
Penlidis (1995b).
Figure 29. Emulsion BA: model prediction of conversion vs time
data from Dube et al. (1995c).
VQ ) [(k
11
+ k
21
)N
1
(-H
1
) + (k
12
+
k
22
)N
2
(-H
2
)] (257)
F
1,in
)
[

1
-
2
1 - R(N
1
/N
2
)
]
N
1
(258)
R ) F
2,in
/F
1,in
(259)
If the two monomers are premixed and fed to the reactor
in one stream, R is a constant. It should be recalled
that
1
and
2
are both functions of N

1
/N
2
and polym-
erization temperature.
1
may be expressed as
The temperature dependence of
1
should be small
because the activation energies of the cross-propagation
constants are similar in magnitude. In fact, the right-
hand side of eq 260 should have a small temperature
dependence. In other words, to maintain constant F
1
for the copolymer being produced, one should control
the monomer feed rate (F
1,in
or (1 + R)F
1,in
) to maintain
VQ/F
1,in
constant with time. The on-line measurement
of VQ is obviously a convenient method for the control
of copolymer composition with any monomer feed policy
(N.B. when R ) 0, Policy I is being employed). On-line
measurement of VQ can also be used to achieve a
desired variation of N
1
/N
2
and spread in copolymer
composition.
To maintain the desired production level of copolymer,
one can increase polymerization rate by increasing the
total polymer radical concentration, [P
]. This can be
done by increasing the reaction temperature while
maintaining VQ/F
1,in
constant. Hendy (1975) used
calorimetric control to produce high AN copolymers of
styrene/acrylonitrile of uniform composition in emulsion
polymerization. Two monomer feeding methods were
employed, and both provided composition control. In
one, a monomer mixture with the same composition as
that desired for the copolymer was fed to the reactor
(Policy II with monomer-starved feeding), and with the
second feeding method, only the more reactive monomer
was fed to the reactor (Policy I). For the high AN
copolymers synthesized by Hendy, it was found that
Policy I (feeding in styrene alone) gave better copolymer
products than Policy II (with monomer-starved feeding).
The specific reasons for this were not given. In the
production of AN/S copolymers by feeding styrene, a
constant feed rate of styrene was employed and this
appeared to give uniformcomposition copolymer at least
up to 80% conversion. Samples were withdrawn during
the polymerization for analysis, and it was found that
at about 80% conversion of AN the copolymer was
slightly richer in styrene (2% higher in styrene) than
the copolymer produced up to 50% conversion. This was
attributed to the partitioning of ANinto the water phase
(10%soluble in water) and the effect on the AN/S ratio
in the polymer particles at higher conversions. Equa-
tion 260 should only apply to stage III in emulsion
polymerization when both monomers have very low
solubilities in the water phase. Hoffman (1984) found
similar results.
Moritz (1989) reviewed the state of the art of isother-
mal bench-scale calorimeters and their application to
polymerization reactions. He developed a microcom-
puter bench-scale polymerization calorimeter with on-
line determination of polymerization rate and monomer
conversion and studied the batch and semibatch emul-
sion polymerization of vinyl acetate. Lately, the use of
on-line reaction calorimeters in emulsion polymerization
has been gaining favor because on-line gas chromato-
graph setups allow only for discrete and delayed mea-
surements.
An automated reaction calorimeter was used to moni-
tor the rate of emulsion polymerization of styrene using
different emulsifier and initiator concentrations in
conjunction with off-line measurements of the evolution
of the particle-size distributions by de la Rosa et al.
(1996). Their experimental results suggested that the
end of nucleation and the disappearance of monomer
droplets take place at approximately the same conver-
sion (x = 36-42 wt %). A method to determine the
minimumtime monomer addition policy for composition
control in the semibatch unseeded emulsion copolym-
erization of BA/VAc using calorimetric measurements
was developed by Gugliotta et al. (1995b). An iterative
Figure 30. Emulsion BA/MMA/VAc (30/30/40 wt %): model
predictions of terpolymer composition vs conversion data from
Dube (1994).
Figure 31. Emulsion BA/MMA/VAc (35/15/50 wt %): model
predictions of terpolymer composition vs conversion data from
Dube (1994).
VQ
F
1,in
)
(k
11
+ k
21
)(-H
1
) + (k
12
+ k
22
)(-H
2
)(N
2
/N
1
)
(k
11
- k
12
)
1
+ (k
21
- k
22
)
2
1 - R(N
1
/N
2
)
(260)
)
1
1 + k
12
N
2
/k
21
N
1
(261)
empirical approach using semistarved conditions was
used. This was accomplished using pure and technical-
grade monomers. Saenz de Buruaga et al. (1996)
presented further results for the same system. Case
studies involving the emulsion copolymerizations of BA/
MMA, BA/VAc, and MMA/VAc were examined by Ur-
retabizkaia et al. (1993) using a similar setup.
7.4.2. On-Line Monomer Concentration Mea-
surements for Control of Monomer Feed. On-line
measurements of the monomer ratio N
1
/N
2
in the
polymerizing phase (polymer particles in emulsion
polymerization) with a feedback systemto adjust mono-
mer feed rates can be used to control copolymer com-
position. Guyot et al. (1981) used an on-line GC to
control copolymer composition in the emulsion copolym-
erization of styrene/acrylonitrile. They employed Policy
I but found in their subsequent analysis of the copoly-
mers that copolymer composition drifted toward higher
styrene levels. They showed that this was due to
significant partitioning of acrylonitrile into the water
phase. This was not corrected for in the monomer feed
rates employed to control copolymer composition at a
uniform level.
Askill and Gilding (1981) produced uniform composi-
tion copolymers of methyl methacrylate/acrylic acid
(r
MMA
2.3 and r
AA
0.31) using semibatch solution
polymerization and Policy II (with monomer-starved
feed). The solvent used was butanone. On-line GC
measurements were used to monitor the monomer ratio
(N
MMA
/N
AA
) in the reactor and adjust monomer feed
rates. For most of the semibatch runs under monomer-
starved conditions, there was no need to adjust feed
rates. Narrower molecular weight distributions were
found for the uniform composition copolymers produced
by use of Policy II (with monomer-starved feed). This
confirms that reactions which form long trifunctional
branches such as transfer to polymer and reaction with
terminal double bonds are insignificant for the MMA/
AA system.
Guyot et al. (1984) monitored monomer concentrations
by GC and used semibatch copolymerization of buta-
diene/acrylonitrile to obtain uniform composition poly-
mers (Policy I). Constant composition copolymers showed
a single glass transition temperature, and the produc-
tion of cross-linked gel was delayed and sometimes
avoided. The production of gel occurred due to polymer
radicals adding to internal double bonds in l,2-butadiene
units bound in the copolymer chains. Reactivity ratios
were estimated to be r
B
) 0.3 and r
A
) 0.04. Semibatch
copolymerization not only produced copolymers uniform
in composition but also polymer with lower levels of
tetrafunctional long-chain branching and cross-linked
gel. The reactive internal double bonds have the vinyl
1,2-structure, and these were responsible for the forma-
tion of cross-linked gel. In butadiene homopolymeriza-
tion about 20% of the internal double bonds have the
1,2-structure. Apparently, during semibatch synthesis
of uniform copolymer the incorporated acrylonitrile
orientated the added butadiene unit to the less reactive
1,4-structure because the sequence length of butadiene
was kept small. In batch copolymerization, acrylonitrile
was consumed preferentially, and at high conversions,
copolymer containing long butadiene sequences and
higher levels of vinyl 1,2-structure was formed. This,
of course, was responsible for the formation of the high
level of cross-linked gel.
Snuparek and Kaspar (1981) investigated the semi-
batch emulsion copolymerization (Policy II with mono-
mer-starved feed) of ethyl acrylate/butyl acrylate. The
copolymerization was followed by gas chromatography.
There is evidence that the copolymerization may be
controlled by monomer diffusion in the polymer par-
ticles, with both reactivity ratios approaching unity.
El-Aasser et al. (1983) investigated the batch and
semibatch emulsion copolymerization of vinyl acetate/
butyl acrylate. Policy II with monomer-starved feed was
employed. Chain transfer to vinyl acetate bound in the
copolymer chains produced long trifunctional branches
and led to broader molecular weight distributions which
were bimodal.
Leiza et al. (1993) used an on-line GC in their
development of a semiempirical approach to determine
minimum time optimal monomer addition policies to
produce homogeneous methyl methacrylate/ethyl acry-
late copolymers. The method involves a series of
semibatch emulsion copolymerizations carried out under
semistarved conditions.
The composition control of a semibatch BA/MMA/VAc
emulsion terpolymerization was achieved with an on-
line GC by Urretabizkaia et al. (1994b). Their strategy
is based on comparing on-line measurements to model
predictions and using the difference as input to a
nonlinear adaptive plus proportional-integral control-
ler. The controller calculates the feed rates of the more
reactive monomers that have to be fed into the reactor
to make sure that, after a sampling time interval, the
monomer ratios in the polymer particles lead to the
formation of a terpolymer of the desired composition.
Experimental verification was performed using a 55 wt
% solids content and a molar terpolymer composition
target of BA/MMA/VAc ) 50/35/15.
7.4.3. On-Line Density Measurements for Com-
position Control. The use of on-line density measure-
ments has gained increasing importance as attested by
some earlier references in Chien and Penlidis (1990).
More recently, Canegallo et al. (1993) used an on-line
densitometer coupled with a kinetic model to monitor
conversion and copolymer composition in batch emulsion
homopolymerizations (Sty and MMA) as well as copo-
lymerizations (Sty/MMA, AN/MMA, and MMA/VAc).
Canu et al. (1994) then developed an a priori monomer
feed policy which requires implementation in conjunc-
tion with the densitometer described above. Experi-
mental verifications with emulsion copolymerizations
(MMA/VAc, Sty/BA) and a terpolymerization (BA/MMA/
VAc) were reported.
7.4.4. Policies I and II in Semibatch Emulsion
Copolymerization. It should be mentioned that the
strict application of Policies I and II is not always
possible in emulsion copolymerization. In stages I and
II, monomer droplets are also feeding the polymer
particles (the major site for polymerization), and this
must be properly accounted for when calculating the
required feed rates of the monomers, F
1,in
and F
2,in
. In
stage III, however, if the solubilities of the monomers
in the water phase are negligible, Policies I and II can
be strictly applied.
8. Concluding Remarks
There is no doubt that the multidisciplinary polymer
reaction engineering horizons will be extended even
further in the future as more value-added specialty
polymers (especially those arising out of and applied to
biological systems) are developed, and the material
science field develops in this area. Certainly more effort
is required in relating the fundamental properties of
polymers, i.e., average molar mass and molar mass
distribution, monomer sequence distribution, branching,
etc., to particular requirements and attributes of specific
applications. Developing a polymerization model is not
an isolated effort; rather, it requires a commitment to
the long-term development in parallel of a comprehen-
sive polymerization database for characteristics of mono-
mers, initiators, solvents, emulsifiers, chain-transfer
agents, inhibitors, etc. Property databases, with the
potential to provide an effective computer-based bridge
between the simulation phase and detailed engineering,
may have a lot to offer to these future directions.
Acknowledgment
M.A.D., A.P., and J.B.P.S. thank Professor Hamielec
for being a great mentor. Financial support for this
research supplied by the Natural Sciences and Engi-
neering Research Council (NSERC) of Canada, the
Ontario Centre for Materials Research (OCMR), ICI
Worldwide, and Uniroyal Chemical Co. over the years
is gratefully acknowledged.
Nomenclature
a ) partition coefficient for monomer radicals between
water phase and particles
a ) root-mean-square end-to-end distance per square root
of the number of monomer units
A ) free-volume theory parameter
a
2
) adjustable parameter
A
d
) total surface area of monomer droplets (dm
2
)
A
j
) jacket heat-transfer area (m
2
)
A
m
) total free micellar area (dm
2
)
A
p
) total surface area of polymer particles (dm
2
)
B ) free-volume theory parameter
B
N3
) average number of trifunctional branch points (#)
B
N4
) average number of tetrafunctional branch points (#)
c ) mass concentration of accumulated polymer in reaction
mixture (g L
-1
)
C ) parameter modifying rate of change of initiator
efficiency
C
fcta
) transfer to chain-transfer agent constant
C
fm
) transfer to monomer constant
C
fmsi
) transfer to monomer-soluble impurities constant
C
fp
) transfer to polymer constant
C
k
) internal double-bond reaction constant
C
pi
) heat capacity of species i (cal g
-1
K
-1
)
[CTA]
p
) concentration of chain-transfer agent in the
particles (mol L
-1
)
D ) reaction diffusion coefficient
d
m
) density of monomer (kg L
-1
)
d
p
) particle diameter (dm)
D
p
) diffusivity of monomer radicals in the particles (cm
2
s
-1
)
[drops] ) concentration of monomer droplets (mol L
-1
)
D
w
) diffusivity of monomer radicals in the water phase
(cm
2
s
-1
)
f, f
o
) overall and initial initiator efficiency
F
i,in
) flow of species i into the reactor (mol min
-1
)
F
j
) instantaneous polymer composition (mole fraction
monomer j bound in polymer)
Fh
j
) cumulative polymer composition (mole fraction mono-
mer j bound in copolymer)
f
j
) mole fraction of monomer j in the particles
F
jw
) mole fraction of monomer j bound in the polymer
formed in the water phase
H
pi
) heat of polymerization of monomer i (cal g mol
-1
)
[I] ) concentration of initiator (mol L
w
-1
)
j
c
) entanglement spacing of pure polymer (# monomer
units)
jcr ) overall critical chain length of polymer radical formed
in the water phase (#)
jcr
j
) critical chain length of polymer radical formed in the
water phase ending in species j (#)
K ) terminal double-bond reaction constant
k
1
) iron oxidation rate constant (L mol
-1
min
-1
)
k
2
) iron reduction rate constant (L mol
-1
min
-1
)
K
3
) free-volume theory parameter
k
a
) radical absorption by particles rate coefficient (dm
min
-1
)
K
c
) controller gain
k
cm
) capture by micelles rate constant (dm min
-1
)
k
cmd
) capture by monomer droplets rate constant (dm
min
-1
)
k
cp
) capture by particles rate constant (dm min
-1
)
K
cta
)partition coefficient for chain-transfer agent between
the droplet and particle phases
k
d
) initiator decomposition rate constant (min
-1
)
k
des
) radical desorption rate constant (min
-1
)
k
des
! ) particle-size-independent radical desorption rate
constant (min
-1
)
k
F
) particle coagulation rate constant (L
w
min
-1
)
k
fcta
) overall rate constant for transfer to chain-transfer
agent (L mol
-1
min
-1
)
k
fctai
) rate constant for transfer to chain-transfer agent
from radical ending in monomer i (L mol
-1
min
-1
)
k
fidb
, k*
p
* ) rate constant for reaction with internal double
bonds (L mol
-1
min
-1
)
k
fm
) overall rate constant for transfer to monomer (L
mol
-1
min
-1
)
k
fmij
) rate constant for transfer to monomer j fromradical
ending in monomer i (L mol
-1
min
-1
)
k
fmsi
) rate constant for transfer to monomer-soluble
impurity (L mol
-1
min
-1
)
k
fp
) overall rate constant for transfer to polymer (L mol
-1
min
-1
)
k
fpij
) rate constant for transfer to monomer j on a dead
polymer from monomer i (L mol
-1
min
-1
)
k
ftdb
, k*
p
) rate constant for reaction with terminal double
bonds (L mol
-1
min
-1
)
k
h
, k
ho
) homogeneous nucleation rate constant (min
-1
)
K
jmw
) partition coefficient for species j between the
monomer droplet and water phases
K
jwp
) partition coefficient for species j between the water
and particle phases
K
msi
) partition coefficient for monomer-soluble impurity
between the droplet and particle phases
k
p
, k
po
) overall propagation rate constant (L mol
-1
min
-1
)
k
p
! )rate constant for reinitiation of oligomer radicals from
monomer radicals (L mol
-1
min
-1
)
k
pij
) propagation rate constant for radical ending in
species i adding monomer j (L mol
-1
min
-1
)
k
pIj
) propagation rate constant for addition of monomer j
to an initiator radical (L mol
-1
min
-1
)
k
t
) termination rate constant (L mol
-1
min
-1
)
k
T
) translational diffusion-controlled termination rate
constant (L mol
-1
min
-1
)
k
to
) termination rate constant at zero polymer concentra-
tion (L mol
-1
min
-1
)
k
tc
) termination by combination rate constant (L mol
-1
min
-1
)
k
td
) termination by disproportionation rate constant (L
mol
-1
min
-1
)
kh
tN
, kh
tW
, kh
tZ
)number-, weight-, and Z-average termination
constants (L mol
-1
min
-1
)
k
tr
) transfer rate constant (L mol
-1
min
-1
)
k
trd
) reaction diffusion-controlled termination rate con-
stant (L mol
-1
min
-1
)
k
tres
) residual termination rate constant (L mol
-1
min
-1
)
k
trm
) transfer to monomer rate constant (L mol
-1
min
-1
)
k
trt
) transfer to CTA rate constant (L mol
-1
min
-1
)
k
tsb
) termination rate constant of polymer radicals in the
sol with those on the gel (L mol
-1
min
-1
)
k
tseg
) segmental diffusion-controlled termination rate
constant (L mol
-1
min
-1
)
k
tw
) water phase termination rate constant (L mol
-1
min
-1
)
k
zj
)rate constant for reaction with water-soluble impurity
j (L mol
-1
min
-1
)
L ) critical chain length for water phase polymerization
l
o
) length of a monomer unit
m ) grouping of terms representing radical exit from the
polymer particles
m ) adjustable parameter for free-volume theory
m, m
i
) coefficient relating to volume characteristics in
partition coefficient equations
m
d
) partition coefficient for monomer radicals between
the water phase and the particles
M
j
) monomer of type j
[M
j
]
m
, [M
j
]
p
, [M
j
]
w
) concentration of monomer j in the
droplets, particles, and water phase, respectively (mol
L
-1
)
Mh
n
) accumulated number-average molecular weight
[M]
p
) total concentration of monomer in the particles (mol
L
p
-1
)
[M]
psat
) total (saturation) concentration of monomer in
the particles (mol L
p
-1
)
[MSI]
p
) concentration of monomer-soluble impurities in
the particles (mol L
p
-1
)
[M]
w
) concentration of monomer in the water phase (mol
L
w
-1
)
Mh
w
) accumulated weight-average molecular weight
M
wc
) saturation concentration of monomer in the water
phase (mol L
w
-1
)
Mh
wcrit
) critical accumulated weight-average molecular
weight
M
weff
) effective molecular weight of copolymer (g mol
-1
)
MW
i
) molecular weight of species i (g mol
-1
)
M
wsat
) saturation concentration of monomer in the water
phase (mol L
w
-1
)
M
wt
) molecular weight of monomer (g mol
-1
)
Mh
z
) accumulated z-average molecular weight
n ) adjustable parameter for free-volume theory
nj ) average number of radicals per particle
N
A
) Avogadros number (molecule mol
-1
)
N
hom
) number of particles formed by homogeneous
nucleation (# L
w
-1
)
N
j
) moles of species j (mol)
N
mj
) moles of monomer j (mol)
N
mic
) number of particles formed by micellar nucleation
(# L
w
-1
)
N
p
, N
T
) total number of particles in the reactor (# L
w
-1
)
N
polj
) moles of monomer j bound in the copolymer (mol)
n
s
) number of monomer units in one polymer chain
segment
P
m
, P
n
) dead polymer molecule of chain length m or n
Q
0
, Q
1
, Q
2
) zeroeth, first, and second moments of the
molecular weight distribution (mol)
Q
j
, Q
R
) heat losses in jacket and reactor, respectively (cal
min
-1
)
r ) particle radius (dm)
r ) radial position in monomer-swollen particle (cm)
R ) universal gas constant (cal mol
-1
K
-1
)
R ) radius of monomer-swollen particle (cm)
r
ij
) reactivity ratio
R
cm
) rate of capture of radicals by micelles (mol L
w
-1
min
-1
)
R
cmd
)rate of capture of radicals by monomer droplets (mol
L
w
-1
min
-1
)
R
cp
) rate of capture of radicals by particles (mol L
w
-1
min
-1
)
[R
I
] ) concentration of initiator radicals (mol L

w
-1
)
R
I
) rate of initiation (mol L
w
-1
min
-1
)
[R
j,i
]
w
) concentration of radicals of chain length j ending
in monomer i in the water phase (mol L
w
-1
)
r
mic
) radius of a micelle (dm)
r
n
, rj
n
) instantaneous and accumulated number-average
chain lengths, respectively
r
w
, rj
w
) instantaneous and accumulated weight-average
chain lengths, respectively
R
n,i
) radical of chain length n ending in monomer i

R
p
) overall rate of polymerization (mol L
p
-1
min
-1
)
R
pj
) rate of polymerization of monomer j (mol L
p
-1
min
-1
)
R
pjp
) rate of polymerization of monomer j in the particles
(mol L
p
-1
min
-1
)
R
pjw
) rate of polymerization of monomer j in the water
phase (mol L
w
-1
min
-1
)
R
tc
, R
td
) rate of termination by combination and dispro-
portionation, respectively (mol L
-1
min
-1
)
[R
TOT
]
des
) concentration of desorbed radicals in the water
phase (mol L
w
-1
)
[R
TOT
]
w
, [R
]
w
) total concentration of radicals in the
water phase (mol L
w
-1
)
[R
TOT
]
wdrop
, [R
TOT
]
wmic
, [R
TOT
]
wpar
) concentration of radi-
cals in the water phase able to be captured by droplets,
micelles, and particles, respectively (mol L
w
-1
)
[R
TOT
]
wdrop
) concentration of radicals in the water phase
that may undergo homogeneous nucleation (mol L
w
-1
)
S
a
) surface area covered by one molecule of emulsifier i
(dm
2
molecule
-1
)
[S]
CMC
) critical micelle concentration (mol L
w
-1
)
[S]
t
) total concentration of emulsifier (mol L
w
-1
)
t ) time (min)
T, T
j
, T
ref
, T
set
) reaction, jacket, reference, and setpoint
temperatures, respectively (K)
T
gi
) glass transition temperature of species i (K)
V
aq
) volume of the aqueous phase (L)
V
F
) free volume (L)
V
Fcrif
, V
Fcrit
, V
Fpcrit
) critical free volumes (L)
V
i
) volume of species i (L)
V
jmd
, V
jmp
, V
jmw
) volumes of monomer j in the droplets,
aqueous phase, and particles, respectively (L)
V
m
) volume of the monomer droplet phase (L)
V
m
) molar volume (L mol
-1
)
V
mj
) total volume of monomer j (L)
V
o
) total volume of the organic (monomer and polymer)
phase (L)
v
out
) total volumetric flow out of the reactor (L min
-1
)
v
p
) average volume of a polymer particle (L
p
)
V
p
, V, V
o
) total volume of polymer particles (L
p
)
V
T
) total volume of reaction mixture (L)
V
w
) volume of water (L)
W(r,y) ) weight fraction of polymer of chain length r and
composition deviation y
[WSI]
i
) concentration of water-soluble impurity i (mol
L
w
-1
)
x ) monomer conversion on a mass basis
x
c
) critical monomer conversion where droplets disappear
Y
o
) total concentration of radicals in the particles (mol
L
p
-1
)
Greek Letters
R ) grouping of terms representing radical entry into the
polymer particles
) molecular weight contribution due to termination by
combination
) reaction radius
) fraction of termination by disproportionation
) measurement error
i
) chemical potential of species i
F
des
) rate of radical desorption from the particles (mol
L
w
-1
min
-1
)
F
m
) density of monomer (kg L
-1
)
F
p
) density of polymer (kg L
-1
)
) Lennard-Jones diameter
) molecular weight contribution due to termination by
disproportionation and transfer to small molecules
) time (min)
i
) mole fraction of radicals ending in monomer i in the
particles
p
) volume fraction of polymer in the particles
i
,
ij
) Flory-Huggins interaction parameter
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Received for review August 1, 1996
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X
IE960481O
X
Abstract published in Advance ACS Abstracts, March 1,
1997.

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Mathematical Modeling of Multicomponent Chain-Growth

Polymerizations in Batch, Semibatch, and Continuous Reactors: A

, i.e., radicals of chain

represents a radical of chain length n ending in

] is the concentration of initiator radicals

, continues propagating with mono-

is the mole fraction of polymeric radicals of

is the rate of -hydride elimination, R

], one can readily solve for F

] consumption rate of polymer radicals

] consumption rate of monomer by radical

] addition rate of polymer chains from

] termination rate of polymer radicals

are both functions of N

] ) concentration of initiator radicals (mol L

) radical of chain length n ending in monomer i

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