c 2005 Wiley-VCH Verlag GmbH & Co.

KGaA, Weinheim
10.1002/14356007.a21 305
Polymerization Processes 1
Polymerization Processes
Archie E. Hamielec, Institute for Polymer Production Technology, Department of Chemical Engineering,
McMaster University, Hamilton, Ontario, L8S 4L7, Canada
Hidetaka Tobita, Department of Materials Science and Engineering, Fukui University, Fukui, 910, Japan
1. Introduction–Trends in Poly-
mer Reaction Engineering . . . 7
2. Polymerization Mechanisms
and Kinetics . . . . . . . . . . . . . 8
2.1. Step-Growth Polymerization . . 9
2.1.1. Linear Polymerization . . . . . . . 9
2.1.2. Interfacial Polymerization . . . . . 12
2.1.3. Nonlinear Polymerization . . . . . 12
2.2. Chain-Growth Polymerization . 14
2.2.1. Free-Radical Polymerization . . . 15 Initiation . . . . . . . . . . . . . . . 16 Propagation . . . . . . . . . . . . . . 18 Termination . . . . . . . . . . . . . 19 Chain Transfer to Small
Molecules . . . . . . . . . . . . . . . 21 Kinetics of Linear Polymerization 22 Effect of Temperature . . . . . . . 25 Branching Reactions . . . . . . . . 26
2.2.2. Ionic Polymerization . . . . . . . . 28 Cationic Polymerization . . . . . . 29 Anionic Polymerization . . . . . . 30 Ziegler – Natta Polymerization . . 32
2.3. Copolymerization . . . . . . . . . 34
2.3.1. Copolymer Composition . . . . . 35
2.3.2. Kinetics of Copolymerization . . 37
2.3.3. Copolymerization of Vinyl and
Divinyl Monomers . . . . . . . . . 38
3. Polymerization Processes and
Reactor Modeling . . . . . . . . . 40
3.1. Introduction . . . . . . . . . . . . . 40
3.2. Processes andReactor Modeling
for Step-Growth Polymerization 41
3.2.1. Types of Reactors and Reactor
Modeling . . . . . . . . . . . . . . . 41
3.2.2. Specific Processes . . . . . . . . . 44
3.3. Processes andReactor Modeling
for Chain-Growth Polymeriza-
tion . . . . . . . . . . . . . . . . . . . 47
3.3.1. Material Balance Equations for
Batch, Semi-Batch, and Continu-
ous Reactors . . . . . . . . . . . . . 47 Rates of Reaction and Copolymer
Composition . . . . . . . . . . . . . 48 Molecular Masses, Long-Chain
Branching, and Cross-Linking . . 50
3.3.2. Examples of Free-Radical Poly-
merization . . . . . . . . . . . . . . 50 Homopolymerization – Linear
Chains . . . . . . . . . . . . . . . . . 50 Copolymerization – Linear
Chains . . . . . . . . . . . . . . . . . 54 Copolymerization – Long-Chain
Branching . . . . . . . . . . . . . . . 55
3.3.3. Polymerization Processes . . . . . 55 Solution Polymerization . . . . . . 55 Polymer Soluble in Monomer . . 55 Addition of a Solvent in which
both Monomer and Polymer are
Miscible . . . . . . . . . . . . . . . . 55 Polymer – Polymer Demixingdur-
ing Polymerization . . . . . . . . . 56 Precipitation Polymerization . . . 57 Polymer Insoluble in its Monomer 57 Monomer Functioning as Solvent
for the Polymer . . . . . . . . . . . 60 Suspension Polymerization . . . . 63 Qualitative Description . . . . . . 64 Dispersants . . . . . . . . . . . . . . 66 Mechanism of Particle Formation 67 Industrial Applications . . . . . . . 70 Emulsion Polymerization . . . . . 73 Theories of Emulsion Polymeriza-
tion . . . . . . . . . . . . . . . . . . . 74 Physicochemical Parameters of
Dispersions . . . . . . . . . . . . . . 85 Inverse Emulsion Polymerization 88 Semi-Batch Emulsion Polymeri-
zation . . . . . . . . . . . . . . . . . 89 Continuous Emulsion Polymeri-
zation . . . . . . . . . . . . . . . . . 90
3.3.4. Miscellaneous Processes . . . . . 93
3.3.5. Ionic Polymerization Modeling . 96 Introduction . . . . . . . . . . . . . 96 Heterogeneous Coordination Po-
lymerization . . . . . . . . . . . . . 96
2 Polymerization Processes
3.3.6. Process Variables, Reactor Dy-
namics/ Stability, On-Line Moni-
toring and Control . . . . . . . . . 97 Influence of Reactor Type and
Configuration on Molecular Mass
and Copolymer Composition Dis-
tributions, and on Long-Chain
Branching and Cross-Linking . . 97 Monomer Coupling with Bimo-
lecular Termination Plug Flowand
Batch Reactors (CPFR/BR) . . . . 99 Monomer Coupling Without Ter-
mination Plug Flowand Batch Re-
actors (CPFR/BR) . . . . . . . . . 103 Polymer Coupling . . . . . . . . . 104 Copolymerization . . . . . . . . . . 107 Long-Chain Branching and Cross-
Linking . . . . . . . . . . . . . . . . 109 Reactor Dynamics and Stability . 111 On-Line Monitoring and Control 112
4. References . . . . . . . . . . . . . . 114
Sections – and were
based on the article Polymerisationstechnik in
Ullmann’s, 4th ed. written by Heinz Gerrens.
List of symbols
A chemical species; vacant adsorptionsite
[A] concentration of species A
initial concentration of species A
, A
, A
adjustable parameters
ABS acrylonitrile – butadiene – styrene
rubber-modified copolymer
ACA aminocaproic acid
A(h) energy required to separate to a distance
h=∞, two drops of diameter d=1 ini-
tially separated by a distance h
surface area of micelles
surface area of polymer particles
B chemical species
BHET bis-hydroxyethyl terephthalate
BR batch reactor
dimensionless moments of polymer dis-
tribution for chain transfer to polymer
surfactant concentration
CCD chemical composition distribution
CMC critical micelle concentration
CPFR continuous plug flow reactor
CSTR continuous stirred-tank reactor with an
ideal residence-time distribution
CTA chain-transfer agent
d particle diameter
d average particle diameter
Sauter mean diameter of a spherical-
particle suspension
diameter at which 50 wt % of particles
pass through a sieve
minimum particle diameter
maximum particle diameter
D stirrer diameter
mean diffusion coefficient for
oligomeric radicals and latex particles
DMT dimethyl terephthalate
activation energy for initiator decompo-
mass fraction of material passing out of
reactor with a residence time t to t +dt
activation energy for chain-transfer re-
activation energy for average chain
activation energy for polymer particle
activation energy for propagation
activation energy for polymerization
E(t) residence-time distribution for a flow
reactor at steady state
activationenergyfor bimolecular termi-
Eu modified power number
EG ethylene glycol
EGDMA ethylene glycol dimethacrylate
EPS expandable polystyrene
ESR electron spin resonance spectroscopy
f initiator efficiency; functionality of
mole fraction of monomer of type j
i, in
molar flow rate of monomer of type i
into the reactor
total molar flow rate (of all monomer
types) into the reactor
Ii, in
molar flowrate of initiator of type i into
the reactor
mole fraction of monomer of type j,
chemically bound in polymer produced
Polymerization Processes 3
mole fraction of monomer of type j
chemically bound in accumulated poly-
mole fractionof monomer 1(containing
an abstractable atom) in accumulated
mole fractionof monomer 2(containing
a reactive carbon – carbon bond
pi, in
molar flow rate of monomer of type i
chemically bound in polymer into the
Fr Froude number
T, in
molar flow rate of chain-transfer agent
T into the reactor
GPC gel permeation chromatography
HCSTR homogeneous CSTR
HDPE high-density polyethylene
H– H Hui – Hamielec styrene polymerization
HIPS high-impact polystyrene
I initiator or catalyst
[I] concentration of initiator or catalyst
K chemical rate constant; equilibrium
absorption constant for oligomeric rad-
icals entering polymer particles
adsorption rate constant
initiator decomposition constant
depropagation constant
desorption rate constant
rate constant for polymeric radical
of type i abstracting an atom from
monomer of type j chemically bound
in polymer
transfer to monomer rate constant
rate constant for chain transfer to poly-
rate constant for chain transfer to CTA
i rate constant for chain transfer from
polymeric radical of type i to CTA
transfer to small molecule X rate con-
rate constant for monomer adding to a
primary radical
propagation rate constant

propagation rate constant for transfer

propagation rate constant for free ion
propagation rate constant for ion pair
∗ rate constant for polymeric radicals
adding to pendant double bonds on
polymer chains
, K
propagation rate constant for
monomer of type j adding to polymeric
active center of type i
rate constant for polymeric radical of
type i adding to a double bond on
a monomer unit of type j chemically
bound in the polymer
propagation rate constant for monomer
of type k adding to a polymeric active
center of type ij
total bimolecular termination constant
total bimolecular termination constant
at zero conversion of monomer
rate constant for bimolecular termina-
tion by combination
termination by combination rate con-
stant for polymeric radicals of types i
and j (chemical control)
number-average bimolecular termina-
tion constant by combination
rate constant for bimolecular termina-
tion by disproportionation
termination by disproportionation rate
constant for polymeric radicals of types
i and j (chemical control)
number-average bimolecular termina-
tion constant by disproportionation
total number-average bimolecular ter-
mination constant
termination rate constant in polymer
(r, s) total bivariate distribution for
diffusion-controlled bimolecular ter-
mination of polymeric species of chain
lengths r and s
termination rate constant in aqueous
total weight- and z-average bimolec-
ular termination constants
L characteristic length of energy-con-
taining large eddies
L length of path traversed by a growing
radical from its point of origin to the
point where it precipitates
L reactor length
LALLS low-angle laser light scattering
LCB long-chain branching
4 Polymerization Processes
LDPE low-density polyethylene
LLDPE linear low-density polyethylene
number of moles of monomer i in ter-
polymer (Eq. 3.101)
average molecular mass between cross-
monomer of type i
aggregation number for emulsifier
molecules in micelles
molecular mass of monomer of type i
number-, weight-, Z and
Z +1-average molar mass (molecular
mass, respectively)
[M] total monomer concentration
initial monomer concentration;
monomer concentration in feed
equilibrium concentration of monomer
at the ceiling temperature
] concentration of monomer of type i
concentration of monomer in the poly-
mer particles
M– H Marten – Hamielec polymerization
MMA methyl methacrylate
MWD molecular mass distribution (molar
mass distribution)
n number of monomer types
n order of reaction
¯ n average number of radicals per particle
, N number of functional groups at time
zero and t
N total number of moles in the reactor;
stirrer speed
number of moles of A-functional
groups; Avogadro number
initial number of moles of A-functional
number of moles of B-functional
initial number of moles of B-functional
moles of monomer of type i in the reac-
number of moles of initiator in the re-
actor; number of growing chains
initial number of moles of initiator in
the reactor
moles of initiator of type i in the reactor
N (r) number chain length distribution
(number-fraction of polymer molecules
of chain length r)
number of monomer units; number
of micelles; number of monomer
molecules consumed
number of polymer particles containing
n radicals
number of polymer particles per unit
moles of CTA in reactor
NBR nitrile – butadiene rubber
NIRS near infrared spectroscopy
p conversion of functional groups
critical threshold
P growing polymer particle; polymer
conversion of functional groups at gela-
tion point
critical chain length for precipitation
moles of monomer of type i chemically
bound in polymer in the reactor
polymer containing i units of monomer
of type 1 and j units of monomer of type
] concentration of polymer with chain
length m
dead polymer chain containing m units
of monomer 1 and n units of monomer
number-average chain length of poly-
mer produced instantaneously
number-average chain length of accu-
mulated polymer
number-average chain length of sol
polymer molecule of chain length r
weight-average chain length of polymer
produced instantaneously
weight-average chain length of accu-
mulated polymer
weight-average chain length of sol
PDI polydispersity index of polymer pro-
duced instantaneously
PDI polydispersity index of accumulated
PE polyethylene
PEK polyetherketone
PES polyethersulfone
PETP poly(ethylene terephthalate)
PFR plug-flow reactor
PMMA poly(methyl methacrylate)
PP polypropylene
PPS poly(phenylene sulfide)
PS polystyrene
Polymerization Processes 5
PSD particle size distribution
PVAL poly(vinyl alcohol), partially hydro-
PVC poly(vinyl chloride)
P∗ polymeric active center
[P∗] concentration of polymeric active cen-
ters (ionic or radical type)

polymeric active center with active cen-
ter located on monomer of type i chem-
ically bound in the polymer chain

polymeric active center with active cen-
ter located on monomer of type j which
is adjacent to monomer of type i chem-
ically bound in the polymer chain

polymer chain containing m units of
monomer 1, n units of monomer 2, with
active center on monomer i
i-th moment of the dead polymer distri-
r polymer chain length
r polymer particle radius
micelle radius
polymer particle radius
, r
reactivity ratios
R gas constant

polymeric radical

] concentration of polymeric radicals
Re Reynolds number
rate of chain transfer
(r) production rate of polymer molecules
with chain length r
rate of radical entry into polymer parti-

initiator/catalyst fragment with an ac-
tive center

initiator radical with a peroxide end

initiator or primary radical

] concentration of primary radicals
radical generation rate in the aqueous
phase via initiator decomposition
rate of initiation (rate of generation of
polymeric radicals with chain length
unity via initiation)
RIM reaction injection molding
rate of polymerization (monomer con-
sumption rate via propagation reac-
consumption rate of monomer of type i
via propagation reactions
consumption rate of monomer of type j
by propagation with polymeric radicals
of type i
initial polymerization rate

polymeric radical of chain length r

] concentration of polymeric radicals of
chain length r
rate of bimolecular termination
rate of bimolecular termination by com-
rate of bimolecular termination by dis-
RTD residence time distribution

concentration of radicals in the aqueous
entropy change of polymerization at the
standard state
S surface area of polymer particle
S surfactant
SAN styrene – acrylonitrile copolymer
SBR styrene – butadiene rubber
SCSTR segregated CSTR
SSH stationary-state hypothesis
t time
half-life of initiator
polymer particle nucleation time
time when polymer particle nucleation
T temperature
T chain-transfer agent

CTA transfer radical
ceiling temperature
glass transition temperature
TPA terephthalic acid
TREF temperature rise elution fractionation
U MWD nonuniformity index
v volume of polymer particle
v volumetric flow rate into and out of re-
capture rate of radicals by polymer par-
flocculation rate of precipitated (pri-
mary) polymer particles
V volume of reacting mixture in the reac-
intial volume of reacting mixture in the
total volumetric flow rate into the reac-
total volumetric flow rate out of the re-
6 Polymerization Processes
specific volume of monomer
specific volume of polymer
volume of solvent in the reactor
s, in
volumetric flow rate of solvent into the
VCM vinyl chloride monomer
We Weber number
weight fraction of gel
W (r) weight chain length distribution
(weight fraction of polymer of chain
length r)
W(r), W(r, t) “instantaneous” weight chain
length distribution
W (r),
W (r, t) weight chain length distribution
of accumulated polymer
, W
weight fractions of homopolymers 1
and 2
x monomer conversion
X small molecule with a labile atom

transfer radical
z exponent indicating dependence of N
on emulsifier and initiator concentra-
α stoichiometric imbalance
, ∆α
differences between thermal expan-
sion coefficients above and below T
for homopolymers 1 and 2
β kinetic parameter (dimensionless)
γ kinetic parameter (dimensionless)
volume fraction of precipitant
δ kinetic parameter (dimensionless)
ε characterizes the radical capture effi-
ciency of latex particles relative to mi-
celles; energy-dissipation rate
ε mean rate of energy dissipation per unit
η moles of monomer consumed per active
site (≡
viscosity of continuous phase
viscosity of disperse phase
density of continuous phase
density of disperse phase
elastic cross-link density
density of monomer i
density of polymer
σ standard deviation
statistical variance
σ interfacial tension
interfacial tension between solid and
interfacial tension between solid and
interfacial tension between solid and
interfacial tension between water and
interfacial tension between water and
τ kinetic parameter (dimensionless)
τ mean residence time
ϕ phase volume ratio
ϕ, ϕ

probability of propagation
volume fraction of monomer
volume fraction of polymer

number fraction of polymeric radicals
of type i (terminal model)

number fraction of active or live poly-
mer molecules of type i (radical or
ionic, terminal model)

number fraction of polymer radicals of
type ij (penultimate model)
Φ kinetic parameter (dimensionless)
χ Flory – Huggins polymer – solvent in-
teraction parameter
ψ (r) number fraction of polymeric radicals
of chain length r
1. Introduction–Trends in Polymer
Reaction Engineering
The worldwide production of synthetic poly-
mers, estimated at ca. 100 ×10
t/a in 1990 [1]
and at ca. 170 ×10
t/a in 2000 [957], continues
to growin spite of criticismfromenvironmental-
ists. Polymer waste has become an urgent topic
for industry, providing new and challenging ar-
eas of research and development on recycling,
reuse, and degradation. The technical principles
of polymer reaction engineering will no doubt
play a significant role in the solution of some
of these problems. With the increase in produc-
tion volumes of commodity polymers (LLDPE,
HDPE, PP, PVC, and PS copolymers), large-
reactor technology (suspension PVC) and con-
tinuous processes (production of LLDPEin con-
tinuous fluidized-bed reactors, e.g., UNIPOL
process) are being developed [1], [2]. In the early
days of the polymer industry, polymers were
specialty materials, produced in batch reactors
by using faithfully followed recipes scaled up
from the chemist’s beaker. The process engi-
neer, although versed in the principles of chem-
Polymerization Processes 7
ical reaction engineering, had little background
in polymer chemistry, polymerization kinetics,
and polymer characterization techniques. This
has changeddramaticallyinthe last twodecades,
as evidenced by the rapid growth of the field of
polymer reaction engineering within the chemi-
cal reaction engineering discipline. Process pa-
rameters, such as residence-time distribution,
micromixing, and segregated flow, whose in-
fluence on productivity and selectivity of small
molecule reactions has been studied for many
years, appear to be far more important for poly-
merization reactors in that they influence poly-
mer properties dramatically [1–7].
The development of engineering and spe-
cialty polymers with a better balance of prop-
erties or with a particular unique property has
been growing rapidly. In this regard, it has been
found to be often more economic to produce
a new polymer from existing commodity poly-
mers rather than to start with a new monomer
and produce polymer in the usual manner. Tech-
niques such as polymer alloying and blending
are particularly attractive. These and other tech-
niques use chemical modifications of existing
polymers by chain scission, long-chain branch-
ing, cross-linking and grafting. These chemical
modifications are usually carried out with poly-
mer melts in an extruder reactor [1]. This pro-
cess is often called reactive polymer processing.
This is a new and commercially promising area
where the principles of polymer reaction engi-
neering could be profitably exploited.
Since 1980, modeling of polymerization re-
actors has become more comprehensive. Inter-
est has focussed on the prediction of polymer
properties (chemical composition and molecular
mass distribution, long-chain branching, cross-
link density, polymer particle size distribution,
and particle morphology). To develop a pre-
dictive model, account must be taken of the
chemistry and physics of all of the relevant mi-
croscopic processes which occur in the poly-
merization process. Detailed physical property
and thermodynamic data on the partitioning of
species among phases is required to quantita-
tively calculate the concentrations of reactants
at the loci of polymerization. Valid kinetic rate
constants (frequency factors and activation en-
ergies) are also required. In this regard, one
should note that the values for individual ele-
mentary rate constants are often not required. In
the models, groups of rate constants often appear
when calculating rates and polymer properties.
A knowledge of the Arrhenius equation (over-
all frequency factor and activation energy) is
usually sufficient. Another factor which should
be noted is that process models, no matter how
detailed, cannot track polymerization rates and
polymer properties in real time without feed-
back fromonline sensors. The variability in trace
impurity levels cannot be accounted for with-
out periodically adjusting kinetic parameters in
a process model. The great effort made by chem-
ical kineticists to measure individual elemen-
tary rate constants are not in vain. Elementary
rate constants can be related to the structure of
the reactants, but more importantly for process
modelers, elementary rate constants can be used
to discriminate kinetic models (for example, the
terminal and penultimate models in copolymer-
ization). At this point it is appropriate to em-
phasize the need for on-line sensors to monitor
polymer properties so that process models can
be used more effectively in state estimation and
2. Polymerization Mechanisms and
Polymerization reactions can be classified as ei-
ther step-growth or chain-growth reactions. It
has been proposed that these mechanisms should
be termed random and sequential polymeriza-
tions [18], [19] since these terms have more sig-
nificance statistically and are devoid of infer-
ence concerning the chemistry of the reactions
involved in the polymerizations. In this article,
however, the conventional terms step-growth
and chain-growth polymerization are used. It is
important to note that this is a classification of
reaction mechanisms, not of the structure of the
repeating unit, since many polymers can be syn-
thesized either by step-growth or chain-growth
polymerization. Generally, however, polymer
physical properties can differ significantly de-
pending on the polymerization mechanism, and
this is often due to the difference in molecu-
lar masses, i.e., polymers synthesized by chain-
growth polymerization often have higher molec-
ular masses.
These two types of growth reaction differ
basically in terms of the time-scale of vari-
8 Polymerization Processes
ous reaction events, namely, the size of poly-
mer molecules increases at a relatively slow
rate over a much longer period of time in step-
growth polymerization. With step-growth poly-
merization, the reactions that link monomers,
oligomers, and polymers involve the same reac-
tion mechanism, and any two molecular species
(monomer, oligomer, or polymer) can be cou-
pled. The growth of a polymer chain proceeds
slowly frommonomer to dimer, trimer, tetramer,
and so on, until full-sized polymer molecules are
formed at high monomer conversions. Polymer
chains continue to growfromboth ends through-
out the polymerization and, therefore, both chain
lifetimes and polymerization times are usually
of the order of hours.
Figure 1. Linear polymers produced via step-growth poly-
On the other hand, in chain-growth polymer-
ization, polymer molecules generally grow to
full size in a time-scale which is much smaller
than the time required for high conversion of
monomer to polymer. The lifetime of a growing
polymer molecule may be less than a few sec-
onds for a free-radical polymerization, which is
a typical example of chain-growth polymeriza-
tion, while a typical polymerization time to ob-
tain high monomer conversion may be several
hours. Chain-growth polymerizations require an
active center, whichmaybe a free radical, cation,
or anion. Once an active center is created, a poly-
mer chaingrows extremelyrapidly, andwhenthe
growing chain is deactivated by a termination re-
action, the polymer chain is dead and no longer
takes part as a reactant. With free-radical poly-
merization, however, the so-called dead polymer
chain is not always truly dead because under cer-
tain circumstances it may itself react with rad-
icals. The active center may initiate the growth
of many polymer chains.
Figure 2. Number chain length distribution in linear step-
growth polymerization
2.1. Step-Growth Polymerization
2.1.1. Linear Polymerization
Figure 1 shows some representative linear poly-
mer chains produced commercially by step-
growth polymerization. In step-growth polymer-
ization, there is generally only one type of chem-
ical reaction which links molecules of all sizes.
Some of the typical chemical reactions are es-
terification, amidation, the formation of ure-
thanes, and aromatic substitution. The growth
reaction in step-growth polymerization can be
represented by the general reaction
mmer +n mer −→ (m+n) mer (2.1)
Polymerization Processes 9
The kinetic study of such reactions would be
extremely difficult if the rate constant for the
coupling reaction depended on the size of both
species. Fortunately, various kinetic studies have
shown that the rate constant is effectively in-
dependent of chain length except perhaps for
oligomers. This is often referred to as the con-
cept of equal reactivity of functional groups.
Consider the example of step-growth poly-
merization shown below.
n A−A+n B−B→——[ A−A−B−B——]
In the case of polyesterification of a diol and a
diacid, A may be a hydroxyl group and B may
be a carboxyl group, although the lowmolecular
mass condensation byproduct is not shown. As
will be shown later, an almost exact equivalence
in the number of functional groups is necessary
to obtain polymers with high molecular mass,
although a nonstoichiometric condition may be
used to control molecular mass. In the case of ex-
act stoichiometric ratio of the two types of func-
tional groups, i.e., [A] =[B], the polymerization
rate or the rate of disappearance of functional
groups is given by

d (V [A])
=K [A]
except for self-catalyzed polymerization, in
which case the rate is third order in monomer
(the self-catalyzed polymerization may not be a
useful reaction from the practical point of view
of productivity). Neglecting the volume change
during polymerization, integration of Equation
(2.3) gives
1/ (1−p) = 1+K [A]
t (2.4)
where [A]
is the initial (at t =0) concentration
of Agroups, and p is the conversion of functional
groups, which is defined as
where N
and N
are the total number of moles
of Agroups at t =0andat anylater time t, respec-
tively. Equation (2.4) has been verified by sev-
eral kinetic studies. As shown here, the rate ex-
pression for a step-growth polymerization is the
same for monomer molecules, oligomers, and
The relationship between the average num-
ber of structural units (A– A and B– B in the
above example), namely, the number-average
chain length
and the conversion of func-
tional groups p for linear step-growth polymer-
ization was first derived by Carothers [20].
is simply given as the total number of monomer
molecules initially present divided by the total
number of molecules present at time t.
= 1/ (1−p) (2.6)
Figure 3. Weight chain distribution in linear step-growth
Equation (2.6) shows that very high conver-
sions are necessary to obtain large chain lengths.
For example,
=100 requires a conversion of
99 %. Equation (2.6) assumes a stoichiomet-
ric ratio of unity. If a slight excess of one bi-
functional monomer is used, all chain ends will
eventually consist of the group present in excess.
When N
, the stoichiometric imbalance
α is given by α=N
. The total number
of monomer molecules initially present is given
by (N
)/2 =N
(1 +1/α)/2. Now con-
sider the situation at conversion p (p is usually
defined with respect to the deficient group, so
that p is defined for A groups in this exam-
ple). Since each chain end is an unreacted func-
tional group, the total number of end groups is
(1 −p) +N
(1 −αp)]. Each molecule
possesses two end groups, so that the total
number of polymer (plus monomer) molecules
is [N
(1 −p) +N
(1 −αp)]/2. Therefore,
Equation (2.6) can be modified as follows
(1 + 1/α) /2
(1−p) +N
10 Polymerization Processes
As conversion p approaches unity,
proaches (1 +α)/(1 −α). Thus if α=0.99, the
maximum number-average chain length is only
199. This example illustrates the importance of
precise control of the stoichiometric ratio to ob-
tain a desired chain length.
In general, in order to produce high molecular
mass polymer by step-growth polymerization,
the system must satisfy the following require-
1) Very accurate control of the stoichiometric
ratio of functional groups
2) Absence of side reactions
3) Availability of high-purity monomers
4) Reasonably high polymerization rate
5) Little tendency towards cyclization reactions
Figure 4. Nonlinear (network) polymers produced via step-
growth polymerization
Since high molecular mass polymer is not
produced until nearly complete conversion of
monomer has occurred, the viscosityis relatively
low throughout most of the conversion range.
Thermal control and mixing is not overly dif-
ficult, which is opposite to the case for chain-
growth polymerization. These are some of the
reasons why bulk polymerization is quite often
used commercially for the production of poly-
esters and polyamides.
The molecular mass distribution can most
easily be derived by using statistical methods for
a stoichiometric ratio of unity [21]. The conver-
sion p can be interpreted as the probability that
a functional group selected at random has re-
acted. Consider the probability that a randomly
selected molecule consists of r monomer units
(this quantity is equal to the number chain length
distribution). This polymer molecule possesses
r −1 reacted functional groups, and one unre-
acted functional group. Therefore, the number
chain length distribution, N (r) is given by
N (r) =p
(1−p) (2.8)
The weight chain length distribution W (r) is
given by
W (r) =r N (r) /

r N (r) =r p
The number and weight chain length distribu-
tions are shown schematically in Figures 2 and
3, respectively. The weight-average chain length
is given by

r W (r) = (1+p) / (1−p) (2.10)
Since the number-average chain length is
given by Equation (2.6), the polydispersity in-
dex, PDI =
, is givenby(1 +p), andthere-
fore the PDI approaches two as complete con-
version is approached.
Various statistical treatments other than that
shown above have been developed to calculate
the molecular mass distribution for linear step-
growth polymerization [22–26]. Although these
statistical methods appear to work well, kinetic
approaches based on the use of material balances
may have greater generality [27–33]. For an A–
B type monomer in a batch reactor, Equations
(2.8) and (2.9) can also be derived from the fol-
lowing infinite set of differential equations.
d [P
] /dt = −2K [P
] [P] (2.11)
d [P
] /dt =K

] [P
−2K [P
] [P] (m≥2) (2.12)
Polymerization Processes 11
where [P
] is the concentration of polymer
molecules with chain length m, and [P] is the
total concentration of polymer and monomer.
For example, it is straightforward to derive
the molecular mass distribution for the cases
in which a slight amount of monofunctional
reagent is used. Kinetic approaches would be
easier to apply to reactors other than batch re-
actors, such as semi-batch and continuous flow
reactors, although a statistical derivation for a
stirred-tank reactor has been reported [34].
2.1.2. Interfacial Polymerization
Interfacial polymerization may provide a
method to produce very high molecular mass
polymers by step-growth polymerization [35],
[36]. In interfacial polymerization, polymers are
formed at or in the vicinity of the phase bound-
ary of two immiscible monomer solutions. This
technique requires an extremely fast polymer-
ization. The best reaction type for step-growth
polymerization would be Schotten – Baumann
reactions involving acid chlorides. For example,
polyamidation is performed at room tempera-
ture by placing an aqueous solution of diamine
over an organic phase containing the diacid
chloride. The polymer formed at the interface
can be pulled off as a continuous film or fil-
ament. The amine – acid chloride reaction rate
is so fast that the polymerization becomes dif-
fusion controlled. Once the polymer molecules
begin to grow and monomer molecules start to
add to polymer chain ends, incoming monomer
molecules tend to react with polymer chain ends
before they can penetrate through the polymer
film to start the growth of new chains. Thus,
polymers with much higher molecular masses
are formed. Since the reaction is diffusion con-
trolled, there is no need to start with an exact
balance of the two monomers. The lower tem-
peratures used reduce the relative rates of side
reactions, and, therefore, the purityof monomers
is not as important as with most other step-
growth polymerizations. In spite of the advan-
tages that interfacial polymerization offers, this
process has not attracted wide industrial use,
mainly because of the high cost of the required
reactive monomers and the large amount of sol-
vent which must be removed and recovered.
2.1.3. Nonlinear Polymerization
Another important class of polymers pro-
duced by step-growth polymerization are non-
linear polymers formed by polymerization of
monomers with more than two functional groups
per molecule. Some of the nonlinear polymers
produced commercially by step-growth poly-
merization are shown in Figure 4.
Inthe course of networkformation, a polymer
molecule of effectively infinite molecular mass
may be formed. At this point, termed the gel
point, the visible formation of a gel or insoluble
polymer fraction is observed. The gel molecule
is insoluble in a good solvent even at elevated
temperatures under conditions at whichdegrada-
tion does not occur. Various physical properties
of the system change abruptly at the gel point.
Gelation should be understood as a critical phe-
nomenon having similarities with other critical
phenomena such as vapor – liquid condensation,
nuclear chain reactions, and ferromagnetism.
It was Carothers [20], who first derived an
equation for the extent of reaction at the gel
point. He defined a gel molecule as one with infi-
nite molecular mass. His criterion that gelation
occurs when the number-average chain length
goes to infinity is not acceptable, since poly-
mer molecules larger than
are always present
and will become gel molecules earlier than this
hypothetical gel point. However, the concept
of the “infinitely large molecule” was fully es-
tablished by Flory [37–39] using a statistical
approach. His criterion for the onset of gela-
tion is that it occurs when the weight-average
chain length
goes to infinity. Since a gel
molecule is the largest molecule in the reaction
system, higher-order moments of the molecu-
lar mass distribution could also be used to de-
termine the gel point. Fortunately, the second-
and higher-order moments approach infinity si-
multaneously, at least for batch polymerizations
[40], [41], and the criterion of infinite
is ac-
Flory devised a simple tree-like model, as
shown in Figure 5, and used the following sim-
plifying assumptions:
1) All functional groups of the same type are
equally reactive
2) All functional groups react independently of
one another
12 Polymerization Processes
3) No intramolecular reactions occur in finite
Figure 5. A schematic drawing of Flory’s tree-like model
(functionality f =3)
The tree-like model is called the Bethe Lattice or Cayley
tree by physicists
Figure 6. Molecular mass change and gel growth during
network formation (functionality f =3)
His basic proposal was that the gel point
is reached when the expectancy of finding the
next generation in a particular existing molecule
is unity. For the tri-functional monomer units
shown in Figure 5, the conversion at the gel
point is given by p
=1/( f −1) =0.5, where f is
the functionality of a monomer unit. His model
was a brilliant development and it provides the
starting point for most theories of polymer net-
work formation. A few years later Stockmayer
[42–44] further developed Flory’s idea based
on the most-probable size distribution, and their
theory is usually called the Flory – Stockmayer
theory. Examples of the calculated development
of the number- and weight-average chain lengths
of the sol fraction and of the weight fraction
of gel are shown in Figure 6. Since the gel is
a molecule with many functional groups, the gel
once formed acts like a giant sponge, rapidly
consuming sol polymer molecules.
This tree-like concept was generalized by
Gordon et al. [45], [46] based on the theory of
stochastic branching processes, which is consid-
ered to be a part of Graph Theory [47], [48]. This
technique involves abstract mathematics and re-
quires the derivation of the probability generat-
ing functions. The method is general but rather
difficult touse for real problems. Toavoidthe use
of probability generating functions, other prob-
abilistic methods have been proposed [49–52].
Among them the Macosko – Miller model [50–
52] using conditional probabilities is becoming
popular due to its simplicity. All the models
mentioned above are fully equivalent, that is,
only the mathematical language is slightly dif-
ferent. These statistical models, which are some-
times called the classical theories, have a long
history and have proven their power of refin-
ability to accommodate highly system-specific
effects such as unequal reactivity [53], [54], sub-
stitution effects [55], [56], and intramolecular
reactions [18], [19], [57–59], which are impor-
tant in real systems.
One drawback of the statistical theories men-
tioned above is that they assume an equilib-
rium system (i.e., the size distribution is calcu-
lated anew at each time) and they do not con-
sider the kinetic buildup of the system. There-
fore, the classical theories may not be appli-
cable for kinetically-controlled systems. It has
been shown that although there is no difference
between equilibrium and kinetically-controlled
systems under Flory’s simplifying assump-
tions, the difference becomes significant as the
conditions deviate further from Flory’s as-
sumptions [60], [61], so that in real systems the
kinetic features may be dominant. It has been
argued that the kinetic buildup can also be ac-
counted for by using a statistical approach [62].
Another disadvantage of statistical ap-
proaches may be the excessive modifications re-
quired to generalize them for different reactor
types (e.g., continuous reactors). The kinetics
approach was originally shown in the appendix
of a paper by Stockmayer [42]. Based on the
chemical kinetics, the reaction rate would be
proportional to the product of the number of un-
reacted functional groups in the respective reac-
tion partner, so that an infinite set of differential
Polymerization Processes 13
equations similar to Equations (2.11) and (2.12)
can be set up. This idea has been applied to poly-
meric systems [60], [63–70].
Figure 7. Example of percolation at the gel point in a square
lattice (p
=0.5) [78]
All the theories mentioned above belong to a
mean-field theory. On the other hand, the perco-
lation theory [71–77], which is considered to be
equivalent to a non-mean-field theory, has been
appliedtopolymeric gelation[78], [79]. The per-
colation theory is usually associated with a lat-
tice model to describe network structure. One
of the simplest examples is the two-dimensional
lattice shown in Figure 7. In this figure, each
bond which has been formed is shown as a
short line connecting two monomers, though the
monomers are not shown. In the random (stan-
dard) percolation theory each site of a very large
lattice is occupied randomly with probability
p, independent of its neighbors. Some nearly
“infinite” molecules can be seen in Figure 7,
where “infinite” means that they span the whole
sample. Mathematical methods to calculate this
threshold exactly are restricted so far to two di-
mensions [77], and therefore, for practical cal-
culations the Monte Carlo simulation is usually
used. It is easy to understand why gelation is
a critical phenomenon from the lattice model,
because in the vicinity of the gel point only a
few additional bonds are necessary to form a
molecule which spans the whole sample. The
percolation theory emphasizes the universality
of critical phenomena and space dimensional-
ity. De Gennes wrote in his book [80] that “it
took more than thirty years to convince exper-
imentalists that mean-field theory was wrong”.
However, at present the percolation models are
far from simulating actual network formation
quantitatively, because the bonds are too rigid,
the movement of molecules is too suppressed,
and necessary chemical rules of bond formation
are ignored. The percolation theory is essentially
devoted to describing the behavior near the criti-
cal threshold p
, where the system-specific fea-
tures are not important.
Network polymers are increasingly used as
engineering materials because of their excellent
stability toward elevated temperature and physi-
cal stress. Since the three-dimensional polymers
are neither soluble nor fusible once made, the fi-
nal stage of polymerization is usually carried out
in a mold of the desired shape.
2.2. Chain-Growth Polymerization
Chain-growth polymerization is initiated by a
reactive species, R

, produced from an initiator
or catalyst I.
I −→n R

Depending on the type of active center, chain-
growth polymerization can be divided into free-
radical, anionic, and cationic polymerization.
The reactive species R

adds to a monomer
to form a new active center, and monomer
molecules are added to the active center suc-
cessively. This process is called the propagation
where M represents a monomer molecule, and
is an active polymer molecule with chain
length r. In general, the propagation reaction is
represented by
In chain-growth polymerization, only
molecules with an active center can propa-
gate, so that polymer molecules once formed
may be considered dead polymer for linear
chain-growth polymerization. Dead polymer
14 Polymerization Processes
molecules do not take part as reactants there-
after. The active center is always on the chain
end when linear chains are being produced ex-
clusively. Polymer chain growth is terminated at
some point by unimolecular and/or bimolecular
termination. Bimolecular termination of active
centers occurs only in free-radical polymeriza-
Carbon – carbon double bonds and the
carbon – oxygen double bond in aldehydes and
ketones are the two main types of func-
tional groups which undergo chain-growth
polymerization. The polymerization of the
carbon – carbon double bond is much more im-
portant, as most commercial monomers with
carbon – carbon double bonds readily undergo
free-radical polymerization (an important ex-
ception is propene). The carbonyl bond is not
generally susceptible to polymerization by rad-
ical initiators due to its highly polarized struc-
ture. Another reason is that most of the carbonyl
monomers (except formaldehyde) possess very
lowceiling temperatures [81], [82] (the tempera-
ture above which active polymer chains depoly-
merize rather than grow).
Most of the commercial vinyl monomers
=CHX and CH
=CXY, and monomers in
which fluorine is substituted for hydrogen) can
be polymerized with free radicals. Whether a
vinyl monomer can be polymerized by anionic
or cationic mechanisms strongly depends on
the type of monomer. Monomers with electron-
donating groups attached to the doubly bonded
carbon atoms form stable carbenium ions and
polymerize best with cationic initiators. Con-
versely, monomers with electron-withdrawing
substituents form stable carbanions and require
anionic initiators. It should be noted that ions
of low stability would be expected to react with
carbon – carbondouble bonds; however, inmany
cases they cannot be formed or else are easily
consumed by side reactions.
2.2.1. Free-Radical Polymerization
Generally, free-radical polymerization consists
of four types of elementary reaction.
1) Initiation reactions, which continuously gen-
erate radicals during polymerization.
The stoichiometric coefficient n is two for
thermal decomposition of initiators. A free-
radical R

derived fromthe initiator is called
a primary or initiator radical.
2) Propagation reactions, which are responsible
for the growth of polymer chains by addition
of monomer to a radical center.
3) Bimolecular termination reactions between
two radical centers, which give a net con-
sumption of radicals. These consist of dis-
proportionation (Eq. 2.19) and combination
(Eq. 2.20).
where P
is a polymer molecule of chain
length r and does not have a radical center,
while a polymer radical (or macroradical) of
chain length r has the symbol R

4) Chain transfer to small molecules which
causes the cessation of growth of poly-
mer radicals while generating small trans-
fer radicals simultaneously. Chain-transfer
reactions do not give a net consumption of
radicals, and if the transfer radicals are as
reactive as polymer radical (or more reac-
tive) these reactions should not affect the
polymerization rate or monomer consump-
tion rate when the bimolecular termination
reactions are chemically controlled. Chain-
transfer reactions to small molecules re-
duce the size of polymer radicals and there-
fore would increase bimolecular termination
rates when these reactions are diffusion con-
trolled (bimolecular termination rates may
be chain-length dependent under these con-
Polymerization Processes 15
X may be monomer, a solvent molecule, or
a chain-transfer agent. When X is a poly-
mer molecule, polymer molecules with long-
chain branches are formed. Long-branch for-
mation is discussed in Section
The sequence of elementary reactions, in
Equations (2.16) – (2.22) results in total radical
concentrations of the order 10
– 10
for most commercial polymerizations. Since
polymer molecules with high molecular masses
are produced from the very start of polymeriza-
tion, the reacting solution can be quite viscous
over most of the monomer conversionrange. The
high viscosities not only cause problems in mix-
ing and heat removal, but also can affect reaction
rates (reactions such as bimolecular termination
of polymer radicals). This topic is discussed in
Free-radical polymerization is the most com-
monly used method for the synthesis of poly-
mers from vinyl and divinyl monomers. Some
typical monomers which readily undergo free-
radical polymerization are ethylene, styrene,
vinyl chloride, vinylidene chloride, acryloni-
trile, vinyl acetate, methyl methacrylate, methyl
acrylate, acrylamide, etc. Of all chain-growth
polymerization processes, it is the most widely
studied and best understood. Initiation
Free radicals may be generated in a monomer in
a number of ways. The most oftenusedmethodis
to add chemical initiators, such as azo and perox-
ide compounds, to the monomer in low concen-
trations (usually <1 wt % based on monomer).
When heated, the initiator decomposes, gener-
ating radicals which act as active centers for
monomer addition. For example, organic per-
oxides (ROOR

) decompose thermally by O– O
bond cleavage to produce two initiator radicals
as follows (other side reactions may of course
where K
is a thermal decomposition rate con-
stant with units of inverse time, most often s
For a batch reactor, the change in the number of
moles of initiator N
is given by
/dt = −K
For isothermal decomposition (isothermal poly-
merization) Equation (2.24) can be integrated
analytically to obtain
exp (−K
t) (2.25)
where N
is the number of moles of initiator at
time t =0.
Thus the half-life of an initiator is given by
= −ln (0.5) /K
= 0.693/K
Knowledge of K
for an initiator therefore per-
mits calculation of the initiator half-life t
Since K
has an Arrhenius temperature depen-
dence, K
and t
both depend on temperature.
Activation energies for peroxides and azo ini-
tiators are ca. 120 kJ/mol, so the decomposition
rate is highly temperature dependent, and the
useful temperature range is quite small (decom-
position rate is either too fast or too slowoutside
the useful temperature range, which normally
spans about 30

To complete the initiation step, the initiator
radicals (R

) must add to the double bond of a
monomer molecule to generate a polymer radi-
cal of unit chain length R

. In most polymeriza-
tions, this step (Eq. 2.17) is much faster than the
rate of initiator decomposition (Eq. 2.16). The
homolysis of the initiator is the rate-determining
step in the initiation sequence, and the initiation
rate R
is given by
= 2K
f [I] (2.27)
where f is the initiator efficiency. The initiator
efficiency is defined as the fraction of radicals
produced by initiator decomposition that initiate
polymer radicals. Note that not every initiator
molecule, which in principle can produce two
polymer radicals, does so. Some primary rad-
icals may react with themselves or with other
molecules to form stable species which do not
form either polymer radicals or molecules. It
should be noted that chain transfer to the initia-
tor does not decrease f . The initiator efficiency
16 Polymerization Processes
usually has values in the range 0.2 – 1.0 at low
monomer conversions, where polymer concen-
trations are low. The major cause of low ini-
tiator efficiency is recombination of the radical
pairs before they diffuse apart, which is called
the cage effect [83], [84]. When an initiator de-
composes, the primary radicals R

are near-
est neighbors for about 10
– 10
s. During
this interval they are surrounded by a “cage” of
solvent and monomer molecules through which
they must diffuse to escape from the cage. Since
reactions between radicals are extremely fast,
there is reasonable probability that reaction bet-
ween primary radicals occurs. Direct recombi-
nation may simply regenerate the original initia-
tor molecules, but other reactions can also occur
that consume initiator radicals without forming
polymer chains. In particular, since azo initiators
decompose with the elimination of a nitrogen
molecule, recombination of the primary radicals
results in the formation of a stable molecule that
cannot generate radicals, and thus there may be
a significant decrease in initiator efficiency. Ef-
ficiency decreases with increasing viscosity of
the reaction medium[85], [86]. Thus f decreases
during the course of polymerization and may ap-
proach zero at very high polymer concentrations
where the diffusion coefficient of primary radi-
cals in the “cage” is very small [87], [88].
When selecting an initiator type, in general
one needs to consider the decomposition rate
constant, water and oil solubility, stability of ini-
tiator fragments on chain ends, and other factors.
Another important point is the activity of the ini-
tiator radical center towards the abstraction of
atoms (e.g., hydrogen atoms) from the polymer
backbone. This can lead to chain scission, long-
chain branching, and possibly cross-linking.
Up to this point, only monofunctional ini-
tiators (initiators with one peroxide or one
azo group per molecule) have been consid-
ered. There are commercially available bifunc-
tional initiators (with two peroxide groups per
molecule) with some potentially useful applica-
tions [89–92]. Their function can be illustrated
as follows:
Even when the K
’s for both peroxide groups
are the same, both groups on the same peroxide
molecule do not decompose at the same time;
thus a significant fraction of the polymer chains
will have a peroxide end group. These terminal
peroxide groups will later decompose, generat-
ing polymer radicals with an initiator fragment
in the backbone. The practical benefits include
higher molecular masses at the same tempera-
ture or comparable molecular masses at higher
temperatures. Polymerization at higher temper-
atures results in higher productivity. These ben-
efits will only accrue when most of the poly-
mer chains are formed by bimolecular termina-
tion of polymer radicals. When chain transfer
to small molecules produces most of the poly-
mer chains, these benefits will no longer exist,
and since bifunctional initiators are more expen-
sive than monofunctional initiators it is recom-
mended that the latter be used.
The decomposition rates of peroxy and azo
compounds can be increased by irradiation with
ultraviolet and visible light. Unlike thermal
decomposition, the activation energy for pho-
tochemical initiation is approximately zero, so
polymerization can be initiated at much lower
temperatures. Compounds such as benzoin and
disulfides, whose bonds are too strong to un-
dergo thermal homolysis, are effective radical
initiators under ultraviolet irradiation. Photo-
chemical polymerization has been applied in
coatings and inks for metal, paper, wood and
plastics, in photo-imaging, printing circuits, and
adhesives, although its use is limited by lowpen-
etration into the polymerizing mass.
Another method of lowering the activation
energy of the peroxide decomposition reaction
is to use redox initiation systems. The addition
of a reducing agent results in radical formation
from an oxidation – reduction reaction between
the two components. Generally, the reaction is
illustrated as follows.




where Ais a reducing agent and ROOR

is a per-
oxide. The integer n is two for Fe
and zero for
N,N-dimethylaniline. The fate of the free radical
depends on the relative concentration of reduc-
ingagent andmonomer. Since the redoxinitiaton
reactions do not produce a pair of radicals, the
cage effect is not operative. At high monomer
Polymerization Processes 17
concentrations most of the free radicals initi-
ate polymerization, and ordinary second-order
kinetics are obeyed. Redox initiation is usually
used in the temperature range 0 – 50

All methods mentioned above employ initia-
tors. There are, however, other means to initiate
polymerization. Styrene (and some substituted
styrenes such as p-methylstyrene) and methyl
methacrylate polymerize at elevated tempera-
tures in the absence of a free-radical initiat-
ing system. The accepted mechanism for ther-
mal initiation of styrene is the Mayo mecha-
nism [93], [94], which involves the formation
of a Diels – Alder dimer intermediate which re-
acts with styrene to produce radicals. The Mayo
mechanism is consistent with an observed initi-
ation rate which can vary from second to third
order in monomer during the course of polymer-
ization [95–97], and some confirming evidence
has been reported [98–100]. Aserious disadvan-
tage of the use of thermal initiation for styrene is
the formation of undesirable byproducts (cyclic
dimers and trimers) which are difficult to remove
to give a high-quality polystyrene.
Irradiation with UV, high-energy electrons,
and γ-rays can initiate polymerization with
or without the presence of initiators. Radia-
tion initiation has been used almost exclusively
for polymer modification (chain scission, long-
chain branching, cross-linking, and grafting).
These radiation processes are characterized by
a zero activation energy for radical generation
and as a consequence a low activation energy
for polymerization. Therefore, they are effective
at both low and high temperatures. With radi-
ation initiation, polymer molecular masses in-
crease with increasing temperature, which is op-
posite tothat for chemicallyinitiatedfree-radical
polymerizations (the high activation energy for
initiator decomposition is responsible for this).
Both UV and electrons have small penetration
depths and are therefore used for polymeriza-
tions in thin layers. Gamma rays have high
penetration depths but require expensive safety
installations. Radiation polymerization may be
initiated by radicals, cations, or anions. The ef-
fectiveness of a radical center depends on the
chemistry of the monomer and the polymeriza-
tion conditions. Most radiation polymerizations
are free-radical except at very low temperatures
where ionic species are sufficiently stable. With
radiation initiation various active intermediates
may be formed, leading to a very complex reac-
tion mixture with the formation of many byprod-
ucts as well as the formation of long branches
and possibly cross-linkages. Since photon ener-
gies for UV are lower, UV radiation generally
gives cleaner polymerizations with the forma-
tion of linear chains, although monomers which
undergo photolysis by UV radiation are limited. Propagation
The propagation reaction (Eq. 2.18) controls
both the rate of growth and the structure
of the polymer chain. Monomers which un-
dergo free-radical polymerization are com-
monly monosubstituted or 1,1-disubstituted eth-
ylenes, CH
=CHX or CH
=CXY. With 1,1-di-
substituted ethylenes both substituents should
not be large, since propagation would be ster-
ically hindered. 1,2-Disubstituted ethylenes are
normally considered very difficult to polymer-
ize since the approach of the propagating rad-
icals to a monomer is sterically hindered. 1,2-
Disubstituted ethylenes can, however, often be
incorporated into copolymers.
Due to steric and resonance effects, vinyl
monomers predominantly undergo head-to-tail
In certain cases when the substituents are
small and do not have large resonance stabiliz-
ing effects, head-to-head propagation may oc-
cur. For example, approximately 16 % head-to-
head placement has been reported for poly(vinyl
fluoride) [101].
In free-radical polymerization, chain mi-
crostructure is largely independent of initiation
mechanism and initiator type. Polymers pro-
duced by free-radical polymerization are largely
atactic, since the terminal carbon – carbon bond
can rotate freely during chain growth. The con-
figuration of a monomer unit in the chain is
not determined during its addition to the rad-
ical center but only when the next monomer
molecule adds to it. The slight preference for
syndiotactic over isotactic placement is caused
by steric and/or electrical repulsion between
18 Polymerization Processes
substituents in the chain, although at high tem-
peratures their effects are progressively dimin-
ished. For example, the fraction of syndiotactic
diads of poly(vinyl chloride) changes from 0.67
to 0.51 as the synthesis temperature increases

Cto 120

C[102]. For methyl meth-
acrylate, it is 0.86 at −40

C and 0.64 at 250

[103], [104].
For most chain-growth polymerizations
(free-radical or ionic) the propagation reactions
are reversible at elevated temperature and the
rate of depropagation is significant [105], [106].
where K
is the rate constant for depolymeriza-
tion (depropagation). The ceiling temperature
, which is the temperature above which active
polymer chains depolymerize rather than grow,
is reached when the propagation and depropa-
gation rates are equal. Based on thermodynamic
arguments, the ceiling temperature can be re-
lated to the equilibrium monomer concentration
as follows:
= ∆H/
+R ln [M]
where ∆H is the heat of polymerization, ∆S
the entropy change of polymerization at unit
monomer concentration, and R the gas constant.
The ceiling temperature T
is not a singu-
lar value but is a function of monomer con-
centration. At any temperature, a concentra-
tion of monomer exists at which the reaction
in Equation (2.31) is at equilibrium. The exis-
tence of this equilibrium concentration prevents
monomer conversion reaching 100 %.
Normally, this equilibriummonomer concen-
trationis toolowtodetect. Anotable exceptionis
α-methylstyrene whose T
for 100 % monomer
concentration is 61

C, and the equilibrium
monomer concentration at 25

C is 2.2 mol/L
Conventionally, it has been assumed that the
propagation rate constant K
is independent of
chain length. Experimental results have shown
that K
is independent of chain length at least
for chain lengths >16 for styrene and >62 for
methyl methacrylate [108]. The propagation rate
constant K
is relatively insensitive to the vis-
cosity of the systemexcept at very high polymer
concentrations [88], [109].
It has long been recognized that some bulk
polymerizations stop at well below 100 % con-
version [110]. This phenomenon has success-
fully been explained as due to a glassy-state tran-
sition of the polymerizing mass [111]. Although
the polymerization can proceed very slowly in
the glassy state [109], [112], for practical pur-
poses it can be assumed that polymerization
stops when the system changes from a viscous
liquid to a solid glass. It has been proposed that
the initiator efficiency f approaches zero when
the system reaches a glassy state [87], [113] and
that this is mainly responsible for the cessation
of polymerization. Termination
An active center on a growing polymer radical
may be destroyed by a variety of processes, in-
cluding termination by added substances. The
latter reactions are called inhibition and retarda-
tion processes, and are not considered here. This
section discusses bimolecular termination reac-
tions between polymer radicals. Although one
of the radicals involved in bimolecular termina-
tion may be an initiator radical, under normal
polymerization conditions such reactions may
be negligible since the concentration of initiator
radicals is much smaller than that of polymer
Bimolecular termination of two polymer rad-
icals can occur by combination or coupling:
or by disproportionation, in which case a hy-
drogen radical is transferred from one polymer
chain to the other. The result is the formation
of two polymer molecules, one of which has a
terminal double bond.
Termination by combination and dispropor-
tionation can occur simultaneously, and the rel-
ative importance of these two modes of termi-
Polymerization Processes 19
nation depends on monomer type and polymer-
ization temperature. Experimental data are not
available for many monomers; however, radicals
which undergo termination by combination ap-
pear exclusively to have the structure (1) [114].
Awell-known example is styrene, which experi-
ences termination by combination almost exclu-
sively over a wide range of temperatures [114],
[115]. Onthe other hand, radicals whichundergo
disproportionation and combination may have
the structure (2).
For methyl methacrylate, combination and dis-
proportionation are both important at low tem-
perature, with disproportionation becoming the
dominant mode at high temperatures [116–118].
Since bimolecular termination reactions are
intrinsically very fast, these reactions are likely
to be diffusion controlled when they involve
radical centers on polymeric reactants. The
autoacceleration of polymerization rate that
is a consequence of diffusion-controlled ter-
mination is usually called the gel effect or
Trommsdorff – Norrish effect. Figure 8 illus-
trates the autoacceleration in rate for the poly-
merization of methyl methacrylate [119]. The
interpretation proposed was that the increase in
rate is a consequence of a decrease in the rate
of termination, due to the large increase in vis-
cosity of the reacting medium, thus giving an
increase in radical concentration.
Figure 8. Conversion – time histories for the polymeriza-
tion of methyl methacrylate in benzene initiated by benzoyl
peroxide at 50

The different curves are for various concentrations of
monomer in solvent [119]
In general, the termination rate constant
should depend on the size of the polymeric rad-
ical reactants, the concentration and molecular
mass distribution of the accumulated polymer,
solvent type, and temperature. As the concen-
tration of entanglement points increases during
the course of polymerization, the functional de-
pendence of the termination rate constant on
the chain lengths of the polymeric radical reac-
tants should change dramatically. At some high
monomer conversion (high polymer concentra-
tion) when the polymeric radicals are trapped
(diffusion of the center of mass of polymer
chains is essentially zero), radical centers may
continue to move (due to monomer addition
by propagation) and undergo bimolecular ter-
mination [118]. With this form of termination,
the termination rate constant should be inde-
pendent of the chain lengths of the polymeric
radical reactants. Originally, upon examination
of the autoacceleration of the conversion – time
curve, it was believed that the termination reac-
tion only became diffusion controlled at some
monomer conversion greater than zero and that
this occurred when the polymer chains were suf-
ficiently entangled (with a sufficient number of
physical entanglement points). It has been rec-
ognized that the bimolecular termination reac-
tions may be diffusion controlled even at zero
monomer conversion (zero polymer concentra-
tion) [114], [120–122]. At low monomer con-
versions, where polymer chains in a good sol-
vent are isolated coils, translational diffusion of
the center of mass of the chains is sufficiently
rapid, and the limiting step is the so-called seg-
mental diffusion rate of the radical center in the
coil. With limited interpenetration of the coils, a
finite and significant time is required for the rad-
ical centers on the partially penetrating coils to
meet in a suitable reaction volume where bimo-
lecular termination may occur. The probability
of finding the radical centers in a suitable reac-
tion volume near the coil surfaces decreases as
the coil sizes increase, and, therefore, the termi-
nation constant should increase with decreasing
polymer molecular mass, with decreasing good-
ness of the solvent (which depends on the nature
and concentration of monomer, inert solvent,
and polymer), and with increasing polymer con-
centration (increasing monomer conversion). It
is well known that in dilute solution the poly-
20 Polymerization Processes
mer coil size decreases with increasing polymer
At somewhat higher conversions, when there
are a sufficient number of chain entanglement
points, the translational diffusion rate of the cen-
ter of mass of polymer coils decreases dramati-
cally and bimolecular termination rates become
translationally diffusion controlled. Of course,
shorter polymer chains will experience transla-
tional diffusion-controlled termination at higher
monomer conversions (higher polymer concen-
trations) than longer chains, and clearly the
bimolecular termination rate constant will be
chain-length dependent and the bivariate distri-
bution K
(r, s) will change its shape dramat-
ically with increasing polymer concentration.
Finally, when the polymer coils are trapped,
should become independent of chain length
Figure 9. Polymerization of acrylamide – rate and molec-
ular mass development (T =60

C, [M]
=3.4 mol/L, initi-
ated by potassium peroxosulfate [I]
=5.2 ×10
– – – =Constant K
; —- =Use of Equation (2.35) [126]
The mechanisms of diffusion-controlled re-
actions in polymer systems are being clari-
fied both theoretically and experimentally (see
for example [122]), but at present developing
a general formulation for K
for the whole
course of polymerization is a formidable task.
Considering the complexity of the mechanisms
of diffusion-controlled termination reactions, in
some cases it may be necessary to use an empir-
ical approach for reactor calculations [96], [97],
[123–126]. For example, K
may be approxi-
mated by

where x is the monomer conversion, K
the termination rate constant at zero monomer
conversion (x =0), and A
, A
, A
are ad-
justable parameters. An application is shown
in Figure 9. The adjustable parameters A
, A
are usually estimated by fitting isothermal
conversion – time curves. The adjustable param-
eters should be functions of temperature and
possibly initiator concentration (radical initia-
tion rate). Note that K
estimated by fitting poly-
merization rate and number-average molecular
masses is a number-average termination rate
constant. Although, this termination rate con-
stant may predict rates of polymerization and
number-average molecular masses adequately,
its use to calculate higher averages will under-
estimate weight-average, and Z-average molec-
ular mass [88].
Figure 10. Effect of inhibitors and retarders
a) No retarder or inhibitor ; b) With retarder; c) With in-
hibitor Chain Transfer to Small Molecules
During free-radical polymerization, chain trans-
fer to small molecules X may occur. The small
molecule may be initiator, monomer, chain-
transfer agent, solvent, inhibitor, or impurity. In
general, these chain-transfer reactions can be re-
presented by Equations (2.21) and (2.22).
Polymerization Processes 21
When K

is approximately zero (i.e., X

is a
stable radical) X is called an inhibitor. If K

smaller than the propagation rate constant K
X is called a retarder. Idealized behavior of in-
hibitors and retarders is shown schematically in
Figure 10. The kinetics of inhibition and retar-
dation can be found elsewhere [127].
For an added agent to be a chain-transfer
agent, K

must be approximately equal to K
(or K

, if chain length is large enough).
Therefore, the chain-transfer agent reduces the
molecular masses but does not affect rates of
The chain-transfer rate constants for most
monomers are about 10
times smaller than
the propagation rate constant (K

The presence of monomer molecules is in-
evitable, so that the value of K
places an
upper limit on the polymer molecular mass that
can be obtained with a given monomer. Larger
values are observed when the propagating
radicals have very high energies (high reactivi-
ties), such as in the case of ethylene, vinyl ac-
etate, and vinyl chloride. Kinetics of Linear Polymerization
The elementary reactions involved in linear free-
radical polymerization (chains produced are lin-
ear with no branches or cross-links) are as fol-
Chain transfer to monomer
Chain transfer to small molecule (T)
Termination by disproportionation
Termination by combination
To derive the kinetic rate equations, the fol-
lowing assumptions are usually made:
1) All rate constants are independent of chain
2) Chain lengths are sufficiently large that the
total rate of monomer consumption may be
equated to the rate of monomer consump-
tion by the propagation reactions alone [this
is often called the long-chain approximation
3) Radicals generated in chain-transfer reac-
tions propagate with monomer rapidly and
thus do not affect the polymerization rate.
4) The stationary-state hypothesis (SSH) is
valid for radical reactions. One can therefore
assume that both the rates of radical genera-
tion and consumption are much greater than
the rate of change of radical concentration
with respect to time [128], [129].
Let us first derive an expression for the poly-
merization rate R
, applying the above assump-
tions. The balanced equation for polymer radi-
cals with chain length r is given by
= R


] [M] −K
] [T] −K
] [M]
− (K
) [R
] [R
] (2.36)
d (V [R
[M] −K
] [M]
] [M] −K
] [T]
− (K
) [R
] [R
] (r ≥2) (2.37)
where R
is the initiation rate (R
=2 K
f [I])
and [R
] =

], which is the total polymer
radical concentration. The transfer radical con-
centration [T

] is given by
22 Polymerization Processes
d (V [T
] [T] −K

] [M] (2.38)
Applying the stationary-state hypothesis gives
] [T] =K

] [M] (2.39)
Summation of Equations (2.36) and (2.37) over
all chain lengths (1 to infinity) and substituting
Equation (2.39) into the sum gives
d (V [R

d (V [R

] [M] −K
] [T] − (K
) [R
− (K
) [R
Application of the stationary-state hypothesis
for the total polymer radical concentration [R

where K
. In the above formalism,
the termination rate, R
is given by
It is worth noting here that R
=2 K

is of-
ten used in the literature, although R

is more widely used in free-radical polymeriza-
tion (e.g., the compilation of kinetic rate con-
stants in [130]). One must distinguish carefully
which type of termination rate constant is being
used when consulting the literature on polymer-
ization kinetics.
From Equation (2.41), the total polymer rad-
ical concentration is given by
] = (R
Based on the long-chain approximation, the
polymerization rate R
is given by
= −
d (V [M])
] [M]
[M] (2.44)
Since R
= 2K
f [I] ,
f [I])
[M] (2.45)
Equation (2.45) predicts a first-order depen-
denceon monomer concentration and a square-
root dependence on initiator concentration, the
latter being a direct consequence of the bimo-
lecular nature of the termination reaction.
Now consider the weight chain length dis-
tribution W (r). Application of the stationary-
state hypothesis for polymer radicals with chain
length r (Eq. 2.36 and 2.37) gives.
] (2.46)
[M] [R
] +K
[T] [R
[M] +K
[M] +K
[T] + (K
) [R
] (2.47)
[M] +K
[M] +K
[T] + (K
) [R
Let us introduce the following dimensionless
τ =
] +K
[M] +K

] [M]; propagation rate

; rate of termination by dis-

; rate of termination by com-

] [M] +K

] [T]; rate of
chain transfer.
Since R
, Equations (2.46) and
(2.47) can be simplified as follows:
] =
τ +β
1+τ +β
] (2.50)
] =
1+τ +β
] = [R
] (τ +β) Φ
Φ=1/(1 +τ +β)
Now consider the production rate of polymer
molecules with chain length r, R
(r), which is
given by
Polymerization Processes 23
(r) =
d (V [P
= (K
[M] +K
[T] +K
]) [R

Substitutingfor [R

] usingEquation(2.52) gives
(r) (2.54)
] [M] (τ +β)
τ +
(τ +β) (r −1)
The instantaneous weight chain length distribu-
tion W (r) is therefore given by
W (r) =

(τ +β)
τ +
(τ +β) (r −1)

1+τ +β
= (τ +β)
τ +
(τ +β) (r −1)

If β ≪τ, that is most polymer chains are formed
by chain transfer and/or termination by dispro-
portionation, Equation (2.55) reduces to
W (r) =τ

Here, 1/(1 +τ) is the probability of growth for
a given polymer radical, and τ/(1 +τ) is the
probability that a polymer radical stops grow-
ing. Therefore, Equation (2.56) is essentially the
same as the distribution derived for linear step-
growth polymerization (Eq. 2.9), based on a sta-
tistical argument.
It is sometimes more convenient to describe
the chain length distribution as a continuous
function rather than a discrete function, and this
can often be done with small error as r is usually
very large. Therefore, the following approxima-
tion may be useful:
W (r) ≈(τ+β)
(τ+β) (r −1)
· exp {− (τ +β) r} (2.57)
Note that (τ +β) has the value of ca. 10

for usual free-radical polymerization
[(τ +β) ≪1].
The weight-average chain length P
polymer produced instantaneously is given by

rW (r) =
τ (2+τ +β) +β (3+τ +β)
(τ +β)

2τ +3β
(τ +β)
The instantaneous number-average chain length
is given by

W (r) /r
(1+τ +β)
(τ +β/2)

(τ +β/2)
The polydispersity index PDI for polymer pro-
duced instantaneously is given by

(2τ +3β) (τ +β/2)
(τ +β)
If β =0, i.e., termination by combination does
not occur, the polydispersity index takes on the
maximum value, PDI =2. On the other hand, if
τ =0, i.e., chain termination is solely by bimo-
lecular termination through combination, PDI
takes on the minimum value, 1.5. Figure 11
shows the PDI as a function of the fraction of
chain termination by bimolecular termination by
combination, β/(τ +β).
Figure 11. Effect of the type of chain termination on the
polydispersity index
The W (r), P
, P
, and PDI derived here
give the instantaneous properties. In linear free-
radical polymerization the polymer molecules
once formed are inert and do not react further.
24 Polymerization Processes
In general, since the concentrations of monomer,
initiator, and chain-transfer agent change with
time, the chain length distribution of the ac-
cumulated polymer is always broader than the
instantaneous distribution. Particularly, when
bimolecular termination is strongly diffusion
controlled and most of the polymer chains are
produced by bimolecular termination, the accu-
mulated distribution broadens significantly with
increasing conversion. The polydispersity index
PDI for commercial polymers is usually larger
than two and this is the result of a drift in mo-
lecular mass averages of the instantaneous dis-
tribution. The accumulated distribution and its
averages can be calculated as follows:
W (r) =
W (r) dx (2.61)
dx (2.62)
Superscript bars denote accumulated properties.
These integrals may be replaced with equiva-
lent ordinary differential equations which then
can be solved by using readily available differ-
ential equation solvers. The variation of the ki-
netic parameters of W (r) with respect to con-
version must be known to calculate the accumu-
lated properties. In a similar manner, accumu-
lated molecular mass properties may be calcu-
lated for semi-batch and continuous reactors. In
a well mixed flowreactor with an ideal residence
time distribution (CSTR), the chain length dis-
tribution produced is the instantaneous distribu-
tion. In batch reactors the distribution is there-
fore broader [131], [132]. Other mathematical
techniques to derive the distribution functions
can be found elsewhere [29], [32], [33], [133–
135]. Effect of Temperature
In free-radical polymerization initiated by the
thermal decomposition of an initiator, the poly-
merization rate is given by Equation (2.45), and
the effect of temperature can be estimated by
the change in the ratio of three rate constants,
. Since each kinetic rate constant
is considered to follow the Arrhenius equation,
the activation energy of polymerization E
given by

where E
, E
, E
are activation energies for
propagation, initiator decomposition, and bimo-
lecular termination. Typical values for E
, E
are 30, 120, and 15 kJ/mol, respectively.
Therefore, E
is ca. 80 kJ/mol and this is largely
due to the very high activation energy for ini-
tiator decomposition. The high activation en-
ergy for polymerization means that the rate of
polymerization increases strongly with increas-
ing temperature. With redox initiation, E
ca. 40 kJ/mol and therefore E
is considerably
smaller at ca. 40 kJ/mol. With radiation initia-
tion, E
is close to zero and E
is ca. 20 kJ/mol.
Nowconsider the effect of temperature on the
molecular mass of polymer obtained. For a sim-
ple example, consider the case where τ ≪β, that
is, termination by combination produces most of
the polymer chains. Equation (2.58) gives

f [I] /K

The activation energy for average chain lengths
is given by


With initiators E
is about −40 kJ/mol. The av-
erage chain lengths decrease significantly with
increasing temperature when initiators are used
and bimolecular termination controls molecular
mass development (most of the polymer chains
are produced by bimolecular termination). With
radiation initiation, E
is about 20 kJ/mol and
molecular masses increase moderatelywithtem-
When unimolecular termination (chain trans-
fer to small molecules) dominates in the produc-
tion of polymer chains, E
is given by
Polymerization Processes 25
where E
is the activation energy for the chain-
transfer reaction. E
depends on the type of
chain-transfer agent, but usually E
andtherefore molecular masses usuallydecrease
with increasing temperature when unimolecular
termination (chain transfer to small molecules)
controls molecular mass development. Branching Reactions
For the elementary reactions shown in Sec-
tion, radical centers are always located
on chain ends, and the dead polymer chains are
chemically inert and are all linear. Branched
or cross-linked polymer can be obtained by
chemical treatment of linear chains using pro-
cesses such as vulcanization, radiation, and melt
processing with peroxides. This section, how-
ever, is mainly concerned with branching reac-
tions which may occur during polymerization.
Branched and cross-linked polymers are of sig-
nificant commercial interest, but quantitative in-
terpretation has been limited due to a lack of an-
alytical techniques for the comprehensive char-
acterization of branched polymers. Some of the
newer analytical techniques are summarized in
Chain Transfer to Polymer. Chain transfer
to polymer involves the abstraction of an atom
from the backbone of a polymer chain and re-
sults in the formation of a backbone radical cen-
ter. Monomer addition to this radical center pro-
duces a tri-branching point and a long-chain
branch whose average length is equal to that of
the primary chains produced at the same instant.
Chain transfer to polymer may be neglected
at lowmonomer conversions as polymer concen-
trations are low. However, under more practical
situations where polymerizations are carried to
very high conversions, it may be important. In
emulsion polymerization the polymer concen-
tration in polymer particles is relatively high
even near zero conversion and therefore long-
chain branching reactions are more significant
in emulsion than in solution or bulk polymer-
ization. Examples of monomers for which long-
chain branching via chain transfer to polymer is
important include ethylene and vinyl acetate.
When long-chain branching is important the
calculation of the full molecular mass distribu-
tion requires excessive computation. However,
the leading moments and molecular mass av-
erages can be readily calculated by using the
method of moments for an infinite set of dif-
ferential equations which describe the chemical
kinetics [61], [134], [139–147]. The i-th order
moment of the polymer distribution can be de-
fined by

] (2.70)
Therefore, the number- and weight-average
chain lengths of the accumulated polymer are
given by
, respec-
tively. For the elementary reactions shown in
Section plus Equation (2.69), some of the
lower order moments for batch polymerization
are given by [61], [145–147]:
d (V Q
=τ +β/2 (2.71)
d (V Q
= 1 (2.72)
d (V Q
2 (1+C
τ +β+C
β (1+C
(τ +β+C
with initial conditions: Q
=. . . . . . =0 at
x =0, where
τ =
] +K
[M] +K
and V
is the initial volume of the reacting mix-
ture. Figure 12 shows calculated weight-average
chain lengths for a range of the kinetic parame-
ters, keeping τ and β constant with conversion.
Note that reactions involving the addition of a
26 Polymerization Processes
polymer radical center to a double bond on the
end of a polymer chain are not accounted for in
the moment equations above (Eq. 2.71and2.73).
Figure 12. Weight-average chain length development dur-
ing polymerization with chain transfer to polymer [147]
It is of interest to know whether chain trans-
fer to polymer can lead to gelation. Flory [148],
[149] predicted that this reaction type would not
cause gelation without the assistance of other in-
terlinking processes. By application of Equation
(2.73) it has been clearly shown that chain trans-
fer to polymer plus termination by dispropor-
tionation (i.e., there is no termination by com-
bination) can never cause gelation. With termi-
nation by combination, however, gelation can
occur under certain circumstances [61], [145],
In general, when long-chain branching oc-
curs, the molecular mass distribution broadens.
This is especially true for polymerization in a
continuous stirred-tank reactor as the reacting
mixture always has a relatively high polymer
concentration. Comparing long-chain branching
frequencies in batch and CSTR reactors at the
same monomer conversion levels shows that the
residence time distribution of the CSTR favors
branching [150], [151].
Figure 13. Effect of temperature on the number-average
chain length of polyisobutylene and isobutene – isopropene
copolymer [161]
a) Polyisobutylene with AlEtCl
as initiator; b) Polyiso-
butylene with BF
as initiator; c) Polyisobutylene with
as initiator; d) Isobutene – isopropene with BF
initiator; e) Isobutene – isopropene with AlEtCl
as initia-
tor; f) Isobutene – isopropene with AlCl
as initiator
When the reactivity of polymer radicals
is high (as with polyethylene), intramolecu-
lar chain transfer (transfer to a location on its
own chain) or backbiting may occur. In this
case polymer chains with short branches are
formed. In the synthesis of low-density poly-
ethylene (LDPE) by high-pressure free-radical
polymerization, short-chain branching frequen-
cies are high (typically 20 – 40 branches per
1000 backbone carbon atoms). For polyethyl-
ene, the amount of short-chain branching is
about ten times greater than long-chain branch-
Polymerization Processes 27
ing. For polyethylene the backbiting reaction
can be represented as follows
with n =3 and 4 most probable [152].
Reactions with Double Bonds in Polymer
Chains. When a radical center on the end of
a polymer chain adds to a double bond on the
end of a polymer chain, a tri-branching point is
Terminal double bonds on the ends of poly-
mer chains may be formed by chain transfer
to monomer, termination by disproportionation,
and by β-scission at backbone radical centers.
Reaction with double bonds located on the
polymer backbone (internal or pendant double
bonds) leads to formation of tetra-branching
Pendant double bonds are obtained when
monomers containing two or more reactive dou-
ble bonds are polymerized. For example, the
homopolymerization of a diene and the co-
polymerization of vinyl and divinyl monomers
produces polymer chains with pendant double
bonds. The photopolymerization of multifunc-
tional monomers is used in surface coatings and
in the replication of optical discs [153–155]. For
densely cross-linked systems the buildup of rad-
ical concentration is so rapid that the stationary-
state hypothesis may not be valid. Superab-
sorbent polymers used in diapers and porous or-
ganic packagings used in size exclusion chro-
matography are lightly cross-linked polymeric
networks. The kinetics of copolymerization of
vinyl and divinyl monomers are discussed in
more detail in Section 2.3.3.
2.2.2. Ionic Polymerization
The energy required to form a pair of ions from
a neutral molecule is large, and therefore these
very unstable ions must be stabilized by sol-
vation at low temperature before polymeriza-
tion will occur. Polar solvents cannot be used
to solvate ions because they are overly reactive
and destroy the ionic initiators. Ionic polymer-
izations are usually carried out at low tempera-
ture in solvents of low polarity. These solvents
may give ion pairs as well as free ions. Thus,
a propagating ionic chain may have a counter-
ion close to the active center during its growth.
The proximity of the ion on the growing chain
to its counterion depends on the type of coun-
terion, which is determined by the initiator type,
and the solvation power of the solvent. There-
fore, unlike free-radical polymerization the type
of initiator and the nature of the solvent have a
large effect on monomer addition during chain
growth. The propagation rate constant, there-
fore, depends not only on temperature but also
on the type of initiator and the type and amount
of solvent.
For ionic chain-growth polymerizations in
solvents with high solvating power where the
distance between the propagating active cen-
ter and the counterion is large, the factors gov-
erning the stereochemistry are similar to those
for free-radical polymerization. However, in sol-
vents with poor solvating power, there may be
extensive coordination between initiator, propa-
gating chain end, and monomer, which results in
isotactic (or syndiotactic) placements almost ex-
clusively, i.e., stereospecific polymerization oc-
Unlike radical polymerization, bimolecular
termination between active centers does not oc-
cur in ionic polymerization. Termination of an
active center on a polymer chain occurs by reac-
tion with the counterion, solvent, monomer, or
other species. Often, the initiation reactions are
very fast, and the initiator is consumed in the
28 Polymerization Processes
early stages of polymerization before the poly-
mer chains have grown much beyond oligomeric
size. In the absence of unimolecular termina-
tion a population of polymer chains having the
same molecular mass can grow. The concentra-
tion of ionic reactive centers is usually much
larger than that of radical centers. Ionic poly-
merization kinetics are not as well understood
as those radical-based polymerizations because
of the requirements of extreme purity for the
components of the reacting mixture.
Elastomers such as butyl rubber and poly-
isoprene; high-density polyethylene; polypro-
pylene and its copolymers are widely produced
by ionic polymerization. Polypropylene of high
molecular mass cannot be produced by radical
polymerization. In addition to carbon – carbon
double bonds, carbonyl double bonds [81], [82],
alkynes [156], and carbon – nitrogen double
bonds [157] can be polymerized via ionic mech-
anisms. However, the discussion here is limited
to carbon – carbon double bonds. Cationic Polymerization
Cationic polymerization proceeds through at-
tack on the monomer by an electrophilic species,
resulting in heterolytic splitting of the double
bond to produce a carbenium ion [158], [159].
The most important commercial high poly-
mers produced by cationic polymerization are
polyisobutylenes and butyl rubber (a copoly-
mer of isobutylene and a 1,3-diene, usually iso-
prene). A typical polymerization is carried out
at about −100

C in chlorinated solvents such
as chloromethane and is initiated by AlCl
. The
polymerization is very fast.
In the following section, interesting features
of cationic polymerization are discussed, but no
attempt is made to develop quantitative rate ex-
pressions. Carbenium ions are very sensitive to
polar impurities and this often precludes the es-
tablishment of a stationary state. It is also diffi-
cult to establish what proportion of the initiator
produces growing polymer chains.
Cationic polymerization of vinyl monomers
is essentially limited to those with electron-
donating substituents such as 1,1-dialkyl,
alkoxy, phenyl or vinyl groups. Cationic poly-
merization involves initiation, propagation, ter-
mination, and chain transfer to small molecules
much as in free-radical polymerization.
To initiate cationic polymerization, protonic
acids such as H
, HClO
, and H
Lewis acids such as BF
, AlCl
, TiCl
, and
are used. Lewis acids are by far the most
important initiators for industrial cationic poly-
merizations. Initiation with Lewis acids requires
the presence of a trace of proton donor such as
water, alcohol, andorganic acidor a cationdonor
such as alkyl halide.
In general,
Most polymerizations exhibit a maximum
rate at some ratio of initiator and coinitiator con-
centrations. This optimum ratio varies widely
fromone initiator systemto another and in some
instances the solvent has an effect on the ratio.
(Note that it has also been proposed that the pro-
togen or catinogen be referred to as the initiator,
and the Lewis acid as coinitiator [159], although
conventional terminology is exactly the reverse.)
The propagationreactioninvolves the succes-
sive insertion of monomers into the partial bond
between the propagating species and its coun-
Polymerization Processes 29
The apparent propagation rate constant K
depends on the type of initiator and solvent used.
In general, K
becomes larger as the acidity of
the initiator and/or the dielectric constant of the
solvent increases. This is due to the fact that the
reactivity of free ions in monomer addition is
much greater than that of ion pairs.
A wide variety of reactions may lead to ter-
mination of chain growth in cationic polymer-
ization, but it is usually ambiguous and difficult
to distinguish termination reactions from chain-
transfer reactions. Chain transfer to monomer is
most often responsible for the formation of dead
If the counterion is sufficiently nucleophilic,
termination by combination may occur:
However, this reaction is not very common.
In fact, true termination in which the activity of
a chain carrier is lost without regeneration of
an active center is very rare if no impurities ca-
pable of destroying an active center are present.
However, since the carbeniumion is highly reac-
tive, it would be a formidable task to remove all
these impurities from the reaction components.
Under commercial conditions it is likely that ac-
tive centers are consumed to a significant extent
by impurities. Termination reactions in cationic
polymerizations are unimolecular, as they are
in anionic and in anionic-coordination polymer-
ization. Generally, for cationic systems the poly-
merization rate is given by
=K [M]
[I] (2.85)
The first-order rate with respect to initiator con-
centration is a consequence of the fact that ter-
mination reactions are unimolecular. The overall
activation energy for polymerization E
may be
ca. −40 to 60 kJ/mol [160]. For many polymer-
ization systems E
is negative and the rather un-
usual phenomenon of increasing polymerization
rate with decreasing temperature is observed.
The activation energy for the degree of poly-
merization is always negative, and therefore the
average chain length decreases with increasing
temperature. Usually, cationic polymerizations
can produce polymer with sufficient molecular
mass only at very low temperatures. Figure 13
shows the Arrhenius plot for the number-average
chain length [161]. There is a change in the slope
of this plot around −100

C. This has been at-
tributed to a change in the chain termination step
fromchain transfer to monomer below−100

to chain transfer to solvent above −100

Table 1. Effect of counterion on the propagation rate constants (K

and K
) in the anionic polymerization of styrene in THF at 25

Counterion K

K ×10
160 6.5 ×10
80 6.5 ×10
60 – 80 6.5 ×10
50 – 80 6.5 ×10
22 6.5 ×10
0.02 Anionic Polymerization
Anionic polymerizations show many of the
same characteristics as cationic polymeriza-
tions. However, since the nature of carbanions
is different from carbenium ions, there are dis-
tinct differences. In contrast to cationic poly-
merization, neither termination nor chain trans-
fer occur in many anionic polymerizations (liv-
ing polymerization) especially when polar sub-
stances are absent. Anionic active centers are
usually much more stable than cationic active
centers. Although anionic polymerizations pro-
ceed rapidly at low temperatures, they are not
usuallyas temperature sensitive as cationic poly-
merizations, and polymerizations usually pro-
ceed well at ambient temperature and higher.
A variety of basic initiators have been used
to initiate anionic polymerizations [162], [163].
The initiation involves the addition of an anion
(base) to the double bond of the monomer.
where the C

· · · G
bond can have character
ranging from partially covalent to completely
ionic. Alkyllithium initiators have been most
widely used in the polymerization of butadiene
and isoprene, since they are easy to prepare and
are soluble in hydrocarbon solvents. A compli-
cation which arises when alkyllithiums are used
30 Polymerization Processes
in nonpolar solvents such as benzene, toluene,
cyclohexane, and n-hexane is association of var-
ious organolithium species. This phenomenon
is important, since the associated species are es-
sentially unreactive in propagation [162], [164].
Propagation occurs by the successive inser-
tion of monomers into the partial bond between
the propagating anion and its cationic counter-
The polymerization rate is fundamentally ex-
pressed by R
[M] [M

], where [M

] is
the concentration of active species. When non-
polar solvents suchas dioxane are used, all active
species may be ion pairs. However, in polar sol-
vents such as THF, the effect of dissociation to
free ions on polymerization rate cannot be ne-
glected. Therefore, the propagation rate is given
by the sum of the rates for free propagating
anions (R

) and for ion pairs, R



[M] +K

[M] (2.88)
The two propagating species are in equilibrium,
where K is the dissociation constant and is given

_ _

Some experimental values for K
and K

are listed in Table 1 [165], [166]. Consider
the simple example of the anionic polymeriza-
tion of styrene in THF at 25

C, initiated by
sodiumnaphthalide with an initial concentration
[I] =1 ×10
mol/L. Assuming the initiation
reaction is instantaneous, [R

] = 1.22 ×10
and [R

)] = 9.88 × 10
mol/L. There-



)] [M]
6.5 × 10
_ _
1.22 × 10
9.88 × 10
= 10.0 (2.91)
As shown here, although the concentration of
free ions is only 1.2 % of the total propagating
species, approximately 90 % of the monomer is
consumed by the free ion.
Since carbanions are relativelystable, anionic
polymerization with carefully purified reagents
may lead to systems in which chain termination
is absent. Such polymers are referred to as living
polymers [167], [168].
Let us now develop an expression for the
chain length distribution for living polymer. As-
suming that initiation is instantaneous, the to-
tal number of growing chains N
is constant
throughout the polymerization. Nowa monomer
molecule adds to a polymer chain as shown in
Figure 14. The probability that it adds to poly-
mer chain (1) is 1/N
, and that it does not add to
polymer chain (1) is 1 −1/N
. Therefore, when
monomer units have been consumed and
bound into polymer chains the probability that
a randomly selected polymer chain possesses r
monomer units is given by a binomial distribu-
N (r) =
N (r) is also the number chain length distribu-
tion. Since 1/N
≪1 and r is large, the binomial
distribution reduces to the Poisson distribution:
N (r) =
where η =N
, which is equal to the number-
average chain length,
Figure 14. Schematic drawing for the derivation of chain
length distribution in living polymerization
The weight chain length distribution W (r)
and the weight-average chain length
given by
Polymerization Processes 31
W (r) =
rN (r)

rN (r)
(r −1) !

rW (r) =η+1 (2.95)
Therefore, the polydispersity index PDI is given
= 1 + 1/
With sufficiently large average chain length, the
polydispersity should approach unity. To obtain
a narrow molecular mass distribution (MWD),
the rate of initiation should be greater than the
rate of propagation. Polystyrenes having poly-
dispersity as low as 1.01 have been synthesized
by using sodium naphthalide as initiator, and
these are widely used in the calibration of gel
permeation chromatography. It is of interest to
note that narrow MWD can be obtained even
when there are two reactive site types (free ion
and ion pair). This is a result of the equilibrium
between the site types, and growing chains will
have both site types attached to their ends for the
same fraction of time during their growth.
Sequential addition of monomers to a liv-
ing anionic polymerization system is at present
the most useful method for synthesizing well-
defined block copolymers. Ziegler – Natta Polymerization
Due to the interactions between the propa-
gating chain end, counterion, and incoming
monomer molecule, ionic polymerizations tend
togive stereospecific polymers. Polar monomers
such as methacrylates and vinyl ethers undergo
stereospecific polymerization initiated by con-
ventional ionic initiators under certain condi-
tions. However, the coordinating power of the
Ziegler – Natta initiators is much stronger than
the usual ionic initiators, so it is appropriate
to treat Ziegler – Natta (ZN) systems separately.
The use of ZN initiators for diene polymeriza-
tion has yielded remarkable results that far sur-
pass the stereospecificity exhibited by organo-
lithium initiators. With butadiene, four different
stereospecific polymer structures, namely, cis-
1,4, trans-1,4, syndiotactic-1,2, and isotactic-
1,2 can each separately be obtained to almost
total exclusion of the others by an appropriate
choice of initiator system, as shown in Table 2
The ZNinitiators are the only ones which can
be used to polymerize α-olefins such as propene
and 1-butene. Although the phenomenon of
stereoisomerismis not applicable tothe symmet-
rical ethylene, the use of ZNinitiators produces a
polyethylene with much less long-chain branch-
ing than that obtained by free-radical polymer-
The ZN initiators consist of a combination of
alkyls or hydrides of group1 – 3metals withsalts
of group 4 – 8 metals. Some of the components
of ZN initiators are as follows:
Group 1 – 3 metal Transition metal
Al, (C
AlCl TiCl
, TiCl
, VCl
, (C
, Ti(OC
Na CrCl
, MnCl
The titanium– aluminum initiator systems,
especially (C
Al – TiCl
, have been most
thoroughly studied. Many important ZN initia-
tors are solids and during polymerization are
suspended in liquid or gaseous media. Hetero-
geneous initiator systems appear to be neces-
sary for the production of isotactic polyolefins,
although soluble initiators are used for the syn-
thesis of syndiotactic polypropylene.
Discussions on the mechanism of ZN poly-
merization can be found elsewhere [169–173].
At present, however, none of the proposed mech-
anisms have been comprehensively verified and
the observed kinetics are usually quite complex.
Some examples of the initial stages of heteroge-
neous ZNpolymerizationare showninFigure 15
[174]. The particles of the transition metal com-
ponent usually consist of aggregates of smaller
crystals, so that when the particle size of the
transition metal component is relatively larger
(curves c and d), the mechanical pressure of the
growing polymer chains cleaves the particles.
This increases both the surface area of the initia-
tor and the number of active sites. After this ini-
tial period, a steady-state rate may be observed.
The time required to reach this steady-state can
be reduced by initially using smaller particles.
When the transition metal particles are ground
or crushed to a very small size just before the
polymerization, the rate of polymerization in-
creases rapidly and exceeds the steady-state val-
ues (curves a and b). This phenomenon may in-
32 Polymerization Processes
Table 2. Stereospecific polymerization of butadiene [169]
dicate the existence of highly active but short-
lived sites. This kind of behavior can be avoided
by aging the initiator system prior to addition of
Figure 15. Effect of previous physical treatment on a sample
of α–TiCl
on the propene polymerization rate (in grams
per gram TiCl
per hour) at constant pressure and
a), b) Ground α–TiCl
(sizes ≤2 µm); c), d) Unground α–
(sizes 1 – 10 µm)
Many ZN polymerizations exhibit a contin-
uous decrease in rate rather than reaching a
steady-state in which the rate curve reaches a
maximum and then continues to decline. The
rate of decline varies with the polymerization
system used. The decline in polymerization rate
has been attributed to (1) a decrease in the num-
ber of active centers, (2) a lowering of activ-
ity of individual active centers due to structural
changes, and (3) a lowering of activity of in-
dividual active centers due to encapsulation by
In this section a very simple example is con-
sidered, too approximate to accurately describe
real systems, but useful to illustrate a model
building process. Consider the following poly-
merization scheme [175].
1) Adsorption of monomer (M) on the active
where P

is a growing chain with unit chain
length and A is a vacant active site.
2) Propagation
where P

is the growing polymer chain with
length r
3) Desorption of polymer chain from the active
where P
is a dead polymer molecule with
chain length r.
Assuming that the polymer chain is suffi-
ciently long (long-chain assumption), the poly-
merization rate R
is given by

] [M] (2.100)
where [P∗] is the total concentration of active
sites, namely, [P

] =


] .
Polymerization Processes 33
If the stationary-state hypothesis is applied to
[M] [A] =K

] (2.101)
Each active site is either occupied by growing
polymer chains or is vacant. Denoting the total
concentration of adsorption sites by [A]
= [A] + [P

] (2.102)
Combining Equations (2.101) and (2.102) gives

] =K [A]
[M] / (1+K [M]) (2.103)
where K =K
. Therefore, the polymeriza-
tion rate is given by
K [A]
[M] / (1+K [M]) (2.104)
Next consider the instantaneous molecular mass
distribution for this process. The population bal-
ance equations for growing polymer chains are

[M] [A]
[M] [P

] −K

] (2.105)
d (V [P


[M] [P


] (r ≥2) (2.106)
By application of the SSH for [P


] =

[A] (2.107)

] =


where τ

[M]). Therefore,
] =K

] =K

where Φ

=1/(1 +τ

The number and weight chain length distri-
butions are given by
N (r) =


_ _

W (r) =
r [P

r [P


where Φ

is the probability that a growing poly-
mer chain adds another monomer molecule, and
(1 −Φ

) is the probability that a growing chain
stops growing.
Therefore, Equations (2.110) and (2.111) are
essentially the same as Equations (2.8) and (2.9)
or Equation (2.56). The polydispersity index
(PDI) for instantaneously formed polymer is
An interesting feature of heterogeneous ZN
initiators is the verybroadMWDof the polymers
produced, although the above simple model pre-
dicts PDI =2 for instantaneously formed poly-
mer. The PDI of accumulated polymer may be
10 or higher. In the case of copolymerization, the
compositional heterogeneity is also large even
when monomer ratios are kept constant during
polymerization. Presently, there are two main
theories which try to explain these large disper-
sities, namely, the presence of a distribution of
activities for the active sites or diffusional ef-
fects which limit the transport of reactants to the
active sites [176].
2.3. Copolymerization
Copolymerization permits the synthesis of an al-
most unlimited number of polymer types and is
therefore often used to obtain a better balance of
properties for commercial applications. Copoly-
mers may be synthesized by chain-growth
and step-growth polymerization. In step-growth
polymerization, different monomers with the
same type of functional group generally show
only minor differences in reactivity. As a result,
most copolymers prepared by step-growth poly-
merization contain essentially random place-
ments of repeat units, with the composition of
the copolymers essentially the same as those of
the original monomer mixture.
In contrast, strong selective effects often oc-
cur in chain-growth copolymerizations, and the
composition of the copolymer formed may dif-
fer greatly from the composition of the origi-
nal monomer mixture. This section deals ex-
clusively with chain-growth copolymerization.
Chain-growth copolymerization can be carried
out with various types of active centers including
free-radical, cationic, and anionic species. Free-
radical copolymerization is most commonly
used due to its higher alternating tendencies.
34 Polymerization Processes
2.3.1. Copolymer Composition
The composition of copolymers cannot be de-
termined from a knowledge of the homopoly-
merization rates of each monomer. In 1944,
the instantaneous copolymer composition equa-
tion was proposed independently by several re-
searchers by assuming that the chemical activity
of a propagating chain depends solely on the ter-
minal monomer unit on which the active center
is located [177–180]. This model is called the
terminal model, and the copolymer chain can
be considered as a first-order Markov chain. For
binary systems, the following four propagation
reactions are possible.
where P

is a live copolymer chain with m
units of monomer 1(M
) andnunits of monomer
2 (M
) bound in the polymer chain and with the
active center located on terminal monomer unit
The reactivity of the propagating species may
be affected by the penultimate monomer unit. In
such cases, the model is referred to as the penul-
timate model or a second-order Markov chain
[181], [182] and propagation consists of eight
reactions. Further expansion is possible by con-
sidering the effects of remote units preceding the
penultimate unit, such as the pen-penultimate
model [183–185].
It is customarily assumed that the propa-
gation rate constants are independent of chain
length and that the chains are sufficiently large
( long-chain assumption, LCA). The LCA in-
cludes the approximation that monomer con-
sumedinreactions other thanpropagationis neg-
ligible and that the SSH is valid for each type
of active center; i.e., the rate of formation of
any type of active center is equal to its rate of
consumption. Statistically, these conditions are
equivalent to the statistical stationary condition
Now consider a binary copolymerization
whose propagation reactions follow the termi-
nal model. The specific polymerization rates of
monomers 1 and 2 are given by

d (V [M

] [M
] +K

] [M

d (V [M

] [M
] +K

] [M
where [P

] and [P

] are the total concentrations
of active centers of types 1 and 2 with

] =




] =



Application of the SSH gives

] [M
] =K

] [M
] (2.120)
Dividing Equation (2.116) by Equation (2.117)
and using Equation (2.120) gives the instanta-
neous copolymer composition equation:
−d (V [M
−d (V [M
] (r
] + [M
] ([M
] +r
where F
and F
are the mole fractions of
monomers 1 and 2 in the copolymer produced
instantaneously, and f
and f
are the mole frac-
tions of unreacted monomer. The reactivity ra-
tios are defined by
It is straightforward to extend this method
to multicomponent polymerization [188–190].
Note that Equation (2.121 a or b) is strictly valid
only for infinitely long polymer chains and its
application to short chains may introduce sig-
nificant error [191–193].
When applying Equation (2.121 a or b), it is
usually assumed that all of the copolymer chains
Polymerization Processes 35
have the same composition. However, since the
chain length of a copolymer is finite, the compo-
sition and chain lengths of the individual poly-
mer molecules cannot all be identical. Therefore,
for copolymer chains produced instantaneously
there is a bivariate distribution of composition
and chain length [194–200]. The variance of the
copolymer composition distribution is approxi-
mately inversely proportional to the chain length
and, therefore, for sufficiently long chains it may
be reasonable to neglect the composition distri-
bution. In order to treat oligomeric molecules,
application of discrete mathematics such as the
finite Markov chain theory [184], [201] is nec-
In batch copolymerization, there is a compo-
sitional drift due to the change in the compo-
sition of the unreacted monomer mixture with
time. The total monomer conversion x is related
to the mole fraction f
of unreacted monomer 1
by the following equation [202]:
, F
at x= 0.
Therefore, if the relationship between f
is known, Equation (2.124) can be solved
numerically. If the terminal model is applicable
to a binary system (Eq. 2.121 a or b), Equation
(2.124) can be integrated analytically to obtain
the following equation [203–208]:
x= 1−
/(1 −r
β =r
/(1 −r
γ =(1 −r
)/{(1 −r
) (1 −r
δ =(1 −r
)/(2 −r
Except for copolymerizations at the
azeotropic point, there will be some composi-
tional drift. (At the azeotropic point, the compo-
sition of the instantaneously produced copoly-
mer and of the unreacted monomers is the same;
hence ina batchreactor there is nocompositional
drift at this point.) An example of compositional
drift during batch polymerization is shown in
Figure 16 [208]. One method to avoid compo-
sitional drift is to use a continuous stirred-tank
reactor with an ideal residence time distribution.
In this instance, the Stockmayer instantaneous
bivariate distribution of chain length and com-
position will be obtained. Another method of
composition control is to use semi-batch oper-
ation in which monomers are fed to maintain a
constant ratio of monomer concentrations in the
reactor [209], [210].
Figure 16. Batch copolymerization of styrene (M
) and
methyl methacrylate (M
) at 60

Cfor f
=0.8, f
=0.53, r
and F
are the accumulated mole fraction of monomer
1 and 2 bound in the copolymers.
In the terminal model, monomer sequence-
length distribution depends only on the product
of reactivity ratios r
[211], [212]. In free-
radical copolymerizations r
is generally less
than unity, indicating a higher alternating ten-
dency. The styrene – maleic anhydride system is
an example of a very highly alternating one with
both r
and r
very close to zero. For ionic co-
polymerizations, there is a general lack of any
tendency towards alternation, and r
is usually
close to or greater than unity. Generally, in free-
radical copolymerization, the reactivity ratios
are relatively insensitive to the reaction medium
and temperature. However, in ionic copolymer-
ization, temperature and reaction medium can
significantly affect reactivity ratios.
Traditional methods for estimating reactivity
ratios [177], [213–215] are based on the trans-
formation of the instantaneous copolymer com-
position equation into a form that is linear in the
parameters r
and r
. While these linearizations
provide simple techniques for parameter estima-
tion, they are generally statistically invalid be-
36 Polymerization Processes
cause the independent variable has experimental
error and the dependent variable does not have a
constant variance [216–223]. Both of the latter
assumptions are necessary for the linear least
squares method to be a statistically valid es-
timation method. Although it has been shown
that proper experimental design can allow the
use of linear least squares analysis [222], [224],
the estimation of the reactivity ratios is a typical
example of a problem in nonlinear estimation.
Reactivity ratios are now generally estimated
by application of procedures based on the sta-
tistically valid error-in-variables-model (EVM)
[220], [221], [225–230]. These methods allow
all the sources of experimental error to be ac-
counted for.
In spite of the fact that reactivity ratios ob-
tained using invalid estimation procedures have
often been used, the copolymer composition
equation based on the terminal model has given
useful predictions. It is generally ineffective to
use the copolymer composition equation for
comparing models. Information on the copoly-
mer microstructure (e.g., monomer sequence
length distribution) is needed to compare the va-
lidity of terminal and penultimate models [179],
[231], [232]. Advancements in NMRtechniques
have provided suitable information on sequence
length distribution. However, cases have been
reported in which sequence length distribution
information does not permit model discrimina-
tion [233].
As will be discussed in Section 2.3.2 the com-
position equation includes the rate constants of
elementary reactions only in ratios, while the
rate equation is dependent on their absolute val-
ues, and therefore success of the former equation
does not insure success of the latter [234].
2.3.2. Kinetics of Copolymerization
Consider the kinetics of free-radical copolymer-
ization of monomers M
and M
, assuming the
terminal model is applicable. Important elemen-
tary reactions are:
Transfer to monomer
Transfer to small molecule
Termination by disproportionation
Termination by combination
where R

m, n, 1
is a polymer radical with m units
of monomer 1 (M
) and n units of monomer 2
) bound in the polymer chain with active
center located on monomer unit 1. P
is a
polymer molecule with m units of monomer 1
and n units of monomer 2. The polymerization
rate, R
is given by
] [M
] +K
] [M
] [M
] +K
] [M
] [M] (2.126)
where [R

] and [R

] are given by
Equations (2.118) and (2.119) and
] = [R
] + [R
] , [M] = [M
] + [M
] , and
is defined by
= (K
) ϕ
+ (K
) ϕ
Polymerization Processes 37
where f
]/[M], and ϕ



Equation (2.127) is an example of a pseudo-
kinetic rate constant [145–147], [209], [210],
[235–238]. For an N-component system, the
pseudo-kinetic rate constants can be defined as

Chain transfer to monomer

Chain transfer to small molecule

Termination by disproportionation

Termination by combination

Even though these pseudo-kinetic rate constants
depend on the monomer mole fraction and
change with time in a batch reactor, the simpli-
fication achieved when dealing with multicom-
ponent polymerizations is very great. Further-
more, since the mole fraction of each polymer
radical type ϕ

is independent of chain length
for sufficiently long chains, these same pseudo-
kinetic rate constants can be used to calculate
molecular mass distribution as well as poly-
merization rate [61],[235] . Therefore, by us-
ingpseudo-kinetic rate constants, a multicompo-
nent polymerization reduces to a homopolymer-
ization, and therefore Equations (2.55) – (2.64)
are all applicable for copolymerization. With
appropriate definitions for pseudo-kinetic rate
constants, this method may also be usefully ap-
plied when copolymerization kinetics followthe
penultimate model [235].
In the early development of the kinetics of
copolymerization, chemically controlled bimo-
lecular termination was assumed to be operable
[239–241]. However, since these reactions have
been shown to be diffusion controlled [120–
122], [242], Equations (2.131) and (2.132) must
be modified by using appropriate models which
account for this. In this context, the use of the
cross-termination factor, ϕ=K
is not acceptable. Several models for diffusion-
controlled termination of binary copolymeriza-
tion have been proposed. Athertonand North
[243], [244] proposed the following for the ter-
mination constant.
The mole fractions of monomers bound in poly-
mer chains F
and F
can be calculated by us-
ing the copolymer composition equation. On the
other hand, Russo and Munari [245] proposed
the use of penultimate effect for the termination
reactions since segmental diffusion is highly de-
pendent on the last two portions of the chain.
Until the mid 1980s, a prevailing view of co-
polymerizationkinetics was that the propagation
process is, in most cases, correctly described by
the terminal model, whereas the terminationpro-
cess involves complexity still to be elucidated.
However, it has also been speculated that it is the
propagation step that needs further study, while
the termination step is well described by simple
models such as Equation (2.133), and the penul-
timate effect on propagation reactions is being
examined from the point of view of copolymer-
ization rates [233], [246–252].
2.3.3. Copolymerization of Vinyl and
Divinyl Monomers
The use of the terms vinyl and divinyl here is
not according to their strict definitions. Here, a
vinyl monomer is defined as a monomer with
a single reactive double bond (a double bond
which will readily add to a radical center) and a
divinyl monomer is a monomer which has two
such double bonds.
The free-radical copolymerization of vinyl
and divinyl monomers is important in the manu-
facture of ion-exchange resins, chromatographic
packings, superabsorbent polymers (with a
rapidly growing market in baby diapers and
38 Polymerization Processes
Figure 17. A schematic drawing of a cross-linked polymer network synthesized by free-radical copolymerization of vinyl and
divinyl monomer
promise of the same in several other market
areas), cross-linked latex polymers, and other
products. Figure 17 shows a schematic of a poly-
mer network synthesized by copolymerization
of vinyl and divinyl monomers. There may be
many radical centers on the polymer network
during polymerization since the mobility of rad-
ical centers chemically bound to the network
can be highly restricted. Strong autoacceleration
in polymerization rate has been reported during
network formation by free-radical copolymeri-
zation [253–260]. The live double bonds located
on polymer chains are called pendant double
bonds. Kinetic behavior of radical centers on
polymer chains and of pendant double bonds are
the most important factors influencing the ki-
netics of network formation during free-radical
polymerization. From the point of view of the
mobility of chains, network polymers may be
considered as a heterogeneous reaction system,
and the formation of microgels before the gel
point is reached may be a general feature of net-
work formation in free-radical polymerization
[257], [261–265]. The number-average molec-
ular mass between cross-links M
is important
from the point of view of the elastic properties
of a gel molecule. As the mole fraction of di-
vinyl monomer increases, the heterogeneity of
the polymer network (i.e., regions having very
different M
) becomes significant [265–268].
Reactivity ratios for the copolymerization of
vinyl and divinyl monomers are rather difficult
to determine. If the reactivities of both double
bonds on the divinyl monomer are the same and
independent, and cyclization does not occur, the
conventional copolymer composition equation
(Eq. 2.121 a or b) is still valid when monomer
concentration is replaced by double bond con-
centration and the reactivity ratios defined with
respect to each type of double bond are used
[269]. However, difficulties generally arise due
to the complicated behavior of pendant double
bonds, which may react inter- and intramolec-
ularly, and whose reactivity may differ from
that of monomer double bonds. At the moment
when a divinyl monomer is chemically bound
in a polymer chain, another double bond on the
just-reacted divinyl monomer may be the nearest
neighbour of the active center, and therefore cy-
clopolymerization may occur under certain con-
ditions. For example, the free-radical polymer-
ization of diallyl quaternary ammonium salts
gives soluble, not cross-linked polymers with lit-
tle or no residual unsaturation [270], [271].
Polymerization Processes 39
In general, cyclization may also involve two
or more monomer units. Since cyclization reac-
tions are controlled by the conformational statis-
tics of the sequence of bonds and do not follow
the conventional rate law, larger cycles, formed
when an active center adds to a pendant double
bond on its own chain or to two double bonds
on another chain, may also affect the copoly-
mer composition even when the terminal model
is applicable. Various copolymer composition
equations which account for cyclization reac-
tions have been proposed [272–276]; however,
it may be difficult to apply these equations to
higher mole fractions of divinyl monomer or to
high monomer conversions. Strictly speaking, in
order to know the copolymer composition, it is
necessary to know the kinetic behavior of pen-
dant double bonds completely; that is, a knowl-
edge of the reactivity ratios r
and r
is insuffi-
cient to estimate the change in composition dur-
ing copolymerization. However, r
and r
usually obtained without taking into account the
monomer consumed by active centers located on
just-reacted pendant double bonds. Such param-
eters may be better regarded as empirical param-
eters which do not reflect the chemical reactivity
of radical centers with double bonds, and they
may change with monomer conversion.
As for the kinetics of network formation,
fundamental models which assume an equilib-
riumsystem(see Section 2.1.3) have been exten-
sively applied to chain-growth polymerization
[39], [43], [51], [52], [148], [277–279]. How-
ever, chain-growth polymerizations are kineti-
cally controlled, so that the application of the
conventional approaches may be in error. It has
been shown that under Flory’s simplifying as-
sumptions, namely that (1) the reactivities of all
types of double bonds are equal, (2) all double
bonds react independently of one another, and
(3) there are no intramolecular reactions in fi-
nite molecules, the predictions of kinetic and
equilibrium models are the same [61], [147],
[280]. However, none of the above idealized as-
sumptions are strictly applicable to a real sys-
tem [265], [281–287]. Kinetic models for net-
work formation by free-radical polymerization
are beingdeveloped[61], [62], [145–147], [288–
295]. Figure 18 shows the change in the av-
erage chain length and weight fraction of gel
during network formation in the copolymeriza-
tion of methyl methacrylate and ethylene glycol
dimethacrylate [147].
Figure 18. Development of average chain length within sol
fraction and weight fraction of gel during batch copolymer-
ization of methyl methacrylate and ethylene glycol dimeth-
acrylate (0.25 mol %) at 70

C initiated by AIBN [147]
• =Experimental data
3. Polymerization Processes and
Reactor Modeling
3.1. Introduction
The polymer reactor model is nowbecoming ac-
cepted as a valuable tool whose use contributes
significantly to all aspects of process technology
for polymer manufacture. This includes process
design, optimization, state estimation, and con-
trol. Through process design, polymers with a
unique and desirable combination of properties
can often be obtained. Process parameters such
40 Polymerization Processes
as residence time distribution (RTD) are usually
not considered by polymer synthesis chemists,
although RTD can influence chemical compo-
sition distribution (CCD), molecular mass dis-
tribution (MWD), long-chain branching (LCD)
and gel/sol ratios. In the early days of the poly-
mer industry, the chemist played the major role
in product and process development and scale-
up. This has changed, with the process engineer
now playing a significant role in all phases of
commercialization of new and improved poly-
mer products. His broad experience with pro-
cess fundamentals and computer modeling are
essential to obtain high-quality products, safely
and economically.
Dynamic reactor models can be used in a
variety of ways. Stability and control of poly-
mer reactors should be considered at the de-
sign stage and control problems minimized then,
rather thantake corrective actionafter the plant is
built. Complex interactions which are involved
in polymerization (highly nonlinear temperature
and concentration effects) preclude optimal de-
sign based on experimentation alone because the
cost would be prohibitive. Models can be used to
identify potential sources of product variability
and strategies to minimize their effects. Models
can be used to store information on process tech-
nology in a concise and readily retrievable and
modifiable form.
Process models can be used to train chemists,
chemical engineers, and plant operators and give
them a feel for the dynamics of the polymeriza-
tion process.
The most expensive aspect of model devel-
opment is experimental estimation of model
parameters; highly instrumented bench-, pilot-
scale, and plant-scale reactors are required. Sta-
tistically designed experiments should be per-
formed to permit efficient parameter estimation
andmodel development. Modelingis aniterative
process and the very act of developing a deter-
ministic model permits a greater understanding
of the relevant microscopic processes which oc-
cur during polymerization or polymer modifica-
tion. As additional data (plant, pilot-plant, and
bench-scale) become available, model structure
and parameters can be updated.
This section considers recent developments
in polymerization/polymer modification pro-
cesses and discusses advances in polymer re-
actor modeling, state estimation, and control.
3.2. Processes and Reactor Modeling for
Step-Growth Polymerization
3.2.1. Types of Reactors and Reactor
In step-growth polymerization, high molecular
mass polymers are usually not produced until the
final stage of reactions, so that thermal control
andmixingof the reactionmixture donot present
serious problems in the earlier stages. However,
since the final stage of polymerizationis veryim-
portant for the production of polymers with high
molecular mass, handling of very high viscosi-
ties and temperatures and high interfacial area
to remove small molecules are required. Various
polymerizationprocesses andreactor types, both
for batch and continuous production, have been
proposed. Examples of reactors for high viscosi-
ties are shown in Figures 19 and 20. Careful se-
lection of the polymerization reactor is very im-
portant to produce high-quality polymers [296],
Figure 19. Vertical cone ribbon blade reactor (Mitsubishi
Heavy Industries)
Polymerization Processes 41
Figure 20. Horizontal high-viscosity reactor
The batch reactor is the most versatile reac-
tor type and is used extensively for specialty
polymers at low production volumes. Some
examples of step-growth polymerizations car-
ried out in such reactors are nylon 6, phe-
nol – formaldehyde, urea – formaldehyde, and
melamine – formaldehyde. In polycondensation
reactions, it may be necessary to remove con-
densation products to attain sufficient conver-
sion. When the volume of the reaction mass de-
creases continuously with time, such reactors
are called semi-batch reactors. (A tank-type re-
actor which does not operate at steady state is
defined as a semi-batch reactor). For example,
in the production of poly(ethylene terephthal-
ate), PETP, since methanol or ethylene glycol
evaporates duringpolymerization, the batchwise
production of PETP is considered a semi-batch
On the other hand, newer high-capacity
plants often use continuous processes. The first
approximation for a continuous process is a
model that consists of plug flow reactors (PFR)
and continuous stirred-tank reactors (CSTR) in
various combinations (Fig. 21), although vari-
ous nonideal effects such as flow pattern in the
reactor, mass- and heat-transfer limitations, and
residence time distribution must be considered
for a detailed analysis and design of real reactors
Molecular mass distribution of linear poly-
mers producedbystep-growthpolymerizationin
a batch or a PFRbasically follows the most prob-
able distribution [303]. (Note that batch reactor
and PFR are, in principle, equivalent). The mo-
lecular mass distribution may be controlled by
varying its reaction path if the reaction systemis
in a nonequilibriumstate. Assuming irreversible
step-growthpolymerizationwithout interchange
reactions, the effect of reactor types, such as ho-
mogeneous CSTR, segregated CSTR and PFR
with a recycle loop, on molecular mass distribu-
tion have been considered [301], [302], [304],
[305]. An important feature of step-growth poly-
merization is that the variance of the molecu-
lar mass distribution is smallest in a batch re-
actor or PFR and is largest in a homogeneous
CSTR, which is quite contrary to that for chain-
growth polymerization. This result may be dis-
appointing, since it is, in principle, impossible
to produce polymers whose polydispersity in-
dex M
is smaller than two in step-growth
polymerization at sufficiently high conversions.
The polydispersity index of polymers produced
in a batch reactor is given by 1 +p, as shown
in Section 2.1.1., where p is the conversion of
the functional group. However, in commercial
polymeric materials, polymers with narrower
distributions are not always superior to those
with broader distributions, since various levels
of properties are required at the same time. The
use of a cascade of CSTRs and/or PFRs with
recycle loops may be one method to obtain a
molecular mass distribution with a polydisper-
sity index larger than two. However, in practice,
these methods may have shortcomings because
they need a long start-up period and, therefore,
problems may occur with the stability of the re-
action system. A method in which additional
monomers are fed intermediately to a batch re-
actor or a PFR has been proposed [306]. The-
oretical analysis of this intermediate monomer
feed method has also been carried out [307], and
it has been shown that the polydispersity index
can be easily controlled over a wide range with
values greater than 2.
In a batch reactor, the reverse reactions and
the interchange reactions (redistribution reac-
tions) do not change the MWD from the most
probable distribution [303], [308–310]. How-
ever, these reactions do change the MWD of
polymers produced in CSTR, PFRwith a recycle
42 Polymerization Processes
Figure 21. Representative models for polymerization reactors
loop, and intermediate monomer feed method.
Some consideration of these reactions in a CSTR
is given in [311]. Qualitatively, these effects
lower the polydispersity and make the MWD
approach the most probable distribution. This
result seems reasonable, since any MWD ap-
proaches the most probable distribution with
a polydispersity index of two when polymer
chains are severed randomly [312], [313].
Other than the common reactor types dis-
cussed above, other special types of reactor sys-
tem may be applied. For example, in the poly-
merization of urethanes, the reaction rates are
so high that reaction takes place even when the
monomers are being mixed and pumped into
molds. In situ polymerization to form the de-
sired articles directly from monomeric liquids
is known as reaction injection molding (RIM)
[314], [315]. A schematic of the RIM process
is shown in Figure 22. The RIM processing of
polyesters, epoxy resins, polyamides, and dicy-
clopentadienes has also been introduced, al-
though more than 95 % of the total produced by
RIM is polyurethane [315]. In the RIM process,
the reaction is almost complete by the time the
material fills the mold, and therefore the mix-
ing and flow equations must be solved simulta-
neously with those for chemical reactions in a
rational model for these complex situations.
Figure 22. Schematic drawing of the RIM process
a) Monomer A; b) Monomer B; c) Polymerizing mixture;
d) Mold; e) Mixer
Polymerization Processes 43
Inthe finishingstage of nylon6, nylon66, and
PETP polymerizations, higher molecular mass
polymers may be obtained by solid-state poly-
merization in which polymerization occurs by
heating chips or flakes of a material below its
melting point in a stream of hot gases in a flu-
idized bed or in a drier operated under vacuum
[316–320]. The monomer, condensation prod-
ucts, and various byproducts diffuse out, and
further reaction takes place inside the solid. The
progress of these types of reaction is affected
significantly by the diffusion of the condensa-
tion products and the morphology of the solid.
Although step-growth polymerization has a
very long history, a systematic kinetic treatment
like that available for free-radical polymeriza-
tion does not exist because of limitations due to
system-specific side reactions and the scarcity
of reliable kinetic data. However, this synthetic
route is becoming more important due to the
development of materials synthesized by step-
growth polymerization such as aramides, PPS,
PEK, and PES. The production technology of
step-growth polymers seems to have revived as
an attractive research area and is enjoying a Re-
naissance period.
3.2.2. Specific Processes
Polyamides (see also →Polyamides) are
manufactured by two basic routes. One of
these is synthesis from cyclic monomers such
as lactams. Polymerization of these substances
requires ring opening and subsequent chain
growth. Another class of synthetic polyamides
is formed from diamines and diacids.
The most common types of polyamides are
nylon 6 and nylon 66. The term nylon is of-
ten used for synthetic aliphatic polyamides. One
number indicates that the product was prepared
from a single monomer and represents the num-
ber of carbon atoms in the repeating unit. Two
numbers refer to the number of carbon atoms in
the diamine and that in the diacid, respectively.
Nylon 6 is typically produced by the hy-
drolytic polymerization of ε-caprolactam [321–
325], although polymers with higher molecular
mass can be produced by ionic polymerization
[321], [323], [326]. The major reactions in the
hydrolytic polymerization are
1) Ring opening of ε-caprolactam by water
(Eq. 3.1), which produces aminocaproic acid
2) Polycondensation of ACA (Eq. 3.2)
3) Acid-catalyzed polyaddition (ring-opening
polymerization) by nucleophilic attack of the
amine nitrogen on the lactam (Eq. 3.3)
Step-growth polymerization of the amino
acid (Eq. 3.2) accounts for only a few percent
of total polymerization of ε-caprolactam. How-
ever, step-growth polymerization is important
since it usually determines the final degree of
polymerization at equilibrium. The molecular
mass distribution is essentially the most prob-
able distribution, except for the presence of
monomer and cyclic oligomers. Since low mo-
lecular mass substances lower the polymer qual-
ity, they are usually removed by leaching or vac-
uum treatment of the polymer melt. The forma-
tion of cyclic oligomers is an important side re-
action [327–329]. For the simulation and opti-
mization of polymerization reactors, only small
ring formation or overall ring formation is con-
sidered to make the analysis easier [330–333].
Various types of polymerization reactors
have been proposed both for batch and continu-
ous processes. Acommonlyusedindustrial reac-
tor for a continuous process is a tubular reactor
such as the conventional VK column (Verein-
facht Kontinuierliches Rohr) [321], [322], [334],
which consists of a vertical tube operating at at-
mospheric pressure. The feed enters the top of
the column and is heated to ca. 220 – 270

The simplest model for this type of reactor is a
PFR. However, according to impulse response
experiments, the flow is approximately laminar
rather than plug flow [322], [335], and the reac-
tor should be modeled as a CSTR followed by
44 Polymerization Processes
a tubular reactor when a large quantity of wa-
ter is used since a significant convection current
and mixing is provided by the evaporating water
Nylon 66 is manufactured by polycondensa-
tion of hexamethylenediamine and adipic acid
[336], usually in a multistage process. First, ny-
lon salt (hexamethylenediammoniumadipate) is
prepared fromstoichiometric quantities of hexa-
methylenediamine and adipic acid in water. The
salt can easily be separated by precipitation with
Figure 23. Continuous melt polymerization of nylon 66
The use of nylon salt guarantees the presence
of equimolar amounts of – NH
and – COOH
groups. Close control of diamine – diacid bal-
ance is important to control the final polymer
molecular mass and reactive end groups.
Nylon 66 is fairly unstable at high tempera-
tures in the presence of oxygen. Not only degra-
dation but also cross-linking may occur. Be-
cause of this instability, polymerization used to
be carried out solely in batch processes. How-
ever, complete eliminationof oxygenhas made it
possible to carry out continuous polymerization.
An example of a continuous melt polymeriza-
tion process is shown in Figure 23. The aqueous
nylon salt solution is heated to above 200

C at
>17 bar in an oxygen-free atmosphere. There-
after, the pressure is reduced to atmospheric and
vapor is separated from polymer to promote
polymerization to the desired high molecular
mass. It has also become possible to polymerize
molten hexamethylenediamine and adipic acid
directly [330], [336]. Polymerization can also
be completed in the solid state.
Several kinetic studies on the synthesis of ny-
lon 66 have been published [337–341]. How-
ever, more information is necessary for detailed
simulation and optimization of nylon 66 reac-
Polyesters (see also →Polyesters). The pro-
duction of high molecular mass polyesters dif-
fers somewhat from that of polyamides. In the
case of nylons, the chemical equilibrium favors
the polyamide under polymerization conditions.
With polyester formation, however, the equilib-
rium is much less favorable. In order to drive
the reaction in the forward direction, the con-
densation product must be removed continu-
ously, usually by application of high vacuum.
For polyester reactors, a high vacuum, a high
temperature, and a high interfacial area with suf-
ficient surface renewal are required, especially
at high conversions.
Both saturated and unsaturated polyesters
are produced. Among the saturated polyesters,
poly(ethylene terephthalate), PETP, is produced
in the largest quantity, and is used for production
of fibers, films, molding plastics, and beverage
containers. In this section, the engineering as-
pects of PETP formation are illustrated as an
example of a polyester production process.
There are two major routes to synthesize
PETPindustrially, although the objective in each
case is to obtain an intermediate product – i.e.,
bis(hydroxyethyl)terephthalate (BHET).
Two major routes to synthesize BHET are es-
ter interchange of dimethyl terephthalate (DMT)
and direct esterification of terephthalic acid.
Figure 24 shows an example of the PETPpro-
duction process via the ester interchange route.
The ester interchange reaction
Polymerization Processes 45
is operated in the temperature range
150 – 210

C at atmospheric pressure. The use
of a catalyst is common [342], [343]. The meth-
anol and ethylene glycol (EG) emerging from
the reactor are passed through a rectifying col-
umn and EG is fed back to the reactor. It is very
difficult to force the ester interchange reaction to
completion, and therefore after a particular con-
version (usually 90 – 95 %), the reaction mixture
is passed on to the polycondensation stage. The
reactionmixture consists of oligomers of various
types. Oligomers with degrees of polymeriza-
tion as high as three may be formed [342], [344],
[345]. Several reactor models for both batch and
continuous processes have been proposed [342–
350]. An optimization study showed that the
ester interchange reactor should be operated
initially at high temperature to obtain high con-
version; the temperature should be lowered to
reduce side reactions [343], [348].
Figure 24. Continuous polymerization process of PETP via
ester interchange route
In the polycondensation stage, the reaction
temperature is raised to 265 – 285

C to keep
the reaction mixture molten and polymerization
For PETP production, a dual catalyst system in
which one component is specially active for es-
ter interchange and the other for polymerization
is quite often used [351]. The production of high
molecular mass polymer requires the complete
removal of ethylene glycol due to the unfa-
vorable equilibrium, and therefore a vacuum
is applied. Especially in the final stage of the
polycondensation reaction, a very high vacuum
is required since the reaction system becomes
highly viscous. Consideration of the limitations
of mass and heat transfer is very important.
Various types of reactors such as rotating disc
contactors, wiped film reactors, partially filled
screw extruders have been developed as fin-
ishers for the polycondensation reaction [342],
[343], [350]. Details of fluid mechanics, mix-
ing, and mass and heat transfer characteristics
are required for a rational analysis and design
of such high-viscosity reactors. In addition to
polycondensation reactions, various side reac-
tions must also be considered since a very high
temperature is used.
Melt polycondensation of PETP is not gen-
erally carried out beyond a particular extent of
polymerization since the degradation reactions
dominate the process and the product quality
may suffer fromvarious undesirable byproducts.
To attain higher molecular masses, the products
may be subjected to solid-state polymerization
[316–320]. Newer processes, especially for bev-
erage and food containers, prefer to stop melt
polymerization at lower conversion, and solid-
state polymerization is extensively applied.
Direct esterification of terephthalic acid
(TPA) and ethylene glycol was generally not
preferred earlier because of the difficulties in
the purification of TPA due to its low solubil-
ity and high melting point. However, with im-
provements in technology, the direct esterifica-
46 Polymerization Processes
Figure 25. Continuous polymerization process of PETP via direct esterification route
tion method has been gaining in importance. The
process is claimed to give polyesters with supe-
rior quality due to their low content of carboxyl
end groups and diglycol linkages [351]. In the
modeling of this process, aside from the diffi-
culties caused by the various reactions and mass
balances involved, it is necessary to take account
of the heterogenityof the reactions due tothe low
solubility of TPA in EG. Simulation and control
of the direct esterification reactors is reported
in [343], [350], [352–354]. Figure 25 shows a
flow diagram of a continuous process for PETP
production by direct esterification.
3.3. Processes and Reactor Modeling for
Chain-Growth Polymerization
3.3.1. Material Balance Equations for Batch,
Semi-Batch, and Continuous Reactors
The following material balance equations ap-
ply for multicomponent polymerization, accom-
modate operation of a well-stirred reactor (no
spatial variations in temperature and concentra-
tions), and may be used to simulate different
comonomer systems under a variety of operat-
ing conditions. Bulk (suspension) and solution
polymerizations are considered first; extensions
required for multiphase systems (emulsion, in-
verse emulsion, suspension, dispersion, and gas-
phase processes) may be found elsewhere [355].
Special cases where spatial variations in temper-
ature and concentrations are important (e.g., in
tubular reactors or packed beds) are also consid-
Bulk, solution, and suspension polymer-
ization systems are characterizedbythe fact that
all of the reactions proceed in a single phase
with no spatial variations in temperature and
concentration. A model for a reactor carrying
out such polymerizations would consist of a set
of material balances giving the rates of accu-
mulation, inflow, outflow and a reaction source
(sink) term for the various monomers, initiators,
chain-transfer agents, and polymer in the reac-
tor. These balance equations are now given in
general form
Monomer balances:
/dt =F
i, in
− (N
/V ) V
V (3.7)
Polymerization Processes 47
is the number of moles of monomer i in
the reactor
i, in
are molar flow rate of monomer i into the
V is the reaction volume in the reactor
is the total volumetric flow rate of all
species out of the reactor
is the net rate of disappearance of
monomer i by reaction
Reaction Volume. Since the densityof a poly-
mer is usuallysignificantlygreater thanthat of its
monomer, the reaction volume V decreases with
conversion for isothermal polymerization in a
batch reactor. This shrinkage must also be taken
into account in semi-batch and continuous op-
erations. Neglecting volume change on mixing
polymer and monomers (thermodynamic data
are most often not available and deviation from
ideality is often not great) the change in reaction
volume (V ) may be calculated by using (assum-
ing V is the equilibrium volume):
dV /dt =V
−shrinkage rate
s, in

i, in




V − V
where n is the number of monomer types, V
s, in
is the volumetric flow rate of inert solvent
into the reactor, M
is the molecular mass of
monomer i, ̺
is the density of monomer i, ̺
is the density of polymer produced instanta-
Polymer Balances. With a batch reactor,
where there is no inflow and outflow of poly-
mer from the reactor, the total amount of poly-
mer formed and its composition can be obtained
directly from the monomer balances. However,
with semi-batch and continuous operation, ad-
ditional balances are required and these follow
/dt =F
pi, in
− (P
/V ) V
V (3.9)
where P
is the number of moles of monomer i
chemically bound in the polymer “in the reac-
tor”, F
pi, in
is the molar flow rate of monomer i
bound in the polymer flowing into the reactor.
Additional Ingredient Balances. In order to
calculate R
for free-radical systems, the to-
tal polymer radical concentration and, therefore,
initiator concentration are required. In addition,
balances for the chain-transfer agent (for mo-
lecular mass calculations) and for the solvent
in solution polymerizations are required. These
balances follow:
/dt =F
Ii, in
− (N
/V ) V
V (3.10)
/dt =V
s, in
− (V
/V ) V
/dt =F
T, in
− (N
/V ) V
V (3.12)
where N
is the number of moles of initiator
of type i in the reactor, F
Ii, in
is the molar flow
rate of initiator i into the reactor, R
is the con-
sumption rate of initiator i by reaction, V
is the
volume of inert solvent in the reactor, N
is the
number of moles of chain-transfer agent (CTA)
inthe reactor, F
T, in
is the molar flowrate of CTA
into the reactor, and R
is the consumption rate
of CTA by reaction.
It is convenient to sum the monomer bal-
ance equation (Eq. 3.7) over n, the number of
monomer types to give
/dt =F
− (N
/V ) V
V (3.7a)
where N
is the total number of moles of
monomer in the reactor, F
is the total molar
flow rate of monomer to the reactor, R
is the
total molar consumption rate of monomer by re-
action. Rates of Reaction and Copolymer
With application of the pseudo-kinetic rate con-
stant method, R
can be expressed as
[M] [P

] (3.13)
[M] =N
/V =

] (3.13a)
and [M
] is the concentration of monomer of
type i in the reactor.
When the terminal model [356] for copoly-
merization is valid
48 Polymerization Processes

] =


] (3.13b)
where [P

] is the concentration of active centers
of type i in the reactor and



where ϕ

is the number fraction of active cen-
ters of type i in the reactor, and f
is the mole
fraction of monomer of type j in the reactor.
When the penultimate model [356] for co-
polymerization is valid

] =




The fraction of active centers of type i (ϕ

) can
be found by using the stationary state hypoth-
esis (SSH). Model development will continue
assuming that the terminal model for copoly-
merization is valid. The ϕ

may be found by


with i =1, . . . n and where R
is the consump-
tion rate of monomer j adding to the active center
For anionic, cationic, and anionic coordina-
tion polymerization, the estimation of the total
number of active centers is not always straight
forward, and this quantity is sometimes used as
an adjustable parameter. For free-radical poly-
merization, a balance between radical genera-
tion rate and bimolecular termination rates pro-
vides the following with use of the SSH
] =
where [R

] is the total concentration of poly-
meric radicals in the reactor, R
is the generation
rate of polymeric radicals of chain length unity,
is the number-average bimolecular ter-
mination constant. When termination by com-
bination and disproportionation are both signif-
For chemically controlled bimolecular termina-
tion, pseudo-kinetic rate constants for
may be found in [355–357]. Details con-
cerning the definitions and use of
, may be found elsewhere [358], [359]. The
definition of


(r, s) ψ (r) ψ (s) (3.14d)
where K
(r, s) is an arbitrary bimolecular termi-
nation constant distribution for reaction of poly-
meric radicals of chain length r and s and ψ (r)
and ψ (s) are the number fractions of polymeric
radicals of chain length r and s. Note that
can be used to calculate R
but if used
tocalculate higher molecular mass averages they
would be underestimated if a significant number
of polymer chains are formed by bimolecular
termination reactions [358].
Realistic calculations of [R] using Equation
(3.14 b) requires that the SSH be valid and that
diffusion-controlled bimolecular termination be
accounted for. The first direct experimental test
by ESR of the validity of the SSH for bulk
polymerization of methyl methacrylate (MMA)
(where linear polymer chains are produced)
and of MMA– ethylene glycol dimethacrylate
(EGDMA) (where chains with long branches
and polymeric networks are formed) has shown
that SSH is valid for bulk MMA polymeriza-
tion, but is not valid when substantial cross-
linking occurs [360]. Coyle et al [361] have
confirmed the validity of SSH for bulk poly-
merization of MMA using numerical solutions
of the full set of kinetic equations. Attempts to
model diffusion-controlled bimolecular termi-
nation is considered later when discussing the
polymerization of MMA (see page 53) which
is considered the model system because of its
extreme Trommsdorff – Norrish effect. At very
high monomer conversions, when the polymer-
ization temperature is below the glass transition
temperature of the polymer being synthesized,
the initiator efficiency and propagation constant
Polymerization Processes 49
both begin to fall dramatically, and these ef-
fects should be properly accounted for. These ef-
fects will also be considered in detail later when
MMA polymerization is discussed. The mod-
eling of diffusion-controlled bimolecular termi-
nation, propagation, and the cage effect on ini-
tiator efficiency is not entirely clear, and much
research must be done before these topics may
be considered standard engineering practice.
The polymerization rates for individual
monomer type j can be calculated from


[M] [P

] (3.14e)
with j =1, . . . n.
The mole fraction of monomer of type j in
copolymer produced instantaneously is given by
Monomer sequence length distributions may be
calculated by using equations given in [356]. Molecular Masses, Long-Chain
Branching, and Cross-Linking
Linear Copolymer Chains. For chain
lengths greater than about 50 and when the
terminal model for copolymerization is valid,
Stockmayer’s bivariate weight chain length
distribution may be used to calculate the com-
position and chain length of binary copolymer
produced instantaneously [356], [362]. The bi-
variate distribution of the accumulated polymer
is readily calculated by integrating the instan-
taneous distribution using weighting factors
based on instantaneous rates of polymer pro-
duction. Unfortunately, an analytical function
for a multidimensional distribution (involving
three or more monomer types) has yet to be
derived. However, part of this problem has al-
ready been solved. In the limit of large chain
lengths, the copolymer composition of chains
produced instantaneously may be assumed to
be independent of chain length, and therefore,
the instantaneous bivariate weight chain length
distribution is that given by the same expres-
sion as for homopolymerization with all of the
chains having the same composition F
. For
more details, see Section 2.3.1 and [356].
Long-Chain Branching and Cross-
Linking. The production of long branches and
cross-links requires that so-called dead polymer
chains take part in branching reactions to pro-
duce tri- and tetrafunctional branch points via
transfer to polymer and by addition of polymer
radical centers to polymer double bonds. The
mechanisms of anionic, cationic, and anionic
coordination polymerization invariably produce
linear polymer chains. There may be a few ex-
ceptions, but these will not be considered.
Pseudo-kinetic rate constants for transfer to
polymer and polymer radical addition to pendant
double bonds may be defined as [355], [357],




when the terminal model is valid; where
is the mole fraction of monomer j chemically
bound in the accumulated polymer. When a sig-
nificant number of labile atoms have been ab-
stracted and when a significant number of dou-
ble bonds have beenconsumed, Equations (3.15)
and (3.16) should be modified to account for this
[363], [364].
When polymer chains that are normally inert
to further reaction undergo long-chain branch-
ing reactions, the instantaneous MWD is no
longer a permanent quantity. Therefore, the
method of moments should be used to calculate
the molecular mass averages. For details on the
use of the method of moments for the calcula-
tion of sol molecular mass averages before and
after the gelation point and other methods for
calculating sol – gel fraction and cross-linking
density, see [363–365].
3.3.2. Examples of Free-Radical
Polymerization Homopolymerization– Linear
The modeling techniques described in Section
3.3.1 are illustrated with actual monomer sys-
tems and experimental kinetic data. The sim-
plest modeling examples (homopolymerization
50 Polymerization Processes
producing linear chains) are considered first, be-
ginning with the thermal bulk polymerization of
styrene, which is relatively easy to model and the
modeling has been most successful in a variety
of applications.
Bulk Thermal Polymerization of Styrene

C). This system is comparatively
easy to model for the following reasons:
1) The Mayo mechanism for thermal initiation
of radicals is valid [366–368]
2) The polystyrene chains are linear
3) The Trommsdorff – Norrish effect (see Sec-
tion, although significantly affecting
the polymerization rate, has at most a minor
effect on molecular mass development be-
cause most of the polymer chains are pro-
duced by chain transfer to the Diels – Alder
intermediate [366].
The size of the polymeric radicals (radical
centers are exclusively on chain ends) depends
on temperature and monomer concentration (or
conversion), and the molecular mass distribu-
tion of the accumulated polymer differs little
from that of the polymeric radicals. In general,
the self-diffusion coefficients of polymer radi-
cals should depend on the size of the macrorad-
ical, the concentration and MWD of the accu-
mulated polymer, and temperature. The size of
the macroradical is of greater importance than
the MWD of the accumulated polymer [369],
An empirical correlation of the bimolecular
termination constant with polymerization tem-
perature and monomer conversion should pro-
vide a model which is applicable over a range
of process conditions (batch and continuous re-
actor operation, temperature programming, etc).
Another important factor, revealedinthe workof
Kirchner and Riederle [367], is that reactions
involved in thermal initiation do not become
diffusion controlled at monomer conversions as
high as 97 %. The first effective model for the
bulk thermal polymerization of styrene was de-
veloped by Hui and Hamielec [371] and later
extended to higher temperatures (T <230

[372] and shown to be valid for a continuous
stirred-tank reactor up to 280

C [373]. This
model has been evaluated by many workers over
a wide range of reactor type and operational con-
ditions. These include:
1) Wu et al. [374] used the model for a theo-
retical/experimental optimization study em-
ploying temperature programming in a batch
reactor with highly successful results.
2) Kirchner et al. [375] applied the model to
a CSTR and obtained accurate predictions.
3) Tien et al. [375] applied the model to a tubu-
lar reactor with internal mixers.
4) DIERS [376], [377] (Design Institute for
Emergency Relief Systems) a consortium of
chemical and insurance companies financed
the design and construction of a unique
adiabatic reactor system (see Fig. 26) for
the measurement of temperature and pres-
sure/time variations during adiabatic run-
away exothermic reactions. They measured
responses for the adiabatic thermal poly-
merization of styrene (Fig. 27 and 28) and
compared them with those predicted by
the Hui – Hamielec polystyrene model and
found excellent agreement.
Figure 26. DIERS VSP (adiabatic batch reactor)–monitors
temperature and pressure changes during runaway of highly
exothermic reactions [377]
a) Containment vessel (ca. 4 L); b) Test cell; c) Outer can;
d) Guard heater; e) Inner heater; f) Insulation; g) Exhaust
and supply; h) Bypass; i) Fill
Polymerization Processes 51
Figure 27. VSPself-heat rate response for the adiabatic ther-
mal polymerization of styrene (80 wt %styrene and 20 wt %
ethylbenzene) compared with the predictions of the H–H
polystyrene model [377]
– – – Constant heat of reaction (−700 kJ/kg); —- Temper-
ature-dependent heat of reaction; • Experimental data
Figure 28. VSP Pressure – time response for the adiabatic
thermal polymerization of styrene (80 wt % styrene and
20 wt %ethylbenzene) compared with the predictions of the
H–Hpolystyrene model withtemperature-dependent heat of
reaction [377]
(kPa =psi ×6.89)
a) Prediction: total pressure (maximum 360 psig);
b) Prediction: partial vapor pressure (maximum 312 psig)
• Experimental data
The pressure calculation required the use of
the Flory – Huggins equation (Eq. 3.17). These
evaluations under extreme conditions confirm
that the H–H model for the thermal polymer-
ization of styrene is indeed useful in a vari-
ety of applications. These kinds of evaluations,
which, however, have not been carried out for
any other polymerization model, should be con-
sidered standard tests for polymerization models
before they are accepted for general engineering
Figure 29. Thermal polymerization of p-methylstyrene:
molecular mass development followed by GPC and light
scattering (LALLS). Deviation for M
between GPC and
LALLS suggests that LCB frequency is increasing with
monomer conversion. Solid curves are model predictions
neglecting chain transfer to polymer [378].
A monomer which polymerizes thermally
and almost identically to styrene is 4-
methylstyrene [378]. With the latter monomer
some long-chain branching occurs due to chain
transfer to methyl hydrogens in the polymer
backbone. An effective experimental technique
to confirmthe presence of long branches [378] is
to measure
by light scattering and by GPC
at different monomer conversions in isothermal
batch polymerization. The molecular mass cali-
bration curve for GPCshould be constructed us-
ing linear poly(4-methylstyrene). At lowconver-
sions, where chains are almost all linear,
light scattering and GPCshould agree. However,
at high conversions where long-chain branching
should be significant (if it is present at all),
by light scattering should be greater than that by
GPC and the difference should increase with in-
creasing monomer conversion. Figure 29 shows
an example of this behavior. Long-chain branch-
ing in poly(4-methylstyrene) has been satisfac-
torily modeled by accounting for chain trans-
fer to polymer and using light scattering
which should be valid for branched homopoly-
mer [378]. Another effective procedure to verify
the presence or absence of long-chain branching
is to add a previously synthesized narrow-MWD
sample of the polymer that is to be synthesized
to the monomer solution and then polymerize.
The newly synthesized polymer is then com-
52 Polymerization Processes
pletely separated from the old polymer by GPC.
If the GPCresponse for the added polymer shifts
towards larger radii of gyration (hydrodynamic
volume) this is evidence for long-chain branch-
ing [379].
Bulk polymerization of methyl methacry-
late (MMA) with free-radical initiator is the
model monomer system for the investigation
of diffusion-controlled bimolecular termination
and propagation and the decrease in initiator ef-
ficiency at high monomer conversions (cage ef-
fect). It has the largest Trommsdorff – Norrish
effect because most of the polymer chains are
produced by bimolecular termination and the
higher average molecular masses (
) increase dramatically in the absence of a
chain-transfer agent. The MWD shifts to higher
molecular masses and sometimes becomes bi-
modal [380]. GPC detector responses, multi-
plied by monomer conversion so that the total
area under the detector response is proportional
to the amount of polymer in the batch reactor, are
shown in Figure 30. At the monomer conversion
where the number of physical chain entangle-
ment points becomes significant a spike of high
molecular mass polymer is produced. There-
after, polymer with lower molecular masses is no
longer produced. The instantaneous MWD has
clearly shifted towards higher molecular mass
(higher molecular mass polymer has a lower
GPC retention volume or retention time). MMA
is generally polymerized below the glass transi-
tion temperature of PMMA (ca. 110

C) and as
a consequence the initiator efficiency and prop-
agation constant decrease dramatically at high
monomer conversions (∼ 80 %) due to restric-
tions on diffusion rates during the glassy-state
transition because of appreciable loss in free vol-
ume. There is also evidence that during the rapid
autoacceleration in polymerization rate (due to
large increase in polymer radical concentration
[360]) radicals become frozen in the glassy-state
[358]. Radical pairs which form in the cage
may become frozen after a few monomer addi-
tions because of monomer starvation. This ho-
mopolymerization is difficult to model. Never-
theless, there have been many serious attempts
to model this system [381–392]. More recent
research has focused on predicting the fall in
initiator efficiency and propagation constant at
high conversion and on the use of a simple chain-
length-dependent model for bimolecular termi-
nation. This work has been summarized in a
recent article by Adams et al. [393]. The first
important models [381–383] for MMA poly-
merization were carefully evaluated [384] using
comprehensive rate and molecular mass data in-
volving three different initiator types measured
by R¨ ohm. The Marten – Hamielec model was
found to better satisfy the specifications for a
polymer reactor model that can be used to op-
timize commercial production systems. It was
pointed out however, that further work should
be done to investigate the applicability of the
model to systems that have been prepolymerized
and also polymerized nonisothermally (perhaps
with temperature programming or adiabatically)
and for systems with mixed initiators. Panke
[394] has more recently shown that when us-
ing prepolymer, simulations are better when the
parameter n is changed from 1.75 to 0.5 in the
M–H model. From a fundamental point of view
the M–H model has several weaknesses which
should be pointed out. Chain-length dependence
of bimolecular termination is accounted for in an
overly simplified manner. The weight-average
molecular mass of the accumulated polymer
does reflect the change in the size of the macro-
radicals but in a dampened fashion. For example,
a sudden change in the size of the macroradi-
cals would not be felt soon enough, particularly
when a substantial amount of dead polymer has
accumulated. This model effectively uses one
termination constant (the number-average ter-
mination constant [358]). It can therefore predict
polymerization rate and number-average molec-
ular mass, but invariably underestimates
and higher molecular mass averages. The M–
H model as well as most others have assumed
that K
becomes diffusion controlled while the
initiator efficiency f remains constant. It has
long been known that the initiator efficiency falls
at high conversions [395–398]. To separate the
product f
which appears in the rate expres-
sion, accurate molecular mass data at high con-
versions are required. This has not been possible
to date, because of the difficulty of measuring
for the very high molecular mass
PMMAproduced during the autoacceleration of
reaction rate. For all of the models for which
f was taken to be independent of monomer con-
version, the observed decrease in K
is actually
Polymerization Processes 53
the decrease in f
. The change in K
at very
high monomer conversions can be measured by
ESR [360], [399] and of course this would per-
mit the estimate f from the product f
. An-
other factor which has been completely over-
looked is that during the autoacceleration when
approaching the glassy-state transition, the ac-
tual volume of the polymerizing mixture may
be significantly greater than the local equilib-
rium volume. This is largely responsible for the
fact that the limiting conversion depends on the
initiator concentration at high initiator and rad-
ical concentration levels [400–402].
Figure 30. GPC chromatograms showing molecular mass
development due to the Trommsdorff–Norrish effect for the
isothermal bulkfree-radical polymerizationof methyl meth-
acrylate in a batch reactor
Parameter x denotes monomer conversion (T =70

[AIBN] =0.3 wt %) [380]
During the autoacceleration in polymer-
ization rate which accompanies diffusion-
controlled bimolecular termination, it is dif-
ficult to maintain isothermal conditions. The
use of large ampoule reactors with inadequate
surface-to-volume ratios for heat transfer has
been recently criticized [403], [404]. The use
of ampoule reactors (3 – 5 mm diameter) is rec-
ommended for kinetic investigations of the
Trommsdorf – Norrish effect [404]. Copolymerization– Linear Chains
The terminal model has been very useful for
predicting the average compositions of binary
copolymers synthesized with vinyl monomers
having a wide variety of structures and range
of reactivities. The terminal model has not been
as successful in the prediction of comonomer
sequence length distributions [405], [406] and
the propagation rate [407–413]. Model discrim-
ination has been based on the use of mea-
surement techniques which provide estimates
of the elementary overall (or pseudo-kinetic)
rate constants K
. These include ro-
tating sector [407–409], spatially intermittent
polymerization (SIP) reactor [414], and pulsed-
laser techniques [411–413]. ESR measurements
[410] have also been used to show the ex-
istence of penultimate effects. Most of these
studies considered the binary copolymerization
of styrene and methyl methacrylate; however,
other monomer pairs have been investigated in-
cluding: styrene – acrylonitrile [408] andstyrene
with a series of alkyl methacrylates [408], [415].
The use of the pulsed-laser technique has a se-
rious limitation when applied to copolymeriza-
tion. One must measure the MWD by GPC and
the potential errors are several and potentially
serious. For example, there is inevitable statis-
tical broadening of composition distribution for
short chains and the uncertainty that the con-
cept of universal molecular mass calibration is
valid. Nonuniform composition of chains in the
detector cell makes the conversion of detector
response to polymer solute concentration uncer-
tain and in addition the errors due to deviation
from the universal calibration curve may be sig-
Most of the serious attempts to model binary
copolymerizations from an industrial perspec-
tive (accounting for diffusion-controlled bimo-
lecular termination and propagation and for
the fall in initiator efficiency at high conver-
sions) have employed the terminal model and
the pseudo-kinetic rate constant method [355],
[357], [416–423]. There have been some recent
attempts to employ the penultimate model in this
regard [424], [425]. It should be stressed that
whether terminal or penultimate models are used
appropriate pseudo-kinetic rate constants can be
defined for calculating rates of polymerization
and molecular mass distribution [356].
54 Polymerization Processes Copolymerization– Long-Chain
The few serious attempts to model polymer-
ization rate and molecular mass development
have employed the pseudo-kinetic rate con-
stant method with the method of moments
[355], [357], [363–365], [418], [419], [422]. The
method of instantaneous MWD, which is such a
powerful method for calculating the full MWD
for linear multicomponent polymers is not use-
ful when dead polymer chains can be reactivated
during formation of long-chain branches. The
instantaneous MWD is no longer a permanent
quantity but loses some of its chains, which be-
come branched during the course of polymer-
ization. It should be noted here that the pseudo-
kinetic rate constant method is equally valid for
the modeling of linear and branched copoly-
mer chain synthesis. The most common ana-
lytical technique for the measurement of long-
chain branching frequency (average number of
branches per polymer molecule or per 1000
backbone carbon atoms) is GPC with a dual de-
tector system (mass concentration detector plus
either a viscometer or light scattering photome-
ter as detector in series) or GPC with off-line
viscometry [426].
3.3.3. Polymerization Processes Solution Polymerization Polymer Soluble in Monomer
Kinetics. A polymerization in which the
polymer being synthesized is soluble in its
monomer may be called a bulk or mass as well as
a solution polymerization. A full description of
the polymerization kinetics and modeling tech-
niques can be found in Section 2.2.1 and Section
Polymerization Processes. The main tech-
nical problems associated with solution poly-
merization are heat removal, recovery of resid-
ual monomer and solvent, and the manipula-
tion of highly viscous solutions and melts. It is
well known that the ratio of cooling surface area
to volume of reacting mixture decreases as the
reactor volume increases. Length-to-diameter
ratios for reactors are usually <2 to achieve
acceptable mixing. When jacket cooling is no
longer sufficient to maintain isothermal poly-
merization, additional modes of heat transfer
must be used, as shown in Figure 31. Internal
cooling coils are often not practical because they
tend to interfere with stirring. External tubular
coolers can, in principle, provide a very large
heat-transfer area, but they may have very large
pumping requirements in the case of highly
viscous solutions. Reflux cooling removes the
heat of polymerization by evaporation of solvent
and/or monomer; the condensed vapor is recy-
cled to the reacting mass. Condensers may be as
large as necessary, with the limiting factor usu-
ally the amount of vapor that can be treated with-
out causing intense foaming or spattering of the
polymer solution. Remixing of the condensed
liquid with the more viscous reacting mass may
also be difficult. Addition of a Solvent in which
both Monomer and Polymer are Miscible
The additionof a solvent inwhichbothmonomer
and polymer are miscible lowers the viscosity
of the reacting mass, thereby improving its flow
and heat-transfer characteristics. As a result, and
depending upon the nature and con-centration
of the solvent, the Trommsdorff – Norrish effect
can be either completely suppressed or signifi-
cantly reduced. Use of solvent can be especially
beneficial when evaporative cooling is used. In
choosing a solvent, it is important to take into ac-
count the possibility of chain transfer to solvent
with a concomitant reduction in polymer mo-
lecular mass. Removal of solvent and residual
(unreacted) monomer from the highly viscous
polymer solution requires very high surface ar-
eas to permit rapid devolatilization at the mod-
erate temperatures required to minimize poly-
merization and degradation of chains during de-
volatilization to reduce off-spec polymer. Fig-
ure 32 illustrates possible designs of devolatiliz-
ers. One of these, the vacuumdegasser, incorpo-
ratinga type of spraydevice [427], operates adia-
batically, which means that the heat for evapo-
ration is supplied by the solution itself. In con-
trast, a degasser in series with a tubular heat ex-
changer causes some of the monomer/solvent to
Polymerization Processes 55
Figure 31. Alternative methods of heat removal for polymerization conducted in a stirred reactor
A) Internal cooling coils; B) External cooler; C) Reflux cooling
evaporate during passage through the heat ex-
changer. This evaporation accelerates the flowof
product, thereby increasing the heat-transfer rate
[428]. Twin-screw extruders with one or more
vapor outlets that can be connected to a vac-
uum source are also utilized for the removal of
monomer and solvent [429], [430]. Intermesh-
ing and self-cleaning screws provide continuous
renewal of the evaporating surface. The use of
thin-film evaporators with rotating wiper blades
has also been suggested [431].
Given stable operation of the devolatilizer,
solution polymerization can be carried out in
a continuous stirred-tank reactor [432], [433].
Conversion is normally lower than with tower
processes, however, requiring large amounts of
monomer/solvent to be recovered and recycled
tothe reactor. Special attentionmust therefore be
paid to the buildup of impurities (e.g., inhibitors,
chain-transfer agents) over time by using appro-
priate purge streams. Problems with processes
involving step-growth polymerization are dis-
cussed in Section 3.2. Polymer – Polymer Demixing
during Polymerization
Polymer – polymer demixing is especially im-
portant in the production of thermoplastics
whose application characteristics are enhanced
by the presence of dispersed domains containing
an elastomer. Generally, the thermodynamics
are unfavorable for complete miscibility bet-
ween different types of polymers. For a system
polymer A– polymer B– solvent, the follow-
ing generalizations are usually applicable [434],
[435]: dilution with solvent and, in most cases,
an increase in temperature increases the compat-
ibility; increasing the molecular masses of the
polymers has the opposite effect. Except in the
case of high dilution, incompatibility in solution
is the rule for pairs of polymers, even when the
solvent is a good solvent for both polymer types.
Systems such as polymer A– polymer B–
block or graft copolymer AB can be re-
garded as a polymeric oil-in-oil emulsion in
which the copolymer functions as an emul-
sifying agent [436–439]. Such systems arise,
for example, in the manufacture of high-
impact polystyrene (HIPS), or in the prepara-
tion of ABS (acrylonitrile – butadiene – styrene)
by solution polymerization. In the simplest
case, ca. 5 – 10 % polybutadiene is dissolved in
monomeric styrene to give a homogeneous so-
lution suitable for polymerization. The poly-
styrene synthesized is incompatible with the
polybutadiene present, causing phase separa-
tion even at very low monomer conversion
and producing a polybutadiene – styrene con-
tinuous phase and a polystyrene – styrene dis-
perse phase. Simultaneously, graft polymeriza-
tion produces polystyrene branches on polybu-
tadiene backbone. The graft copolymer serves
as an emulsifier, accumulating at the interface
and stabilizing the oil-in-oil emulsion.
With increasing conversion, the volume frac-
tion of the polystyrene phase (which is initially
small) increases considerably due to formation
of additional polystyrene which absorbs styrene
monomer. Finally, often at a phase-volume ra-
tio of about unity, a phase reversal occurs, with
the rubber phase nowthe disperse phase, and the
56 Polymerization Processes
Figure 32. Options for removing residual monomer and solvent
A) Strand degasser; B) Tubular evaporator; C) Degassing extruder; D) Thin-film evaporator
polystyrene phase the continuous phase. Agita-
tion is essential for the completion of phase re-
versal, since rapid approach to equilibrium with
respect to transfer of monomer/polymer must be
attained in a highly viscous medium. Acommon
result of inadequate agitation is the interpenetra-
tion of two continuous phases [438], [440–442].
Phase reversal can also lead to various
types of emulsions; e.g., polystyrene – styrene
droplets can be occluded within the rubber par-
ticles of the disperse phase. This is actually de-
sirable as it increases the volume fraction of the
disperse rubber phase. A reinforcing effect is
observed, with the resulting HIPS having higher
impact strength for a given mass of rubber in
comparison with materials prepared by emul-
sion grafting, in which occluded polystyrene is
not formed [443], [444]. Rather than rely on in
situ formation of grafted rubber, it is also possi-
ble from the outset to utilize block copolymers
of styrene and butadiene as an additive in the
recipe. The desired particle size distribution and
morphology of the rubber particles in HIPS is
then achieved by varying the intensity of agita-
tion, the viscosities of the disperse and continu-
ous phases, the graft activity of the primary rad-
icals of the initiator, the molecular mass of the
continuous phase, and the mass fraction and mo-
lecular mass of the blocks in the diblock copoly-
mer [445–454].
Figure 33 provides examples of the morphol-
ogy of these rubber-modified polystyrene sys-
tems. Morphologies of commercial significance
are essentially limited to cell and capsule struc-
tures, since the other morphologies shown gen-
erally provide lower impact strength. Precipitation Polymerization
The term precipitation polymerization refers to
processes in which the initial ingredients of
a recipe are soluble, giving a homogeneous
solution, but the synthesized polymer precipi-
tates during the course of polymerization. The
precipitated polymer is generally swollen with
monomer and with nonsolvent if present. To
ensure convenient handling the disperse phase
must be finely divided. This is achieved by ef-
fective agitation, and a protective colloid (steric
stabilizer) is often used. The associated prob-
lems are similar to those with HIPS manufac-
ture. Polymer Insoluble in its Monomer
Polymers that are insoluble in their monomers
include poly(vinyl chloride) and other polymers
derived from halo or pseudohalo-substituted
ethylenes such as vinyl bromide, vinylidene
chloride, trifluoroethylene, and acrylonitrile.
Polyethylene also falls into this category, at least
when produced under moderately high pressure.
For the system vinyl chloride – poly(vinyl chlo-
ride), for example, virtually no polymer dis-
solves in the monomer in the temperature range
30 – 60

C. Solubility of the monomer in the
polymer is described well by the simplified
Polymerization Processes 57
Figure 33. Possible morphologies for rubber particles in impact resistant polystyrene [454]
Length of the scale bar: 1 µm
Flory – Huggins equation (3.17) [435, p. 511],
= ln (1−ϕ
) +ϕ
is the vapor pressure of pure vinyl chloride
p is the partial pressure of vinyl chloride
is the volume fraction of poly(vinyl chlo-
χis the polymer – solvent interaction param-
According to [457], deviations from Equa-
tion (3.17) are expected at low vapor pressures.
The conversion – time curves for the bulk poly-
merization of such monomer – polymer systems
all display rate increases with increasing con-
version. This phenomenon has been especially
thoroughly investigated for the bulk polymer-
ization of vinyl chloride. Its cause may be in-
terpreted as follows: even at very low conver-
sion, poly(vinyl chloride) precipitates, forming
a monomer-swollen polymer-rich phase. Initia-
tor is partitioned between the phases, and thus
radical generation and polymerization occur in
both phases. The bimolecular termination rate
is diffusion controlled in the polymer-rich phase
and hence the concentration of radicals is higher
in this phase. Even though the monomer con-
centration is lower in the polymer-rich phase,
the specific polymerization rate R
is higher. In
addition, the volume of the polymer-rich phase
grows at the expense of the monomer-rich phase
with increasing monomer conversion. This ex-
plains the autoacceleration in rate as monomer
conversion increases.
Figure 34. Time – conversion curve for the bulk polymer-
ization of vinyl chloride [459]
Polymerization temperature 50

C, initiator lauryl perox-
ide, theoretical curves dashed
[I]: • 0.78 ×10
; 1.57 ×10
; △ 3.38 ×10
; ×
5.50 ×10
mol/mol vinyl chloride
Talamini has suggested that such a reac-
tion may be described in terms of two homo-
geneous polymerizations occurring in parallel,
with rapid monomer transfer fromthe monomer-
rich to the polymer-rich phase [458], [459]. As-
suming that the monomer/polymer mass ratio in
the polymer-rich phase is independent of con-
version or time, and that the ratio of the spe-
cific polymerization rates in the two phases re-
58 Polymerization Processes
mains constant (Talamini suggests a ratio of ca.
19at 50

C), thenthe observedconversion – time
curve can be described well up to ca. 70 % con-
version, as shown in Figure 34. However, Ta-
lamini’s model fails at higher conversions be-
cause the monomer-rich phase disappears, and
polymerization now occurs only in the remain-
ing polymer-rich phase, with a monomer con-
centration which decreases with increasing re-
action time. Several authors have offered exten-
sions and modifications of the original Talamini
model [460–468].
Figure 35. Schematic diagram of the Union Carbide gas-
phase process for manufacturing HDPE [474]
a) Fluidized-bed reactor; b) Catalyst transfer tanks; c) Cata-
lyst feeders; d) Product discharge tanks; e) Multiclone dust
separator; f) Air coolers; g) Compressor; h) Product de-
gassing tank; i) Filter; j) Ethylene tank; k) Pneumatic trans-
port system
An industrial example of precipitation poly-
merization is the Pechiney – Saint Gobain two-
stage bulk polymerization process [469–472],
or the more popular suspension polymerization
where poly(vinyl chloride) precipitates in the
monomer droplets (→Poly(Vinyl Chloride)).
Precipitation polymerization also encompasses
what has been called “gas-phase” polymeriza-
tion, a process in which polymer particles form
within a monomer vapor. Such polymerization
does not actually occur in the gas phase, how-
ever, because the catalyst resides either within
or on the surface of existing polymer particles,
and a significant amount of monomer is dis-
solved in the polymer. The actual site of poly-
merization is thus within the polymer particle,
to which a continuous supply of monomer flows
from the gaseous phase. Commercial examples
of gas-phase processes include the Union Car-
bide Unipol process [473–476] and the BASF
process [477–481] for low-pressure polymeriza-
tion of ethylene and propylene (→Polyolefins,
Chap. 1.5.3., →Polyolefins, Chap. 2.5.6.). Fig-
ure 35 shows a schematic of the Unipol process
in which polyethylene powder is produced us-
ing ethylene as a fluidizing gas in a fluidized-
bed reactor that contains a modified chromium
catalyst. A high-density polyethylene (HDPE)
which has a very broad molecular mass distri-
bution and linear chains is produced. Copoly-
merization of ethylene with propene, 1-butene,
and 1-hexene gives products with a controlled
amount of short-chain branching and lower
polymer density (LLDPE) [482]. The densities
of LLDPE are between those of HDPE and
LDPE made in the high-pressure free-radical
Polymer – monomer – precipitant systems
employ a nonsolvent for the polymer, while
the precipitant is miscible with the monomer.
The most important example is probably the
so-called slurry process for the manufacture
of high-density polyethylene (HDPE), iso-
tactic polypropylene, and their copolymers
(→Polyolefins, Chap. 1.5.2., →Polyolefins,
Chap. 2.5.1.) Ziegler – Natta (transition-metal
catalysts) are used in these processes. Polymeri-
zation is often conducted continuously in a train
of well-mixed reactors in the presence of a non-
solvent hydrocarbon, usually a C
bon, at ca. 50 – 100

C and 5 – 30 bar. Polymer
chains growonsuspended, veryfine catalyst par-
ticles. Soluble, homogeneous catalysts of the
Ziegler – Natta type are also known and have
gained commerical interest. The productivity of
modern catalysts is so high (greater than 100 kg
polyethylene per gramtransition metal) that sub-
sequent removal of the catalyst fromthe polymer
product is not required. An overview of earlier
developments with respect to these catalysts is
provided in [483].
Stirred-tank reactors are generally used for
this process, often linked in series to give
a cascade or train [484], [485]. A simplified
schematic of the Hoechst process is shown
in Figure 36. Similar slurry processes also ex-
ist for polypropylene [486] and copolymers
Polymerization Processes 59
Figure 36. Schematic of the Hoechst slurry-process for HPDE [484]
a) Mixing vessels; b) Reactor; c) Postreactor; d) Centrifuge; e) Stripper; f) Dryer; g) Silo for HDPE powder
based on ethylene – propene (EPM) and ethyl-
ene – propene – diene (EPDM) mixtures. Acry-
lonitrile, sometimes together with a comonomer,
can be polymerized in aqueous phase using
a redox system such as K
[487]. The polymer precipitates as
a fine powder, which is then filtered, washed,
and dried. Dissolution of the polymer powder
in dimethylformamide produces a spinning so-
lution that can be used to produce polyacryloni-
trile fibers. This process has been conducted in a
continuous manner [488]. One of the first com-
mercial precipitation polymerizations was the
belt conveyor process for polyisobutylene devel-
oped by BASF (Fig. 37; see also →Polyolefins,
Chap. 4.2.4.). Equal amounts of isobutene and
ethylene are first mixed and then deposited in
the liquid state on a circulating steel belt. A sec-
ond inlet is used to add a solution of BF
ethylene. Cationic polymerization occurs very
rapidly, and the heat of polymerization is dissi-
pated by the evaporation of ethylene. Thus, eth-
ylene functions here not only as a precipitant but
also as a medium for evaporative cooling. The
resulting gaseous ethylene is purified, liquefied,
and recycled.
A similar process is used by Exxon for the
synthesis of butyl rubber [489]. In this case, iso-
prene serves as the comonomer and methyl chlo-
ride takes the place of ethylene. Polymerization
is carried out in a continuous stirred-tank reac-
tor. Residual monomer and diluent are removed
from the resulting polymer suspension by strip-
ping with hot water. Monomer Functioning as Solvent
for the Polymer
The Polymer – Monomer – Precipitant
System. If the polymer is soluble in its
monomer, precipitation polymerization requires
the addition of a precipitant that is miscible with
the monomer. Polymerization then begins in a
solvent – nonsolvent mixture and it ends in a
phase consisting only of pure precipitant once
conversion of the monomer is complete. Thus,
the solubility relationships change during the
course of the polymerization, and polymeriza-
tion may initially occur in a homogeneous man-
ner prior to the onset of precipitation, induced by
the enrichment in precipitant that accompanies
the consumption of monomer.
60 Polymerization Processes
Figure 37. Schematic diagram of the BASF process for manufacturing polyisobutylene [433]
a) Storage vessel for liquid isobutene; b) Storage vessel for liquid ethylene; c) Refrigerating condenser; d) Storage vessel
for ethylene containing 0.03 % boron trifluoride; e) Conveyor belt reactor; f) Heated degassing screw; g) Gaseous ethylene;
h) Purification with calcium oxide ; i) Gasometer; j) Compressor
Figure 38. Volume-fraction ∗γ
(—-) of methanol as a
function of conversion for various initial concentrations of
monomer [M]
Azeotropic precipitation copolymerization of
styrene – acrylonitrile in methanol (– – –), precipita-
tion point determined using cloud-point titration for two
different degrees of polymerization
Figure 38 illustrates these relationships, us-
ing as an example the copolymerization (in
methanol as precipitant) of 40 mol % acryloni-
trile and 60 mol % styrene (at the azeotropic
composition). The volume fraction ∗γ
methanol in the reaction mixture, defined as

volumeof precipitant
volumeof precipitant + volumeof solvent
is plottedinFigure 38as a functionof conversion
for various initial concentrations of monomer
. The dashed lines represent extrapola-
tions from experimental cloud-point titration
data, which give the ∗γ
values at which the
first polymer fractions precipitate at 65

C. For
an initial concentration [M]
<4.1 mol/L, ex-
tremely small conversions suffice to cause pre-
cipitation. At high monomer concentrations the
polymer initially remains in solution because the
volume fraction of methanol required for poly-
mer precipitation has not yet been reached. In
such cases, the critical value of ∗γ
is ex-
ceeded only at higher conversion: the greater
, the higher the conversion required.
In precipitation polymerization of this type it
is especially important to ensure that the poly-
mer precipitates in finely divided form. Among
other things this ensures that the particles do
not overheat during polymerization. The pro-
cess has been employed on large scale by BASF
[490–492], with batch polymerization occur-
ring in stirred reactors under reflux at 65

Azobisisobutyronitrile was employed as inita-
tor, and poly(vinyl pyrrolidone) or poly(vinyl
ether) as a protective colloid. The resulting
styrene – acrylonitrile copolymer was separated
by centrifugation and the recovered methanol
was distilled and recycled to the next batch.
Polymerization Processes 61
Polymer dispersions in nonaqueous media
with particle size in the range 0.01 – 10 µm(non-
aqueous dispersions, colloids, organosols) have
been thoroughly investigated by Barret and
coworkers [493]. Barret characterizes “disper-
sion polymerization” as a process in which an
insoluble – and thus dispersed – polymer is pre-
pared from a monomer dissolved in an organic
diluent to which has been added an amphiphatic
block or graft copolymer to serve as a dispersant.
However, here this is regarded as a special case
of precipitation polymerization in which com-
plete coagulation of polymer particles is pre-
vented and the particle size is controlled.
The key to controlling particle size is the se-
lection of dispersant type. Among the most ef-
fective dispersing agents are the so-called am-
phipathic molecules: block and graft copoly-
mers made up of two polymeric components,
only one of which is insoluble in the continu-
ous, diluent-containing phase. Graft copolymers
of this type often formduring the polymerization
as a result of grafting on the dissolved polymer,
but it is not absolutely essential that the insoluble
portion of the dispersant be identical to or solu-
ble in the disperse phase. In many cases its insol-
ubility in the diluent is sufficient to ensure ade-
quate adsorption on the particle surface. These
amphipathic dispersing agents act as steric sta-
bilizers [494].
Figure 39. Steric stabilization of precipitating poly-
mer/monomer particles with the aid of amphipathic block
and graft copolymers [495]
A) Schematic representation of adsorption of amphipathic
molecules on the polymer particles; —- insoluble groups,
· · · · · soluble groups; B) Equilibrium established in the
course of a precipitation polymerization P=(growing) poly-
mer particle; C) Schematic representation of flocculation
due to multifunctional amphipathic molecules
Figure 39 A is a schematic representation of
the adsorption of di-block, multiple-block, and
graft copolymers onthe surface of growingpoly-
mer particles. Soluble and insoluble portions of
the dispersant molecules must be kept carefully
in balance. If the insoluble part is too small, or
if it interacts too weakly with polymer particles,
then adequate adsorption will occur only when
the dispersant concentration in the continuous
phase is very high. If the soluble portion is too
large, the dispersant will be present largely as
aggregates or micelles with little tendency to
dissociate and be adsorbed on the interface. Fig-
ure 39 B depicts the equilibrium situation. Fi-
nally, it is important to note that multifunctional
amphipathic molecules like those shown in Fig-
ure 39 C can also function as weak flocculating
In a well-stabilized dispersion, each particle
is covered by a layer of freely moving poly-
mer chains, which are in turn dissolved in the
continuous phase. These layers prevent the fre-
quently colliding particles from approaching so
closely that Van der Waal’s attractive forces be-
come dominant. A simplified model (Fig. 40)
suggests that the mechanism of steric stabiliza-
tion involves an increase in the local concentra-
tion of polymer chains or segments as a result of
overlapping and mutual chain interpenetration
[496] as two polymer particles approach. This
induces an osmotic pressure and increase in the
free energy ∆G
. To compensate for this effect,
solvent flows into the regions of higher polymer
concentration and drives the particles apart. A
positive value of ∆G
−T ∆S
can be
due either to enthalpic effects (∆H
) or to en-
tropic effects (T ∆S
). It is therefore possible
to divide the contributions to steric stabilization
into three categories [498]:
1) Enthalpic stabilization
and ∆S
are both positive
>T ∆S
The dispersion flocculates on warming
2) Entropic stabilization
and ∆S
are both negative
T ∆S
The dispersion flocculates on cooling
3) Combined enthalpic – entropic stabilization
is positive
is negative
62 Polymerization Processes
The dispersion is stable over a wide range of
Figure 40. Model for steric repulsion caused by the overlap
of two spheres containing dissolved molecular chains [496],
C =Concentration of the polymer chains in the adsorption
More complete discussions of steric stabi-
lization may be found elsewhere [495], [498–
503]. A survey of precipitation polymerization
is available [504]. Suspension Polymerization
Definition. The term “suspension polymeriza-
tion” includes a series of processes, all of which
involve emulsifying monomers to droplets by
stirring them in a suspending medium in which
they are insoluble in the presence of a free-
radical initiator, usually one that is soluble in
the monomer. When the polymer formed is
soluble in the monomer, nonporous spherical
“beads” are formed, hence the term “suspension
bead polymerization”. If, however, the polymer
precipitates during polymerization, the result-
ing polymer particles are composed of many
smaller primary particles. They are opaque, usu-
ally possess an irregular surface, and may have
substantial internal porosity. This type of poly-
merization has been called “suspension pow-
der polymerization”. The dispersants (protective
colloids) are either macromolecules that are in-
soluble in the suspending medium or insoluble,
usually inorganic, powders, the so-called Pick-
ering emulsifiers [505]. Their function is first
to assist in the formation of the initial monomer
emulsion and then to stabilize the resulting poly-
mer particle suspension. The following recipes
are examples for suspension polymerization in-
volving protective colloid and inorganic powder
With protective colloid:
Temperature 80

Reaction time 8 h
Styrene 100 parts (by mass)
Water 200 parts (by mass)
Benzoyl peroxide 0.4 parts (by mass)
Poly(vinyl alcohol)
[partially hydrolyzed poly(vinyl acetate)]
0.5 parts (by mass)
With pickering emulsifier:
Temperature 80

Reaction time 10 h
Styrene 100 parts (by mass)
Water 200 parts (by mass)
Benzoyl peroxide 0.2 parts (by mass)
Barium sulfate 1.0 part (by mass)
Na 0.002 parts (by mass)
The term“suspension polymerization” is per-
haps inappropriate, because precipitation and
emulsion polymerizations also produce suspen-
sions of polymer particles in a continuous phase.
The distinction from precipitation polymeriza-
tion is that it is initiated in a homogeneous
mixture, while suspension polymerization takes
place in an emulsion. The beads or powder par-
ticles produced in a suspension polymerization
are roughly of the same size as the original
monomer droplets with diameters on the or-
der of 10
to 0.5 cm. Emulsion polymeriza-
tion also starts with a monomer emulsion, but
the initiator is usually one that is soluble in the
continuous suspending phase rather than in the
monomer. Moreover, the resulting latex particles
are very much smaller (diameter range 5 ×10
to 3 ×10
cm or 0.05 to 0.3 µm) than the orig-
inal monomer droplets. Borderline cases which
might be called emulsion or suspension poly-
merization are discussed later in Section
In the vast majority of cases, the suspend-
ing medium for suspension polymerization is
water, although inverse-suspension polymeriza-
tions are also known and used commercially
to produce very high molecular weight poly-
mers and copolymers based on the comonomer
acrylamide. Here a water-soluble monomer is
dispersed in a hydrophobic organic suspending
medium, usually in the presence of water in the
disperse phase.
Polymerization Processes 63 Qualitative Description
Generally, dispersants are employed at a con-
centration (relative to the aqueous phase) of
0.1 – 5 wt % in the case of protective colloids
and 0.1 – 2 wt % for Pickering emulsifiers. A
typical initiator concentration is 0.1 – 1 wt %
relative to the monomer. The volume ratio
monomer/aqueous phase is usually between
25 : 75 and 50 : 50, and the stereometric limit,
which cannot be exceeded with spheres of uni-
form size, is 74 : 26.
The reactor vessel is usually a stirred tank.
The monomer is subjected either to turbulent
pressure fluctuations or viscous shear forces,
which break it into small droplets that assume
a spherical shape under the influence of inter-
facial tension. These droplets undergo constant
collision (collision rate ≥1 s
), with some of
the collisions resulting in coalescence. In the ab-
sence of stabilizers, a dynamic equilibrium is
eventually established, leading to a stationary
mean particle size. Individual drops do not re-
tain their unique identity, but instead undergo
continuous breakup and coalescence. This phe-
nomenon can easily be demonstrated by the ad-
dition of a small amount of a monomer that has
been labeled with a water-insoluble dye. The dye
is rapidly distributed uniformly in the disperse
monomer phase.
In some cases, an appropriate dispersant can
be used to induce the formation of a protective
film on the droplet surface. As a result, pairs or
clusters of drops that tend to coalesce are bro-
ken up by action of the stirrer before the crit-
ical coalescence period elapses. A stable state
is ultimately reached in which individual drops
maintain their identities over prolonged periods
of time. In this case, addition of dye-bearing
monomer does not result in migration of the dye
into other droplets. Such a system is described
as a turbulence-stabilized emulsion.
In the simple case of a polymer that is
miscible in all proportions with its monomer
(e.g., styrene and methyl methacrylate), various
viscosity states of the disperse phase are tra-
versed during the course of polymerization. The
initially nonviscous, liquid monomer is trans-
formed gradually into an increasingly viscous
solution of polymer in monomer, and as conver-
sion proceeds the disperse phase acquires the
characteristics of a solid polymer. Particularly
in the tacky intermediate stage, individual poly-
mer particles tend to form incompletely fused
clumps. Coagulation at this critical stage of con-
version is somewhat inhibited by the action of
the dispersant, but other effective measures to re-
duce coagulation may also be taken, including
adjusting the densities of the two phases to make
them more similar, or by increasing the viscos-
ity of the aqueous continuous phase. Rapid poly-
merization during the sticky stage minimizes the
number of collisions among polymer particles
and thus should reduce coagulation.
An experiment with dye-labeled monomer is
also applicable when polymerization occurs in
the disperse phase [506–508]. In this case dye-
containing polymer beads generated in a paral-
lel polymerization are added to the suspension
during polymerization. It is observed that be-
yond a certain conversion (which depends on
the reaction conditions) coagulation and parti-
cle breakup cease entirely. This is known as the
“particle identity point” or the limit of dynamic
equilibrium. Increasing the dispersant concen-
tration (i.e., reducing the size of particles) dis-
places the identity point towards lower conver-
sion [509], [510].
The schematic diagram in Figure 41 shows
these fundamental relationships. The upper part
of the diagram corresponds to dynamic equilib-
rium in a monomer emulsion that contains no
dispersant, or to an emulsion undergoing poly-
merization that has not yet reached the identity
point. The monomer phase is broken up into long
strands by the stirrer, and these in turn fragment
into spherical droplets due to interfacial tension
forces. The droplets may then agglomerate into
larger aggregates, finally coalescing into larger
drops, which either break apart again due to stir-
ring or collect as an extended monomer phase.
The lower portion of Figure 41 shows the var-
ious stages that lie between the identity point
and the end of the polymerization process. In
a turbulence-stabilized emulsion, one in which
monomer drops maintain their identity, the prob-
ability is high that individual drops will poly-
merize directly to primary beads. Nevertheless,
even in a suspension bead polymerization, ir-
regular particles sometimes appear, composed
of many individual smaller polymer particles, a
consequence of some clusters surviving past the
identity point.
64 Polymerization Processes
Figure 41. Schematic diagram of dispersion and polymerization in a suspension bead polymerization
A) Monomer emulsion in the absence of dispersant, or a polymerization mixture that has not yet reached the identity point;
B) Polymerizing mixture after passing the identity point
A polymerizing bead with a diameter
d =10
cmcontains ca. 10
growing polymeric
radicals. The effects of subdivision due to parti-
cle breakupinsuspensionpolymerizationare not
anticipated to occur at the levels found in emul-
sion polymerization (polymer particles are sub-
micron in size) where radical contents of 0.5 or
lower per particle occur [511], [512]. Each bead
may be regarded as a small, isolated reactor. For
this reason, the observed polymerization kinet-
ics correspond directly to those for bulk poly-
merization [506], [513], [514]. Here again the
Trommsdorff – Norrish and glass effects must be
taken into account, as must the effects associated
with demixing when the polymer is insoluble in
its monomer [459], [460], [462], [515]. Indeed,
the process is sometimes referred to as a water-
cooled bulk polymerization. To ensure that con-
version is as complete as possible, it is common
to employ mixtures of initiator types with dif-
ferent half-lifes, and to allow the polymeriza-
tion temperature to increase in the final stages
of conversion [516], [517]. With many industri-
ally important suspension polymerizations, sim-
ply preparing a polymeric material is not suffi-
cient. Often a particular particle-size distribu-
tion and morphology must be achieved, as in
the manufacture of expandable polystyrene, or
poly(vinyl chloride), whose particles must later
absorb substantial quantities of plasticizer for
some applications.
For what has already been said about the
course of suspension polymerization, together
with various results from the literature [507],
[510], [513], [518], [519], it is possible to estab-
lish a number of special factors – apart from
those common to all free-radical polymeriza-
tions – that exert an important influence on par-
ticle size and size distribution:
1) Geometric factors of the reactor: profile, type
of stirrer, stirrer diameter D relative to the
reactor dimensions, bottom clearance of the
stirrer, and internal fittings
2) Operating parameters: stirrer velocity N,
stirring and polymerization time, phase vol-
ume ratio ϕ, fill level of reactor, and temper-
ature T
3) Substance parameters: dynamic viscosities
and η
and densities ̺
and ̺
of the con-
tinuous and disperse phases, and interfacial
the tension σ.
During monomer fragmentation, in colli-
sions leading to agglomeration, and in de-
agglomeration of clusters, the most important
consideration is the energy introduced into the
reaction mixture per unit time. This can be ex-
pressed in terms of the mean rate of energy dis-
sipation per unit mass ε. In the case of a stirred
reactor containing baffles and operated with a
high Reynolds number, the following equation
is applicable [520]:
¯ ε=KN
or Wkg
Polymerization Processes 65
where K is a dimensionless constant that de-
pends on the type of stirrer. Increasing the stirrer
speed N causes a decrease in particle size.
The concentration of dispersant [S] deter-
mines the maximum particle surface area that
can be stabilized and influences the interfacial
tension. Increasing [S] leads to a decrease in
particle diameter, as does lowering the interfa-
cial tension. Increased disperse phase viscosity
reduces particle breakup and thus leads to larger
Figure 42. Schematic representation of the adsorption of
partially hydrolyzed poly(vinyl alcohol) on the surface of a
dispersed particle [510]
All −OH groups (omitted for clarity) are directed toward
the aqueous phase, and residual acetate groups toward the
disperse phase Dispersants
Protective Colloid Dispersants. Organic
protective colloids include natural products
such as alginates, tragacanth, agar, and starch
as well as modified natural polymers such as
carboxymethylcellulose (sodiumsalt), hydroxy-
ethylcellulose, and methylcellulose. Among the
effective synthetic polymers are styrene – maleic
anhydride copolymer, poly(methacrylic acid),
poly(vinyl pyrrolidone), poly(vinyl alcohol),
and partially hydrolyzed poly(vinyl acetate).
The important feature of all these materials
is their amphipathic character, which explains
their ability to lower the interfacial tension and
to concentrate at the monomer – water interface.
As shown in Figure 42, protective colloids are
probably adsorbed in such a way that they form
loops near the particle surface. In the case of par-
tially hydrolyzed poly(vinyl alcohol), the resid-
ual acetate groups act as hydrophobic points of
attachment, while the OH groups are directed
into the continuous aqueous phase. The most
important factor in dispersant effectiveness is
an appropriate balance between hydrophilic and
hydrophobic groups [521]; molecular mass is of
considerably less significance. The wettability
of a polymer can be varied by the addition of
trace amounts of a low molecular mass surfac-
Higher concentrations of protective colloid
may cause a bead polymer to be contami-
nated by a small amount of a much more
finely divided emulsion polymer. This should be
avoided because it results in polymer loss dur-
ing workup. The chance of encountering such
a problem is enhanced by increased solubility
of the monomer and initiator in the continu-
ous phase. However, emulsion polymerization
via homogeneous nucleation in the continuous
phase can be suppressed by addition of a water-
soluble inhibitor such as NH
SCN or a copper
salt [513], [522].
Powdered Dispersants (Pickering Emulsi-
fiers). Finely divided, usually inorganic, insol-
uble solids may also be employed as disper-
sants in suspension polymerization [505], [513],
[523]. Common choices include barium sul-
fate, talc, aluminum hydroxide, hydroxyapatite,
tricalcium phosphate, calcium oxalate, magne-
sium carbonate, and calcium carbonate. It is ad-
vantageous to dissolve out the dispersant after
the polymerization (e.g., in dilute acid), thereby
minimizing polymer contamination. Monomer
emulsions based on systems of this type are re-
ferred to as three-phase emulsions, a term intro-
duced by Wenning [507]. In the case of a poly-
mer that is insoluble in its monomer, a fourth
phase occurs during the course of polymeriza-
Solid dispersants must be wet by two immis-
cible liquids, and they must also exhibit a certain
degree of self-adhesion. The wettability can be
modified by adsorption of low molecular mass
surfactants. This technique is referred to as mod-
ulation and it has much in common with tech-
niques used in mineral flotation processes.
The wettability of a solid (S) by a liquid such
as water (W) in the presence of a gas (G) de-
pends upon the wetting angle α, which results
66 Polymerization Processes
from equilibrium between three interfacial ten-

· cosα=σ
Figure 43. Wetting of a Pickering dispersant by monomer
and water, modulated by addition of a surfactant
S solid; G gas; M monomer; W water
For further explanation, see text
Figure 43 Aillustrates the significance of this
relationship. An angle α=0

corresponds to
total wetting. For α=90

, σ

, and at

no wetting occurs. In a three-phase
emulsion, two immiscible liquids compete for
wetting the solid S: monomer M and water W.
As indicated in Figure 43 B, there is again an
equilibrium condition:

· cosα=σ
Taking the example of barium sulfate as the dis-
persant ina styrene – water beadpolymerization,
the barium sulfate is at first wetted more effec-
tively by water than by styrene, so σ

Water wets the barium sulfate with a small con-
tact angle α and cos α is positive (Fig. 43 D).
Addition of a surfactant whose polar groups are
adsorbedonthe bariumsulfate makes the surface
more hydrophobic (or lypophilic). As a result,
increases and σ
decreases, leading to the
states shown in Figure 43 Eand F. In the limiting
case (Fig. 43 G), the particle is fully immersed in
the monomer phase and loses its effectiveness as
a dispersant. In the course of passing fromDto F
it is not uncommon for a phase reversal to occur:
the oil-in-water emulsion is transformed into a
water-in-oil emulsion and the polymer forms a
block that contains water-filled voids [507]. It is
clear that the limiting cases C and G are inap-
propriate for suspension polymerization. Agood
Pickering dispersant must possess amphiphatic
characteristics, thus leading to one of the cases
D– F. Many pure inorganic substances are com-
pletely wetted by water, the chief reason why
modulationis soimportant inpractice as a means
of inducing the transition from C to D. Mechanism of Particle Formation
Suspension polymerization always begins with
dispersion of a monomer in water. It thus seems
reasonable to first consider the formation of a
monomer emulsion – or more generally, the for-
mation of an emulsion of an organic liquid in
water – and then examine the effects of poly-
merization in the disperse phase.
Droplet Size in an Emulsion Subject to
Turbulent Mixing. Especially simple relation-
ships should govern the suspension polymeriza-
tionof a turbulence-stabilizedemulsioninwhich
single drops maintain their separate identities.
However, such an emulsion must fulfill a series
of conditions [524–526]:
1) Stirring must be sufficiently intensive to sep-
arate any droplet pairs or clusters that begin
to form. The adhesive forces between two
drops increase roughly linearly with the drop
diameter d, while the forces exerted on the
drops by stirring show a higher order depen-
dence on drop diameter. The probability of
separationtherefore increases withdiameter;
given a particular stirring intensity, the diam-
eter must remain above a specific minimum

¯ ε
where C

is an empirical constant, ̺
is the
density of the continuous phase and A(h)
is the energy required to separate to a dis-
tance h =∞two drops of diameter d =1 ini-
tially separated by a distance h
. The value
of A(h) is strongly dependent upon the thick-
ness and characteristics of the adsorbed pro-
tective film. Equation (3.19) may be used
Polymerization Processes 67
to convert Equation (3.22) to the following

If d <d
, drops will coalesce until a diam-
eter d
has beenreached. If energydissipa-
tion in the stirred reactor is not uniform(e.g.,
if only near the stirrer blades is it sufficient to
break up drop clusters), then material circu-
lation within the vessel must be sufficiently
rapid to ensure that each cluster approaches
the stirrer blades at least once during the crit-
ical coalescence time.
2) The dissipated stirring energy must not be
so large as to cause significant breakup of
individual drops, that is, the critical Weber
number We (crit) or a maximum drop diam-
eter d
must not be exceeded:
W e (crit) =C

¯ ε
which is transformed by using Equation
(3.19) into:
where C

and C
are empirical constants and
σ is the interfacial tension. Equation (3.25)
is only applicable if the viscosity ratio η

is not too large. Otherwise, the stable drop
diameter increases with increasing values of

, because turbulent oscillations in the
disperse phase are damped (viscosity stabi-
lization of drop size).
3) A density difference between the phases re-
sults in a tendency towards settling, and this
increases with increasing drop size. Stirring
energy must be sufficient to counteract this
tendency. The maximumdropdiameter d
that can be sustained in an emulsion at a par-
ticular rate of energy dissipation ε is given

f (ϕ) ¯ ε
and using Equation (3.19) one obtains
f (ϕ) N
where C

and C
are empirical constants,
g is the acceleration due to gravity, ϕ
is the volume ratio (disperse phase vol-
ume/continuous phase volume), and f (ϕ) is
an empirical function.
According to [524–526], turbulence stabi-
lization is only possible if the drop diameter is
larger than d
as given by Equation (3.23),
andsmaller thanbothd
and d
from Equation (3.27). It is reasonable
to assume that the Sauter mean diameter given
is proportional to the maximum diameter d
Figure 44 illustrates these relationships. Stabil-
ity is achieved only in the shaded region bet-
ween the lines defined by Equations (3.23),
(3.25), and (3.27). If ε <ε
, then d
alescence) >d
(demixing) and the emulsion
will separate into two phases. On the other hand,
if ε >ε
, then d
(coalescence) >d
(breakup) and the emulsion will be unstable
because the energy necessary for separating a
droplet pair is sufficient to breakup the droplets
Figure 44. Theoretical relationship governing the frag-
mentation (Eqs. 3.22 and 3.23), coalescence (Eqs. 3.24 and
3.25), and demixing (Eqs. 3.26 and 3.27) of droplets in a
stirred reactor. Only in the shaded region can a turbulence-
stabilized emulsion form [525]
A prerequisite for the validity of Equa-
tions (3.22) – (3.27) is the applicability of Kol-
mogoroff ’s theory of local isotropy [527–529].
The characteristic length L of the energy-con-
taining large eddies (L ≈0.08 D, according to
68 Polymerization Processes
[244]) must be larger, and the characteristic
length l of the energy-dissipating small ed-
dies [l =(γ
], where γ
is the kinematic
viscosity of the continuous phase] must be
much smaller than the drop diameter d (i.e.,
L ≫d ≫l). Equations (3.24) and (3.25) [531–
534] as well as (3.22) and (3.23) [525], [526],
[535] have been verified experimentally. Nev-
ertheless, they apply only for very small phase
ratios ϕ<0.015, which are unrealistic for indus-
trial suspension polymerizations. The polymer-
izing system is also subject to nonnegligible ef-
fects of the viscosity ratio η

. In [536], for ex-
ample, this has been taken into account by intro-
duction of the viscosity group η

σ d)
which depends only on the physical properties
of the disperse phase. At higher phase ratios,
both d
and d
increase with increasing dis-
tance fromthe stirrer [534], [537], [538]. Various
corrections [531], [534], [539], [540] have been
suggested for Equation (3.25), all of which take
the form:
=A(1+Bϕ) W e
where A and B are numerical constants. For
phase relationships such as those applicable on
an industrial scale it is therefore not possible to
assume a homogeneous energy-dissipation rate
ε; instead, it must be anticipated that ε is large
in the vicinity of the stirrer, becoming smaller
in more remote circulation zones. A simulation
program has been described [541–543] that ap-
proaches this problem by dividing the reactor
into various stirring and circulation zones and
then applying Monte Carlo methods.
The Size of the Polymer Particles. Con-
version of a monomer into polymer increases
the viscosity η
and density ̺
of the disperse
phase, and lowers the volume phase ratio ϕ. The
interfacial tension σ also changes, and grafting
reactions between polymeric radicals on the or-
ganic protective colloid and the monomer may
have to be accounted for. As has been demon-
strated by Hopff et al. [544–547] in the case
of a suspension bead polymerization of methyl
methacrylate with a relatively high concentra-
tion of a protective colloid [poly(vinyl alcohol),
Mowiol N70 (88)], systems exist in which the
final particle size is already established at very
low conversion. Polymerizing droplets main-
tain their identity, and subsequent reduction
in stirring speed has no influence on particle
size. Apparently, a turbulence-stabilized state
is reached at the very onset of polymerization.
Evaluation with respect to particle size is partic-
ularly straightforward in this case, since changes
in the above-mentioned parameters during poly-
merization are irrelevant.
Aseries of experiments in geometrically sim-
ilar reactors (see Fig. 45) coupled with dimen-
sional analysis, permitted derivation of the fol-
lowing dimensionless equation in the case of this
especially simple system:
W e
where d
is the bead diameter below which
50 wt % of the particles pass through the sieve
(in other words 50 wt % of the particles have a
diameter less than d
), Dis the stirrer diameter,
which throughout the experiments was kept in a
constant ratio to the reactor diameter, and k is a
numerical constant.
Figure 45. Dependence of the bead diameter d
on the
stirrer velocity N [545]
Experiments conducted in four geometrically similar stirred
reactors with stirrer diameter D
Curve parameter: protective colloid concentration in
g/100 cm
The dimensionless groups are:
Polymerization Processes 69

= ratio of inertial/viscous forces
Fr =
ratio of inertial/gravitational forces (3.30a)
W e=
ratio of inertial/interfacial forces
It follows that d
A relationship similar to Equation (3.30) has
been found for the suspension polymerization
of vinyl chloride [548], [549]. In this case, how-
ever, a large particle diameter region was identi-
fied with d =kN
at low stirrer speeds (with
correspondinglylarge particle diameters) as well
as a fine-particle size region with d =kN
An analogous effect has also been reported for
styrene [550].
In contrast to the very early establishment of
particle diameter in the experiments of Hopff et
al., dye-labeling experiments have shown that in
other systems [506–508], [550], [551] the par-
ticles reach the so-called identity point only at
high conversion. With these systems it is appar-
ently necessary to take into account the time and
conversion dependence of the parameters enu-
merated above. Another important observation
[550], [552] is the fact that in certain systems the
stirring time in which the unpolymerized emul-
sion reaches its final droplet diameter is longer
than that taken by the polymerizing system to
reach 50 % conversion. A faster polymerization
would therefore give larger polymer particles
due to viscosity stabilization.
The problems associated with scaling up
from small to industrial scale, particularly for
particle size, are an important concern in sus-
pension polymerization. In principle, Equation
(3.30) should be applicable, suggesting that all
that is required for maintaining constant d/D
when scaling up is to keep Re, We, Fr, and η

constant. However, Equations (3.30 a) showthat
this is not possible without changing the com-
position of the system. Furthermore, it is d, not
d/D, that must be kept constant in an industrial
scaleup. To what extent it is possible at high
Reynolds numbers to avoid an exact similarity
transformation and scale the process up on the
basis, for example, of [553], [554]
=kW e
has not yet been established experimentally (Eu
is here a modified power number in power per
unit volume). A not further defined suspension
polymerization of methyl methacrylate in 1 %
polyacrylamide solution was transformed with
constant particle size on the basis of
from a laboratory reactor (1) with D=10.1 cm
to a half-tonne scale (2) with D=81.2 cm [555]. Industrial Applications
Suspension polymerization is used for produc-
ing a wide variety of polymer types, the most
important of which are mentioned briefly. Stan-
dard polystyrene for use in injection molding
is manufactured by suspension bead polymer-
ization, as is poly(methyl methacrylate) and its
copolymers containing small amounts of acry-
late esters. Clear transparent polymers are of-
ten required, so formulations involving Picker-
ing dispersant (e.g., MgCO
) that can be dis-
solved out of the polymer with dilute acid after
polymerization are particularly advantageous.
In the case of styrene – acrylonitrile copoly-
mers, the method of choice for batch suspen-
sion polymerization is normally that involving
the azeotropic composition to minimize compo-
sitional drift. Nevertheless, complications often
arise, because considerably more acrylonitrile
than styrene dissolves in the aqueous contin-
uous phase. As conversion proceeds, acryloni-
trile diffuses into the polymer particles and the
monomer ratio in the beads changes, causing
the composition of the copolymer to change as
well [556]. The same phenomenon can accom-
pany copolymerization in heterogeneous sys-
tems generally [557].
High-impact polystyrene and ABS are often
prepared in a combined process. This begins
with a solution of polybutadiene in styrene or
70 Polymerization Processes
styrene/acrylonitrile and permits bulk polymer-
ization to occur under stirring until phase rever-
sal or inversion has occurred. Water and disper-
sant are then added and the polymerization is
completed in suspension [558], [559].
Expandable polystyrene is prepared by sus-
pension polymerization in the presence of a
blowing agent, such as pentane [560], [561]. It
is also possible to introduce the blowing agent in
a second step after polymerization, allowing it
to diffuse into the beads [562], [563]. Warming
to 80 – 110

C, generally with steam, causes the
beads to expand by foaming, their volume in-
creasing by a factor of ca. 30 – 50. Particle size
and size distributions both play important roles.
For example, if thin-walled objects are to be
made from expandable polystyrene, especially
small polymer particles are required. The un-
foamed product is fractionated by sieving prior
to drying. Figure 46 shows a schematic of a typ-
ical EPS production facility.
Figure 46. Schematic representation of the manufacture of
Styropor by batch suspension polymerization
a) Mixing tank; b) Stirred reactor; c) Puffer tank; d) Cen-
trifuge; e) Sieving; f) Drying; g) Silo; h) Packaging
The required amount of deionized water is
loaded into the reactor at ambient temperature
and agitation is started. Styrene and the initiator
pair, AIBN or benzoyl peroxide plus a finishing
initiator such as di-tert-butyl peroxide or tert-
butyl peroxybenzoate are pumped into the reac-
tor at a constant rate, while the stabilizer, either
an inorganic, insoluble, finely divided powder or
a polymeric steric stabilizer is added. The reac-
tor is closed and the heating cycle starts. Droplet
size development occurs during the heating cy-
cle. When the polymerization temperature is
reached, between 75

Cand 95

Cdepending on
the initiator type, the polymerization proceeds
until a conversion in the range 32 – 35 % is ob-
tained. This point marks the beginning of the
so-called “sticky-stage” at which point the co-
alescence rate begins to increase, causing the
beads to grow from a mean particle diameter
of about 0.2 mm to the desired size, depending
on the original stabilizer formulation, for the fi-
nal application of the resin product. During this
stage of the process, particle size is monitored
by periodic sampling of particle size growth
rate. Additional stabilizer may be added if the
growth rate is too large. At 65 – 68 % conver-
sion of monomer, the identity point is reached.
At this point the particle viscosity is sufficiently
large that collisions between particles are elas-
tic and particle size growth ceases. In addition,
the density of dispersed and continuous phases
are almost identical, and the suspension is very
stable. Autoacceleration of the polymerization
rate becomes appreciable at the identity point
and increases until ca. 95 % conversion where a
glassy-state transition occurs and the beads be-
come hard. Once the beads are hard the reac-
tion mixture is heated to a temperature above
the glass transition temperature of the polysty-
rene (T
≈ 100

C). During heating, the reactor
is pressurized with a blowing agent (5 – 8 %with
respect to polymer), a low-boiling hydrocarbon
– C
). The reactor is then pressurized with
nitrogen at 700 – 950 kPa and the so-called im-
pregnation stage starts and proceeds for 3 – 8 h.
During impregnation the blowing agent diffuses
into the beads. At the same time, the free vol-
ume increases, and the finishing initiator rapidly
generates radicals, causing a relatively rapid in-
crease to a monomer conversion of ca. 99.9 %.
The impregnation time should be sufficient to
allow the blowing agent to reach the core of the
particle and to cause the breakup of hydrocarbon
domains withinthe polymer matrix, givinga uni-
formdistribution. At the end of the impregnation
stage the suspension is cooled to 20 – 30

C, de-
pending on the blowing agent type, to freeze in
the ingredients and prevent bead expansion dur-
ing handling. Some typical properties of an EPS
grade are:
Monomer conversion >99.9 %
200 – 300
Polydispersity 2.2 – 2.4
Mean particle diameter
d 0.4 – 1.5 mm
PSD breadth σ/
d 0.20 – 0.25
Blowing agent concentration 5.0 – 8.0 %
Polymerization Processes 71
Table 3 lists required properties of the bead
for different applications.
Table 3. EPS bead properties and applications
d, mm σ/
d Density, kg/m
1.5 0.20 8 – 16 construction
1.0 0.15 12 – 20 packaging
0.4 0.10 50 – 70 coffee cups
Figure 47. Growth path for EPS beads (mean diameter
versus monomer conversion) during suspension polymer-
ization of styrene [564]
Stage I: breakup and coalescence rates are about equal
Stage II: coalescence rate exeeds breakup rate
Stage III: conversions exceed identity point (no further
breakup and coalescence)
Suspension polymerization processes give a
rather broad PSD. In some EPS applications,
such as for coffee cups, a very narrow PSD is
required and for this grade the suspension poly-
merization process is commonly carried out in
two stages to minimize off-spec resin. In the first
stage, styrene is polymerized to give the nar-
rowest PSD possible and then the suspension is
removed from the reactor and the polymer par-
ticles are classified by sieving to give the re-
quired narrow PSD. The particles are then re-
suspended in the reactor to permit impregnation
with a blowing agent in the second stage. Sus-
pension polymerization for EPS production is a
three stage process. In the first stage, the parti-
cle viscosities are low and an equilibrium par-
ticle size is obtained (rates of droplet breakup
and coalescence are equal). In the second stage,
where the viscosity of the particles is sufficiently
high, the particles grow (coalescence rate ex-
ceeds breakup rate). For EPS, Villalobos [564]
observed that no further breakup occurs beyond
50 %monomer conversion when the particle vis-
cosity is about 10
cP. Addition of stabilizer is
used to obtain the desired
d at the identity point.
At the identity point both breakup and coales-
cence rates are zero. At the end of stage II, the
PSDhas been established except for some minor
shrinkage in the third stage due to density dif-
ferences between monomer and polymer. Fig-
ure 47 shows a typical growth path for EPS
beads with
d =0.425 mm. Since
d continually
increases during stage II, the variance of the PSD
also increases significantly. Figure 48 shows the
broadeningof the PSDwithconversionobserved
by Konno et al. [565].
Figure 48. Transient drop size distributions for styrene sus-
pension polymerization [565]
◦ 3 % monomer conversion, 10 min
20 % monomer conversion, 120 min
△45 % monomer conversion, 240 min
A potentially practical method of narrowing
the PSD is to speed up the polymerization rate,
by, for example, employing bifunctional initia-
tors [566] to reduce the time for coalescence in
stage II. This approach is based on the interac-
tion of polymerization variables with the fluid
dynamical variables to achieve a desired PSD.
Suspension polymerization is the most im-
portant commercial process for the manufacture
of poly(vinyl chloride) [→Poly(Vinyl Chlo-
ride), Chap. 4.1.]. Porous beads with a rough sur-
face are advantageous for rapid incorporation of
plasticizers. This effect can be achieved by suit-
able choice of dispersant [515], [567–569] or
by the addition of a few percent n-butane [570],
[571]. A review provides a comprehensive sur-
vey of polymer particle morphology develop-
ment during suspension polymerization of vinyl
chloride [572]. A serious attempt to predict the
size distribution of primary polymer particles
72 Polymerization Processes
and bead porosity has been made [573]. Ion-
exchange resins are almost always made by sus-
pension polymerization giving spherical beads
in the size range ca. 0.3 – 1.2 mm. Most prod-
ucts use polystyrene cross-linked with divinyl-
benzene to which functional groups are subse-
quently attached (e.g., – SO
groups by treat-
ment with sulfuric acid, chlorosulfonic acid, or
). Weakly acidic cation exchangers are pre-
pared by copolymerization of divinylbenzene
with methacrylic acid, acrylate esters of lower
alcohols, or acrylonitrile. In this case the func-
tional groups are incorporated during polymer-
ization, or they result from subsequent hydroly-
sis. Macroporosity is achieved by addition of an
inert liquid which is a solvent for the monomer
but a nonsolvent for the polymer and which can
readily be removed after polymerization is com-
plete [574].
With water-soluble monomers, especially ac-
rylamide and comonomers (e.g., acrylic acid,
dimethylaminoethyl acrylate) it is common to
use “inverse microsuspension polymerization”
in which a concentrated aqueous solution of the
monomer is emulsified in an oily continuous
phase, usually a hydrocarbon, and then polymer-
ized with either an oil- or water-soluble initiator.
When an oil-soluble initiator is used with an aro-
matic continuous phase, the kinetics have been
shown to resemble those of emulsion polymer-
ization [575–577]. The resulting polymer parti-
cles are much smaller than the original monomer
droplets, and the number of radicals per polymer
particle is small (<1). However, when paraffinic
oil continuous phases are used, as is most com-
mon commercially, the locus of polymerization
is in the monomer droplets. This has been ver-
ified by dynamic light scattering measurements
which failed to detect inverse micelles and indi-
cated a constant particle morphology with in-
creasing conversion [578–580]. The polymer-
ization therefore physically and kinetically re-
sembles a suspension polymerization and the
prefix “micro” is added because average poly-
mer particle diameter is nominally 1 µm, well
below the usual size range for suspension poly-
merization. Suitable dispersants include Picker-
ing emulsifiers, polymers bearing hydrophilic
groups, or block or graft copolymers whose
components differ in solubility [581–583].
Stirredbatchreactors are byfar the most com-
mon for suspension polymerization, reaching
sizes up to 200 m
. Their construction presents
numerous engineering problems [554], [584–
588]. The most effective stirring in large reac-
tors is achieved with impellers driven from be-
low. The patent literature describes a wide va-
riety of approaches for continuous suspension
polymerization. Apparently to date there are no
continuous suspension polymerizations carried
out commercially. The main problems relate to
the fact that, on the one hand, it is important to
assure the most uniformshear gradients possible
(i.e., total back-mixing) to establish the desired
particle size distribution and to prevent coagula-
tion and clumping in dead spaces. On the other
hand, maximum conversion is also desirable,
and this is only possible in a continuous process
with a narrowresidence time distribution. Diffu-
sion of monomer through the continuous phase
may not be sufficiently rapid to ensure that con-
version is the same in all particles, independent
of their residence time in the reactor. A particle
that has a long residence may have a very low
monomer concentration with concomitant high
level of branching, cross-linking, and gel. Emulsion Polymerization
Emulsion polymerization is probably the most
versatile of the polymerization techniques, ap-
plicable with many monomer types in batch,
semi-batch (semicontinuous), and continuous
processes. The product is a finely divided (par-
ticle diameters ca. 0.05 – 0.3 µm) aqueous poly-
mer dispersion (latex) containing up to 60 wt %
solids, which can either be used in latex form
or first coagulated and dried. Particle size dis-
tribution may play an important role in the fi-
nal application, as with emulsion PVC paste
products. However, with some polymers (e.g.,
styrene – butadiene rubber), the latex particles
are coagulated during work up to rubber bales
and so their size is irrelevant, except perhaps in
the coagulation stage of the process.
Suspension and emulsion polymerization
are both begun in an aqueous emulsion of a
monomer with low water solubility. In emul-
sion polymerization, however, the locus of poly-
merization is in latex particles and not monomer
droplets, the latex particles being much smaller
and having a much larger total interfacial area
[589]. Various theories exist for the mechanism
Polymerization Processes 73
of latex particle formation, differing primar-
ily with respect to the effect of the degree of
monomer solubility in water. The polymeriza-
tion process in the latex particles is also quite dif-
ferent from that in monomer – polymer droplets
in suspension polymerization, because the pri-
mary radicals generally formin the aqueous con-
tinuous phase and migrate from there into the
latex particles. The most obvious difference in
the kinetics compared to solution or suspension
polymerization is the fact that polymerization
rate and molecular mass of the polymer pro-
duced may be increased simultaneously in emul-
sion polymerization. Various explanations have
been offered for the observed kinetic behavior.
The differences relate primarily to the question
of whether or not radicals, once they have en-
tered a latex particle, are then capable of leav-
ing again and entering other particles. The de-
cisive factors are the prevalence of chain trans-
fer to small molecules (e.g., monomer) and the
water solubility of the monomer. Finally, the
Trommsdorff – Norrish effect also plays an im-
portant role but with some modified features.
It should also be noted that polymer particles
in emulsion polymerization have a rather high
polymer concentration even at their birthtime.
Several reviews discuss kinetics and mecha-
nisms [590–602] as well as mathematical mod-
els [357], [603] applicable to emulsion polymer-
ization. Proceedings from various symposia on
emulsion polymerization and related topics have
also been published [604–611]. Theories of Emulsion
Qualitative Theory. The qualitative theory
of batch emulsion polymerization is due pri-
marily to the groups of Fikentscher [589],
[612–614] and Harkins [615–618]. It is based
on a system consisting of water, a monomer
with low water solubility, an emulsifier, and a
water-soluble initiator that decomposes to pro-
duce radicals in the aqueous phase (see Fig. 49).
The emulsifier concentration is above the criti-
cal micelle concentration (CMC) and thus mi-
celles form. The hydrophobic interior of the
micelles contains solubilized monomer, which
is apportioned by diffusion out of the emul-
sified monomer drops and through the aque-
ous phase. Initiator decomposes in the water
phase to generate primary radicals, which prop-
agate with monomer dissolved in water to form
oligomeric radicals. When an oligomeric radical
enters a micelle it propagates rapidly with sol-
ubilized monomer to form a polymer particle.
In a typical emulsion polymerization there are
about 10
monomer droplets per liter of emul-
sion, with an average droplet size of about 3 µm.
This compares with ca. 10
micelles, each con-
sisting of ca. 100 emulsifier molecules with a
diameter of about 5 – 10 nm. The total interfa-
cial area of the micelles is about three orders-
of-magnitude larger than that of the monomer
droplets. Consequently, oligomeric radicals in
the aqueous phase are much more likely to dif-
fuse into a micelle swollen with monomer than
into a monomer droplet. Polymerization thus oc-
curs almost exclusively in the micelles and poly-
mer particles which are later formed, consum-
ing monomer that arrives by diffusion through
the aqueous phase from the monomer droplets.
Micelles are thus gradually transformed into
polymer (latex) particles with a diameter of ca.
0.1 µm and a concentration of ca. 10
per liter. As polymerization proceeds a form of
subdivision occurs, with monomer being trans-
ferred from large monomer droplets with a con-
comitant increase in total interfacial area. As a
consequence, micelles are consumed by being
“stung” with an oligomeric radical from the wa-
ter phase and by being adsorbed on new inter-
facial area which is continuously being formed.
When all the micelles are consumed and the con-
centration of emulsifier in the aqueous phase is
just about to fall belowthe CMC, polymer parti-
cle nucleation (via micellar nucleation) ceases.
The interval from the start of the generation of
oligomeric radicals in the aqueous phase to the
point where micelles have been consumed is
called Stage I in the emulsion polymerization
process. At the end of Stage I, as illustrated in
Figure 50, there is a rapid drop in the free emul-
sifier concentration (which throughout Stage I
is equal to the CMC due to equilibrium with
micelles) and the surface tension (head-space
gas/latex) rises rapidly from its previously sta-
tionary value. Because the fractional coverage
of the surface of polymer particles falls after the
end of Stage I problems with particle stability
and coagulation may occur.
74 Polymerization Processes
Figure 49. Schematic representation of an emulsion poly-
A) Particle nucleation stage; B) Particle growth stage; C)
Monomer finishing stage
a) Monomer droplet; b) Micelle; c) Emulsifier molecule;
d) Latex particle; e) Water; f) Radical; g) Monomer
Figure 50. Overall rate of reaction R
and surface tension
σ as a function of conversion during the three phases of
emulsion polymerization (schematic)
Stage II is known as the polymer particle
growth stage, during which the number of par-
ticles remains constant (in the absence of co-
agulation), as does the monomer concentra-
tion [M]
in the latex particles as a result
of monomer diffusion from the reservoir of
monomer droplets. Because of the extremely
high interfacial areas (polymer particle/water
andmonomer droplet/water) andassociatedvery
rapid mass transfer of monomer, there is an
equilibrium with respect to monomer transfer
frommonomer droplets to polymer particles (the
chemical potential of monomer is the same in all
three phases, monomer droplet/water/polymer
particle). The interfacial energy per unit volume
for the small polymer particles contributes sig-
nificantly to the free energy and thus must be
accounted for as shown in Equation (3.34):
= −
ln (1−ϕ
) +ϕ
where V
is the molar volume of monomer, σ
is the interfacial tension (latex particle/aqueous
phase), r is the radius of the latex particle; ϕ
is the volume fraction of polymer in the la-
tex particle (ϕ
=1 −ϕ
, with ϕ
the volume
fraction of monomer); χ is the Flory – Huggins
polymer – solvent interaction parameter [435,
p. 522], [455].
Swelling and monomer concentration [M]
both increase with decreasing interfacial tension
σ, increasing particle radius r, and with a de-
crease in the parameter χ (which is equivalent
to the monomer being a better solvent for the
polymer; only when χ<0.5 are monomer and
polymer completely miscible).
Since σ and r increase simultaneously dur-
ing Stage II, both ϕ
and [M]
remain rela-
tively constant [619], [620] provided monomer
droplets are present. The constancy of N
total number of polymer particles per liter) and
usually results in a constant polymeriza-
tion rate R
during Stage II.
Stage III, known as the depletion or monomer
finishing stage, begins with the disappearance
of all monomer droplets. The only reservoir of
monomer for the polymerization in the latex par-
ticles is the aqueous phase. This is hardly suffi-
cient and in Stage III the monomer concentration
falls with time and conversion. The viscos-
ity of the latex particles increases dramatically
due to increase in the number of physical chain
Polymerization Processes 75
entanglement points as the polymer concentra-
tion increases. The self-diffusion coefficients of
polymeric radicals fall and the Trommsdorff–
Norrish effect, which was active in both Stages I
and II, increases in intensity with monomer con-
version [621], [622]. This can lead to a heat-kick
when temperature control of the polymeriza-
tion is inadequate. Another phenomenon which
may occur is a glassy-state transition in the la-
tex particles. This occurs when the polymeriza-
tion temperature is lower than the glass transi-
tion temperature of the polymer being synthe-
sized. The monomer acts as a plasticizer for
the polymer, and propagation essentially ceases
when the polymer – monomer solution under-
goes glass transition at the polymerization tem-
Overall Rate of Polymerization with a
Given Number of Particles. To calculate the
rate of polymerization it is necessary to knowthe
number of polymer particles containing n radi-
cals (or the average number of radicals per latex
particle). Assuming a stationary state, the fol-
lowing particle population balance may be writ-
ten [623]:
The formation rate of particles with n radicals
equals the disappearance rate of particles with n
where R
is the rate of radical entry (radical
); K
is the rate constant for radical exit
(cm/s); S is the particle surface area (cm
); K
the rate constant for bimolecular termination in
the polymer particles (cm
); and
v is the particle volume.
Smith and Ewart have derived expressions
for several limiting cases [623]:
Case 1) Rate of radical exit ≫rate of radical

In this case the average number of radicals per
particle which is given by
¯ n=


≪ 1 (3.37)
is much less than unity.
Case 2) Rate of termination >rate of en-
try ≫rate of exit

This case leads to ¯ n =1/2 on the basis of the
following simple considerations [511]: when an
oligomeric radical enters a polymer particle con-
taining no radicals polymerization is rapid and a
particle containing one radical is formed. When
a second radical enters this particle, termina-
tion is instantaneous and two radicals are anni-
hilated (two radicals cannot coexist for any sig-
nificant time). Instantaneous termination occurs
for small latex particles when the termination
constant K
is sufficiently large. Since the exit
rate is negligibly small, a given latex particle
will alternately contain either one or no radical.
Thus averaged over time ¯ n =1/2. One can also
obtain this result with a simple kinetic analysis:
application of the stationary-state hypothesis for
= 2R
and ¯ n=
= 1/2 (3.39)
where N
Since water-phase termination affects R
the same factor (on both sides of the equation)
its magnitude is irrelevant. Radical scavengers in
the water phase will for the same reasons have
no effect on ¯ n. Radical scavengers in the poly-
mer particles would, however, lower N
and ¯ n
to values below 1/2.
Case 3) Rate of exit ≪rate of entry ≥rate of


Here the latex particles are effectively flooded
with radicals, so that ¯ n ≫1, and it can be shown
that the kinetics in the polymer particles corre-
spond to those in bulk polymerization. During
the buildup of radicals in the particles with time,
76 Polymerization Processes
radical entryrate will exceedthe bimolecular ter-
mination rate; however, a stationary-state with
respect to radical concentration will be reached
as with bulk polymerization.
A general solution to Equation (3.35) has
been provided by Stockmayer [624] with mi-
nor corrections by O’Toole [625]. After multi-
plication by v/K
and the substitutions
, m=
, a= (8α)
Equation (3.35) is transformed into:
(n+2) (n+1) +N
(n+1) m+N
α =
[n(n−1) +mn+α]
Solutions to this equation follow:
¯ n=
for m= 0 (3.41a)
¯ n=
for 0<m<1 (3.41b)
¯ n=
for m≥1 (3.41c)
Here the expressions I
(a) =i
(ia) are
first-order Bessel functions, tabulated in [626],
[627]. An approximate solution to the Bessel
functions is available in [597, pp. 556, 602 ff].
Figure 51 shows the dependence of ¯ n on a and
m. Knowledge of ¯ n allows calculation of R
ing the relationship:
¯ nN
where N
is Avogadro’s number.
Figure 51. Average number of radials ¯ n in latex particles as
a function of the parameters a and m Equation (3.41) [625]
Gardon has described a series of investi-
gations in which the assumption dN
/dt =0 in
Equation (3.35) was not made [620], [628]. Re-
alistic parameters when used in the nonstation-
ary form of Equation (3.35) led to the conclu-
sion that negligible errors were introduced in
Equation (3.35) by neglecting the transient ac-
cumulation term [597, pp. 566, 602 ff], [629].
One possible exception is a system subject to
a very large Trommsdorff–Norrish effect and
where K
is no longer valid. In princi-
ple, Equations (3.41) and (3.42) may be used
to estimate the magnitude of the Trommsdorff–
Norrish effect in emulsion polymerization.
Using an appropriate relationship for the ter-
mination constant K
and its dependence on
polymer concentration or monomer conversion
in Stage III, one can calculate ¯ n versus conver-
sion as shown in Figure 52 for styrene emul-
sion polymerization. Figure 53 shows calculated
conversion – time curves for several monomer
systems using appropriate expressions for K
as a function of conversion. It is clear that the
Trommsdorff–Norrish effect is of greater impor-
tance in emulsion polymerization when Case 2
kinetics are obeyed and when the polymer par-
ticles are larger (vinyl acetate is clearly a Case
1 system).
Figure 52. Theoretical course of the average number of rad-
icals ¯ n per latex particle with increasing conversion [630]
Emulsion polymerization of styrene, calculated on the basis
of Equation (3.41)
Polymerization Processes 77
Figure 53. Time – conversion curves for emulsion polymer-
A) Methyl methacrylate (60

C); B) Styrene (60

C); C)
Vinyl acetate (50

—- calculated with the Trommsdorff–Norrish effect
· · · · · calculated without the Trommsdorff–Norrish effect
◦ experimental data
It seems remarkable that the empirical rela-
tionships for K
as a function of conversion
found for bulk polymerization can be applied
so effectively to emulsion polymerization, as
shown in Figure 53. Part of the answer as to
why this agreement exists may be that when
two radicals cannot coexist in a polymer parti-
cle (instantaneous termination), ¯ n is independent
of K
. At higher conversions when ¯ n is clearly
>0.5 for a Case 2 system, the size of polymeric
radicals in the latex particles should depend on
the rates of termination and radical entry when
chain transfer to monomer is negligible. How-
ever, if chain transfer to monomer is significant,
the size of polymeric radicals depends only on
polymerization temperature and not on the type
of polymerization process.
To explain kinetic results obtained with
styrene, for which R
fails to decline on entering
Stage III, it has been suggested that one should
consider uneven swelling of latex particles com-
posed of a monomer-rich shell and a polymer-
rich core [631–633]. The monomer concentra-
tion in the shell, which is the site of polymeriza-
tion, should then remain constant even in Stage
III. These kinetic arguments have been criticized
by several other authors [630], [634], [635] and
the observed facts can also be largely accounted
for by considering the Trommsdorff – Norrish
effect in which a simultaneous decrease in [M]
and K
effectively compensate for each other.
However, experiments involving the polymer-
ization of styrene on a seed latex where either
the monomer or the seed latex is labeled [632]
clearlysuggest that inStage II the monomer does
indeed polymerize preferentially in the outer
shell. The contradiction with respect to Equation
(3.34), which has also been verified experimen-
tally [620], [636], [637], has not been adequately
explained. Neutron scattering experiments indi-
cate that the polystyrene latex particles are uni-
formly swollen by styrene.
If the exit rate of radicals is negligible (m=0),
then a sudden reduction in the rate of initiation
in the water phase to R
=0 should result in a
constant R
. In fact, however, experiments in-
volving intermittent γ-Co [638] or UVradiation
[639] as initiator reveal that R
decreases rapidly
as soon as irradiation ceases. This suggests that
radicals can be desorbed from one latex parti-
cle and reabsorbed in another. There thus exists
an alternative termination process: interparticle
termination that reduces the mean concentration
of radicals ¯ n. Equation (3.35) makes no provi-
sion for possible reentry of a desorbed radical.
According to Ugelstad [640–643], the rate of
radical entry R
is a function of both the rate of
radical formation in the aquous phease by initia-
tor decomposition R
i, w
and the rate of desorp-
tion, diminished by the rate of termination in the
aqueous phase:
i, w

In contrast to Eq. (3.35), this expression contains
the desorption constant K
S/v [s
], re-
moving the precondition that the rate of radical
exit be proportional to the latex particle surface
area. Assuming that the radical absorption rate
into polymer particles is proportional to [R

and substituting for R

and multipli-
78 Polymerization Processes
cation by


and making the following
; α

i, w
; Y =
α = α

+m¯ n−Y α
where Y is a dimensionless group.
Equations (3.41) and (3.44) permit calcula-
tion of ¯ n as a function of a

, m, Y. The results
for Y =0 (i.e., negligible termination in the water
phase) are shown in Figure 54. It is apparent that
there is a rather large range of parameter values

and m) for which ¯ n <0.5; this is discussed
further in [640] and [597, p. 559 ff].
Figure 54. Average number of radicals ¯ n per latex particle,
assuming interparticle termination and a negligible amount
of termination in the aqueous phase (Y =0), calculated by
using Equations (3.41 and 3.44) [640]
The number of radicals in a polymer par-
ticle clearly depends on rates of radical entry,
desorption, bimolecular termination, and chain
transfer. Althoughradical capture efficiencies by
polymer particles can be high [644], efficiencies
considerably below 100 % have been observed
[645]. Brooks [644] has presented general ex-
pressions for radical absorption rates which ac-
count for reabsorption and give capture efficien-
cies less than 100 %. Various experimental tech-
niques for the measurement of desorption rates
have been employed [645–647]. Lichti et al.
[648] obtained significantly enhanced desorp-
tion rates from polystyrene particles containing
soluble hydrocarbon diluents. It has been sug-
gested that in some systems desorbed radicals
cross-terminate in the water phase and are not re-
absorbed. Nomura et al. [649] used the pseudo-
kinetic rate constant method to develop expres-
sions for nfor binary copolymerizations that fol-
low the terminal model. Nomura et al. [650]
also observed that the extent of Stage I (particle
nucleation stage) could be lengthened by radical
Mechanism of Particle Formation. As
emulsion polymerization always involves a cer-
tain amount of monomer in the aqueous phase,
and for this reason all the routes depicted in
Figure 55 represent possible reactions of the
radicals or radical ions that form in the water
phase by initiator decomposition:
1) Entry into micelles, which are then trans-
formed into latex particles
2) Propagation within the aqueous phase until
a specific critical degree of polymerization
is reached, at which point the growing
macroradical precipitates to forma latex par-
3) Entry into an existing monomer droplet,
which is converted into a latex particle
4) Entry into an existing latex particle, which is
then subject once again to propagation (seed
Figure 55. Possible radical reactions leading to particle for-
mation during emulsion polymerization (schematic)
Polymerization Processes 79
With all of these reactions, newly formed par-
ticle surface area must somehow be stabilized,
either by emulsifier or through the charge orig-
inally present on the radical ion, which usually
remains at the surface of the particle as the end
group of the resulting polymer. If the available
degree of stabilization is insufficient, the inter-
facial area will decrease by coagulation (or floc-
culation) until a point is reached at which the
charge carriers present once again permit stabi-
Depending on the nature of the rate-
determining step, the rate of absorption of rad-
icals into particles or micelles may be propor-
tional to the particle radius, surface area, or vol-
ume. Latex particles and micelles can also dif-
fer in their capture efficiencies, and differences
may even be observed between various latex par-
ticles as a result of differences in size, surface
charge, and concentration of monomer and rad-
icals [643].
In principle, the various reaction paths in Fig-
ure 55 may compete with each other, in which
case the system is extremely complex. It is of-
ten possible in practice to select reaction condi-
tions that cause one particular pathway to dom-
inate. Further elaboration of the theory is fre-
quently based on assumptions which led to one
mechanism being dominant in polymer parti-
cle formation. Smith and Ewart [623] fol-
lowed the Fikentscher – Harkins theory in as-
suming that latex particles form only as a result
of the entry into an emulsifier micelle of a rad-
ical formed in the aqueous phase. Particle for-
mation would then continue until the total sur-
face area of the latex particles A
exactly to the interface-covering capacity of the
emulsifier a
· [S] minus the area of monomer
droplets. Acorrection for emulsifier dissolved in
the water should also be made. In this expression
[S] is the emulsifier concentration and a
is the
emulsifier covering capacity per unit of emulsi-
fier (per mole or gram). Based on this assump-
tion, two limiting cases can be described, in each
of which it is further assumed that ¯ n =constant
and [M]
=constant, and that the polymer par-
ticles grow with a constant volumetric growth
rate, dv/ dt =µ=constant.
Model 1) All of the radicals formed in the
water phase by initiator decomposition enter mi-
celles, so that the rate of formation of polymer
particles equals the rate of generationof radicals.
i, w
at time t =t
, where A
· [S], it follows that
i, w
Consequently, N
i, w
· t
= 0.53
i, w
This approximation leads to an upper limit for
, because even during Stage I some radicals
enter existing polymer particles.
Model 2) Latex particles and micelles absorb
radicals at a rate proportional to their current in-
terfacial areas A
and A
. The rate of particle
formation is therefore
i, w
and it follows that
= 0.37
i, w
where µ is the volume growth rate of the latex
Table 4. Influence of various parameters on the number of particles
, the overall rate of reaction R
, and degree of polymerization
Parameter N

Temperature E
2/5 (E
3/5 (E
∗Ignoring chain transfer
Table 4 illustrates the interdependency of the
number of particles N
, the rate of polymeriza-
tion R
, and the degree of polymerization P
based on Equations (3.42) and (3.47) or (3.49)
[612]. The relationships have been confirmed
experimentally over wide ranges of the rele-
vant variables for suchrelativelywater-insoluble
monomers as styrene, butadiene, isoprene, and
chloroprene [651–658]. By contrast, other rela-
tionships are found to apply in certain situations,
80 Polymerization Processes
especially in the case of more soluble monomers
with large transfer-to-monomer rate constants,
including vinyl acetate and vinyl chloride [640],
[642], [659–664]. Even in the case of styrene it
is not possible to explain all the experimental
results on the basis of the Smith – Ewart theory.
If particle formation were to conform to Model
1, then at the end of Stage I, each latex par-
ticle would contain precisely one radical, i.e.,
¯ n =1 [665]. In addition the molecular mass of the
polymer chain in a particle nucleated near t =0
would be extremely large at the end of Stage I.
For Model 2, ¯ n =0.67 at the end of Stage I [628].
Since ¯ n =0.5 during Stage II, R
must peak at
the end of Stage I. However, no such maximum
has been observed with styrene. Moreover, N
calculated by using Equations (3.47) or (3.49)
often exceeds observed values by a factor of
2 – 3. These discrepancies can be rationalized by
assuming that latex particles are more efficient
at capturing radicals than micelles [665], [666].
Some particle coagulation would also reduce the
discrepancy. If radicals formed in the aqueous
phase can enter either micelles or latex particles,
the condition for radical balance assures that
d [R
i, w
] [R
] −K
] (3.50)
where [M
] is the micelle concentration. Assum-
ing a stationary state is valid, one obtains
] =
i, w
] +K
Particle formation should only occur after the
entry of a radical into a micelle, so
] [R
] (3.52)
Substitution of Equation (3.51) into (3.52) gives
] R
i, w
] +K
i, w
i, w
where [S]/[M
] =M
is the aggregation number
for emulsifier molecules in micelles (in many
cases, M
≈100); K
] =ε N
/[S] is
the ratio of the rate of entry into latex particles
versus micelles, and ε =(K
izes the radical capture efficiency of latex parti-
cles relative tomicelles. For ε N
/[S] ≪1, Equa-
tion (3.53) is equivalent to Equation (3.45) and
Smith – Ewart kinetics are applicable in the form
of Equation (3.47).
On the other hand, in the case where
ε N
/[S] ≫1, there is a somewhat differ-
ent dependency, with N
i, w
. To obtain agreement between cal-
culated and experimental N
, it is necessary to
introduce the values ε =1.3 ×10
for styrene
[666] and ε =1.2 ×10
for vinyl acetate [667].
This is explained by assuming that radicals exit
very rapidly from very small latex particles as
well as micelles – so rapidly that they do not have
sufficient time topropagate tothe extent required
for insolubility in the water phase. Hansen and
Ugelstad [597, p. 556, 602 ff], [668] have ap-
plied Danckwerts theory of diffusion with ho-
mogeneous reaction [669] to this problem. The
rate of absorption by latex particles that already
contain a radical is significantly larger than that
of latex particles and micelles containing no rad-
icals, because the rate of termination between
two radicals is much higher than the rate of prop-
agation. Termination by combination with a sec-
ond radical normally leads to molecules that are
no longer able to desorb due to having exceeded
the critical degree of polymerization P
In the derivation of Equations (3.47) and
(3.49) the volumetric growth rate µ of a latex
particle, given by
·¯ n (3.54)
was considered constant since ¯ n was taken to be
a constant, independent of the latex particle age.
This assumption is no longer valid when Case
1 kinetics apply, and ¯ n increases with particle
growth. Reference [643] has therefore adopted
the following general relationship for the rate of
particle formation:
where N
is the number of micelles, r
is the
micelle radius, and r
is the particle radius, χ
(=1, 2, 3) is the exponent that characterizes the
dependence of the capture rate on the radii of the
micelles and polymer particles, and δ is an effi-
ciency factor for the capture of radicals by mi-
celles relative to polymer particles. This in turn
is a function of the factor ε in Equation (3.56):
Polymerization Processes 81
δ =
Neglecting termination in the aqueous phase,
Equation (3.43) is transformed into
i, w
¯ nN
and Equations (3.55) and (3.57) then lead to
¯ nN
δ N
_ (3.58)
Assuming that only monomer transfer radicals
are capable of desorbing from latex particles,
Hansen and Ugelstad [643] constructed a
balance equation for the formation and disap-
pearance of latex particles containing a single
monomer transfer radical, and then proceeded
to solve it under the assumption of steady state.
One can then assume either that desorbed radi-
cals do not add monomer in the aqueous phase,
and instead simply wander from one particle
to another, or that such radicals do in fact add
at least one monomer molecule in the aqueous
phase. In the latter case, no monomer transfer
radicals absorb into the latex particles, and the
chain-transfer reaction becomes the sole source
of monomer radicals in the particles. For further
details refer to the original article [643]. What
finally results from these calculations is a set
of curves representing the number of particles
as a function of the emulsifier concentration
[S] and the rate of initiation R
i, w
as shown in
Figure 56 for various monomer types, assum-
ing there is no chain transfer to monomer in the
aqueous phase. Other graphs of interest corre-
sponding to various values of δ and χ may be
found in [643]. These curves serve as a basis for
the rule that the sumof the orders with respect to
[S] or [I] (or R
i, w
) for styrene, methyl methac-
rylate, vinyl acetate, or vinyl chloride is always
in the vicinity of 1.0. Stated more generally
∼ [S]
, N
∼ [I]
where 0.6 <z <1.0. If desorption and reabsorp-
tion dominate (total radical entry rate ≫R
i, w
z =1.0; if there is no desorption of radicals,
z =0.6 (usual value for styrene). The actual value
of z may vary with [S] and [I]. If all other vari-
ables are held constant, then an increase in [S]
or [I] leads to an increase in the order z relative
to [S] or [I], while the order with respect to the
variable that is held constant decreases [643].
Figure 56. Number of particles N
as a function of A) the
initial emulsifier concentration [S]
and B) the rate of initi-
ation R
i, w
for five different monomers [643] δ =1.0; x =1;
i, w
in A=10
; [S]
in B=1.0 g/L
dotted lines: Smith – Ewart theory (Eqs. 3.47 and 3.49)
VAc: vinyl acetate; VC: vinyl chloride; MMA: methyl meth-
acrylate; BMA: n-butyl methacrylate; S: styrene
In the case of monomers that are significantly
more soluble in water than styrene, it is also nec-
essary to take into account the fact that latex par-
ticles can be formed by homogeneous nucleation
in the aqueous phase [655]. However, Equations
(3.47) and(3.49) basedonthe Smith – Ewart the-
ory(which, incidentally, donot explicitlyrefer to
particle formation from micelles) remain valid
even when homogeneous nucleation is signifi-
cant [670]. The rate of particle formation then
becomes equal to either R
i, w
(for Model 1 and
Eq. 3.47) or R
i, w
minus the rate of radical cap-
ture by previously formed latex particles (Model
2 and Eq. 3.49). The volumetric growth rate µ is
taken here to be constant, and particle nucle-
ation ceases when the total latex particle surface
area corresponds to a
[S]. The concentration of
free emulsifier should at this point be somewhat
lower than the CMC.
Fitchand coworkers have developed the the-
ory of homogeneous particle nucleation further
[606, pp. 73 – 102, 103 – 116], [671–675]. With
[S] <CMC, a radical produced in the aqueous
phase by initiator decomposition continues to
grow in this phase until it is either absorbed by
an existing latex particle or a specific critical de-
gree of polymerization P
has been exceeded,
82 Polymerization Processes
whereupon the macroradical precipitates and
forms a primary polymer particle. In this case
the rate of particle formation is described by
i, w
− v
A steady-state (where R
i, w
) is reached at
t =t
, which means that the number of polymer
particles nucleated is given by
s _
i, w
− v
dt (3.61)
originally, the rate of capture v
was taken to be
[628], [673].
i, w
L (3.62)
where L is the length of the path traversed by
the growing radical from its point of origin to
the point where it precipitates as a primary par-
ticle (collision theory). This proposal has been
subjectedtocriticism[493, pp. 163 ff], [629] and
the expression
= 4πD
r (3.63)
where D
is the mean diffusion coefficient
for oligomeric radicals and latex particles in the
aqueous phase and C
is the concentration of
oligomeric radicals in the same phase in fact pro-
vides a better fit than Equation (3.62) to exper-
imental data on particle nucleation in the pres-
ence of seed particle [675]. The effectiveness
of seed particles in capturing oligomeric radi-
cals before they grow and precipitate to form
newparticles corresponds not to N
but rather
to N
r. Hansen and Ugelstad [597, pp. 556,
602 ff ], [643] have proposed a model for radical
capture that takes into account not only the pos-
sibilityof radical desorption, but alsothe electro-
static repulsion between radicals and particles.
One practical application of these considera-
tions relates to stepwise seed polymerization as
a means of preparing uniformly large (monodis-
perse) latex particles [676], [677], in which the
key consideration is keeping v
as large as pos-
sible; i.e., preventing the formation of newpoly-
mer particles.
Figure 57. Number of particles N
as a function of
conversion in the emulsion polymerization of methyl
methacrylate with sodium dodecylsulfate as emulsifier
[606, pp. 73 – 102]
Concentrations in mol/L: [S
] =7.35 ×10

] =1.14 ×10
; T =30

In certain formulations (e.g., in the absence of
emulsifier, or where the emulsifier concentration
is very low) charge density on the polymer par-
ticle surface is insufficient to stabilize the result-
ing particles. Moreover, with relatively soluble
monomers such as methyl acrylate the interfa-
cial tension is especially low, and emulsifiers are
apparently less strongly adsorbed. The relation-
ships here are further complicated by the fact
that particles tend to coagulate until the surface
area has been reduced (surface charge density
has increased) sufficiently to restore stability, a
process for which experimental evidence also
exists [590, pp. 292 ff], [629], [678]. Figure 57
shows experimental data for the production of
particles by homogeneous nucleation, in which
methyl methacrylate was polymerized with var-
ious rates of initiation R
i, w
and sodium dodecyl
sulfate concentrations ranging from zero to the
CMC. With increasing conversion the number
of particles passes through a maximum before
falling to a constant value. The conversion at this
maximumas well as the final constant number of
polymer particles is lower for lower R
i, w
and lower emulsifier concentrations. Very sim-
Polymerization Processes 83
ilar results have been obtained with ethyl acry-
late [679]. Electron micrographs of the resulting
polyacrylate latex particles after etching with O
clearly show that they were formed by coagula-
tion of a large number of smaller primary parti-
If limited coagulation (or flocculation) oc-
curs, it is necessary to also take into account
the rate of flocculation v
, transforming Equa-
tion (3.60) into
i, w
− v
− v
The Smoluchowski theory [680] can be used to
calculate the flocculation rate v
If to an anionic or cationic emulsifier there is
added a small amount of a straight-chain alco-
hol whose chain length corresponds at least to
that of the emulsifier, then emulsification leads
to an especially stable emulsion consisting of
many very small monomer droplets. Polymeri-
zation of such an emulsion with an oil- or water-
soluble initiator can, in an appropriate formula-
tion, lead to almost total adsorption of the emul-
sifier on the surface of the monomer droplets.
Since the number of micelles is no longer large
compared to the number of monomer droplets,
polymerization occurs partially or even princi-
pally within the monomer droplets. The conse-
quence is a bimodal distribution of polymer par-
ticle sizes, where small particles formed in the
aqueous phase are accompanied by large parti-
cles whose origin is in the monomer droplets. In
the limiting case, the size distribution of the la-
tex particles corresponds almost exactly to that
of the original monomer droplet size distribution
[681], [682]. These relatively large latex parti-
cles may contain considerably more than one
radical and the observed polymerization kinetics
are similar to those for homogeneous bulk poly-
merization [683], [684]. This therefore repre-
sents a transition toward suspension bead poly-
An emulsion polymerization in which poly-
merization occurs in both latex particles (formed
from micellar or homogeneous nucleation) and
monomer droplets is called miniemulsion poly-
merization (a term coined by the Lehigh Uni-
versity Group). For such systems bimodal PSD
as well as polymerization rates have been both
measured and predicted [685–687].
Song and Poehlein [688–690] have devel-
oped newapproaches to modeling homogeneous
nucleationfor monomers havinga range of water
solubility. They account for the variation of the
critical chain length for precipitation with con-
centration, and for sparingly soluble monomers
suggest that oligomers generated in the water
phase form micelles which are then stung by a
radical to generate polymer particles. They also
showed that the number of polymer particles N
increases slowly with emulsifier concentration
[S] below the CMC, where homogeneous nu-
cleation is dominant, but rapidly increases above
the CMCdue to micellar nucleation. Others have
concluded that micellar nucleation is dominant
even for monomer with appreciable water solu-
bility [691].
Radical scavengers (e.g., O
and monomer
inhibitors such as tert-butyl catechol) can have
interesting effects on the number of polymer par-
ticles formed and ¯ n. Radical scavengers have
been classified as water soluble and monomer
(organic) soluble [692], [693]. Oxygen, which
dissolves in water, monomer droplets, micelles,
and polymer particles, mainly influences the ini-
tiation of particle nucleation. Oxygen dissolved
in the aqueous phase reacts rapidly with primary
radicals, preventing particle nucleation. This re-
sults in an induction period in which no poly-
merization occurs. The induction period ends
when the oxygen content of the aqueous phase
has been reduced to an almost indetectable level.
After the induction period, apart from usually a
minor loss of initiator, the polymerization takes
its normal course. However, in the presence of,
say, tert-butyl catechol (an oil-soluble inhibitor)
in the micelles and polymer particles, polymer
particles are nucleated, but ¯ n can be very low
due to radicals reacting with inhibitor. This re-
duces the volumetric growth rate µ and hence
a larger number of polymer particles are nu-
cleated (refer to Equations (3.47), (3.49), and
(3.54). Once the organic-soluble inhibitor has
been consumed, the polymerization rate recov-
ers but to a rate higher than originally expected
in the absence of the inhibitor. This phenomenon
can cause low-frequency oscillations in reactor
trains when inhibitor contents in monomer recy-
cle streams vary and potential safety problems
for all reactor types (heat generation rate may be
84 Polymerization Processes Physicochemical Parameters of
This section treats some properties of disper-
sions that can be unambiguously described in
terms of physiochemical quantities. In addition
to these, applications technology makes use of
a number of other characteristics, primarily em-
pirical quantities and tests, [694], [695].
Molecular Mass Distribution of Linear
Homopolymer Chains. In emulsion polymer-
ization, chain transfer to monomer is more im-
portant than in homogeneous bulk polymeriza-
tion because bimolecular termination rates for a
givenpolymerizationrate are generallylower for
emulsion polymerization. This is why it is pos-
sible to obtain high molecular mass at high poly-
merization rates in these systems. When transfer
to monomer is dominant in controlling molec-
ular mass development, the process type is ir-
relevant and molecular masses of linear chains
depend solely on polymerization temperature.
Therefore, equations developed in Section 2.2
for bulk and solution polymerization in homoge-
neous media may be used to calculate molecular
mass distributions. A useful experimental test
to determine whether chain-transfer reactions
to small molecules (monomer or chain-transfer
agent) are dominant in producing polymer is to
change the concentration of initiator by several
fold. If molecular masses decrease with increas-
inginitiator concentrationthena significant frac-
tion of polymer chains are formed by bimolec-
ular termination. However, if polymer molecu-
lar mass is independent of initiator concentra-
tion, then chain-transfer reactions are dominant
in producing polymer chains [696].
When termination reactions are significant in
molecular mass development, the calculation of
MWD and average molecular masses is gener-
ally not straightforward. There are several com-
plicating factors. Firstly, the MWD depends on
the polymer particle size distribution, which is
difficult to predict in commercial latex systems.
Even if the PSD were known one would still
need to know the mechanism by which radicals
enter particles. Attempts to predict the PSDhave
been made by using population balance methods
Experimental verification of these PSD pre-
dictions is lacking in most cases. The molecular
masses depend on radical entry rate per parti-
cle, which in turn is some unknown function of
particle size and number. For the special case
of a monodisperse latex the radical entry rate
is known, however, and this case can be easily
treated when termination is instantaneous (rate
of radical entry is much smaller than the rate of
termination in the polymer particle; or in other
words two radicals cannot coexist in a poly-
mer particle). This is true for Case 2 kinetics
(¯ n =1/2). An expression is now derived which
describes molecular mass development for this
special case. Transfer to monomer and to chain-
transfer agent are included in the analysis.
Consider an oligomeric radical in a polymer
particle. The probability that this radical adds r
monomer molecules and then terminates either
by chain transfer to monomer or chain-transfer
agent T or by instantaneous termination with a
new oligomeric radical which enters the particle
from the aqueous phase is given by ϕ
(1 −ϕ),
i, w
The instantaneous weight chain length distribu-
tion W(r, t) is therefore given by
W (r, t) =
r (1 −ϕ) ϕ

r (1−ϕ) ϕ
=r (1−ϕ)
exp (− (1−ϕ) r) (3.66)
where K
and K
are rate constants for chain
transfer to monomer and chain-transfer agent T.
Equation (3.66) is the most probable distribu-
tion, with number- and weight-average degrees
of polymerization given by
= 2 (3.68)
These expressions should be valid for systems
such as styrene and methyl methacrylate when
Case 2 kinetics apply and the PSD is quite nar-
row. It is worth mentioning that in bulk polymer-
ization of styrene at low conversions the poly-
dispersity (P
) is 1.5 because bimolecular
termination by combination produces most of
Polymerization Processes 85
the polymer chains. A polydispersity of 2 in
emulsion polymerization is due to the fact that
when termination is instantaneous, termination
by combination acts like termination by dis-
proportionation. In fact the polydispersity (for
polymer produced instantaneously) obtained in
emulsion polymerization of any monomer type
will always be equal to or greater than that in
homogeneous solution or bulk polymerization.
Equations (3.66) – (3.68) apply to an essentially
monodisperse latex. For polydisperse PSD it is
clear that instantaneous molecular mass proper-
ties will be broader as will the MWDof polymer
accumulated in the polymer particles over poly-
merizationtimes of several hours. For most com-
mercial recipes, chain-transfer agents are used to
control molecular mass development. In these
cases, the MWD is independent of the PSD,
and molecular mass calculations for both poly-
mer produced instantaneously and accumulated
polymer are straightforward. ϕ is then equal
to K
, the instantaneous weight
chain length distribution is again given by Equa-
tion (3.66), and the MWD of the accumulated
polymer for a batch reactor is given by Equation
W (r, t) =
W (r, t) R
Several theoretical papers dealing with MWD
development in emulsion homopolymerizations
are available [701–705]. The problem has now
been fully solved [706], [707] for the case when
two or more radicals can coexist in a polymer
particle (zero – one – two, systems). When the
PSD is broad, the population balance equations
for particle size and molecular mass are cou-
pled, requiring numerical solution of a large set
of partial differential equations [708].
Polymer Chains withLong-ChainBranch-
ing. Long-chain branching and cross-linking
can occur as a result of chain transfer to polymer
and by addition of polymeric radicals to termi-
nal and pendant double bonds. The dimension-
less groups which are relevant in polymer chain
modification by these reactions are


where K
, K

are chain transfer to polymer
rate constant and rate constant for the addition
of polymeric radicals to terminal and pendant
double bonds, respectively; Q
is the number of
moles per liter of monomer molecules chemi-
cally bound to polymer chains (proportional to
grams per liter of polymer); Q
is moles of poly-
mer per litre which have a terminal double bond;
is the fraction of monomer molecules in the
polymer chains which have an extractable atom;
is the fraction of monomer molecules in the
polymer chains which have a pendant double
bond. As these dimensionless groups increase
in value, long-chain branching and cross-linking
(cross-linkingdensityandgel/sol ratio) increase.
These groups increase with monomer conver-
sion and usually increase with polymerization
temperature. Long-chain branching and cross-
linking reactions are more important in emul-
sion polymerization than in homogeneous so-
lution, bulk, and suspension polymerization be-
cause evenat the birthof a latexpolymer particle,
the concentration of polymer in the particle is
large [709]. Chain branching, cross-linking, and
gel formation are undesirable for the manufac-
ture of cold SBR and NBR by continuous emul-
sion polymerization. To minimize long-chain
branching, three important features of plant de-
sign are:
1) Alarge number of back-mixed reactors in se-
ries (this gives a narrow residence-time dis-
tribution which is desirable for low levels of
2) The final conversion is kept rather low (ca.
63 % monomer conversion for cold SBR)
3) The polymerizationtemperature (ca. 5

cold SBR) is kept low to reduce K

When carrying out semi-batch emulsion
polymerization, extending the addition time of
monomers lowers [M]
, and this can lead to
higher levels of long-chain branching and cross-
Linear and Branched Copolymer Chains.
For such calculations, it is recommended that
the pseudo-kinetic rate constant method be em-
ployed. Emulsion copolymerizations can be suc-
cessfully modeled (calculations of polymeriza-
tion rate, chain microstructure, molecular mass,
86 Polymerization Processes
and long-chain branching and cross-linking) by
application of the pseudo-kinetic rate constant
method [417], [649], [710] and properly ac-
counting for changes in chemical and physical
properties during the course of polymerization
Copolymer composition is usually control-
ling semi-batch operation [357], [405], [714],
[715]. The composition of polymer particles de-
pends on the thermodynamic compatibility of
polymer chains and is not always spatially uni-
form. Core/shell morphology, which is often
the planned particle morphology for specialty
products, can be effected by grafting and cross-
linking reactions as well as compositional drift
[715–718]. Special end use properties can be ob-
tained by controlling morphology [719], [720].
The morphology of latex particles is also a func-
tion of the mechanism of particle formation.
Limited coagulation (flocculation) leads to latex
particles composed of a number of not entirely
fused smaller primary particles. Such particles
are often not smooth and spherical, displaying a
rather rough surface and an irregular lumpy or
“potato-like” shape [721].
Polymer Particle Size Distribution. In
general, the PSD is narrower the lower the
conversion at the end of Stage 1 is relative
to the final conversion at the end of the poly-
merization. In the limiting case of stepwise seed
polymerization, no new polymer particles are
produced, even though a very high monomer
conversion is reached, resulting in larger latex
particles that are nearly monodisperse in PSD
[676], [677]. A semiquantitative calculation
[590, p. 275 ff] based on Smith – Ewart Case 2
kinetics shows that PSDnarrows with increasing
monomer/water ratio, as well as with increasing
temperature, increasing initiator concentration
in the aqueous phase, and decreasing emul-
sifier concentration [S]. Experiments involving
styrene have confirmed these predictions. Quan-
titative calculations are also in good agreement
with experiment [606, pp. 153 – 161] for styrene
emulsion polymerization. A more comprehen-
sive population balance model which accounts
for coagulation in the seeded emulsion poly-
merization of vinyl chloride has been developed
[722]. The predicted bimodal distributions of
particle size are in good agreement with experi-
mental data.
Gianetti [699] in a theoretical study of the
evolution of PSD in Stage 2 has reviewed the
more important theoretical studies anddiscussed
their limitations. The results obtained represent
a generalization of previous theories in that
1) A comprehensive description for monomer
systems which conform to zero – one kinet-
ics has been made
2) The contribution of latex particles having
more than one growing radical has been
properly accounted for
3) Bimolecular termination has been explicitly
included in the model (at least where mutual
annihilation of two growing chains is not the
main termination reaction)
4) General expressions for the time evolution
of the cumulants of the PSDs (both in the
transient and nontransient case) have been
Gianetti’s solutions not only revise theoret-
ical misinterpretations which appeared in the lit-
erature, but also allow rate coefficients to be ex-
tracted with more precision fromreliable experi-
mental data. In this connection it has been shown
that rate coefficients obtained from experimen-
tal PSD data are in good agreement with val-
ues found by using dilatometry to measure rates
of polymerization. Recent interest in analyzing
the experimental time evolution of PSD is due
mainly to the possibility of determining kinetic
rate constants with a small confidence interval
[602], [723]. According to Gianetti’s solutions
PSDand kinetic data are not independent of each
other at steady state (in other words, if a certain
volume dependence for the entry rate constant is
assumed, from the analysis of an experimental
PSDone must find the same volume dependence
for the exit rate constant). Apparently, PSDs for
systems with ¯ n ≤1/2 are insensitive to assump-
tions about the mechanisms of radical entry and
exit. In this connection, a newapproach based on
the effect of PSD on MDW has been proposed
[724]. In fact, a similar approach was proposed
much earlier by DeGraff and Poehlein [725].
A CSTR was used to obtain a broad PSD for
styrene emulsion polymerization, and assuming
that radical capture was according to the colli-
sion theory (capture rate ∼r
), a polydispersity
of 4.84 was calculated for the MWD, DeGraff
and Poehlein’s MWD measurements showed
that the molecular mass averages
Polymerization Processes 87
were independent of mean residence time and
that the polydispersity was ca. 3. The discrep-
ancy between theory and experiment may be due
to any number of possibilities, including:
1) Perhaps the collision model is not valid (try
the diffusion model)
2) Larger latex particles may not obey Case 2
3) Transfer to monomer may not be insignifi-
Similar experimental data were found for
continuous emulsion polymerization of styrene
in a CSTR [726]. Simultaneous growth of la-
tex particles by polymerization and coagulation
may occur at various stages in emulsion poly-
merization [688–690], [723], [727–730]. For the
calculation of PSD in the emulsion polymeriza-
tion of vinyl chloride, it may be necessary to
account for coagulation [731], [732].
The extent of coverage of the particle sur-
faces by emulsifier is an important factor in the
stability of a dispersion. For example, this cover-
age should not be too large if the polymer is to be
later recovered by controlled coagulation. The
surface coverage is evaluated in a detergent titra-
tion [733], [734], in which the amount of emul-
sifier that must be added to give total monomo-
lecular coverage of the surface is measured. To-
tal coverage is indicated, for example, by the
point where additional emulsifier no longer low-
ers the surface tension (surface tension remains
constant after micelles are formed). If the sur-
face coverage required for particle stability is
known, emulsifier can be added during Stage II
to maintain stability but not form new micelles
with the danger of nucleating a second family of
particles. More is involved here than simply the
adsorption of an emulsifier on the particle sur-
faces, however. The majority of the hydrophilic
end groups on polymer molecules also tend to
migrate to the interface (e.g., – OH, – SO
, –
COOH), thereby contributing to stabilization of
the polymer particles. A comparable effect is
achieved by the addition of small amounts of
hydrophilic comonomers (e.g., acrylic or meth-
acrylic acid), which polymerize preferentially at
the particle surface [721].
The minimum film-forming temperature
of a polymer is the lowest temperature at which
a dispersion can be converted into an integral
film on a surface by evaporation of the water.
This normally corresponds approximately to the
glass transition temperature T
of the polymer
and is one of the most important application pa-
rameters of a polymer dispersion. Copolymer-
ization of monomers whose homopolymers have
a range of glass transition temperatures makes
it possible to achieve desired values for both
the glass temperature and the minimum film-
forming temperature. The glass transition tem-
perature [T
] of the copolymer can be calculated
by using the equation
with K=
where W
and W
are mass fractions of
monomers 1and2inthe copolymer, T
are the glass transition temperatures of the cor-
responding homopolymers, and ∆α
and ∆α
are the differences between the thermal expan-
sion coefficients above and below T
(melt and
glass) for the two homopolymers. Inverse Emulsion Polymerization
In inverse emulsion polymerization, a hy-
drophilic monomer is dissolvedinwater, emulsi-
fied in a continuous hydrophobic oil phase with
a water-in-oil emulsifier, and polymerized by us-
ing an oil- or water-soluble initiator. The product
is a latex consisting of very small polymer par-
ticles, swollen with water and suspended in an
oil continuous phase. The emulsified monomer
droplets are also very small, and they may serve
as the source of some of the latex particles
(a form of miniemulsion polymerization). The
overall rate of polymerization is significantly
higher here than in the corresponding solution
polymerization. This observation strongly sup-
ports the idea that what is occurring is a true
inverse emulsion polymerization rather than an
inverse suspension polymerization. When oil-
soluble initiators are used with aromatic con-
tinuous phases the kinetics have been shown
to resemble those of emulsion polymerization
[576], [577], [735] with the locus of nucleation
of particles in inverse micelles. However, when
paraffinic oil continuous phases are used, as is
most common commercially, the locus of par-
ticle nucleation and polymerization is in the
88 Polymerization Processes
monomer droplets and the process is properly
called inverse suspension polymerization (the
term microsuspension is often used because the
monomer droplets are nominally 1 µm in diam-
eter) [575]. This has been verified by dynamic
light scattering measurements which failed to
detect inverse micelles and indicated a con-
stant particle size throughout the polymeriza-
tion [578–580]. Reviews of polymerization in
inverse emulsions and microemulsions are avail-
able [736–738]. Inverse microsuspension poly-
merization has been used to study the kinetics
of polymerization of acrylamide with cationic
comonomers (quaternary ammonium cationic
monomers) [739].
Water-in-oil emulsions of high molecular
mass polyacrylamide and acrylamide copoly-
mers (anionic and cationic) are particularly use-
ful as flocculating agents in sewage treatment
and as retention aids in papermaking. At the
present time inverse emulsion and microsuspen-
sion polymerization is the only technology for
the large-scale production of very high molec-
ular mass polymers in a liquid-like form that
affords a convenient suspension viscosity, high
solids content, and easy phase inversion during
application [740–742]. Semi-Batch Emulsion
In semi-batch polymerizations, water,
monomers, initiators, and emulsifiers may be
added to a reactor over a time period which
is comparable to the total polymerization time
(usually over several hours). Several feed poli-
cies have beenemployed. For example, a starting
mixture of water, emulsifier, and initiator is first
prepared, usually also containing a portion of
the monomer; the remaining monomer (often to-
gether with initiator) is added during the course
of polymerization (monomer feed) [743]. With
another procedure, the polymerization is begun
in a portion of the total batch, the rest being
fed into the reactor gradually after the onset of
polymerization in the form of a monomer emul-
sion (emulsion feed), although the composition
of the feed may well differ somewhat from the
material used to initiate the process [744].
Semi-batch processes are intermediate bet-
ween batch and continuous polymerization pro-
cesses. A monomer-feed process based on a
very large starter mix resembles more batch pro-
cesses, whereas an emulsion semi-batch process
involving a small initial charge with most of the
monomers being fed in during the semi-batch
period is more similar to continuous processes.
These two semi-batch methods are often men-
tioned in the patent literature [745]. Their advan-
tages include better control of polymerization
and heat-generation rates by appropriate manip-
ulation of feed rates. Moreover, the concentra-
tion of unreacted monomer can be minimized
(offering a safer process which is less prone to
runaway) and cold feed can give higher produc-
tivity (less demand for jacket or condenser cool-
ing, for example). In the case of copolymeriza-
tions, it is possible to manipulate monomer feeds
to control copolymer composition [746–751]. In
particular, such methods are often exploited for
the purpose of reachinga specific degree of poly-
merization, particle size, or particle size distri-
bution without changing the overall composition
of the copolymer in the latex particles. Adjust-
ment of the process parameters can also have
an influence, for example, on the stability of an
acrylate dispersion [752–755].
Kinetic studies [756], [757] have shown that,
provided the feed rate is not too large, both
types of semi-batch polymerization experience
a quasi-steady state in which the polymeriza-
tion rate and feed rate of monomer remain com-
parable. During the semi-batch feeding period,
the concentration of monomer [M]
is rela-
tively constant and it stays below the satura-
tion concentration predicted by Equation (3.34).
The resulting conversion – time curves are lin-
ear over a wide range of monomer feed times.
Increasing the monomer feed rate causes an in-
crease in [M]
and according to Equation (3.42)
this also leads to increases in both R
and P
Slower feed rates prolong the steady state pe-
riod, and this should result in a narrower MWD
for the polymeric product [757], [758]. Prolong-
ing the monomer feed period lowers [M]
raises polymer concentration. For certain types
of monomer this can lead to greater long-chain
branching and cross-linking [355], [357].
When every ingredient except a reserve por-
tion of the monomer is initially charged to the
reactor, the phase ratioof monomer/water differs
from the corresponding batch process, but this
has no effect on the number of particles nucle-
Polymerization Processes 89
ated. On the other hand, when polymerization is
initiated in a portion of the complete recipe, the
number of polymer particles nucleated per unit
volume of emulsion may not be the same as for
a batch process. Clearly the number of particles
nucleated in the initial charge will be much less.
If the onset of addition is delayed until some
time after polymerization has begun, then Stage
I (the nucleation stage) for the initial charge may
have been completed. If no further particles are
nucleated during the semi-batch feed period, the
feed will be entirely directed towards the growth
and stabilization of the existing polymer parti-
cles. The number of polymer particles is then
fewer and their size at the end of the polymer-
ization is larger. Based on the same total recipe,
the two semi-batch processes just described can
be compared and contrasted as follows:
When the initial charge and the semi-batch
feed have the same recipe (composition), fewer
(hence larger) latex particles are produced than
for the batch process or the semi-batch process
with just monomer fed to the reactor over time.
If particle formation is avoided during the semi-
batch period, then the initial rate of polymeriza-
tion R
p, o
and the number of particles nucleated
will be proportional to the size of the initial
Assuming particle formation does not oc-
cur during the semi-batch feed period, emulsion
feed provides a narrower PSD than monomer
feed or batch polymerization. If particle for-
mation does occur during emulsion feed, then
the PSD becomes broader, and in extreme cases
it can be even broader than with the other
processes. Particle formation during semi-batch
feed can be suppressed by using a larger amount
of initial charge and prolonging the time period
before semi-batch feed is initiated (i.e., more
polymer particles are nucleated and grow larger
before semi-batch feed is initiated). Taking the
increasing surface area into account also makes
it possible to adjust the emulsifier feed so that
new polymer particles are not nucleated and no
coagulation occurs [759].
As long as the rate of addition of monomer is
sufficiently large to keep the polymer particles
saturated, then the rate and degree of polymer-
ization for both semi-batch processes are inde-
pendent of feed rate.
If the monomer concentration falls below its
saturation value in the polymer particles (due
to slow monomer feed, for example) then the
rate of polymerization will equal the monomer
feed rate. The rate of polymerization and heat-
generation rate will increase with increasing
monomer feed rate. The polymerization temper-
ature can therefore be controlled by manipulat-
ing the monomer feed rate.
For the control of copolymer composition
distribution, various monomer feed policies may
be used and equations have been developed to
determine the appropriate time-dependent feed
rates required [356], [357], [405]. Consideration
of molecular mass, long-chain branching, and
cross-linking is also possible [357]. Continuous Emulsion
Continuous emulsion polymerization is used
particularly where the latex is to be coagu-
lated and the solid polymer recovered. Im-
portant examples include the manufacture of
styrene – butadiene rubber (cold SBR) [760–
762], acrylonitrile – butadiene rubber (NBR)
[763], polychloroprene [764], [765], SAN and
ABS polymers [766–769], and poly(vinyl chlo-
ride) [733], [770]. For products used in latex
form, most manufacturers prefer the flexibility
associated with batch and semi-batch processes,
especially with product lines that are subject to
frequent change. Apparently, however, there is
also a certain amount of large-scale polymer dis-
persion manufacture by the continuous process.
Systematic investigations have been carried
out on the kinetics and mechanisms of par-
ticle formation in continuous stirred-tank or
stirred-cascade reactors for styrene [771–781],
styrene – butadiene [782], [418], [419], ethylene
[783], vinyl chloride [733], [784], [785], vinyl
acetate [786–791], methyl methacrylate [786],
and methyl acrylate [776]. A tubular reactor has
also been analyzed [780] and review articles are
available [792], [793] on the general subject of
continuous emulsion polymerization.
The most important elements of the theory
of emulsion polymerization in a stirred reac-
tor or stirred reactor cascade have been pre-
sented by Gerhsberg and Longfield [771].
They began with the Smith – Ewart assumption
that latex particles originate with the entry of
an oligomeric radical into a micelle, and that
90 Polymerization Processes
radicals enter both latex particles and micelles
according to their surface areas (collision the-
ory, with no distinction between micelles and
polymer particles). The following equation then
describes the steady state with particle formation
rate equal particle outflow rate (Case 2 kinetics
i, w

= 0 (3.71)
where A
and A
are the surface areas per unit
volume of latex for micelles and polymer parti-
cles and τ is the mean residence time of a single
CSTR. The residence-time distribution for latex
particles in a CSTR is given by
E(t) dt =
exp (−t/τ) dt (3.72)
where E (t) dt is the fraction of latex particles in
the exit streamwithage t. Because latexparticles
are very small and have a density close to that of
water, the continuous phase, it is reasonable to
assume that the residence-time distribution of la-
tex particles and the aqueous phase are the same
(latex particles follow streamlines).
It is further assumed that the role of molecu-
larly dissolved emulsifier in the aqueous phase
can be neglected relative to the amount of emul-
sifier in micelles and adsorbed on latex particles.
Additional assumptions are that [S] ≫CMCand
[S] N
The number of particles is then given by
i, w
The particle surface area A
for spherical lat-
exparticles with various ages and sizes thus be-
= 4.85
Substitution of v =f (K
, t, [M]
, ¯ n) into Equa-
tion (3.75), where [M]
is constant (due to the
very rapid diffusion of monomer frommonomer
droplets to polymer particles and, if monomer
droplets are absent, due to rapid diffusion of
monomer frompolymer particle to polymer par-
ticle; the direction of monomer diffusion should
be towards older and larger polymer particles)
and ¯ n =0.5 and combination with Equations
(3.72) and (3.74) then gives
__ (3.76)
As can be seen the comparison of Equations
(3.74) and (3.76), the second term in the de-
nominator of Equation (3.76) is analogous to the
quantity A
. At low concentrations of emul-
sifier [S] and high values of R
i, w
and τ, it can
be assumed that A
≫1, so Equation (3.76)
takes on the simplified form
Substitution into Equation (3.42) then gives
[S] K
Here the constants K
are functions of the
specific volumes V
and V
of monomer and
polymer as well as of the molecular masses of
the monomers; K
assumed constant ¯ n =0.5 within the latex parti-
cles [771].
In order to compare exprimental data ob-
tained over a wide range of conditions, it is con-
venient to rewrite Equation (3.76) in dimension-
less form [772]:
i, w
= 1+K
i, w
= 1+π
If N
is expressed in terms of Equation (3.42)
andintroducedintoEquation(3.79), what results
is a second dimensionless equation for R
¯ n
= 1+K
= 1+π
Comparisons of data supplied by three differ-
ent authors [771], [772], [776] are presented in
Polymerization Processes 91
Figures 58 A and 58 B. In Figure 58 A, essen-
tially all of the points lie above the 45

that is, fewer latex particles are formed than
predicted by theory. By contrast, the experi-
mental values for R
in Figure 58 B, which are
more precise, correspond well to the theoretical
straight line. Overall, one may conclude that in
the case of styrene the theory is well substanti-
ated. The Gershberg – Longfield theory has been
extended and modified a number of times. Thus
DeGraff and Poehlein dropped the assump-
tion that ¯ n =0.5 and instead calculated ¯ n using
the Stockmayer – O’Toole solution for different
particle sizes (Eq. 3.41) [772]. This accounts for
the possibility of more than one radical per par-
ticle for the larger particles. Nomura et al. [773]
also applied Equation (3.53), according to which
radicals are absorbedmore rapidlyintolatex par-
ticles than into micelles, to continuous emulsion
polymerization and obtained a prediction that is
in better agreement with experiment (as com-
pared to that in Fig. 58 A). Brooks [794] dis-
cusses various equations for the entry of rad-
icals into latex particles and micelles, assum-
ing among other things that micelles disintegrate
only slowly under subsaturation conditions, and
that even in the presence of micelles the surface
of the latex particle may not be saturated with
Figure 58. A) Number of particles according to Equation
(3.79), and B) Overall rate of polymerization according to
Equation (3.80) for the continuous emulsion polymeriza-
tion of styrene (dimensionless representation) [772]
from [772]
from [771]
◦ from [776]
• calculated from values for R
with the assumption that
¯ n =1/2
The existence of multiple steady states for
the isothermal operation of a CSTR was first
demonstrated in the case of continuous emulsion
polymerization by Gerrens et al. [776–778], al-
though it had earlier been predicted on theoret-
ical grounds for autocatalytic processes in gen-
eral [795–806]. Autocatalytic acceleration here
is a consequence of the Trommsdorff –Norrish
effect. The mass balance for monomer at steady
state is given by
˙ v [M]
− ˙ v [M] −R
V = 0 (3.81)
where ˙ υ is the volumetric flow rate to and from
the reactor, [M]
is the monomer concentration
in the feed, [M] is the monomer concentration
in the reactor and exit stream, V is the volume of
the reacting mass in the reactor, and R
is the rate
of polymerization in the reactor. Furthermore,
− [M]
where τ =V/ ˙ υ is the mean residence time in the
Figure 59 shows a graphical solution of Equa-
tion (3.82) and R
versus monomer concen-
tration, in which data have been plotted as a
function of both monomer concentration [M]
and conversion X. At low values of mean res-
idence time τ, there is one intersection (one so-
lution) between experimental R
=f ([M]) and
the straight line (Eq. 3.82) which implies a single
stable operating point at lowconversion. By con-
trast, longer residence times lead to three points
of intersection, with stable operating points at
both low and high conversions and an unsta-
ble operating point at an intermediate conver-
sion. For a train or cascade of n stirred reactors
there may be as many as n +n (n +1)/2 stable
operating points and n unstable operating points
for the individual reactors as well as n +1 sta-
ble states for the entire cascade. Oscillations in
the number of particles, the polymerization rate,
and the interfacial tension have attracted consid-
erable theoretical attention. These are attributed
to bursts of particle formation that accompany
swings between states of supersaturation of the
latex particle surfaces, indicating large amounts
of free emulsifier (and micelles), and states char-
acterized by undersaturation, in which particle
formation almost ceases. This phenomenon has
long been recognized in industrial-scale con-
tinuous emulsion polymerization [733] and has
now been thoroughly investigated in the case of
styrene [771], [778], methyl methacrylate [786],
[807], [808], and vinyl acetate [786], [798],
[799], [809].
92 Polymerization Processes
Figure 59. Emulsion polymerization of styrene. Stationary
operating points for a continuous stirred reactor at various
residence times τ [778]
• Stable, ◦ unstable operating points; R
in milligrams
styrene per gram latex per minute
Figure 60. Oscillations in the continuous emulsion poly-
merization of vinyl acetate at three different initiator con-
centrations [I]. Comparison between experimental (◦· ◦· ◦)
[786] and calculated (– – –) values [787]
Model calculations are available for styrene
[800], vinyl acetate [787], [790], [791], and
vinyl chloride [785]. Figure 60 illustrates the
close agreement between experiment and the-
ory. Radical desorption has a strong influence
(with accompanying more rapid polymer parti-
cle nucleation rates) on the oscillatory behavior
of continuous emulsion polymerization in a
CSTR [810–812] and radical desorption rate
constants have been measured using a CSTR
[810], [813]. In the absence of particle nucle-
ation, oscillations (at least those not due to
thermal effects) do not occur. A CSTR (with
split flow) or tubular reactor operating as a poly-
mer particle seed generator in series with one or
more larger finishing reactors has been used to
eliminate oscillations for Case 1 systems (vinyl
acetate and vinyl chloride) [785], [646], [814],
To complete the discussion of emulsion poly-
merization, a few brief comments will be made
about an area which has almost been completely
neglected in the literature. This is the effect of
cross-linking in the polymer particle on emul-
sion polymerization kinetics and modeling (ef-
fect on particle nucleation and growth). The first
and very important effect of cross-linking is on
the equilibriumswelling of polymer particles by
monomer. Taking into account the elastic free
energy change due to the cross-linking network
structure as well as the free energy contributions
of mixing and interfacial tension, it is possible to
derive an equation which gives the equilibrium
monomer concentration in polymer particles
= −
ln (1−ϕ
) +ϕ


¯ ̺
where ̺
is the elastic cross-link density of the
accumulated polymer [816]. The first thing to
notice is that cross-linking reduces the monomer
concentration and hence the volumetric growth
rate of polymer particles. According to Equation
(3.47) or (3.49) the number of polymer parti-
cles nucleated in Stage I will be larger. In an
experimental study using styrene and divinyl
monomers, Nomura et al. have confirmed [817]
that much higher numbers of particles are gener-
atedwheninitiatedparticles are cross-linked. An
obvious effect of cross-linking is the strength-
ening of the Trommsdorff – Norrish effect with
concomitant earlier and larger decrease with
conversion of the termination constant and the
consequences thereof. When the molecular mass
of primary chains produced in smaller polymer
particles is larger, one might expect gelation
to occur earlier in smaller particles. There are
clearly many interesting phenomena related to
cross-linking in latex particles which await in-
3.3.4. Miscellaneous Processes
The modeling of high-pressure tubular and au-
toclave reactors for the manufacture of LDPE
Polymerization Processes 93
has received a great deal of attention [818–836].
These models are notable for the detailed kinet-
ics, which include transfer to polymer, backbit-
ing, and β-scission in an attempt to calculate
both short- and long-chain branching frequen-
cies. The polymerizations are almost adiabatic,
with large temperature increases, and phase sep-
aration between ethylene and polyethylene may
occur in autoclave reactors. The tubular reactor
is considered to be in plug flow, while mixing
in the autoclave is rather complex and various
mixing models have been considered. A com-
prehensive copolymerization model for ethylene
and comonomers in a high-pressure continuous
tubular reactor has been developed [836].
A comprehensive tubular reactor model for
the solution polymerization of vinyl acetate has
been developed by Hamer and Ray [837]. The
kinetics employed account for transfer to poly-
mer and reaction with terminal double bonds
(trifunctional branching frequencies are calcu-
lated). The model solves the equations of mo-
tion for both axial and radial velocity profiles.
Experimental validation of the model has been
carried out.
The bulk and solution polymerization of
styrene in tubular reactors has also been exten-
sively studied both theoretically and experimen-
tally [375], [838]. Spatial distributions of veloc-
ity, temperature, and concentration were mod-
eled [838] and it was shown that for tube diame-
ters >2 cm, thermal runaway may occur. Inter-
nal mixers were used in larger diameter tubes
to give better radial mixing and this technique
appears to give polystyrenes with high molecu-
lar mass at a productivity of commercial interest
[375]. References to other important studies on
styrene production in tubular reactors may be
found elsewhere [375], [838].
Chemical Modification of Polymers in Ex-
truders The commercial incentive for the chem-
ical modification of polymers by chain scission,
long-chain branching, cross-linking, and graft-
ingis the enhancement of the physical andchem-
ical properties of polymers and polymer mix-
tures (alloys, blends, additives) and/or improve-
ment of their processability. In many cases, the
extruder has been found to be an effective chem-
ical reactor in which chemical modification of
high molecular mass polymers in the melt can
be done economically for low-volume products.
It is particularly effective for chemical modi-
fication of high molecular mass, solvent-free,
commodity polymers to tailor-made products
to meet the growing diversity in polymer ap-
plications. The extruder reactor provides short
and controlled residence times; efficient mix-
ing, particularly for reactants at low concentra-
tions; and good heat transfer. Multistage reac-
tion, with sequential feeding of reactants and
removal of byproducts, is possible. There are
certain advantages of twin-screw over single-
screw extruders [839]. These include: intense
shear mixing (with better surface renewal rates)
giving molecular-level mixing (micromixing),
improved heat transfer, multistage feeding, vent-
ing of volatile byproducts, and screw speed can
be changed without changing the throughput.
These attributes of the twin-screw extruders are
ideal for chemical modification where a small
amount of the low molecular mass compound to
be grafted on the polymer chains must be ho-
mogeneously mixed with a highly viscous base
Chemical modifications are often carried out
using free-radical reactions in the temperature
range 170

C– 350

C. When a polymer con-
taining a peroxide and a compound to be grafted
is melt processed, chain scission, long-chain
branching, cross-linking, and grafting reactions
may occur simultaneously. To optimize product
properties, the rates of these reactions must be
Chain Scission. Polymer chain scission oc-
curs when chemical bonds (usually C– C) along
the backbone break. Since a higher molecu-
lar mass chain has a greater number of such
bonds, it experiences chain scission preferen-
tially (for polypropylene, scission seems to be
random with respect to the position of the bond
along the chain backbone [840], [841]). There-
fore, the broad MWDs, usually found for poly-
olefins narrow as the average molecular mass
falls. With random scission occurring exclu-
sively, the limiting polydispersity for all initial
MWDs is two and the limiting MWDis Flory’s
most-probable distribution. A reduction in mo-
lecular mass improves processability. The out-
standing commercial example of the use of con-
trolled chain scission of polypropylene (PP) is in
the production of controlled-rheology PP used
for fiber manufacture, film-extrusion, and for
fast molding applications [842].
94 Polymerization Processes
Long-Chain Branching and Cross-Linking.
Long-chain branches (tetrafunctional) are
formed when radical centers on the backbone of
polymer chains experience bimolecular termina-
tion by combination. If this long-chain branch-
ing process continues, a three-dimensional net-
work (cross-linked gel) is formed. The pro-
duction of higher molecular mass chains by
long-chain branching produces a polymer that
exhibits increased die swell and melt strength,
and improved strain-hardening properties [842].
Cross-linking of polymer chains results when
bimolecular coupling (via bimolecular termina-
tion by combination of polymer backbone rad-
icals or the reaction of grafted chemical groups
such as those with silane functionality [843],
[844]) of polymer chains to form tetrafunc-
tional branches occurs repeatedly. The cross-
linked polymer is a mixture of polymeric gel,
of effectively infinite molecular mass, and sol
which is made up of linear and branched chains.
Property enhancement due to cross-linking in-
cludes: increased service temperature, solvent
resistance, flexural modulus, low-temperature
impact strength, environmental stress cracking
resistance, and reduced creep [842].
Grafting onto polymer chains can occur
when a mixture of the polymer, peroxide, and
unsaturated or saturated compound to be grafted
are melt processed in an extruder. For exam-
ple, acrylic acid or maleic anhydride can be
grafted onto PP or PE to enhance compatabil-
ity with more polar blends or to improve adhe-
sion to metals, glass fibers, and to other polymer
types [845], [846]. Vinyl silanes can be grafted
to polyolefins to subsequently produce cross-
links in the presence of moisture [843]. Func-
tionalized additives (antioxidants, flame retar-
dants, pigments) can be grafted onto the host
polymer to give the desired property enhance-
ment. These chemically bound additives are ef-
fectively mixed on a molecular scale and do not
diffuse out of the matrix during use [847].
Source of Radicals. During normal extrusion
of polyolefins, alkyl radicals may be formed
thermomechanically, but at too lowa rate to initi-
ate chemical modification to the extent normally
desired. To provide a suitable source of radicals,
organic peroxides are added to the polymer be-
fore melt processing. In these applications the
peroxides used must generate radicals which are
sufficientlyenergetic toabstract backbone atoms
and generate backbone radical centers.
Other reaction types, including anionic,
cationic, anionic coordination, andcondensation
can be carried out in an extruder reactor [839].
Kowalski [848] describes an extruder process
for halogenation of butyl rubber. Saleem and
Baker [849] describe a process in which poly-
styrene and polyethylene along with their re-
active counterparts (polystyrene with oxazoline
groups, and polyethylene with carboxylic acid
groups) are reacted to form polymeric compata-
bilizers in situ.
Kinetics and Extruder Reactor Modeling.
Reviews of the kinetics of chemical modifica-
tion of polymer by free-radical mechanisms are
available [839], [850], [851]. Motha et al. [852]
have developed a model for the grafting of unsat-
urated acids and silanes on polyethylene. This
model does not attempt to predict the gelation
point nor the gel/sol ratio in the post-gel re-
gion. A very general model which permits one
to followthe change in the MWDof polymer be-
ing modified by simultaneous random scission,
long-chain branching, cross-linking, and graft-
ing has been developed [850], [851]. The model,
which is in the form of an integro-differential
equation is based on a simpler version devel-
oped earlier by Saito [851], [852]. Saito found
an analytical solution for the limiting case of
random scission occurring exclusively. Kimura
[853] obtained a limiting analytical solution for
the case in which random cross-linking is oc-
curring exclusively. The general case can be
handled by using the method of moments to
give the molecular mass averages. The widely
used Charlesby – Pinner equation was obtained
by using an idealization which is questionable
[854]. Simultaneous scission and cross-linking
are treated as two processes in series, with ran-
dom scission occurring first and then cross-
linking. In addition, the initial MWD must be
Flory’s most probable distribution. Numeri-
cal methods must be used to solve the integro-
differential equationfor the case of simultaneous
scission and cross-linking. This is not a trivial
problem and has not been successfully solved to
The design of extruders for reactive process-
ing is much more challenging than for purely
physical processing [839]. Extruders must han-
dle polymer melts with continuously changing
Polymerization Processes 95
properties. Residence-time distribution (RTD)
and micromixing can significantly affect the
properties of the chemically modified polymer.
One of the important advantages of twin-screw
over single-screwextruders is the greater control
they allow over RTD and mixing. The modeling
of conventional or physical extrusion processes
has been well documented in the literature, par-
ticularly for single-screw extruders. Details of
the modelingof extruders maybe foundinthe re-
viewarticle byTzoganakis [839]. Tzoganakis
et al. [855] developed a comprehensive rheoki-
netic model for the random scission of isotactic
polypropylene in a single-screwextruder. Finite-
element or finite-difference methods will play
an important role in the solution of the three-
dimensional flow equations for both single and
twin-screw extruders [856].
3.3.5. Ionic Polymerization Modeling Introduction
The most powerful processes for the control of
MWD of linear chains are living anionic and
cationic polymerizations. These processes are
interesting from the point of view of process en-
gineering because the MWD of the product can
be varied widely by changing the RTD of the
process or by oscillating the process in a con-
trolled manner. These living ionic processes will
be considered from this perspective in Section Heterogeneous Coordination
The commercially important anionic coordina-
tion processes (heterogeneous ZN polymeriza-
tion) are now discussed. Seppala and Auer
have published an excellent review of much
of the relevant subject matter [857]. Third-
and fourth-generation catalysts have already
been commercialized for slurry polymeriza-
tions. These newer catalysts possess high and
stable activity, high stereospecificity indepen-
dent of polymerization time, and increase in ac-
tivity with increasing temperature up to about

C. Electron donors may be used to regulate
isotacticity. Catalysts may also be designed to
control the size and shape of polymer particles.
The gas-phase UNIPOL process has become
one of the most successful commercial processes
for the production of polyolefins [858]. In this
process, homo- and copolymerizations of ethyl-
ene with α-olefin comonomers are carried out
in a fluidized-bed reactor using heterogeneous
Ziegler – Natta or Philips supported metal oxide
catalysts [859].
Modeling of these processes can be classified
into three categories [857], [860]:
1) Microscale kinetic phenomena: coordina-
tion kinetic mechanism, multiple active site
types, stereoregularity, copolymer composi-
tion and molecular mass distributions, and
catalyst deactivation kinetics
2) Mesoscale particle phenomena: fracture of
catalyst particles, heat generation in parti-
cles, mass transfer, and growth and influence
of changing properties of reaction environ-
3) Macroscale reactor phenomena: overall
mass and energy balances, gas – liquid
mass transfer effects, influence of reaction
medium, effects of particle motion, and heat
transfer limitations and influence of reactor
Similar modeling categories could be con-
sidered for the manufacture of PVC and EPS by
free-radical suspension polymerization, where
particle morphology and foamed cell structure
are important considerations.
One of the major challenges in modeling het-
erogeneous coordination polymerizations has
been to rationalize the very broad MWDs
andcopolymer compositiondistributions (CCD)
that are often observed. There have been two
schools of thought. Ray and coworkers have
until recently attempted to explain the broad
MWDs in terms of diffusional resistances for
reactants, which increase as the catalyst parti-
cles are enveloped by a growing shell of poly-
mer. An additional resistance may result from
the crystallization of polymer chains. Others
have attempted to explain the broad MWDs and
CCDs as due to multiple sites of different ac-
tivity. These sites have different compositions.
To model a binary copolymerization it can be
assumed that each site type produces a poly-
mer with Stockmayer’s bivariate distribution
[861], [862]. The more difficult problem is, of
96 Polymerization Processes
course, to determine the number of active site
types and the concentration of each. Two active-
site-type models have been used [862], [863]
as well as site-type distribution functions [864].
Among the diffusion-limited models, the multi-
grain model is the most comprehensive. It is as-
sumed that fragmentation of the original cata-
lyst particle is complete before appreciable poly-
mer has been produced [865], [866]. Thus, the
large macroparticle is composed of many cata-
lyst fragments encapsulated by polymer [865],
[867–869]. Both macroparticle and microparti-
cle mass transfer can be important for large cat-
alyst particles of high activity [857]. Ray et al.
[868] found that the maximum possible temper-
ature rise in both micro and macroparticles is
negligible in slurry polymerization of propyl-
ene. However, in gas-phase processes the tem-
perature inside the polymer particle could reach
its melting point under some conditions [866].
Near the beginning of polymerization, the poly-
mer particles may heat up because of the high
catalyst activityandpolymerizationrate. Insum-
mary, it can be said that the very broad MWDs
and CCDs can be explained by invoking mul-
tiple site types. However, under certain condi-
tions, mass- and heat-transfer resistances may
also play a significant role. The development
of more realistic models for copolymerization
on heterogeneous coordination catalysts will re-
quire the measurement of the bivariate distri-
bution of molecular mass and composition by
a combination of analytical techniques such as
TREF/GPC and TREF/NMR to observe the de-
tailed microstructure of the copolymer chains
3.3.6. Process Variables, Reactor Dynamics/
Stability, On-Line Monitoring and Control Influence of Reactor Type and
Configuration on Molecular Mass and
Copolymer Composition Distributions, and
on Long-Chain Branching and
Survey of Idealized Reactor Types and
Simple Polymerization Reactions. Molecular
mass and copolymer composition distributions,
long-chain branching, and cross-linking can ex-
ert a significant influence on the properties of
all polymers. It is thus important to know the
distribution functions that correspond to vari-
ous polymerization mechanisms and how these
distributions change with reactor type and con-
figuration. Another way of expressing this is to
note that these molecular properties are strong
functions of the residence-time distribution of
the polymerizing mass and that once an optimal
residence-time distributionhas beenestablished,
one can choose reactor types and manipulate re-
actor configuration to obtain this residence-time
distribution in a practical manner. Most devia-
tions of predicted and measured molecular prop-
erties are likely to be due to assumptions about
levels of micromixing and segregated flow and
the comparison of predicted instantaneous mo-
lecular properties with measurements of these
properties on accumulated polymer (e.g., instan-
taneous properties can change with time in a
batch reactor as, say, [M] decreases and hence
the distributions for molecular properties for
the accumulated polymer will have larger vari-
ances). From an industrial standpoint, however,
any process of interest involves high – if not
complete – conversion, and a wide variety of
batch and continuous reactors is utilized. The
relationships between reactor types and config-
urations and the various polymerization mecha-
nisms are often quite complex, and it will only
be possible within the confines of this article to
treat certain simple ideal reactors and reaction
Figure 61 shows four ideal reactors, char-
acterizing them on the basis of residence-time
distribution and the temporal and spatial course
of chemical reaction. Batch reactors (BR), con-
tinuous plug flow reactors (CPFR), and homo-
geneous continuous stirred-tank reactors (HC-
STR) are treated in the article Stirred –Tank and
Loop Reactors. With a homogeneous continu-
ous stirred-tank reactor, perfect mixing down to
the molecular level is assumed, and for a CSTR
with an ideal residence-time distribution, there
are bydefinitionnospatial variations intempera-
ture and concentrations. Mixing at the molecular
level is often called “micromixing”. This condi-
tion is often not achieved in practice, however,
and for this reason a fourth ideal reactor type
is introduced, the segregated continuous stirred-
tank reactor (SCSTR) [801–803]. Here the fluid
phase is regarded as subdivided into many small
Polymerization Processes 97
isolated compartments. Each compartment con-
tains a large number of molecules, which are
permanently confined within the limits of that
compartment; therefore, the individual compart-
ments function as miniature batch reactors with
different residence times in the flowreactor. The
compartments themselves are taken to be ideally
mixed, leading to what is called “macromix-
ing” despite total segregation of molecules in
different compartments. Thus, the sum of all
the compartments in a segregated continuous
stirred-tank reactor have the same residence-
time distibution as the contents of the homoge-
neous stirred-tank reactor. A macroscopic mean
taken over all the compartments in the efflu-
ent stream and in the reactor itself would show
concentrations and temperature that are constant
both spatially and with respect to time. On the
other hand, a probe capable of microscopic sam-
pling of individual compartments would reveal
concentrations that varied in a statistical man-
ner from one compartment to another. Given the
high viscosity of a typical polymerizing solution
it is quite likely that many solution polymeriza-
tions actually occur in segregated systems [804].
Ideal reactors are discussed in greater detail in,
for example, [795], [805].
Polymerization reactions can be divided ac-
cording to their kinetics into three classes:
1) Monomer coupling with bimolecular termi-
nation (e.g., free-radical polymerization)
2) Monomer coupling without termination
(e.g., living anionic polymerization)
3) Polymer coupling (e.g., polycondensation)
In both cases of monomer coupling, many in-
dividual monomer molecules add successively
to the growing chains. Monomer coupling with
bimolecular termination is characteristic of free-
radical polymerizations. Termination may occur
through the combination of two growing radi-
cals (degree of coupling K =2). Termination by
disproportionation is an example of a process
in which K =1 [806]. Monomer coupling with-
out termination is encountered, for example, in
living anionic or cationic polymerizations. Poly-
mer coupling between macromolecules is char-
acteristic of polycondensation and polyaddition
reactions. The discussion that follows has been
restricted deliberately to the simplest reactions
possible, with precisely simultaneous initiation
of all active centers in the case of anionic poly-
merization and exact stoichiometric balances in
polycondensation. Chain-transfer reactions will
be neglected, as will exchange reactions (e.g.,
transesterification, transamidation). A few con-
sequences of these complex reactions are out-
lined in [871].
The three types of polymerization differ con-
siderably in the way the degree of polymer-
ization of the accumulated polymer
aged over the course of the conversion process)
changes as a function of conversion. As shown in
Figure 62, a high degree of polymerization
reached at very small conversions in free-radical
polymerization. In a batch reactor this value sub-
sequently decreases with increasing conversion
as a consequence of decrease in the monomer
concentration [M] (assuming that the Tromms-
dorff effect is negligible and that the radical ini-
tiation rate is essentially constant). With living
polymerization in the absence of termination re-
actions, on the other hand,
increases linearly
with conversion, and in polycondensation a high
degree of polymerization is achieved only at
very high conversion (e.g., 95 % conversion is
required to reach
98 Polymerization Processes
Figure 61. Schematic illustration of the course of reaction in various types of reactors
=mass fraction of the material throughput traversing the reactor with a residence time between t and t +dt; C
tration of component A; t =time; τ =mean residence time; x =spatial coordinate; L =reactor length; n =order of the reaction
Figure 62. Cumulative degree of polymerization
as a
function of conversion for various polymerization reactions
a) Monomer coupling with termination; b) Monomer cou-
pling without termination; c) Polymer coupling
Batch and plug flow reactors provide equiva-
lent results, so they can conveniently be consid-
ered together. There are thus nine different com-
binations possible for the three types of poly-
merization and the three ideal reactor types, as
summarized in Table 5, which also includes a
qualitative description of the resulting molecu-
lar mass distributions. Monomer Coupling with
Bimolecular Termination Plug Flow and
Batch Reactors (CPFR/BR)
Under the assumption that R
=constant (con-
stant radical generation rate; half-life t
the initiator ≫residence time τ of reactor con-
tents) and [M] =constant (small conversion in-
crement), the instantaneous degree of polymer-
Polymerization Processes 99
Table 5. Molecular mass distribution for polymerization reactions in various types of reactors
ization P
, when termination is exclusively by
disproportionation, is given by
and the instantaneous mass chain length distri-
bution is given by the Schulz – Flory (or most
probable) distribution [872], [873]:
W (r) = (1−ϕ)

≈ (1−ϕ)
r exp = [− (1−ϕ) r] (3.85)
[M] + (K
The breadth of the distribution is described ei-
ther by the nonuniformity U or by the polydis-
persity index PDI.
U =
−1 (3.86)
with PDI =2 for k =1 (bimolecular termina-
tion by disproportionation); PDI =1.5 for k =2
(bimolecular termination by combination). The
PDI (or U) can be expressed in terms of
the moments of the frequency distribution of
chain lengths Q as shown in Equation (3.87).
Thus, if one examines the entire range of con-
versions (i.e., dropping the assumption that
[M] =constant) what results with increasing
conversion x (decreasing monomer concentra-
tion [M]) is a set of Schulz – Flory distributions
with different P
for decreasing degrees of poly-
merization, as shown in Figure 63.
Figure 63. Mass distribution W (r) of instantaneously
formed polymer for monomer coupling with termination.
Batch reactor at small conversion increments, or homoge-
neous continuous stirred-tank reactor.
N, 0
=1000, P
N, x
N, 0
(1 −x); degree of coupling
k =1
Note that PDI =2 for all the molecular mass
distributions (actually mass chain length distri-
butions to be more precise) in Figure 63. By con-
trast, the statistical variance σ
of the associated
100 Polymerization Processes
frequency distribution decreases with increasing
conversion. However, since σ
(PDI −1),
continuously decreases as P
decreases with
conversion, except in the case of a monodisperse
MWD with PDI =1. For this reason, one of the
quantities PDI or U is preferred for expressing
distribution breadth.
Figure 64. Cumulative mass distribution W (r) for polymer
formed throughout the conversion interval x =0 to x =x for
monomer coupling with termination in a BR/CPFR
N, x
=1000, k =1
Integration of the distributions in Figure 63
with appropriate weighting factors gives the mo-
lecular mass distribution of the final polymer
product at the end of the batch [874–877]. To
simplify comparison, the distributions in Fig-
ure 64 have been calculated in such a way that
for each conversion x, the degree of polymeriza-
tion of the accumulated polymer
=1000. It
is clear that distributions broaden with increas-
ing conversion. Representations of PDI and
as functions of conversion follow in Figures 68
and 69. Theoretical treatments of this case can
be foundin[878–888] andinSection2.2. Before
leaving CPFR/BR reactors, the following points
should be noted. Firstly, the Trommsdorff effect
can have a significant effect on molecular mass
development with increasing conversion. The
significant lowering of either K
or K
chain transfer to small molecules (monomer or
chain-transfer agents) is negligible can cause
dramatic increases of molecular mass with con-
version. See, for example, data for the change of
molecular mass distribution with conversion for
the bulk homogeneous polymerization of methyl
methacrylate [380]. On the other hand, when
chain transfer to monomer (as in vinyl chloride
polymerization) or to chain-transfer agent pro-
duces most of the polymer chains, the Tromms-
dorff effect has no influence on molecular mass
development. In particular, when chain trans-
fer to monomer produces most of the polymer
chains, molecular mass development will de-
pend on temperature and be independent of pro-
cess type and reactor type [889].
Figure 65. Radical polymerization of styrene in an HCSTR
at low viscosity. Comparison between observed (– – –) and
calculated (—-) molecular mass distributions [891]
Reaction conditions:
Feed: 2.39 mol/L monomer, 7.44 mol/L solvent (benzene),
0.0152 mol/L initiator (AIBN); temperature 74.1

C; vis-
cosity η =1.5 mPa · s; mean residence time τ =160 min
Figure 66. Mass distribution W (r) of polymer formed by
monomer coupling with termination in an SCSTR [883]
N, 0
=2000; k =2
Polymerization Processes 101
In a CPFR/BR, the width of the copoly-
mer composition distribution can be substan-
tial if one monomer type reacts much faster
than the other in propagation. For the same final
conversion, the residence-time distribution for
CPFR/BR is ideal compared to the other reactor
types when minimization of long-chain branch-
ing, cross-linking and gel/sol ratios is required.
Figure 67. Mass distribution for radical polymerization in
three different reactors [885]
Conversion x =0.6; P
=1000; k =2
Figure 68. Polydispersity index PDI =P
as a function
of conversion for radical polymerization in three different
Homogeneous Continuous Stirred-Tank
Reactor (HCSTR). Denbigh has shown that in
a homogeneous CSTR two opposing factors in-
fluence the molecular mass distribution [878–
881]. The constancy of [M] at steady state leads
to a narrowing of the distribution relative to that
obtained in a batch reactor, while the range of
residence times leads in principle to broadening
of the distribution. However, in radical polymer-
ization, the lifetime of a growing radical is ca.
1 s, very small compared to the mean residence
time of any industrial reactor. This first factor
(constant [M]) thus predominates and the result-
ing distribution is narrower in an HCSTRthan in
a CPFR/BR. With polymerization reactions that
do not involve termination, the lifetime of the
growing chain is comparable to the mean resi-
dence time of the reactor, so that broadening of
the MWD by the residence-time distribution is
In the steady state with [M] =constant, the
same conditions are present in the stationary
state as in a batch reactor at low conversion or at
some higher conversion over a small conversion
increment, resulting in the Schulz – Flory dis-
tribution described by Equations (3.85) – (3.87).
A comparison of observed and calculated mo-
lecular mass distributions for an HCSTR, as
shown in Figure 65, indicates very good agree-
ment in regions of low viscosity where the
Trommsdorff – Norrish effect plays no signifi-
cant role. Even when the Trommsdorff – Norrish
effect is appreciable, the Flory – Schulz distribu-
tion should still apply when diffusion-controlled
bimolecular termination is not chain-length de-
pendent [358]. Additional experimental studies
on continuous free-radical polymerization are
described in [367], [373], [890–895].
Experimental Theoretical
=20 990 M
=20 440
=14 020 M
=13 650
PDI =1.50 PDI =1.50
Segregated Continuous Stirred-Tank Re-
actor (SCSTR). Individual compartments, all
of which can be regarded as miniature batch re-
actors, display residence times or reaction times
according to the exit-age distribution function of
a CSTR which is
E(t) =
exp (−t/τ) (3.88)
102 Polymerization Processes
The effect of segregation is a broadening of the
MWD to a breadth greater than that for a batch
reactor, and the breadth increases with con-
version. Figure 66 provides several examples,
starting with the Schulz – Flory distribution at a
conversion x =0. Figure 67 compares molecular
mass distributions for free-radical polymeriza-
tion in the three reactor types. The correspond-
ing changes in the polydispersity index PDI are
illustrated in Figure 68, and Figure 69 shows the
degree of polymerization for the accumulated
polymer as a function of conversion. Thus, the
narrowest possible molecular mass distribution
for free-radical polymerization is the Schulz –
Flory distribution and it is obtained in an HC-
STR, and the broadest distribution is obtained in
a SCSTR. For additional theoretical studies, see
[883], [885], [896], [897].
Figure 69. The course of the degrees of polymerization of
the accumulated polymer
as a function of con-
version during radical polymerization Monomer Coupling Without
Termination Plug Flow and Batch Reactors
In the absence of termination reactions the ki-
netic chain length η corresponds to the ratio of
the initial concentrations of monomer and ini-
or at incomplete conversion
− [M]
If initiator molecules are counted as chain units
= 1+η (3.91)
The assumption is made here that initiation is
much faster than propagation, i.e., K
At t =0, all active molecules will have a de-
gree of polymerization P
=1, and the num-
ber of propagation steps per active site (i.e.,
the kinetic chain length) is η =P
−1. The case
leads to a broader distribution [898],
[899], but one that is still narrower than the
Schulz – Flory distribution. The molecular mass
distribution corresponds to a Poisson distribu-
tion [435, pp. 346 – 339], [900] (see also Section
W (r) =
(1+η) (r −1) !
with a polydispersity
= 1+
Figure 70. Mass distribution W (r) of polymer formed by
monomer coupling without termination in a SCSTR [885]
=100; Schulz – Flory distribution for x =0; Poisson dis-
tribution for x =1
Polymerization Processes 103
Thus the distribution becomes narrower as
the contribution from statistical broadening de-
creases with chain growth (increase in η) (cf.
the bottom curve in Fig. 71). A comparison of
Equations (3.87) and(3.93), or inspectionof Fig-
ure 70 indicates that Poisson distribution is sig-
nificantly narrower than the Schulz – Flory dis-
Figure 71. Polydispersity index PDI =P
as a function
of P
for polymerization by monomer coupling without ter-
mination in a SCSTR [885]
Homogeneous Continuous Stirred-Tank
Reactor (HCSTR). If it is assumed that chain
growth terminates abruptly as growing chains
leave the reactor, then the lifetime of an active
growing chain is equal to its residence time in
the reactor. According to [879–881], the mo-
lecular mass distribution in an HCSTR should
be broader than for a CPFR/BR. Several au-
thors have demonstrated that the Schulz – Flory
distribution is obtained for living polymeriza-
tion (with instantaneous initiation) in an HCSTR
[882], [883], [885], [901–904].
Segregated Continuous Stirred-Tank Re-
actor (SCSTR). The rate of living polymeriza-
tion is first-order with respect to [M], so R
and x
are the same for both HCSTR and SCSTR [795,
pp. 309 – 331], [805]. Segregation inhibits total
molecular mixing, whereas in an HCSTR all
molecules are distributed according to Equation
(3.88), this is true for a SCSTRonly with respect
to all compartments, each of which contains a
large number of molecules with equal residence
times. The molecular mass distribution is there-
fore subject to less broadening relative to a batch
reactor than in the case of the HCSTR. At very
lowconversion, it is possible to assume constant
monomer concentration, so the distributions in
the three reactor types are almost identical. At
high conversion the effect of the residence-time
distribution diminishes. At complete conversion
the lifetime of the active species must be signifi-
cantly shorter than the mean residence time, and
the molecular mass distribution becomes equiv-
alent to that in a batch reactor. Figure 70 shows
the transition from a Schulz – Flory to a Pois-
son distribution with increasing conversion. Fig-
ure 71 is a plot of polydispersity PDI as a func-
tion of P
and x. The bottom curve (for x =1.0)
corresponds to Equation (3.93) for a batch reac-
tor. Polymer Coupling
Only the formation of linear chains, either from
monomer of type A– B or from exact stoichio-
metric mixtures of monomer types A– A and
B– B is considered here. Ring formation is also
Plug Flow and Batch Reactors
(CPFR/BR). The functional group conversion
p is defined as the fraction of functional groups
that have reacted at a given time
For the degree of polymerization it follows that
The molecular mass distribution is given by
W (r) = (1−p)
r p
= 1+p (3.98)
and is once again the Schulz – Flory distribu-
tion with PDI =2 at high conversions [435,
104 Polymerization Processes
pp. 336 – 339], [873], [882], [883], [902], [905–
Figure 72. Molecular mass distribution W (r) of polymer
formed by polymer coupling in a CPFR/BR [873]
Figure 73. Molecular mass distribution W (r) for polymer-
ization by polymer coupling in three different reactors [883]
Figure 72 shows the molecular mass distri-
bution at various conversions. For free-radical
polymerization the Schulz – Flory distribution
always has a PDI =2 because ϕ, the probabil-
ity of propagation, is almost always very close
to unity. This is not so for polycondensations,
where p can vary from0 to 1, and thus PDI varies
from 1 to 2.
Figure 74. Polydispersity index PDI =P
as a function
of P
for polymer coupling [885]
Homogeneous Continuous Stirred-Tank
Reactor (HCSTR). Monomer and polymer
molecules are capable of reacting with each
other throughout their entire residence time in
the reactor. Thus, according to the principle of
Denbigh [879–881], a broader molecular mass
distribution is to be expected in an HCSTR than
in a batch reactor. The broad distribution of res-
idence times means that material leaving the re-
actor always contains a relatively large amount
of monomer and polymer with a low degree of
polymerization. On the other hand, with increas-
ing molecular mass the probability of the forma-
tion of very large macromolecules by the cou-
pling of two smaller ones increases greatly. Cal-
culations give a very broad distribution (Fig. 73)
in which the number-average degree of polymer-
ization P
is the same as in a batch reactor, but
the weight-average P
is much higher [883],
[885], [902], [907], [909], [910]:
Polymerization Processes 105
Figure 75. Composition of the copolymer produced in a batch reactor (BR) as a function of monomer composition of the
charge as well as conversion
First column: instantaneous composition; second column: instantaneous compositions, starting with monomer ratios
] : [M
] =1 : 3, 1 : 1, and 3 : 1; third column: cumulative compositions based on the same starting ratios
This corresponds also to a considerably higher
PDI, which increases rapidly with increasing
conversion (Fig. 74):
Segregated Continuous Stirred-Tank
Reactor (SCSTR). Segregation reduces the
amount of polymer with very high or very low
molecular mass [883], [885]. Figure 73 com-
pares the molecular mass distributions expected
for the three reactor types and Figure 74 shows
the polydispersity index PDI as a function of
. In terms of both P
and PDI, the SCSTR
lies between the CPFR/BR and the HCSTR.
Note that the conclusions drawn in the pre-
ceding two sections are a result of purely the-
oretical considerations, and they actually have
little to do with practice. On the one hand, Equa-
tion (3.95) (see also Fig. 62) indicates that at-
taining a reasonably high degree of polymer-
ization requires a very high conversion; HC-
106 Polymerization Processes
Figure 76. Ternary copolymerization in the system styrene (M
), 2,5-dichlorostyrene (M
), and acrylonitrile (M
) [912]
A) Instantaneous copolymer composition (arrow point) as a function of composition of the monomer mixture (origin of the
arrow); B) Partial azeotropes, where arrows outside the diagram indicate the positions of binary azeotropes
STR and SCSTR systems would therefore ap-
pear inappropriate (extreme viscosities would
be inappropriate for a CSTR). On the other
hand, many polycondensations and polyaddi-
tions are accompanied by rearrangements at
the heteroatoms, including transesterifications
or transamidations. This means that polymer
with a Schulz – Flory distribution would be ob-
tained even in an HCSTR [435, pp. 336 – 339],
[911]. Copolymerization
The theory of copolymerization kinetics is co-
vered in Section 2.3. However, the performance
of the three reactor types (CPFR/BR, HCSTR,
and SCSTR) were not compared and therefore
this topic is considered here.
Copolymerization in CPFR/BR Reactors.
Figure 75 gives several illustrations of composi-
tional drift for binary copolymerization for var-
ious comonomer pairs in continuous plug flow
and batch reactors. The first two columns are
for the mole fraction of monomer 1 chemically
bound in copolymer chains produced instanta-
neously (over a small conversion or time in-
terval) as a function of mole fraction of free
monomer 1 and of conversion. The third col-
umn shows the mole fraction of monomer 1 in
the accumulated copolymer chains versus con-
version. Azeotropes also occur in systems with
more than two comonomers. Figure 76 shows a
three-fold combination represented in terms of
triangular coordinates. The compositions of var-
ious comonomer mixtures are indicated by the
origins of arrows, with the corresponding arrow
points showing the instantaneous compositions
of the resulting polymers. The length of an ar-
row is thus a measure of the deviation between
compositions of free monomer and copolymer.
Such an arrow degenerates to a point in the case
of an azeotropic composition. A phenomenon
known as “partial azeotropy” is of interest in the
context of multicomponent systems, with only
one of the monomers represented by an identical
mole fraction in both copolymer and monomer
mixture. Thus, for ternary copolymerization
] + [M
] + [M
A systematic computer search of the literature
has produced copolymerization parameters for
37 ternary azeotropes, 4 quaternary azeotropes,
and one 5-component azeotrope [912]. Fig-
ure 77 shows copolymer composition distribu-
tions (CCDs) for the monomer pairs and com-
positions treated in Figure 75. Copolymer of
uniform composition can be expected during
a batch polymerization only at the azeotropic
composition, or at extremely low conversions.
Strictly speaking, a copolymer is not uniform at
all molecular masses even under azeotropic con-
ditions. What is in fact produced is more nearly a
Polymerization Processes 107
Figure 77. Copolymer composition distributions (CCDs) for the monomer pairs of Figure 75. CCDs of completely polymer-
ized batches with molar ratios [M
] : [M
] =1 : 3 (first column), 1 : 1 (second column), and 3 : 1 (third column)
The mean composition of the copolymer corresponds to that in the batch. The height of each block represents that fraction of
the overall copolymer that has a composition within the block width of 0.05
Experimental data and calculated values as a function of f
; 60

C, [I] =1 g/L azobisisobutyronitrile
statistical distribution about a mean [913], [914],
although at high degrees of polymerization this
variation is minor in comparison to the hetero-
geneity that results from progressive changes in
the composition of the monomer mixture with
Copolymerization in an HCSTR. In an
HCSTR operating at steady state the tempera-
ture and concentration are constant in both space
and time. The result is therefore a chemically
uniform copolymer. In the limiting case of very
lowconversion, the copolymer composition cor-
responds to the predictions of Equation (2.121)
and Figure 75 when concentrations of monomer
in the inlet streamare used to calculate monomer
composition. The only other situation in which
the composition of the copolymer corresponds
precisely to the composition of the monomer
mixture in the feed is the technically unrealis-
tic limit of complete conversion, which would
require impractically long residence times. The
instantaneous copolymer equation, of course,
can always be used when monomer composi-
tion in the exit stream is used (as opposed to
inlet stream) [915], [916]. Figure 78 shows the
change in steady-state copolymer composition
for the system styrene/acrylonitrile (40/60) as
a function of conversion. Thus, a copolymer
with a particular composition can be made in
practice (at least approximately) either by estab-
lishing in advance a preferred composition for
108 Polymerization Processes
the monomer feed and then varying the extent of
conversion, or by varying the feed composition
at a fixed conversion.
Figure 78. Continuous copolymerization in the system
styrene ( f
=0.4) / acrylonitrile ( f
=0.6) [915]
Composition of accumulated copolymer F
as a function of
Copolymerization in a SCSTR. It was
noted earlier that true mixing is often less com-
plete than envisioned by the HCSTR concept in
a polymerization reactor operating under condi-
tions of high viscosity. Most industrial reactors
probably provide an efficiency of mixing that
falls between the values assumed for the HCSTR
and SCSTR. By introducing certain simplify-
ing assumptions, O’Driscoll and Knorr [917]
were able to calculate CCDs corresponding to
the three reactor models CPFR/BR, HCSTR, and
SCSTR. Figure 79 A shows a representation of
a typical instantaneous copolymer composition
diagram. Figure 61 B shows CCD curves for the
three ideal reactor types at two conversions. The
feed composition is fixed at f
=0.4 for all cases
shown. Open circles represent mean copolymer
compositions F
which are not very different in
the three cases. The differences in the CCDs are
greater, however. At 35 % conversion the CCD
is relatively narrow in a CPFR/BR (curve 1),
absolutely uniform in an HCSTR (curve 2), and
already quite nonuniform in a SCSTR (curve
3). In the latter, more than 10 % of the poly-
mer is homopolymer of monomer 2. A SCSTR
always provides several batch-reactor-like com-
partments with very long residence times, high
conversions, and extreme changes in monomer
and copolymer compositions. At 73 % conver-
sion the CCD shows nearly as much nonuni-
formity with a CPFR/Batch (curve 4) as with a
SCSTR (curve 6), only the HCSTR (curve 5)
again producing a uniform CCD. The amount
of homopolymer produced is, of course, greater
at 73 % than at 35 % conversion.
Figure 79. Copolymerization of methyl methacrylate
) – vinyl acetate (M
) in three types of reactor: BR,
HCSTR, and SCSTR [917]
A) Instantaneous composition, calculated with r
=0.015; B) Copolymer composition distribution (CCD)
at f
=0.4, 35 and 73 % conversion in a BR (curves 1 and
4), a HCSTR (2 and 5), and a SCSTR (3 and 6)
Curve: 1 2 3 4 5 6
Conversion x: 0.35 0.35 0.35 0.73 0.73 0.73 Long-Chain Branching and
The amounts of long-chain branching and cross-
linking (with gel formation) obtained in free-
radical polymerizations depend strongly on the
residence-time distribution of the reactor and the
conversion (or polymer concentration). Com-
pared to the HCSTR, the CPFR/BR gives
less long-chain branching, cross-linking (cross-
linking density), and gel for the same con-
version. Apparenty, calculations on long-chain
branching and cross-linking in a SCSTR have
not been performed; however, one could specu-
late that the extent of long-chain branching in a
SCSTR would lie between that for a CPFR/BR
and HCSTR. Graessley et al. [918] have car-
ried out theoretical modeling and experiments
for CPFR/BR and HCSTR using vinyl acetate
homopolymerization. Their experimental poly-
dispersity data are shown in Figure 80 for
CPFR/BR and HCSTR. Note that long-chain
branching is due to chain transfer to polymer and
additionof polymeric radicals toterminal double
bonds on polymer chains and that such branch-
ing leads to increases in the polydispersity in-
dex starting at 2.0 for linear chains produced at
Polymerization Processes 109
low conversion (in other words, the larger the
PDI, the higher the long-chain branching fre-
quency). A survey by Reichert and Moritz
[918] covers the effect of reactor type as well
as the effect of changes in the properties of
the reacting mixture on the polymerization pro-
cesses. For example, the reaction mixture vis-
cosity may increase by several orders of magni-
tude with conversion and this may affect kinetic
rates (e.g., Trommsdorff – Norrish effect, reduc-
tion in initiator efficiency, and propagation rate
constant), as well as processes of heat, mass, and
momentum transfer, the quality of mixing and
the residence-time distribution of the continu-
ous process. They also point out that the reactor
type (RTDand degree of segregation) can signif-
icantly affect long-branching and cross-linking
levels in free-radical polymerization.
Figure 80. Polydispersity index PDI =P
as a func-
tion of conversion for batch and CSTR bulk polymerization
of vinyl acetate
a) Continuous; b) Bulk
A semi-batch process has been investigated
using a comprehensive kinetic model for long-
chain branching and cross-linking for the pur-
poses of producing homogeneous polymeric
networks [356], [363–365], [919], [920]. In the
model, “the cross-linking/branching density dis-
tribution” was proposed. The use of the dis-
tribution enables one to calculate MWD irre-
spective of the reactor type [921]. This model
has been successfully applied to various batch
copolymerizations involving methyl methacry-
late – ethylene glycol dimethacrylate and acryl-
amide –N,N

-methylene bisacrylamide. It has
been shown that the variance of the cross-link
density distribution is reduced with the use of
a chain transfer agent. Boots [922] confirmed
the effect of shorter primary chains qualitatively
using a Monte Carlo simulation.
Figure 81. Anionic (living) polymerization of butadiene
showing measured versus model-predicted heterogeneity
index HI (polydispersity index PDI) [923]
Figure 82. Anionic (living) polymerization of butadiene
showing the effect of RTDon heterogeneity index or breadth
of MWD [923]
a) Batch/plug flow reactor; b) 2 CSTRs
The MWDs produced by living anionic poly-
merization, as shown earlier, are strong func-
tions of RTD. Chang et al. [923] used changes
in RTD to modify MWD in butadiene poly-
merization in experiments involving a reactor
train, while Meira et al. [924–930] used peri-
odic operation (in residence time) to broaden
the MWD as well as controlled addition of
killing agent in semi-batch operation. Chang et
al. [923] developed a comprehensive model for
the anionic solution polymerization of butadiene
with n-butyllithium initiator, tetramethylethyl-
enediamine modifier, and hexane solvent. The
model successfully predicted monomer conver-
sion, vinyl structure, and polydispersity for both
batch reactors and continuous reactor trains.
110 Polymerization Processes
Figure 81 shows predicted versus measured
heterogeneity index (polydispersity index or
), covering the range fromthat obtained
in a PFR or batch reactor to that obtained in a
single CSTR. Figure 82 shows the polydisper-
sity for 2 CSTRs of equal volume in series with
equal conversion of monomer in each, giving the
lowest value of polydispersity, 1.5. Reactor Dynamics and Stability
Reichertand Moritz[918] discuss reactor sta-
bility and safety under the subtopics thermal and
concentration stability. The strong nonlinear de-
pendence of polymerization rate (or heat pro-
duction rate) on temperature is due to the Ar-
rhenius dependence of rate on temperature and
to the large activation energy and heat of poly-
merization. The dynamic behavior of polymer
reactors is therefore greatly affected by temper-
ature. The influence of the nonlinear dependence
of polymerization rate on monomer concentra-
tion, on reactor dynamics is much smaller than
that for thermal effects. Both static and dynamic
instabilities may occur when stability limits are
crossed. The reactor is statically unstable if tem-
perature and conversion rapidly move from one
state toanother as if alternatelyexperiencing“ig-
nition” and “extinction”. Dynamic instabilities
give rise to periodic changes in temperature and
monomer conversion with certain phase shifts
observed [931], [932]. Thermal instabilities may
occur in various reactor types (CSTR, PFR, non-
ideal reactors) [933], [934]. Henderson [935]
points out that for all prior publications on mul-
tiple steady states and instability for free radical
polymerization in a CSTR, three basic assump-
tions were made:
1) The heat-transfer coefficient of the vessel
wall does not change with monomer conver-
2) The viscous dissipation termfor the agitation
is negligible
3) Perfect mixing(ideal RTDandmicromixing)
Mechanical work of the agitator can be a sig-
nificant factor in the energy balance for a pilot-
scale reactor (perhaps for solutionandbulkpoly-
merization, but not for suspension and emulsion
polymerization), while it is almost negligible for
commercial scale. Assumptions (2) and (3) may
be valid for low-viscosity solution processes;
however, in bulk polymerization, the viscosity
can increase by several orders of magnitude and,
therefore, all 3 assumptions are questionable.
Henderson again points out that a thermal run-
away can occur when:
1) The process side heat-transfer coefficient de-
creases significantly
2) The agitator provides insufficient mixing of
the reaction mass, allowing hot spots to de-
3) The agitator is putting more mechanical
work into the system than designed for
Ray et al. [788–791], [936–945] have made
the most significant contributions to the under-
standing of polymer reactor dynamics and sta-
bility. Comprehensive reactor models were de-
veloped for a range of polymerization processes
and reactor types: nonisothermal solution homo-
and copolymerization in a CSTR [931], [939],
[940]; batch and continuous emulsion polymer-
ization reactors [788–791], [941], [942]; hetero-
geneous coordination polymerization for both
liquid and gas dispersion reactors [943–945].
The contributions by Ray et al. are notable not
only for the comprehensive mathematical mod-
els but also for attempts at experimental verifi-
cation. In this regard, the experimental investi-
gation of the effect of chain-transfer agents on
the stability of continuous latex reactors is very
revealing. Whereas under most operation con-
ditions the continuous emulsion polymerization
of styrene is stable, the addition of a chain-trans-
fer agent to the recipe can lead to sustained os-
cillations. Some of Ray’s general conclusions
1) Bifurcation analysis reveals a parame-
ter space rich in dynamic phenomena. It
confirms limit cycle behavior (in which
monomer conversion does not smoothly ap-
proach a constant steady-state value, but
rather oscillates with constant frequency and
amplitude indefinitely) and analyzes the sta-
bilityof periodic branches indetail providing
useful guidelines for experimental design.
2) Full-scale reactors exhibit dynamic behavior
of high complexity.
3) Semi-batch reactors can be operated under
conditions that insure a fast approach to a
Polymerization Processes 111
steady-state operating value, hence permit-
tingalmost perfect control. The possibilityof
oscillatory behavior was, however, demon-
4) Multiplicity (multiple steady states) oc-
curs under isothermal conditions due to the
Trommsdorff – Norrish effect and there ap-
pears to be no relationship between phenom-
ena causing multiplicity and reactor oscilla-
5) The PSD plays a major role in latex reac-
tor stability. Models which calculate only a
mean diameter d (and not the full PSD) can-
not predict oscillations under any operating
6) Polymer particle multiplicity, which leads to
polymer melting and sticking (in gas-phase
heterogeneous coordination polymerization,
such as UNIPOL) can cause a thermal run-
away of the reactor (UNIPOL is open-loop
unstable). Multiplicity and Hopf bifurcation
of the fluidized-bed reactor can lead to run-
away and long periods of slowly damped os-
cillations. The reactor is prone to runaway
even under feedback control because of cool-
ing limitations and nonlinear sensitivity to
process disturbances.
Luand Brooks [946] have confirmed that la-
tex reactor startup policy can have a significant
effect on reactor stability.
It is clear, based on these studies of reactor
stability, that a comprehensive dynamic model
of the polymerization reactor is required to prop-
erly design a continuous manufacturing process
(process stability, control, and startup proce-
dures should be considered at the design stage).
The interactions are too complex to permit an ef-
fective design based on costly experimentation
alone. On-Line Monitoring and Control
The goals in commercial polymerizations are
consistent polymer properties, high productiv-
ity, and safe operation achieved in the most eco-
nomic manner possible. Polymerizations (par-
ticularly ionic and free-radical) are very sensi-
tive to temperature and impurities (radical scav-
engers and poisons at ppmlevels) and, therefore,
adjustments may have to be made during poly-
merization. Process models when applied in real
time require measurements and parameter up-
dating to track and control the process. The need
for monitoring the polymerization is clear and
to be most effective in controlling the process,
on-line monitoring is highly desirable. A survey
of on-line sensors for polymerization reactors
was made by Chien and Penlidis [947]. Al-
though considerable advances have been made
in polymer reaction engineering over the past
two decades, sensor technology for on-line mon-
itoring is still in its infancy. The major problem
has been the on-line measurement of polymer
and particle properties (copolymer composition,
molecular mass averages, long-chain branching,
as well as cross-linked gel content and poly-
mer particle size distribution in suspension and
emulsion polymerization). Sensors in the reac-
tionmixture are readilyfouledbystickypolymer
and polymer particles. Another factor to explain
the lack of progress is the fact that sensor devel-
opment is a multidisciplinary task with exper-
tise required in statistics, mathematical model-
ing, process understanding, reactor design, ad-
vanced control concepts, electronics, and in-
strumentation engineering [947]. Even the mea-
surement of polymer properties off-line is diffi-
cult (e.g., measurement of molecular mass aver-
ages and long-chain-branching frequencies for
heterogeneous copolymers [870]). Chien and
Penlidis [947] classify sensors as those which
monitor reactor operation [by measuring tem-
perature, pressure, flows and level (of reaction
mixture in the reactor)], and those that moni-
tor polymer properties (e.g., by measuring den-
sity, viscosity, concentrations, copolymer com-
position, particle size, using densitometers, vis-
cometers, gas andliquidchromatographs, IRand
UV spectrophotometers, light scattering, ultra-
sonics, fiber-optic techniques, robotics, reactor
energy balances, and state estimation/filtering
techniques). Most of the commercial applica-
tions of on-line monitoring involve those which
monitor reactor operation, although reactor en-
ergy balances are commonly used to monitor
monomer conversion. The main problem with
the successful use of reactor energy balances lies
in the evaluation of the transient accumulation
terms (time derivatives of temperature) and in
accounting for the propagation of measurement
errors (temperature and flow rate) into the cal-
culated heat release term. Acceptable results are
112 Polymerization Processes
often obtained through rapid sampling and then
averaging or filtering all the measurements at
regular short intervals [949].
Two promising on-line monitoring tech-
niques are based on the use of ultrasound and
NIRS (near infrared spectroscopy) [948]. Ul-
trasonic velocity and attenuation measurements
have been used for monitoring high-temperature
compositioninextruders andmelt-transfer lines;
high-temperature imaging studies in extruders;
and for ultrasonic spectroscopy of dispersions.
NIRS is an older technique which has been im-
proved by newly available computing power.
It is the most promising process spectroscopy
available at present because of its process com-
patability and ability to analyze multicomponent
mixtures. NIRS has been applied as an on-line
monitoring technique for both extruders used for
chemical modification and polymer reactors.
The on-line monitoring and control of poly-
mer and polymer particle properties should pro-
vide a major improvement in product consis-
tency and productivity.
There have been a number of excellent re-
views on control of polymerization reactors
[947], [949], [950]. Most industrial control prac-
tice to date has centered around batch reactor
sequencing and the control of process variables
such as temperature, pressure, and viscosity. Re-
actor energybalances, as mentionedearlier, have
also been used to infer polymer production rates
and monomer conversion.
Much of the academic literature has focused
on the computation of optimal operating poli-
cies for batch reactors by using nonlinear pro-
gramming or the maximum principle [374].
These policies are open-loop in that they provide
optimal feed and temperature policies versus
time. Kozub and MacGregor [951] presented
a much simpler solution to the optimal trajec-
tory problems based on an “instantaneous prop-
erty” approach. This latter approach is applica-
ble only to chain-growth polymerizations (see
Section 2.2 for details of instantaneous property
calculations), but it allows for the feedback im-
plementation of these optimal policies via non-
linear control.
Due to the lack of sufficient on-line sen-
sors to monitor polymer properties of interest or
because some property measurements are only
available infrequently from quality control lab-
oratories, various methods for inferring or es-
timating these properties on-line by using fun-
damental mathematical models have been pro-
posed. State estimators suchas the KalmanFilter
[952], [953] and recursive parameter estimators
[954] have been advocated to update model pa-
rameters and predict polymer properties.
Feedback control over measured or inferred
properties in continuous reactors has been ac-
complished by using empirical models [955],
However, in spite of the many advances that
have been made in the methodology for the ad-
vanced control of polymerization reactors, there
are still few industrial applications.
Figure 83. Continuous emulsion polymerization in a reac-
tor train with a split feed (small polymer particle nucleating
reactor followed by one or more larger finishing reactors)
a) Small seeding reactor; b) First large reactor in train
To again emphasize the point that control
problems should be considered at the design
stage of a polymer manufacturing process, ref-
erence is made to the well-known stability prob-
lems that are experienced with continuous emul-
sion polymerization (in a single CSTR) involv-
ing monomer(s) that experience Case I kinetics
(e.g., vinyl acetate and vinyl chloride). Modern
control theory did not provide suitable control
methodology for the single CSTR. It was de-
cided, therefore to go back to the design stage,
redesign the process by using a dynamic reac-
tor model and minimize control problems at the
design stage. The new design which is shown
in Figure 83 has almost trivial control problems
[949], [956]. Experimental verification of the in-
crease in stability of this newdesign may be seen
in Figure 84. The initial response (conversion
Polymerization Processes 113
Figure 84. Conversion responses to CSTRreactor systemshown in Figure 83 for continuous emulsion polymerization of vinyl
Part A: operation with a single CSTR (shows sustained oscillations)
Part B: switching over to seed reactor followed by one finishing reactor (responses for both reactors are shown, with very
stable response for downstream reactor and minor disturbance for seed reactor) [611]
versus time) is for a single CSTR. The follow-
ing two responses are for the small seed reactor
and for the larger finishing reactor.
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Polymerization Technology → Polymerization Processes
c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
10.1002/14356007.a21 429
Polymers, Electrically Conducting 1
Polymers, Electrically Conducting
Herbert Naarmann, BASF Aktiengesellschaft, Ludwigshafen, Federal Republic of Germany
1. Introduction . . . . . . . . . . . . . . . . . 1
2. Synthetic Routes . . . . . . . . . . . . . . 2
3. Principles of Electrical Conduction . . 3
4. Orientation Processes . . . . . . . . . . . 4
5. Types of Electrically Conducting Or-
ganic Materials . . . . . . . . . . . . . . . 5
5.1. Polyacetylene . . . . . . . . . . . . . . . . 5
5.2. Polydiacetylenes . . . . . . . . . . . . . . 7
5.3. Polypyrrole . . . . . . . . . . . . . . . . . 8
5.4. Polythiophene . . . . . . . . . . . . . . . . 10
5.5. Polyphenylene . . . . . . . . . . . . . . . 10
5.6. Poly(Phenylene Sulfide) . . . . . . . . . 12
5.7. Poly(Phenylene Vinylene) . . . . . . . . 13
5.8. Polyaniline . . . . . . . . . . . . . . . . . . 13
5.9. Miscellaneous Polymers . . . . . . . . . 15
6. Uses . . . . . . . . . . . . . . . . . . . . . . 18
7. References . . . . . . . . . . . . . . . . . . 18
1. Introduction
Electrically conducting polymers (ECPs) are
materials with an extended system of C=C con-
jugated bonds. They are obtained by reduction
or oxidation reactions (called doping), giving
materials with electrical conductivities up to
S/cm. These materials differ from polymers
filled with carbon black or metals because the
latter are only conductive if the individual con-
ductive particles are mutually in contact and
form a coherent phase.
This review concerns the synthesis routes,
polymerization techniques, doping, orientation,
and development of well-defined, highly con-
ducting polymeric materials. Their wide range
of potential uses from electrodes in recharge-
able batteries to organic transistors is limited
by their vulnerability to air and moisture due to
their highly conjugated structures and the dop-
ing agents. Electrically conducting materials are
compiled, their specific properties and potential
applications are described.
Numerous attempts have been made to syn-
thesize “conductive organic materials”. The
first was the synthesis of polyaniline by
F. Goppelsroeder in 1891 [1]. After decades
interest grew in organic polymers as insulators,
but not as electrical conductors.
In the late 1950s organic semiconductors be-
came the focus of investigations. Preliminary
studies in this field up until the mid 1960s
are reviewed in [2]. The semiconducting poly-
mers were termed “covalent organic polymers”,
“charge-transfer complexes”, “organometallic
polymers”, “hydrogen-bonded polymers”, and
“mixed polymers”. Highest conductivity values
reached about 10
S/cm. In 1964 Little the-
oretically evaluated the possibility of supercon-
ductivity in polymers and suggested a model,
consisting of a polyene chain with cyanine, dye-
like substituents [3]. In the same year system-
atic studies were presented based on aromatic
and heterocyclic compounds exhibiting electri-
cal conductivities of 0.5 S/cm [4], followed by
studies correlating doping, pressure, irradiation,
and chain length to conductivity, with values up
to 100 S/cm [5].
Interest heightened and became acute
from 1975 when IBM scientists showed that
poly(sulfur nitride), (SN)
, was superconduc-
tive [6] and MacDiarmid’s group reported
[7] the doping of polyacetylene films prepared
by Shirakava [8] reaching conductivity values
of 38 S/cm. Since then many expectations have
been raised, but scientific progress and practi-
cal applications have been limited; they depend
on the reproducible production of well-defined
specimens, the determination of synthesis con-
ditions, and the laws relating these conditions to
product properties. Synthetic methods are im-
proving; more easily processible, soluble, flexi-
ble materials are now being produced.
2. Synthetic Routes
The synthesis of electrically conducting poly-
mers with conjugated −HC=CH− bonds re-
quires the controlled coupling of a large number

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