6.
Polymerization processes
6.4.1 Polymerization reactions
Polymers are macromolecules of natural or synthetic origin
which present different chemico-physical properties,
allowing them to be used in numerous sectors of human
activity. Worldwide polymer production is in the order of a
billion tonnes a year and now involves all industrial sectors:
from transportation to food products, from construction to
materials for the electronics industry, from textiles to
pharmaceuticals.
Polymers are made starting from relatively simple
molecules known as monomers, which are assembled with
one another with different mechanisms and geometries to
form macromolecules which may contain from a few tens (in
this case we speak of oligomers) to several thousand
monomer units. Generally speaking, this assembly process
takes place through two possible chemical mechanisms: a
step-growth mechanism and a chain-growth mechanism.
In the light of the chemical reactions characterizing the
polymerization process, a simple classification of synthetic
polymers can be established. The most common are
thermoplastic polymers, consisting of linear or branched
macromolecules and with a melting point above which they
liquefy reversibly. In the presence of high degrees of cross-
linking, and therefore far higher molecular weights,
thermosets are obtained which decompose when the
temperature rises but do not melt. Finally, elastomers are
also linear or branched macromolecules, but contain double
bonds which at a later stage are made to react with a suitable
cross-linking agent at high temperature, to obtain a
cross-linked material with the properties typical of rubbers.
Step-growth mechanism
This polymerization reaction is characterized by the fact
that all the molecules present in the reaction environment
(monomers, oligomers and polymers) maintain the same
probability of reacting throughout the process. This is the
case of polyesters, which are synthesized with the
esterification reaction starting from monomers containing
two acid groups (A) or two alcohol groups (B). For example,
polyethylene terephthalate is obtained from terephthalic acid
and diethanol. Generally speaking, using A
A and B
B
to represent the two monomers, where A and B represent the
VOLUME V / INSTRUMENTS
acid and alcohol groups, the following reaction
stoichiometry is obtained:
( ) ( )
[1] n A 688 A + n B688 B


➤ ||||

➤ B688 B68 8 (A 688 A 688 B688 B)n−1 688 A 688 A

||||
Other reactions leading to the synthesis of other types of
macromolecules can be represented in a similar way, as for
the polyamides, in which the reagent groups are an amine
and a carboxylic acid, or the polyurethanes, obtained for
example from a diol and a diisocyanate.
The same polymerization mechanism is applied to
monomers containing both functional groups, as shown
schematically by the following reaction stoichiometry:
[2] (
n A 688 B
)

➤ A 688 B688 A 688 B
||||
( ) n− 2
688 A 68 8 B
This is the case, for example, of the reaction between
amino acids in which the peptide bond, typical of the
structure of proteins, is formed from an amine group and a
carboxyl group:
[3] H 2 N 688 R 688 COOH + H 2 N 688 R'688 COOH


➤ ||||



➤ H 2 N 688 R 688 COHN 688 R'688 COOH + H 2O
||||
Some of these reactions are shown in Table 1, where it
can be seen that the addition of a monomer unit often entails
the elimination of a molecule of low molecular weight, such
as water or methanol. This is an important characteristic of
this type of polymerizations, which in order to be completed
require the removal from the reaction environment of these
low molecular weight species.
As is clear from reaction stoichiometry [1], the monomer
units alternate along the chain. As such, to obtain complete
conversion and thus macromolecules with a high molecular
weight, it is necessary to operate with an exact equivalence
of functional groups.
Kinetically, the main characteristic of the step-growth
mechanism is that the polymer chains remain active, and
thus continue to grow, throughout the polymerization
process, in other words for the entire time needed to
completely consume the monomer species. In fact, since the
reactive groups remain unaltered in the final polymer chains,
these may begin to grow again at any time if placed in
369
PROCESS ENGINEERING ASPECTS

Table 1. Polymers produced by step polymerization

Polyester
n HOOC COOH  n HO (CH2)2 OH HO C CO (CH2)2 O H  (2 n
1)H2O
O O n

Polyamide
H H

n HOOC (CH2)4 COOH  n H2N (CH2)6 NH2 HO C (CH2)4 CN (CH2)6 N H  (2n
1)H2O

O O n

Polyurethane H H
(n1) HO (CH2)4 OH  n OCN (CH2)6 NCO HO (CH2)4 OCN (CH2)6 NCO (CH2)4 OH
O O n

Polyester
n HO COOH n HO CO H  (n
1)H2O
O n

contact with monomers. For this reason, these polymers are
described as living, and this property is exploited in many of
their applications.
In the case of monomers containing two reactive groups,
linear chains are obtained, as shown in equation [1]. By
contrast, in the case of monomers containing three or more
reactive groups, non-linear chains are obtained which may
present very different structures. A typical situation is the
formation of structures with an extremely high molecular
weight, in which the chains are strongly interconnected and
form a macroscopic phase whose chemico-physical
properties are completely different from those of the starting
mixture of monomers or the corresponding linear polymers.
These macromolecules are often known as gels and can be
separated from the rest of the reagent mixture since they are
insoluble in all solvents. Another peculiar structure is that of
copolymers synthesized from monomers containing two or
more type A functional groups and monomers containing
two or more type B functional groups, which react with one
another but not with themselves and where at least one of the
two monomers has at least three such functional groups. In
this case, hyper-cross-linked polymers are obtained whose
structure is relatively compact but which have an extremely
high molecular weight.
An example of this type is polycarbosilane
obtained by the synthesis of monomer species in which
groups A and B above are a CHCH2 group and a Si
H
group. These structures are particularly useful for various
types of applications in the surface coating sector since,
compared with linear polymers of identical chemical
composition and equal molecular weight they are
significantly less viscous.
monomer species takes place, also involving the formation
of a similar active centre on the unit added (allowing for the
successive addition of various monomer units and thus the
formation of the polymer chain). Finally, there are reactions
which lead to the interruption of the chain’s propagation
and therefore to the production of a definitive or dead
polymeric chain, which is no longer able to add monomer
units. These reactions are known as terminations if they
entail the disappearance of the active centre, or chain
transfers if the active centre is simply transferred to another
molecule, thus allowing for the propagation of a new chain.
Kinetically, the fundamental property of the chain
growth mechanism is that the life time of the growing chain,
in other words the time between the activation of a chain and
its termination, is extremely short with respect to the
duration of the polymerization process. As such, unlike the
step-growth mechanism, new active centres must be
continually created during the process, to replace those
suppressed by the termination reactions and allow the
process itself to be completed.
As mentioned above, depending on the nature of the
active centre which allows the polymer chain to propagate,
free radical, cationic or anionic polymerizations may
occur. Some catalytic polymerizations, such as those of
olefins on Ziegler-Natta catalysts, also follow an identical
reaction mechanism, also known as a coordination
mechanism. Table 2 lists some polymers which are
produced through these various chain growth mechanisms.
Below, the kinetics of radical polymerization will be dealt
with in more detail, as this is certainly the most common
type of polymerization.

Chain-growth mechanisms 6.4.2 Kinetics of step-growth

This polymer formation mechanism is characterized by a polymerization
sequence of three processes: the first is initiation in which
an active centre is created; this may be a free radical, a In step-growth polymerization, the life time of the polymer
cation or an anion. On this centre the addition reaction of the chains is comparable with the characteristic time of the

370 ENCYCLOPAEDIA OF HYDROCARBONS

 POLYMERIZATION PROCESSES

Table 2. Polymers produced by different types of chain polymerization

Radical Cationic Anionic Coordination

Polyethylene Polyisobutylene Polybutadiene Polyethylene
Polyvinylchloride Polyvinyl ether Polymethyl cyanoacrylate Polypropylene
Polystyrene Polyoxymethylene
Polyacrylonitrile Polyamide
Polymethyl metacrilate Polydimethylsilane
Polytetrafluorethylene
Polyvinylidenec fluoride

process, in other words the time needed to completely that a functional group chosen at random in the reagent
consume the monomer species. As such, in contrast to mixture has reacted is given by the conversion XA, it is
radical polymerization, in this case the molecular weight of possible to calculate the fraction of chains N(r) which
all the chains increases in a uniform way throughout the have length r as follows:
process. As a consequence, high molecular weights are
reached only for very high conversions and as such during
[6] ()
N r = X A( ) 1 − XA
r −1
( )
most of the process viscosity remains moderate making heat This in turn makes it possible to calculate the fraction of
exchange processes relatively easy. monomer units contained in chains of length r
Considering two bifunctional monomers, such as a diol
()
W r = rX A( ) 1 − XA
r −1
( )
2
[7]
and a diacid, the reaction occurs according to reaction
stoichiometry [1]. In the kinetic treatment of these processes whose mean value is given by:
it is usually assumed that the reactivity of the functional 1 + XA
groups is independent of the length of the chain to which [8] nW =
they are attached. When, as is often the case in practice, the 1 − XA
initial molar concentration of the two monomers is identical, Figs. 1 and 2 show distributions for some characteristic
the conversion of the functional groups XA(NA0
NA)ⲐNA0, values of the conversion XA. It is evident that for conversions
where NA and NA0 represent the number of moles of the of about 99%, the mean values of the chain lengths are in the
diacid, at generic time t and initial time t0 respectively, is order of a few hundred. Additionally, the mean ponderal
given by value is always higher than the mean numerical value. The
1 relationship between the two, s, generally known as
[4] XA = 1 − polydispersity:
1 + A0 kt
where k is the second order kinetic constant of the
esterification reaction [1] and A0 is the initial concentration
of the diacid.
In these systems, the mean numerical chain length, in 0.03
XA  0.95
other words the mean number of units present in a chain, nN,
is simply given by the ratio of the number of moles of A at
the beginning to the number at generic time t of the process,
which in terms of conversion gives
0.02
NA0 1
[5] nN = =
NA 1 − XA
N (r)

showing that high molecular weights can only be obtained

for very high conversions. Furthermore, when even a very XA  0.97
small deviation from the stoichiometric composition of the 0.01
two monomers is present, the maximum admissible
molecular weight decreases significantly. Consequently, XA  0.99
chain-growth polymerization techniques are normally
used in order to obtain polymers with a high molecular
weight. 0
To estimate the distribution of the lengths of 0 100 200
polymer chains, it is necessary to calculate the chain length, r
probability of a chain consisting of r monomer units.
This can be done by considering that this chain must Fig. 1. Numerical distribution
consist of (r
1) functional groups which have reacted of chain lengths, N(r), for a polymer produced
and one which has not reacted. Since the probability by step polymerization.

VOLUME V / INSTRUMENTS 371

PROCESS ENGINEERING ASPECTS
2.0 XA  0.95
W(r).102
1.0 XA  0.97
XA  0.99
0 nitrogen molecule.
0 100 200
chain length, r
Fig. 2. Ponderal distribution
of chain lengths, W(r), for a polymer produced
by step polymerization.
nW
[9] σ= = 1 + XA
nN
supplies an estimate of the breadth of distribution. At the
beginning of the process, XA0 and s1, since all the
chains (monomers) are of equal length. As conversion
increases, so does polydispersity, which nevertheless remains
fairly low. When conversion is complete (XA1), we obtain
s2 which, compared with the values typical of chain
polymerization processes, is a fairly low value.
We can conclude that step polymerization processes, like
all living processes, are characterized by a high degree of
uniformity of the polymer chains. This is true particularly of
the distribution of polymer chain lengths which is generally
fairly narrow, though characterized by fairly low average
values. These decrease still further when shifts away from
the stoichiometric composition of the two monomers or
impurities are present.
6.4.3 Radical chain polymerization
Initiation
The radical generation reaction most frequently adopted
is the thermal decomposition of a relatively unstable
chemical species, such as a peroxide. The choice of the
initiator is generally made on the basis of the temperature
and duration of the process, to guarantee the necessary
production of radicals until the monomer species have been
fully consumed.
The typical decomposition stoichiometry of a peroxide is
as follows:
kd
[10] RO 688 OR'




➤ RO+ R'O
||||
However, of the radicals produced by this or similar
decomposition reactions, only a fraction give rise to a
chain able to propagate. This is indicated by a magnitude
known as the initiator efficiency ( f ) which has values in
the range of 0.2 to 1. The mechanism mainly responsible
for this phenomenon is the recombination reaction of the
two radicals just formed. This reaction is encouraged by
the so-called ‘cage effect’, due to the cage formed by the
372
solvent and monomer molecules which surround the
initiator molecules at the moment of their decomposition.
The two radicals formed must be able to diffuse outside
this cage before the recombination reaction takes place.
Therefore, efficiency values will generally decrease as the
viscosity of the reagent system increases and thus as
polymerization proceeds. It is worth noting that the
recombination reaction does not always lead to the
reconstitution of the original initiator molecule, which
would thus be able to produce radicals again. This is true,
for example, of azobisisobutylonitrile (AIBN), whose
decomposition takes place through the removal of a
300 A peculiar situation arises in the case of
polymerizations which must be conducted at low
temperatures; it is difficult to find initiators for these able
to produce enough radicals to sustain the development of
the polymerization reaction. In this instance, it is possible
to accelerate the decomposition reaction of the initiator
photochemically, using visible or ultraviolet radiation.
Alternatively, the reaction may be catalyzed with a
reducing agent, such as a Fe2 salt, giving rise to an oxide
reduction reaction which leads to the formation of a
radical species and which becomes dominant with respect
to non-catalyzed decomposition [10]
[11] Fe 2+ + RO 688 OR'


➤ Fe3+ + RO+ R'O
||||
Types of radiation whose photons are sufficiently
energetic, such as UV or gamma rays, can be used to initiate
radical polymerization reactions even in the absence of an
initiator. This method, which has the advantage of being
completely temperature-independent, is mainly used in
polymer post-treatment cross-linking processes.
At sufficiently high temperatures, the monomer
molecules themselves may give rise to decomposition
reactions with the formation of radicals. A typical example is
styrene which, through a fairly complex mechanism, is able
to give rise to a radical production mechanism which follows
a third order kinetics with respect to the concentration of
monomer. This reaction is used in high temperature bulk
polymerization processes of styrene, used to produce
oligomer species.
Generally speaking, the decomposition of the monomer
with the formation of radicals is in fact an undesired
reaction. It may take place during the storage or
transportation of the monomers, leading, generally over long
periods of time, to their polymerization. To avoid this,
polymerization inhibitors are introduced. These are chemical
species such as hydroquinones, able to react rapidly with any
radicals that may form, producing species which are still
radicals but stable and therefore unable to initiate a chain of
radical reactions.
Propagation
The chemical species most frequently used in
polymerization processes are vinyl monomers, consisting of
an ethylene molecule in which only one of the two carbon
atoms has one or two substituents (CH2CHR or
CH2CRR') so that the double bond opening reaction is
not excessively sterically inhibited. In the propagation
reaction the radical on the growing chain opens the
monomer’s double bond, adding it to the chain and
transferring radical activity to it:
ENCYCLOPAEDIA OF HYDROCARBONS

R disproportionation, in which one of the two radical chains
[12] kp
n
1
R [15]
kp
n
The propagation reaction generally follows an
Arrhenius type kinetics. Since the monomer species is
able to diffuse significantly faster than the large radical
macromolecules, diffusion processes do not limit the
kinetics of these reactions. However, this is no longer true
when the reaction temperature falls below the vitreous
transition temperature and the reagent system passes from
the viscous liquid to the solid state. Under these
conditions, the diffusion of the monomer is strongly
inhibited and the propagation reaction, and with it the
entire polymerization process, is blocked. This
phenomenon is responsible of the numerous instances
found in practice of these reactions, in which it is
impossible to attain complete conversion.
Another potentially important aspect in this context is
the depropagation reaction. The temperature value at which
the velocity of this reaction is equal to that of the
propagation reaction, thus creating conditions of
equilibrium, is known as the ceiling temperature. Using the
usual condition of thermodynamic equilibrium and
indicating the variation of Gibbs free energy linked to the
propagation reaction with DG(T ), we obtain:
[13] ( )
∆G T = RT ln M
where M is the concentration of the monomer. From [13] it is
obvious that this equilibrium temperature depends on the
concentration of monomer present in the reagent system. It
is worth noting that most polymerization processes are
conducted at temperatures such that the depropagation
reaction is negligible until the conversion of the monomer is
practically complete.
Terminations
The reactions responsible for the suppression of a
radical, ignoring the possible presence of inhibitors or
impurities, are bimolecular terminations between two
growing radical chains. The most frequent reaction of this
type is the combination of the two radicals with formation of
a single dead chain:
R R
[14] k tc
n
1 m
1
R
k tc
mn
1
VOLUME V / INSTRUMENTS
POLYMERIZATION PROCESSES
An alternative reaction is termination by
removes a hydrogen atom from the other, inducing the
formation of a double terminal bond on it:
R R
k td
n
1 m
1
R R
ktd
n
1 m
1
It should be noted that in this case the two chains
terminate, keeping their individuality and in particular their
length unaltered, in contrast to what occurs in the case of
termination by combination.
Kinetically, termination by combination presents the
peculiarity of being controlled by diffusion phenomena, a
fact generally described as the Trommsdorff effect. This is a
reaction characterized by a reactive act, the combination of
the two radicals, which is extremely fast. However, it must
be proceeded by a fairly complex diffusion process which
must lead to the superimposition of two specific points (the
radicals) of two macromolecules which have a coil
conformation. The relative movements of these two
molecules are significantly reduced by the numerous
interactions between the atoms of the two reagent molecules
and with those of the other macromolecules surrounding
them. The result of the Trommsdorff effect is a kinetic
constant that, in contrast to the classic Arrhenius effect,
presents a strong dependence on the viscosity of the reagent
system and a far more modest dependence on temperature,
typical of material diffusion processes. Furthermore, this
kinetic constant is relatively insensitive to the chemical
nature of the radical species involved, but far more sensitive
to their dimensions.
In some cases, termination by disproportionation is also
controlled by the Trommsdorff effect, though this occurs less
frequently than for termination by combination. This is due
to the reactive act which, since it involves the cleavage of a
C
H bond, is significantly slowed.
Chain transfer
These are reactions which stop the growth of the radical
chain, but do not suppress radical activity, which instead is
transferred to another chemical species from which a new
chain begins to propagate. If the radical does not change its
own activity in the transfer, the velocity of monomer
consumption and therefore the duration of the
polymerization process, are not altered by this reaction
which does, however, affect the length of the polymer chains
produced. Considering the effects which transfer reactions
may have on the structure of the molecules produced, a
distinction must be made between different cases.
These are known as transfer to small molecule reactions
when the radical is transferred to a solvent, monomer or
chain transfer agent molecule, which is a species deliberately
373
PROCESS ENGINEERING ASPECTS
added to the reaction environment to limit the length of the
macromolecules produced. It should be noted that each of
these reactions often corresponds to a different terminal
group on the final polymer chain. Measuring the distribution
of these terminal units is often an excellent way of
identifying and quantifying the kinetics of these reactions.
The chain transfer to monomer reaction may proceed in
accordance with the following stoichiometry:
R involves two macromolecules, is not controlled by the
[16] k fm
R
k fm
The radical species formed leads, after the addition of a
suitable number of monomer units, to a dead polymer chain
characterized by a terminal double bond, identical to that
produced by termination by disproportionation.
It is worth observing that propagation and transfer to
monomer reactions involve the same reagents and are
therefore inseparable, but always occur simultaneously and
proportionally to their respective kinetic constants. For any
given monomeric species the transfer to monomer reaction
therefore determines the maximum attainable molecular
weight, were it possible to suppress every other termination.
Since the cleavage of the C
H bond required by the
transfer reaction [16] is certainly more difficult than the
opening of the double bond involved in the propagation
reaction [12] there is a difference of at least three orders of
magnitude between the two reactions for the monomers
commonly used.
Transfer reactions may also involve macromolecules, as
in the case of the transfer to polymer reaction:
R R
[17] k fp
R R
k fp
In this case, the growing radical removes a hydrogen
atom from any point on a dead chain, leaving behind a
radical which may propagate to create a new chain. However,
since the new chain is joined to the earlier one at a point
which in reaction [17] is represented by a tertiary carbon, a
side branch is formed.
This reaction presents two important peculiarities with
respect to all the reactions hitherto considered: the ability to
374
reactivate a dead chain and the formation of non-linear or
branched chains. This significantly complicates the
description of the process kinetics and enormously broadens
the range of structures which can be formed, making a
detailed mathematical description unrealistic.
Since the transfer reaction may take place on any one of
the monomer units present in the dead polymer chain, the
corresponding reaction velocity is proportional to the mass
concentration and not to the molar concentration. This also
explains why the transfer to polymer reaction, although it
Trommsdorff effect. Although the reactive act is very similar
to that of the disproportionation reaction, the diffusion
process is significantly facilitated by the fact that any point
in the dead chain can react.
The transfer to polymer reaction may also be
intramolecular; in other words, the radical positioned at the
end of a chain may remove a hydrogen atom from within the
chain itself. In most cases, this occurs through a backbiting
reaction, in which the chain, folding in upon itself, allows
the extraction of a hydrogen atom from a monomer unit only
a few units away from the radical end. The number of such
units and the fact that this reaction may or may not occur
depend on the specific chemical structure of the chain,
which determines its intramolecular mobility. In any case,
this reaction produces short branches distinct from the long
branches typical of the intermolecular transfer reaction
described above. A typical polymer in which short branches
prevail over long ones is low density polyethylene (LDPE).
In this case, the short branches consist of no more than four
or five monomer units and have a concentration at least an
order of magnitude higher than that of long branches.
b-scission reaction. The b-scission reaction occurs
starting from a radical located at any point along the
polymer chain. It entails the cleavage of the C
C bond in
the b position with respect to the radical and leads to the
formation of a dead polymer chain with a terminal double
bond and an active radical chain of smaller size than the
original chain:
k
[18]
R
n
k
R
n
Since b-scission always occurs after the formation of a
radical inside the chain and therefore after a transfer to
polymer or backbiting reaction, the entire process can be
seen as a chain transfer reaction, with the peculiarity that it
entails the rupture of the macromolecule transferred.
This reaction obviously presents a high activation energy
and is determining only at very high temperatures. A typical
instance is the high temperature bulk polymerization of
styrene, where the distribution of the molecular weights of
the oligomers produced is controlled by the backbiting
reaction followed by b-scission.
Controlled or pseudo-living radical polymerization
As seen above, the fundamental characteristic of the
kinetics of chain polymerization with respect to step
polymerization is that in the former the life of the radical
ENCYCLOPAEDIA OF HYDROCARBONS

chains is significantly shorter than the duration of the
polymerization process. This means that some polymer chains
are produced at the beginning and others at the end of the
process, when many of the operating conditions, such as the
concentration of the various reagent species, viscosity and
temperature may be very different. This can give out some
differences between lenght and composition of polymer chains,
that imply unwanted lack of uniformity in the final product.
This situation does not occur in the step polymerizations
seen earlier in which the chains, described as living, all grow
at the same time throughout the process and are therefore
more uniform. The fact that the chains are living and
therefore remain reactive even after the synthesis process
may lead to significant advantages in subsequent
applications, such as the creation in situ of cross-links
between macromolecules, and above all the production of
block copolymers. For all these reasons, it is of interest to be
able to conduct radical chain reactions under these
conditions as well.
Since the termination reactions between radicals
described above are irreversible and certainly impossible to
eliminate, the objective is to attain controlled or pseudo-
living conditions, under which termination reactions are
significantly reduced, if not completely eliminated. This is
done by introducing reversible termination reactions into the
system with a capping species, indicated by X, through
which the growing radical chains form so-called sleeping
chains, unable to propagate but also to terminate. In this
case, every radical chain R may follow three different
reactions: propagate with a monomer molecule, terminate
irreversibly with another R radical or react reversibly with
the X species to form a sleeping chain. Since bimolecular
termination is the only one of the second order with respect
to the concentration of radicals, its velocity with respect to
the other two can be lowered by reducing the total
concentration of radicals in the system. This creates a
concentration of ‘sleeping’, and therefore living, chains
which is higher than that of dead chains, making it possible
to approach the conditions of living polymerization.
These conditions are attained by selecting the
concentration and reactivity of the X species in such a way
as to bring most of the radicals into the system in the form of
sleeping species. In this case, the process is extremely slow,
since the concentration of radical chains which consume the
monomer is low; by way of compensation, the formation of
dead chains is reduced significantly. Each chain thus grows
during numerous time intervals distributed within the
polymerization process. During each of these a few
monomer units are added, after which the chain returns to
the sleeping state in which termination cannot occur.
It is important to note that this mechanism only works to
reduce the effect of bimolecular terminations; it is
ineffective in reducing the dead chains produced by the
transfer to monomer reaction.
Living polymerization is normally initiated by
introducing an initiator into the system which also contains
the X species, indicated by RX. Through various activations
and disactivations, this species inserts several (n) monomer
units M giving rise to the sleeping species which take the
form R
(Mn)
X.
Different chemical systems can be selected to create the
conditions described above, giving rise to various living
polymerization mechanisms.
VOLUME V / INSTRUMENTS
POLYMERIZATION PROCESSES
Nitroxide Mediated Polymerization (NMP). This living
polymerization mechanism consists in the reversible
combination of the growing living chain Rn and the so-called
persistent radical species X (for example the nitroxide
radical group) to form the sleeping polymer chain, RnX:

R + X



 R X
䉴
[19] n
䉳
n
Today various possibilities for carrying out this process
exist, based on different types of persistent radicals. Of
these, the most widely used is certainly
2,2,6,6-tetramethylpiperidin-1-oxyl (TeMPO), which has the
limitation that it is difficult to apply to monomers other than
styrene and that it requires relatively high polymerization
temperatures (120-140°C).
Atom Transfer Radical Polymerization (ATRP). This
mechanism is based on the radical addition by atomic
transfer reaction and is catalyzed by a metal (typically
copper): the homolytic cleavage of the bond in an organic
halogenide occurs through the transfer of halogen to the
metal complex accompanied by the oxidation of the metal.
The catalytic cycle is ended by the return of the halogen to
the end product by the transition metal. It is clear that, if the
radical produced can carry out propagation reactions before
giving rise to the inverse transfer reaction and if this product
is still able to give rise to a transfer cycle, the reaction can be
used to produce the same exchange between active and
sleeping species seen in the former mechanism. The
resulting reversible reaction can be shown as follows:
( n+1)

[20] R + X 688 Me
n / L
R X + Me( n )/ L
䉳
䉴
n
where X indicates the halogen, Me(n) the metal at oxidation
stage n and L the binder.
The ATRP mechanism owes its success to the fact that it
can be applied to a broad range of monomers, such as
styrene, the acrylates, metacrylates, acrylamides and
acrylonitrile, making it possible to use this technique to
produce different types of block polymers of considerable
practical interest. The presence in the system of a metal and
a relatively complex binder needed to bring it into solution,
and the strong colouring normally conferred upon the
polymer by this complex are the main disadvantages of this
process.
Degenerative Transfer (DT). In both the mechanisms
seen above the exchange between the active and sleeping
state is based on a reversible termination reaction (though a
different one). As a consequence, the exchange reaction
affects the total concentration of radicals. In living radical
polymerizations by degenerative transfer, the exchange
reaction takes place through the direct transfer of the
terminal group from the active to the sleeping chain. If
iodine is used as the chain terminal, the exchange reaction
may be represented as follows:
[21] Rn + R m I


➤ Rm + R n I
||||
Since this reaction does not alter the total concentration
of active radicals, the total concentration of chains
terminated by bimolecular termination is equal to half the
initial concentration of initiator. As such, the initial
concentration of the species containing iodine (described
below simply as the chain transfer agents) determines the
final degree of polymerization, assuming that the initial
concentration of initiator is small with respect to the initial
concentration of chain transfer agent.
375
PROCESS ENGINEERING ASPECTS
Polymerization by Reversible Addition-Fragmentation
Transfer (RAFT). The RAFT process can be seen as a
particular example of degenerative transfer. The so-called
RAFT transfer agent has the general structure
Q
Y
C(Z)Y, where Y is sulphur, C is carbon, Z is a
group which is normally phenylic and Q is the living group.
The reaction proceeds through the interaction between a
radical chain and a sleeping chain with the formation of a
reaction intermediate from which the reaction may return to
the initial radical or proceed with the transfer of the group
YC(Z)
Y from the sleeping species to the active chain:
[22] ( )
Rn + YC Z YR m
䉳
䉴
( )

R n YC• Z YR m


➤ ||||



➤ Rm + R n YC(Z)Y
||||
The correct choice of the Q group is of fundamental
importance not only because it will later become a chain
terminal group (with the other terminal being occupied by
the RAFT group), but above all because it determines the
initial reactivity of the RAFT agent, significantly influencing
the stability of the intermediate radical with respect to the
active radical chain.
Although the most important results have been obtained
for the RAFT polymerization of styrene, the process is
effective for various other monomer species, such as
acrylates and metacrylates. Additionally, this process is
effective at moderate temperatures and may be successfully
applied to emulsion polymerization systems, where it is
possible to exploit the segregation of the radicals in the
particles to improve the productivity of the process. A
significant disadvantage of this process is the need to
remove sulphur from the reaction product, since this often
has an undesired effect on the colour of the end product.
Non-linear chains
The main mechanism used to create non-linear
polymer chains is based on the formation of a radical on a
dead polymer chain; its propagation forms a so-called long
branch. This occurs through the transfer to polymer
reaction (the backbiting reaction produces only short
chains, not considered in this instance), whose importance
increases as conversion proceeds and thus as the
concentration of dead chains increases. An alternative
mechanism is linked to the propagation of the terminal
double bond which exploits the residual reactivity left
inside the dead chain by some termination reactions and in
particular termination by disproportionation, transfer to
monomer and b-scission. In this case, too, a point is
created on the chain from which three branches of
comparable length depart, as shown in Fig. 3 A.
Fig. 3. Diagram showing A
propagation reactions
of the terminal double
bond (A) and cross linking
reactions (B).
376
As in the case of step polymerization, the most effective
procedure for producing strongly non-linear chains is based
on the use of monomers which have more than one reactive
functional group, as in the case of the dienes or divinyl
monomers. In this way, dead polymer chains are obtained
which, however, contain various double bonds which may
propagate with other growing radical chains through cross-
linking reactions. As shown in Fig. 3 B, each of these
reactions creates a cross-linking point, in other words a
centre from which four branches of comparable dimensions
begin.
The cross-linking reaction increases the molecular
weight of the macromolecules extremely effectively and
therefore easily leads to the formation of gels. This system
behaves in a very similar way to step polymerization
systems, since the polymer chains remain reactive even after
the termination reaction due to the presence of the internal
double bonds. However, the cross-linking shown in Fig. 3 B
is not the only reaction which may lead to the formation of
gels in the radical polymerization process. To obtain a gel,
the macromolecules must grow exponentially and therefore
significantly faster than by simply adding monomer units as
in propagation. This condition is created by the cross-linking
reaction, but may also be attained by coupling two reactions:
one which reactivates the dead chains, such as the transfer to
polymer reaction, and another which couples them, such as
bimolecular termination by combination. If the latter is
replaced by termination by disproportionation, it is possible
to obtain polymers with very high degrees of ramification
but which are not gels, since the contribution to growth
provided by the termination by combination reaction is
lacking.
6.4.4 Kinetics of radical polymerization
Below, a radical polymerization reaction is considered with
the aim of deriving appropriate kinetic expressions to
describe its evolution over time in terms of the composition
and properties of the polymer produced. We consider a
generic system in which all the reactions listed below (with
the corresponding expressions of reaction velocity) are
present:
[23] initiation: I




➤ R1
||||
r2fkd I⬅RI
kp
propagation: RnM




➤ Rn1 ||||
rkpMRn
k fm
RnM




➤ R1Pn ||||
rkfmMRn
k fs
chain transfers: RnS




➤ R1Pn ||||
rkfsSRn
 monomer
 monomer
ENCYCLOPAEDIA OF HYDROCARBONS

ktc
RnRm




➤ Pnm
||||
rktcRnRm
ktd
terminations: RnRm




➤ PnPm ||||
rktdRnRm
where n, m1,…,
It should be noted that the capital letters indicate both
the symbol for and (in italics) the molecular concentration of
the species involved. Specifically, Rn and Pn represent
macromolecules containing n radical and dead monomer
units respectively, M is the monomer, I the initiator and S a
chain transfer agent. The reactions reported have been
discussed above; the reactions leading to the formation of
branches have been omitted here to limit the treatment
exclusively to linear chains.
The kinetics of all the reactions considered are of the
second order, with the one exception of the decomposition of
the initiator which is of the first order. For each of these
reactions it is possible to calculate a characteristic time,
indicating the order of magnitude of the time needed for the
reaction to unfold completely under the typical conditions of
the processes considered. Calculating these times makes it
possible to outline in a simple and easily understood way the
peculiar properties of the kinetics of radical polymerization
processes. It appears that these processes occur through
reactions characterized by three different characteristic time
levels, whose relative values determine not only the kinetics
of the evolution of the process but also the properties of the
polymer produced, such as the length and composition of the
chains.
The characteristic time of the process indicates the time
required for its completion, which in the instance under
examination corresponds to the complete consumption of the
monomer species. The velocity at which the monomer is
consumed is given by:
dM
[24] = − k p RM
dt
where R is the sum of the concentrations of all the radicals

present in the system, R兺n1Rn. It is thus possible to
define as the characteristic time of this second order process
the magnitude:
1 we must fall back on the material balances of the reagent
[25] τM =
kp R
where kpR represents the pseudo-first order kinetic constant
for the monomer consumption reaction. Under the typical
conditions of such processes, the characteristic time tM is in
the order of 103-104 s.
The characteristic time tI of the decomposition of the
initiator, which is a first order process, is simply given by the
inverse of the first order kinetic constant, kd:
1 Monomer consumption
[26] τI =
kd
Since, as noted earlier, the polymerization process
requires a continuous production of radicals in order to
unfold, this characteristic time must be higher, though not by
much, than that of the process, in other words tI tM.
By contrast, the characteristic times of all the reactions
leading to the interruption of the growth of the
macromolecule by termination or transfer are of a far lower
order of magnitude. These are the characteristic times of the
termination reaction by combination, ttc, and by
VOLUME V / INSTRUMENTS
POLYMERIZATION PROCESSES
disproportionation, ttd, of the chain transfer to monomer
reaction tfm and of the chain transfer to transfer agent
reaction tfs, all defined as the reciprocals of the pseudo-first
order kinetic constants of the corresponding reactions:
1 1 1 1
[27] τ tc = τ = τ = τ fs =
ktc R td ktd R fm kfm M kfs S
For every specific polymerization system only some of
these reactions may occur and with frequencies that differ
depending on the chemistry of the system. Generally
speaking, the reaction which dominates the termination
process is the one with the shortest characteristic time,
which in the most common systems is in the order of 1 s.
This determines the average time available to each radical to
propagate and add monomers before chain termination
occurs. It therefore corresponds to the life time of the chains
which, as noted above, is significantly shorter than the
characteristic time of the process, tM.
The third level of characteristic times corresponds to the
fastest processes, in other words the addition of the single
monomer unit by the radical. As in the case of the
characteristic time of the process, reference is made to the
propagation reaction, but in this case the process of
disappearance of the radical species is considered. The
corresponding characteristic time is therefore defined by
1
[28] τp =
kp M
which is in the order of 10
3-10
4 s.
The kinetic evolution of a radical polymerization process
depends on the interaction between these three process and
especially on the relationship between their characteristic
times. This also determines the properties of the polymer
chains produced. For example, the number of monomer units
contained on average within a polymer chain is given by the
relationship between the characteristic time of the dominant
termination process, which as mentioned above is of the
second order, and the characteristic time of the propagation
process. To speak of polymers, this ratio must be in the order
of at least 100 or 1,000.
However, for a more accurate quantitative description,
species, considering for each of these all the reactions in
which it is involved. The form taken by these balances
however, depends on the type of reactor under consideration
and this would significantly lengthen the discussion. As
such, the discussion below will make reference to the most
commonly used batch reactors, into which all the reagents
are introduced at the beginning of the process, without
further additions or withdrawals during the reaction.
The monomer is mainly consumed by the growing
radical chains present in the reactor. The first step is
therefore to calculate the overall concentration R of these
chains, independently of their length. This concentration can
be calculated from the overall material balance of the active
chains:
dR
[29] = RI − kt R 2
dt
where ktktcktd is the overall kinetic constant of the
bimolecular termination reactions and RI the velocity at
377
PROCESS ENGINEERING ASPECTS
which radicals are produced. If these are produced by the
decomposition of an initiator I as indicated by the first of the
reactions [23], we have:
[30] RI = 2 fkd I
In turn, the concentration of the initiator, I, is obtained
from a material balance which in the simplest instance of an
isothermal reactor leads to the analytical equation
[31] (
I = I 0 exp − kd t ) Chain length distribution
where I0 is the initial concentration of initiator.
As has already been shown, the essential feature of
radical chain polymerization processes is that the
characteristic time of chain termination is very short
compared to that of their production, comparable to that of
the decomposition of the initiator, tI. This makes it possible
to apply to their balance [29] the pseudostationary state
approximation according to which the accumulation term
can be ignored with respect to the terms of generation and
consumption. This reduces [29] to an algebraic equation
which makes it possible to calculate the concentration of
radicals as
RI
[32] R =
kt
where ktktcktd. At this point, it is possible to consider the
material balance for the monomer species which, again
referring to an isothermal batch reactor, is reduced to
dM
[33] = − k p MR
dt
Assuming that the velocity at which radicals are
produced, RI , remains constant during the process and that
the kinetic constants ktc and kp do not vary, the above
formula can be analytically integrated, leading to the typical
exponential equation for the concentration of the monomer:
 RI 
[34] M = M 0 exp  − k p t
 kt 
M0 is the initial concentration of monomer.
From this equation, it emerges that for a given initiation
system (which thus has the value RI), the kinetics of
monomer consumption is determined solely by the ratio
kp Ⲑ冪 kt. This also means that measuring the velocity of
1
monomer consumption makes it possible at most to estimate
the value of this ratio, but not the absolute value of the
individual kinetic constants. As a consequence, the literature
often reports the values of the ratio kp Ⲑ冪 kt for different
1
monomer species. The absolute values of the kinetic
constants can be estimated using more complex techniques,
such as pulsed laser polymerization, which requires the
characterization of the length of the polymer chains
produced.
In practice, equation [34] is only an approximation,
since the terms of the balance [33] vary over time.
Particularly important is the effect of the variation of the
system’s viscosity which, through the Trommsdorff effect,
produces a decrease in the termination by combination
constant and therefore a rapid increase in the
concentration of radicals and thus the velocity of
monomer consumption. This effect may be compounded
by the decrease in the reactor’s heat exchange coefficient,
378
caused by the increase in the viscosity of the reagent
system which leads to a decrease of the velocity at which
the heat produced is lost and therefore an increase in
temperature which further accelerates the monomer
consumption process. In conclusion, the monomer
concentration profiles within the reactor deviate from the
ideal exponential form, as shown in Fig. 4.
The applicative properties of a polymer are determined
by the composition and the structure of the macromolecules
of which it is formed. As will be seen below, the
macromolecules are not all identical but generally constitute
a population of individuals with different characteristics; it is
the distribution of these characteristics, and not simply their
mean values, which determines the applicational properties
of a polymer material. As such it is particularly important to
describe the kinetics through which these distributions
evolve as a function of the particular operating conditions of
the polymerization process. To this end, specific material
balances are used, known as population balances, which
refer to specific individuals in these populations and in
particular to those characterized by a particular value of the
characteristic element under consideration. If the latter is the
length of the polymer chain (also known as the degree of
polymerization, which represents the number of monomer
units in the chain) the corresponding population balances
make it possible to calculate the Chain Length Distribution
(CLD).
The CLD of the dead polymer chains present in a batch
reactor at the end of the process can be calculated with the
following steps: calculation of the instantaneous CLD, in
other words the CLD of the chains produced at a given
instant during the polymerization process; and summing
together all the instantaneous CLDs, weighed against the
corresponding quantities of polymer produced, to calculate
the cumulative CLD, in other words that of the end product
(see also chap. 8.1).
It should be remembered that this procedure is possible
thanks to the peculiar characteristic of these processes,
where the chains are produced in extremely short time
intervals with respect to the duration of the process.
The numerical instantaneous chain length distribution,
fN (n), such that fN (n)dn represents the numerical fraction of
polymer chains of length n produced at a given instant, is
given by the equation
1
conversion
eq. [34]
Trommsdorff effect
time
Fig. 4. Role of the Trommsdorff effect on the pattern
of conversion as a function of time in a batch reactor.
ENCYCLOPAEDIA OF HYDROCARBONS
 POLYMERIZATION PROCESSES

α ( )
 γ + 12 n − 1 αβ 
[35] ()
fN n =   f(n) f N(n) f W(n)
(1 + α ) γ + 12 β
n
 

into which two new adimensional kinetic parameters have

been introduced, defined as the relations between the
characteristic times:
k R τ
[36] β = tc = p
k p M τ tc
ktd R k fm k fs S τ p τ p τ p
[37] γ = + + = + +
k p M k p k p M τ td τ fm τ fs
where abg. From the equations above, it can be
observed that the kinetic parameters b and g influence the
instantaneous CLD in different ways, even though it has
been ascertained that as both increase, the chains obtained
are, on average, shorter. This is reasonable, since higher
values of these parameters correspond to higher values of
terminations with respect to propagation. It is interesting to
note that parameters b and g comprise the characteristic
times of termination processes which are qualitatively
different from one another. In the former we find
termination by combination, where the chains which
terminate lose their identity in the termination process,
forming a single chain whose length is the sum of the two
original chains. By contrast, g comprises three termination
processes which resemble one another in that the chain’s
identity remains unaltered during termination. This structural
difference between the terminations means that they affect
the CLD differently and that the relevant kinetic parameters
therefore appear in different adimensional parameters.
In practical applications, another type of CLD is also
used, the ponderal chain length distribution, indicated by
fw(n). This is the fraction of monomer units present in chains
of a given length n and can be calculated directly from the
corresponding numerical distribution with the equation:
()
()
nf N n
[38] fW n = ∞
∑ nf ( n)
n =1
N
As an example, the two distributions are shown in Fig. 5
for the same polymer. It can be observed that the ponderal
distribution tends to give greater weight to the longest chains
nN nW n
Fig. 5. Comparison of the instantaneous numerical distribution,
fN (n), and ponderal distribution, fW (n), of chain lengths.
two CLDs become increasingly different. It is therefore
natural to introduce a specific parameter, known as the
polydispersity of distribution, defined as the relationship
between the mean ponderal and numerical molecular
weights:
[41] σ= =
(
nW 2 γ + 23 β γ + 12 β )( )
( )
2
nN γ +β
which takes on a unitary value for Dirac delta distributions
and increases as the breadth of distribution increases. This
parameter is widely used in practice as a measurement of
distribution breadth.
Through equations [35-41], it is possible to obtain a
good description of the instantaneous CLD, in other words of
the characteristics of the infinitesimal quantity of polymer
produced at a given instant during the polymerization
process. Generally speaking, however, as mentioned above,
we are interested in calculating the properties of the end
product, in other words the entire population of polymer
chains found inside the reactor at the end of the process. In
the case of a batch reactor, this entails calculating the so-
called cumulative CLD, fNc (n,t), which corresponds to the
average of all the instantaneous CLDs weighed against the
corresponding quantities of polymer produced from the
beginning of the process until a given time t:
number of chaains of length n

and therefore has a higher mean value. Using equations [35]   
produced in a given time unit
t
 dP 
and [38] it is possible to obtain the following analytical c
( )
n, t =
1
( )
∫0 f N n, t  dt  dt
()
[42] f N
equations for the mean numerical molecular weight nN and P t
the mean ponderal molecular weight nW :    

number of chains of length n

produced until a given time t
1
[39] nN = where the term dPdt represents the overall production
γ + 12 β
velocity of polymer chains of any length. This is obtained by
[40] nW =
(
2 γ + 23 β) adding the corresponding quantity relative to a specific

(γ + β )
2 chain length given by equation [35] over all the possible
From these equations, simply by multiplying by the
molecular weight of the monomer, it is possible to obtain the
mean numerical and ponderal molecular weights, which
represent the averages of the numerical and ponderal
Molecular Weight Distributions (MWD) respectively.
In the ideal case of a population of polymer chains
which are all of equal length, the numerical and ponderal
CLDs coincide and both are given by a distribution of Dirac
delta type. If the breadth of this distribution is increased, the
values for this length, and is given by:
[43]
dP
dt
(
= Rp γ + 12 β )
The procedure reported above for calculating the CLD of
the end product is also a useful conceptual tool for defining
the optimal operating conditions to create a polymer with
specific properties. For example, it is frequently considered
necessary to create a polymer in a batch reactor with a very
narrow distribution of molecular weights, in other words

VOLUME V / INSTRUMENTS 379

PROCESS ENGINEERING ASPECTS
with the minimum possible polydispersity; this problem can
be broken down into two successive stages. First, the
conditions required to create an instantaneous CLD with
minimum polydispersity are identified; it is then ensured
that the same instantaneous CLD is always produced
throughout the process. It is clear that, by adding portions of
polymer whose CLDs are different, even if they have low
polydispersity, the end product obtained is strongly non-
uniform, as shown schematically in Fig. 6. Below, two
examples of this approach are examined.
Consider the suspension polymerization of vinyl
chloride, where the dominant termination process is chain
transfer to monomer. From equations [36] and [37], it can be
seen that in this case gb and the mean values of the
instantaneous CLD [39-41] can therefore be simplified as
follows:
1 2
[44] nN = nW = σ =2
γ γ
Considering furthermore that in this case gkfm kp, it
follows that this parameter is essentially a function of
temperature alone. Since the instantaneous polydispersity is
a fixed value, if we wish to minimize the polydispersity of
the cumulative CLD, it is simply necessary to ensure that the
same instantaneous CLD is produced during the entire
process. This can be achieved, at a good approximation, by
maintaining a constant mean value for the instantaneous
CLD, which, as shown by the equations above, is in this case
a function of temperature alone. On the basis of this
simplified analysis it is therefore possible to conclude that
keeping the batch reactor isothermal during the process
makes it possible to obtain the narrowest cumulative CLD
possible, corresponding specifically to a polydispersity value
of two.
Another interesting instance is that of some styrene
polymerization processes, where the dominant termination
mechanism is termination by combination. In this case g b
and the mean values of the instantaneous CLD [39-41] can
therefore be simplified as follows:
2 3 3 The distribution of the monomer units along a polymer
[45] nN = nW = σ=
β β 2 number depends on the monomer species involved. Adopting
where the kinetic parameter is 14defined by equation [36],
which using [32] gives: b冪 ktcRI ⲐkpM. It should be noted
422
that in this case, too, the instantaneous polydispersity is
fN(n)
cumulative, t3
instantaneous, t2
instantaneous, t3
instantaneous, t1
n
Fig. 6. Schematic diagram of the instantaneous CLD
at three different times, t1t2t3 (dashed curves)
and the corresponding cumulative CLD
(non-normalized) at time t3 (continuous curve).
380
lower than when the dominant termination processes are
those appearing in the g parameter. This is a consequence of
the fact that the process of combination entails an averaging
operation on the length of the dead chains, leading to a
greater uniformity in their distribution. This operation does
not occur when other termination processes are dominant.
In this case it is therefore possible to create a cumulative
CLD with a polydispersity of 1.5, as long as the
polymerization conditions are such as to keep the
instantaneous CLD, and therefore the value of the parameter
b, constant. This is not an easy task since, as can be seen
from the expression reported above for this parameter, it
depends on variables such as the concentration of monomer
and the production velocity of the radicals. Results which
are satisfactory at least from the practical viewpoint can be
obtained by using different polymerization techniques such
as those based on semibatch reactors with the addition over
time of initiator and monomers, or on emulsion processes.
6.4.5 Radical copolymerization
processes
The need to create polymeric materials whose properties are
increasingly tailored to specific applications often entails the
introduction along the chain of different monomer species,
which help to confer specific chemico-physical properties on
the chain. This leads to the appearance of a new dimension
in the characterization of the population of polymer chains,
which refers to their composition. Specifically, two types of
distribution are introduced. The Chain Composition
Distribution (CDD) describes the fraction of chains which
have a given overall monomer composition, independently of
the order of the monomers within the chain itself; the Chain
Sequence Distribution (CSD) describes the probability of
finding a given sequence of monomer units inside the chain.
The ability to control these distributions is an essential factor
in a good copolymerization process, since they determine the
applicative properties of the copolymers produced.
chain is controlled by the propagation reactions, whose
the terminal kinetic model, it is assumed that the reactivity
of a radical chain is determined only by the last unit added,
that on which the radical activity is found. In this context, in
the case of a copolymerization involving two monomers, A
and B, two types of radical chains may be formed. Using An
and Bn to indicate two chains containing a total of n
monomer units but in which the radical activity occurs on a
unit of type A or B respectively, since each of these chains
may react with a monomer unit of type A or B, a total of four
propagation reactions will occur, two of which are described
as direct and two as cross:
[46] An + A


➤ An+1 ||||
r = k pAA An A
[47] Bn + B


➤ Bn+1
||||
r = k pBB Bn B
[48] An + B


➤ Bn+1
||||
r = k pAB An B
[49] Bn + A


➤ An+1
||||
r = k pBA Bn A
Next to each of these propagation reactions the
corresponding expression giving the reaction velocity is
ENCYCLOPAEDIA OF HYDROCARBONS

shown. In accordance with the terminal kinetic model the
velocities are described by second order kinetics, whose
kinetic constants are determined exclusively by the type of
unit on which the radical activity in the reagent chain is
found and by the monomer species involved.
In these processes, in addition to propagation reactions,
initiation, termination and chain transfer reactions are also
present, identical to those present in homopolymerization
but greater in number since more radical types are present.
A more accurate kinetic model, the penultimate kinetic
model, makes it possible to take account of the effect of the
penultimate monomer unit on the reactivity of the radical.
This naturally entails an increase in the number of possible
propagation reactions since each of the reactions [46-49]
takes place at a different velocity depending on whether the
monomer unit before the one on which the radical activity is
located is of type A or B. This model is not often used in
practice, due in part to the good results generally obtained
using the terminal kinetic model.
Chain length distribution
The first piece of information needed to describe the
growth kinetics of copolymer chains concerns the
composition of the reagent mixture in terms of active radical
chains. Specifically, it is necessary to know the fraction of
chains which terminate with each of the monomer units
present since, according to the terminal kinetic model
adopted, this defines its reactivity.
To this end, it is necessary to consider the material
balances of the radical species, differentiating them only on
the basis of the type of radical unit. In these balances, all
the reactions entailing the disappearance or the production
of a given type of radical must be taken into consideration.
In addition to the initiation and termination reactions,
which lead to the formation or elimination of a radical
species, we must therefore also consider cross-propagation
reactions, since these modify the type of radical unit.
Considering that these reactions are generally considerably
faster than those of termination and initiation, the latter are
generally ignored in the context of long chain
approximation. Consider for example a polymerization
with three monomers, A, B and C. Using A, B and C to
indicate the overall concentration of radical chains which
terminate with each of the three monomer units, the
balances mentioned above take the form
[50]
dA
dt
( )
= k pBA B A + k pCAC A − k pAB B + k pAC C A
[51]
dB
dt
( )
= k pAB AB + k pCBCB − k pBA A + k pBC C B
[52]
dC
dt
( )
= k pAC AC + k pBC BC − k pCA A + k pCB B C
Adding together the above equations member by
member, it follows that the variation over time of the total
concentration of radicals, RABC is zero. Obviously,
this is incorrect and reflects the fact that these balances were
written in the context of long chain approximation. In fact,
they only make it possible to calculate the composition of
the mixture of radicals and not the absolute values of their
concentrations. Introducing the molar fractions pi of radical
chains of all types:
VOLUME V / INSTRUMENTS
POLYMERIZATION PROCESSES
A B C
[53] pA = pB = pC =
R R R
and substituting in equations [50] and [51] in which the
terms of accumulation are ignored according to the
approximation of pseudostationary state, we obtain
( )
[54] k pBA ApB + k pCA ApC − k pAB B + k pAC C p A = 0
− (k C) p
[55] k pAB Bp A + k pCB BpC A + k pBC =0
pBA B
[56] p A + pB + pC = 1
It should be noted that the final consistency equation is
added to close the system; its solution provides the desired
composition of the reagent system in terms of chains with
differing radical activity. This system can easily be extended
to any number of monomer species and in particular produces
the following solution for a binary system:
k pBA A k pAB B
[57] pA = pB =
k pBA A + k pAB B k pBA A + k pAB B
These equations are valid in the context of long chain
approximation which can be applied with a good degree of
accuracy to all copolymers with the exception of block
copolymers. The latter consist of a very few homopolymer
sequences, reflecting the fact that cross propagations are far
slower than direct propagations, to such an extent that they
are comparable to terminations and initiations. Obviously, in
this case the latter cannot be ignored in balances [50-52].
The description of the kinetic behaviour of a system
involving numerous monomer species certainly appears
fairly complex due to the high number of reagent species
involved. However, in the context of the approximations
described above, a very simple analytical solution can be
developed, known as the pseudokinetic approach. This
involves using the same equations derived above for
describing the kinetics of the homopolymerization process,
replacing the kinetic constants of the reactions involved with
appropriate pseudokinetic constants. The latter are obtained
from the real kinetic constants of the copolymerization
process through suitable averages weighed against the molar
fractions of the different radical species in the system.
These averages differ depending on the order of the
reaction with respect to the radical species. Specifically, with
reference to a ternary system, for the propagation reaction of
the monomers A, B and C, we have:
[58] k ∗pA = k pAA p A + k pBA pB + k pCA pC
[59] k ∗pB = k pAB p A + k pBB pB + k pCB pC
[60] k ∗pC = k pAC p A + k pBC pB + k pCC pC
from which the overall pseudokinetic propagation constant
k*p is obtained by an average weighed against the molar
fractions of the monomers xA, xB and xC:
[61] k ∗p = k ∗pA x A + k ∗pB x B + k ∗pC xC
For chain transfer reactions, we obtain the following
equations for the pseudokinetic constants:
[62] k ∗fm = k fmA p A + k fmB pB + k fmC pC
[63] k ∗fs = k fsA p A + k fsB pB + k fsC pC
381
PROCESS ENGINEERING ASPECTS
which differ for termination reactions since these are of the
second order with respect to the radical species
[64] ktc∗ = ktcAA p 2A + ktcBB pB2 + ktcCC pC2
+2 ktcAB p A pB + 2 ktcAC p A pC + 2 ktcBC pB pC
[65] ktd∗ = ktdAA p A2 + ktdBB pB2 + ktdCC pC2
+2 ktdAB p A pB + 2 ktdAC p A pC + 2 ktdBC pB pC
In the context of the pseudokinetic model it is thus
possible to calculate the total concentration R of radicals
using the same equation [32], replacing the kinetic constants
of homopolymerization with the corresponding
pseudokinetic constants:
RI
[66] R=
ktc∗ + ktd∗
This in turn makes it possible to calculate the velocity at
which the individual monomeric species is consumed; for
example, that of monomer A:
[67] RpA = k ∗pA AR
The CLD of a copolymer can also be calculated using
the same equations [35-41] valid for the homopolymer, using
the corresponding pseudokinetic constants to calculate
parameters b and g. In this case, the variable M represents
the total concentration of all the monomer species in the
system.
Chain composition distribution
The distribution of the different monomer species along
the polymeric chain is determined by the probability that
each radical adds one or other of the monomeric species
present. In turn, this probability is determined by the intrinsic
reactivity of the individual monomer and its concentration.
Generally speaking, different monomers have different
reactivities and are therefore consumed in different ways
during the polymerization process, with the consequence that
the monomeric composition varies over time. Since the life
time of the chains is far shorter than that of the process,
chains will be produced at different moments throughout the
process and therefore presumably with differing
compositions since they are produced from different
compositions of the monomer mixture. This process, usually
described as compositional drift, often represents a
significant problem from the applicative point of view, since
it gives rise to highly non-uniform end products, in the sense
that the chains have very different compositions.
To study this process quantitatively, it is necessary to
calculate the average composition of a polymer chain. Since
during the life of a polymer chain the consumption of
monomer and therefore changes in composition are
negligible, we can calculate the composition of the chain
starting from the instantaneous velocity of consumption of
the individual monomer species. So, for example, in the case
of two monomer species A and B, the molar fraction FA of
monomer A present inside a copolymer chain produced at a
given instant is given by the equation:
RpA
[68] FA =
RpA + RpB
where RpA and RpB represent the consumption velocities of
the different monomer species calculated with [67] at that
382
same moment. With appropriate modifications, [68] can be
rewritten as
[69] FA =
( rA x A + x B x A)
( ) (
rA x A + x B x A + rB x B + x A x B)
This equation indicates that the instantaneous
composition of the polymer chain is determined by the molar
fraction of the monomer species xA and xB, and by two
adimensional kinetic parameters:
k pAA k pBB
[70] rA = rB =
k pAB k pBA
which are known as reactivity ratios and for each type of
radical represent the relationship between the kinetic
constant of direct and cross-propagation.
Equation [69] is normally plotted on a graph in the form
of a Mayo and Lewis diagram. As shown in Fig. 7, this
diagram shows the instantaneous composition of the
polymer chains FA as a function of the monomer composition
xA of the mixture from which they are generated. The
diagonal represents the case in which the monomers have
identical reactivity, in other words rA1 and rB1 in [69],
and the polymer chains therefore have the same composition
as the monomer mixture from which they derive, in other
words FAxA. Generally speaking, however, monomers have
differing reactivity and the resulting diagram may take
various forms, as demonstrated by the different curves in
Fig. 7. For example, if monomer A is more reactive with
both radical species, then rA1 and rB 1 and the polymer
chains are richer in monomer A than the monomer mixture
from which they derive. By contrast, if rA 1 and rB1, the
polymer chains are enriched in monomer B. These two
situations are illustrated in Fig. 7 by curves I and II
respectively.
However, if rA 1 and rB 1, cross-propagation reactions
prevail over direct propagation reactions. In this case,
1
FA
I
III
II
0
0 xA 1
Fig. 7. Mayo and Lewis diagram showing
the instantaneous molar fraction FA of monomer A
as a function of its molar fraction xA in the reagent mixture
of monomers for three different pairs of values
of the reactivity ratios: rA1 and rB 1 (curve I), rA 1
and rB1 (curve II) and rA 1 and rB 1 (curve III).
ENCYCLOPAEDIA OF HYDROCARBONS

depending on the monomer composition, either monomer A
or monomer B may be more reactive. The result is curve III
in Fig. 7, characterized by a specific point, known as the
azeotrope, in which the polymer chains and the monomer
mixture from which they derive have the same composition.
The same is true if direct propagations prevail over cross
propagations, in other words rA1 and rB1.
Using the Mayo and Lewis diagram it is also possible to
follow the process of compositional drift mentioned earlier
in quantitative terms. Consider a copolymerization system in
which the Mayo and Lewis diagram is the one shown in Fig. 8
and assume that the monomer mixture initially introduced
into the reactor has the composition xA0. The first
infinitesimal amount of polymer produced has the
composition FA0 indicated in the figure; since FA0xA0, it
follows that a portion more concentrated in monomer A than
the original mixture is removed from the monomer mixture.
As a consequence, the molar fraction of A, xA, in the reactor
decreases and with it the molar fraction of this monomer in
the polymer. However, since the molar fraction of A in the
polymer remains higher than in the monomer, both continue
to decrease giving rise to the process of compositional drift.
The breadth of this variation can be calculated qualitatively
by observing that at the end of the process, when the
monomers have fully reacted, the mean molar fraction of A
present overall in all the polymer chains must be identical to
that initially present in the monomer phase, in other words
xA0. From the diagram in Fig. 8 it is easy to deduce that for
the mean value of FA to be equal to xA0, since the first chains
have a composition of FA0, the last chains produced must
have a fairly low content of A.
Controlling the composition of copolymers
In most cases, the applicative properties of a copolymer
require that the polymer chains be highly uniform, especially
in terms of composition. As seen above, this is impossible to
achieve using a batch reactor because of the process of
compositional drift. It is therefore necessary to use a
semibatch reactor into which suitable quantities of monomer
1 ease of temperature control, resulting from the low monomer
FA
FA0
xA0
0
0 xA0 1 that a given initial quantity of monomers with this
xA
Fig. 8. Schematic diagram of the compositional
drift process in a copolymerization batch reactor
with an initial composition of the monomer mixture
equal to xA0.
VOLUME V / INSTRUMENTS
POLYMERIZATION PROCESSES
are introduced during the process so as to keep the
composition of the reagent monomer mixture and
consequently the chains produced during the process
constant over time. There are two different strategies which
make it possible to attain this objective.
Feed Controlled Process. This operating methodology is
based on slowing down the process to the point where it can
take place, for most of the time, under pseudostationary
conditions so that the velocities of consumption of the
individual monomers are identical to the feed rate and
therefore easy to control. This situation is attained by
adopting a feed time, tf , which is extremely long compared
to the characteristic time of monomer consumption:
1
[71] τ f >>
k *p R
In this way the characteristic time of the process is
identical to the feed time and the monomer consumption
process, whose characteristic time at this point becomes
much shorter, is in pseudostationary conditions with respect
to the feed time.
The feed controlled process therefore simply involves
feeding in a monomer mixture with the same composition as
the polymer desired, but at a sufficiently slow rate to meet
condition [71], without necessarily knowing either the
process kinetics or the corresponding Mayo and Lewis
diagram. As a consequence, chains with the desired
composition are produced for most of the process; however,
productivity decreases as the process is slowed down
because the feed rate is far lower than the velocity at which
the monomers are able to react. This operating procedure is
therefore usually described as starved.
In these processes, the concentration of monomer in the
reactor essentially remains constant throughout the process.
This may be particularly advantageous in various situations,
such as that discussed in the context of equation [45] where
the aim is to produce a very narrow distribution of molecular
weights (for a homo- or copolymer) when bimolecular
termination by combination is dominant.
Other important characteristics of these processes are the
consumption velocity and the fact that conversion inside the
reactor is always extremely high. This means that the
concentration of polymer significantly prevails over that of
monomer; consequently transfer to polymer reactions and
the kinetics controlled by the Trommsdorff effect tend to
prevail.
Power Feed Process. This second operating procedure,
usually described as power feed, is more ambitious than the
former procedure since it aims not only to keep the
composition of the chains produced uniform over time, but
also to maintain high process productivity. However,
achieving this requires a greater understanding of the
kinetics of polymerization and in particular the Mayo and
Lewis equation which determines the monomer composition
needed to create a polymer chain with the desired
instantaneous composition. The procedure therefore requires
composition be introduced into the reactor, and then that the
reactor be fed with a flow of these so as to keep the
composition constant throughout the process. The flow rate
is calculated to feed in the necessary amount to balance any
imbalances in composition due to the differing reactivity of
383
PROCESS ENGINEERING ASPECTS
the monomers. Using appropriate material balances, we
obtain the following equation:
[72] ( ) (
N B QA − k *pA RN A = N A QB − k *pB RN B ) even less controllable.
where QA and QB are the molar flow rates of the two
monomers fed into the reactor, NA and NB are the moles of
the two monomers present inside the reactor at any given
moment and the terms containing the pseudokinetic
propagation constants k *pA and k *pB indicate the moles of the
two monomers consumed by propagation reactions per unit
of time.
Since equation [72] represents a link between the two
flow rates of the monomers, at this point there is still a
degree of freedom left to optimize the process. This may be
saturated, for example, by requiring that the process have
maximum productivity, in other words the maximum amount
of polymer produced per unit of time. It can be demonstrated
that this objective is attained simply by introducing all of the
less reactive monomer at the beginning of the reaction and
therefore feeding in only the most reactive monomer during
the process so as to meet condition [72] where the flow rate
of the less reactive monomer is equal to zero.
In this case, alongside productivity, the heat production
velocity also increases and the reactor must therefore be
designed to remove heat and avoid dangerous phenomena of
runaway temperature increases.
A final observation concerns the practical application of
equation [72] This requires that at every moment during the
process all the terms appearing in it be known. Since kinetic
parameters are involved, this requires a good understanding
of the kinetics of the polymerization reaction but also of
process variables such as the quantities of the two monomers
present in the reactor. As such, suitable on-line and in situ
sensors must be used to monitor these variables accurately.
The sensors most frequently used for this purpose are based
on the heat balance of the reactor or measurements of other
magnitudes indirectly linked to conversion such as density or
the propagation velocity of ultrasounds. It is evident that the
application of this operating methodology requires greater
effort than the feed controlled process, which must therefore
be compensated for by the higher productivity of the reactor.
6.4.6 Operative characteristics
Radical polymerization reactions can be conducted using
processes with different operative characteristics. One of the
most significant problems lies in the removal of the heat
generated by polymerization reactions. These are strongly
exothermal reactions, comparable in this sense to
combustion reactions, and as conversion increases the
reaction mixture tends to become more viscous, thus slowing
down heat transportation processes. This situation makes it
difficult to control the temperature of the reactor, leading to
undesired non-uniformities in the end product or even
uncontrolled heat increase processes with consequences that
may also be significant from the point of view of safety. In
these cases, the temperature self accelerates as a
consequence of the fact that an increase in temperature
produces, due to the higher polymerization velocity, an
increase in the velocity of heat production which in turn
causes a further increase in temperature and so forth. This is
compounded by the fact that, as the reaction proceeds, the
384
removal of heat may be slowed by the increased viscosity of
the reagent mixture, making the temperature of the reactor
Polymerization processes are generally classified as
homogeneous or heterogeneous with reference to the reagent
mixture. This is kept homogeneous in bulk and solution
polymerization processes. In the former, only the monomer
and the initiator are introduced into the reactor. The result is
an extremely pure product, particularly suitable for various
applications. The problem is disposing of the reaction heat,
which is especially difficult when, as conversion increases,
the viscosity of the system increases. However, these
processes are adopted, for example, for the continuous
production of various types of rubbers, making sure that
conditions of complete conversion are not reached in the
reactor and devolatilizing the monomer which has not
reacted in appropriate separation units. Another example is
the production of waxes, based on oligomers of styrene,
which is conducted at very high temperatures with
viscosities similar to those of liquids.
To prevent the viscosity of the reagent mixture from
increasing, solution polymerization can be used. This
requires the use of a solvent which dissolves both the
monomer and the polymer to keep polymerization
homogeneous throughout the process. As well as the
difficulties of identifying such a solvent, which must be
satisfactory both in economic and regulatory terms, these
processes require high volumes to circulate large amounts of
solvent which do not contribute to productivity.
Heterogeneous suspension and emulsion processes are
based on the idea of making polymerization occur in small
particles dispersed in an aqueous matrix. The particles are
characterized by an extremely high surface area/volume
ratio, allowing for a very rapid transfer of the heat of
reaction from inside the particles to the aqueous mass, from
which it is then removed easily with traditional cooling
elements, since the viscosity of the continuous phase
obviously remains fairly modest. The result is a dispersion of
polymer particles in water which requires appropriate
coagulation and desiccation processes downstream of the
reactor. These processes are carried out starting from a
dispersion of drops of monomer in water, stabilized with
ionic and steric mechanisms from suitable emulsifiers. The
initiator is then introduced to these dispersions; this may be
soluble in the dispersed monomer phase or in the aqueous
phase, giving rise to suspension or emulsion polymerization
processes respectively.
In the former case the drops of monomer and initiator
behave like small segregated reactors, thermally well
controlled, inside which a normal bulk polymerization
reaction takes place. In this case, the result is a final
dispersion of polymer particles very similar to the initial
dispersion of monomer drops, with mean dimensions in the
order of 100–1,000 mm. Kinetic behaviour is therefore
similar to that of homogeneous polymerization processes, for
which the equations and considerations outlined above hold
true. Emulation polymerization is different. In this case, the
radicals produced in the aqueous phase must nucleate the
polymer particles that then grow during the process.
Consequently the final dispersion of polymer particles is
fairly different from the initial one of drops of monomer,
with mean dimensions smaller by three or four orders of
magnitude; in other words, in the order of 100 nm. In such
ENCYCLOPAEDIA OF HYDROCARBONS

small particles, bimolecular termination reactions become
very fast, in extreme cases allowing only one radical chain
per particle to be present. This gives rise to the radical
segregation phenomenon, which makes the kinetics of
emulsion polymerization and the properties of the final
polymer completely different from those of the preceding
processes, as discussed below.
6.4.7 Kinetics of emulsion
polymerization
The kinetic mechanism behind emulsion polymerization
was identified by W.V. Smith and R.H. Ewart and later
analyzed in depth and described in mathematical terms by
various researchers. The process is subdivided into three
basic phases. In the first, known as nucleation, the
polymer particles are formed. Two types of nucleation are
possible. Micellar nucleation takes place when the
emulsifier is initially present in the reagent mixture in a
concentration higher than its critical micellar
concentration. In this case, very small micelles of
emulsifier, typically in the order of a few nanometres, are
present in the system. Compared to the drops of monomer,
in the order of at least 100 mm, their surface area/volume
ratio is at least four orders of magnitude larger. As a
consequence, although the monomer is present in
significantly higher quantities than the emulsifier in the
reaction mixture, the total surface area of the micelles is at
least two orders of magnitude higher than that of the
monomer drops. This explains why most of the radicals
produced in the aqueous solution diffuse into the micelles,
where polymerization begins using the solubilized
monomer molecules inside the micelles, which from this
point onwards constitute polymer particles.
An alternative mechanism, dominant for example in
polymerizations conducted in the absence of emulsifier, is
the homogeneous nucleation mechanism. In this case, the
polymer molecules produced in water themselves form
micelles, which may then be stabilized by the emulsifier
present. It is worth noting that, since the decomposition
products of the initiator are often of ionic or in any case
hydrophilic nature, the polymer chains themselves may
behave as emulsifier molecules.
In this process, the number of particles, Np, grows over
time according to a law which derives from the overlapping
of various chemico-physical process. For example, in the
case of micellar nucleation, as new particles are nucleated
these begin to grow and in order to remain stable adsorb
onto their surface the emulsifier molecules present in the
water. This leads to the dissolution of the micelles present to
keep the concentration of emulsifier in solution equal to the
critical micellar concentration, and consequently slows down
the nucleation rate. Nucleation later stops when all the
micelles have been consumed, either by dissolution or
because they have turned into polymer particles. A
simplified mathematical analysis of these processes gives a
non-linear dependence of the number of final particles on
the initial concentrations of emulsifier and initiator,
characterized by an exponent of 0.6 for the former and 0.5
for the latter.
When nucleation ends, the concentration of emulsifier
in the water Ew falls below the critical micellar
VOLUME V / INSTRUMENTS
POLYMERIZATION PROCESSES
concentration (c.m.c.) and from this moment the growing
particles can no longer adsorb significant quantities of
emulsifier from the aqueous phase. This may make them
less stable from a colloidal point of view and lead to
phenomena of partial coagulation. Through the formation
of larger aggregates, the surface area to be stabilized is
reduced and so stability problems decrease. To avoid
coagulations and keep the dispersion stable, it is important
to add emulsifier during the reaction. A good rule of
thumb is that emulsifier should be added in proportion to
the growth of the total surface area of the particles. It is
worth noting that the addition of excessive amounts may
lead to the formation of new micelles and therefore the
production of a new generation of particles; this might
lead to a final dispersion with a bimodal, or in any case
very broad, distribution of polymer particle sizes.
In this context it is worth noting that in some
applications it is desirable to produce dispersions with
monomodal and very narrow distributions of particle size.
This can be done by rendering the nucleation phase very
short with respect to the duration of the process, so that all
the particles essentially have the same time available to
grow. According to the treatment by Smith and Ewart, in
the presence of micellar nucleation the duration of the
nucleation period is proportional to the power 0.6 of the
initial concentration of emulsifier and inversely
proportional to the same power of the initial concentration
of initiator.
Before describing the next two phases of the emulsion
polymerization process, it is worth considering the
phenomenon of radical segregation inside the particle which,
as mentioned above, is its distinctive feature. Below, a
simplified description of this process is given (for a more
detailed discussion, see Chap. 8.1).
Consider a polymer particle which initially does not
contain a radical and inside which, therefore, no reaction
occurs. Indicate with te the mean time interval needed for a
radical from the aqueous solution to enter a particle. As
shown in Fig. 9, after time te the particle receives a radical
which, as it is alone, can only give rise to propagation
reactions (for the moment we will ignore transfer reactions)
until, after a further interval te, a second radical enters the
particle. At this point the two radicals, in addition to
propagation, may give rise to a bimolecular termination,
whose characteristic time is tt. It follows that the two
radicals propagate together for time tt, after which
termination occurs and, as shown in Fig. 9, the particle
returns to its initial state of an absence of radicals. Since this
is obviously a periodic process, it is possible to calculate the
mean value of the number of radicals per particle, n̄, which,
with reference to a period on the graph shown in the figure,
is given by
τe + 2τ t
[73] n=
2τe + τ t
Given the extremely small size of the polymer particles,
the kinetics of the meeting of the two radicals is extremely
high; this is reflected in a very small value for the
corresponding characteristic time, so that tt te, and the
above equation gives
[74] n̄ ⬇0.5
in other words, on average, in this process at any moment
385
PROCESS ENGINEERING ASPECTS
number of radicals in a particle
tt
2 longer be replaced, its concentration Mp decreases over time
te
1 An examination of the kinetics of the emulsion
te
0 aspects mentioned above.
time
Fig. 9. Number of radicals in a particle
as a function of time.
half of the particles have a radical and are growing, whilst
the other half remain inert.
The second phase of the process, known as growth, is
characterized by an overall monomer consumption velocity,
Rp, which remains essentially constant over time. This
pattern can be explained by analyzing the behaviour of the
monomer. It is initially dispersed in the form of large drops
in the aqueous phase which, as seen above, remain basically
inert and are only minimally solubilized in the aqueous
phase, which is in fact saturated with monomer. The polymer
particles which form during the process also contain
monomer and it is specifically this monomer which
participates in the polymerization reaction, as this is where
the concentration of radicals is highest. Since monomer
species are usually barely soluble in water, during this stage
of the process most of the monomer is present in the drops
of monomer and in the polymer particles, which swell up to
50% in volume. The monomer is consumed only within the
latter stage and the process therefore requires a continuous
transportation of monomer from the drops (which thus act as
a reservoir) to the particles where it is consumed, through
the aqueous phase. Since both the dispersed phases have
extremely high surface area/volume ratios, the controlling
factor of the process is the polymerization reaction and the
concentration of monomer therefore remains constant in
both the aqueous solution and the particles, and is equal to
the corresponding saturation values.
The velocity at which the monomer is transported inside
a particle can therefore be calculated from the monomer
consumption velocity inside the individual particle, Rpp,
which is given by
n
[75] Rpp = kp Mp V n
Vp NA p
where Mp is the concentration of monomer in the particle, Vp
the volume of the particle and the term n̄Ⲑ(VpN) represents
the concentration of radicals in the particle, where N is
Avogadro’s number. It is easy to see that since the particle
volume is eliminated in equation [75], the term Rpp tends to
remain constant at this stage of the process, implying that the
particles grow at an essentially constant rate. Considering
that the number of particles, Np, at this stage is constant, it
can be concluded that the overall velocity of polymerization
RpNpRpp is also constant.
The growth stage of the process lasts until all the
monomer contained in the initial drops is consumed and the
386
drops therefore disappear from the system. At this point the
third and final stage known as consumption begins, during
which the monomer inside the particles continues to be
tt consumed by the polymerization reaction and, since it can no
to below the saturation value, Mpsat, until the reaction is
te exhausted.
polymerization process allows some characteristics to
emerge which render it particularly interesting for its
te possible applications, disregarding the temperature control
In a classic homogeneous radical polymerization process
(including suspension polymerization) in which bimolecular
terminations dominate, it was seen above that the overall
velocity Rp of monomer consumption is given by
[76] Rp = kp MR
whilst the mean chain length is given, according to [45], by
2 kp M
[77] nN =
kt R
Comparing these equations, it can be seen that the
velocity of polymerization and the length of the polymer
chains are linked by the concentration of radicals.
Specifically, when the latter increases the productivity of
the process improves, but shorter chains are produced. As
such, it is impossible to produce chains with a high
molecular weight and simultaneously maintain high
productivity.
This link does not exist in emulsion polymerization
due to the presence of the radical segregation
phenomenon. As emerges from the discussion of Fig. 9, in
the case of extremely rapid bimolecular terminations, the
polymer chain has a mean life essentially equal to te, in
other words the time which passes, on average, between
the entry of two radicals into a particle. The average
length of the chains thus produced can therefore be
calculated by dividing this term by the characteristic time
of addition of a monomer unit, given by tp1ⲐkpMp, thus
obtaining
[78] nN = kp M pτe
where the characteristic time te is proportional
to the concentration of radicals in the aqueous phase
and to the surface area of the polymer particle. On the
other hand, using equation [75], it can be observed
that the overall velocity of monomer consumption,
RpNpRpp, is given by
[79] Rp = kp Mp N
NA p
Comparing equations [78] and [79] it is clear that the
two magnitudes are now uncoupled: emulsion
polymerization makes it possible to obtain higher molecular
weights than homogeneous polymerization processes
(including suspension polymerization), given identical
productivity.
Another peculiarity of the emulsion reaction is that
during most of the process (except the third phase), the
concentration of monomer inside the particles remains
constant; the reaction therefore takes place with a constant
concentration of monomer, making it easier to control the
ENCYCLOPAEDIA OF HYDROCARBONS
 POLYMERIZATION PROCESSES

architecture of the chains produced and therefore providing a B concentration of monomer B

more uniform end product. This becomes evident, for B total concentration of radicals of type B
example, from equation [78], which shows that the Bn concentration of chains containing a total of n
instantaneous molecular weight of the chains produced is monomer units with radical activity on a unit of
proportional to the concentration of monomer in the particles. type B
C concentration of monomer C
C total concentration of radicals of type C
Bibliography Ew concentration of emulsifier in the aqueous phase
f initiator efficiency
Biesenberger J.A., Sebastian D.H. (1983) Principles of fN (n) instantaneous numerical chain length distribution
polymerization engineering, New York, John Wiley. fW (n) instantaneous ponderal chain length distribution
Cooper W. (1976) Kinetics of polymerization initiated by Ziegler- fNc(n,t) cumulative numerical chain length distribution
Natta catalysts, in: Bamford C.H., Tipper C.F.H. (edited by)
Fi molar fraction of monomer i in the polymer
Comprehensive chemical kinetics, Amsterdam, Elsevier, 1968-
1976, 18v.; v.XV.
I concentration of initiator
kd kinetic constant of initiator decomposition
Fitch R.M. (edited by) (1971) Polymer colloids. Proceedings of an
American chemical society symposium on polymer colloid held in kfm kinetic constant of transfer to monomer
Chicago, 13-18 September 1970, New York, Plenum Press. kfp kinetic constant of transfer to polymer
Flory P.J. (1953) Principles of polymer chemistry, Ithaca (NY), Cornell kfs kinetic constant of transfer to chain transfer agent
University Press. kp kinetic constant of propagation
Gilbert R.G. (1995) Emulsion polymerization. A mechanistic approach, kpij propagation kinetic constant of radical i with
London, Academic Press. monomer j
Gupta S.K., Kumar A. (1987) Reaction engineering of step growth kt ktcktd
polymerization, New York, Plenum Press. ktc kinetic constant of bimolecular termination by
Hamielec A.E., Tobita H. (1992) Polymerization processes, in: combination
Ulmann’s encyclopedia of industrial chemistry, Weinheim, VCH, ktd kinetic constant of bimolecular termination by
1985-1993, 37v.; v.A21, 317-336. disproportionation
Lovell P.A., El-Aasser M.S. (edited by) (1997) Emulsion ktcij , ktdij kinetic constant of termination of radical i
polymerization and emulsion polymers, New York, John Wiley. with radical j
Mayo F.R., Lewis F.M. (1944) Copolymerization. I: A basis for M concentration of monomer
comparing the behaviour of monomers in copolymerization. The Mp concentration of monomer inside the particle
copolymerization of styrene and methyl methecrylate, «Journal of n̄ mean number of radicals in the particle
the American Chemical Society», 66, 1594-1601. nN numerical mean of the number of monomer units in
Min K.W., Ray W.H. (1974) On the mathematical modeling of emulsion the chain
polymerization, «Journal of Macromolecular Science. Part C. nW ponderal mean of the number of monomer units in
Review in Macromolecular Chemistry», 11, 177. the chain
Ray W.H. (1977) Polymerization reaction engineering, in: Lapidus N Avogadro’s number
L., Amudson N.R. (editors) Chemical reactor theory, Englewood N(r) numerical distribution of chains of length r
Cliffs (NJ), Prentice-Hall. Ni moles of monomer i
Ray W.H. (1983) Current problems in polymerization reaction Np number of particles per unit volume
engineering, «American Chemical Society Symposium Series»,
pi molar fraction of radicals of type i
226, 101.
P total concentration of dead chains
Reichert K.H., Moritz H.U. (1989) Polymer reaction engineering,
in: Comprehensive polymer science: the synthesis, characterization, Pn concentration of dead chains containing n monomer
reactions & applications of polymers, New York, Pergamon Press, units
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Seymour R.B., Carraher C.E. (1988) Polymer chemistry, New York, ri reactivity ratio for radical of type i
Marcel Dekker. R total concentration of radicals
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«Journal of Chemical Physics», 16, 592-599. Rn concentration of radicals containing n monomer
Tirrel M. et al. (1987) Polymerization reactors, in: Carberry J.J., units
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New York, Marcel Dekker. Rpi overall velocity of consumption of monomer i
Trommsdorff E. (1954) Pearl polymerization, «Makromolekulare Rpp overall velocity of monomer consumption in a
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RI velocity of radical production
S concentration of chain transfer agent
List of symbols t time
T temperature
A concentration of monomer A Vp volume of the particle
A total concentration of radicals of type A W(r) ponderal distribution of chains of length r
An concentration of chains containing a total of n Xi molar fraction of monomer i in the reagent
monomer units with radical activity on a unit of mixture
type A XA conversion of monomer A

VOLUME V / INSTRUMENTS 387

PROCESS ENGINEERING ASPECTS

Greek letters ttd characteristic time of the termination by

a bg disproportionation reaction
tp
b adimensional kinetic parameter 12 ttc tM characteristic time of the polymerization process
tp tp tp
g adimensional kinetic parameter 12 ttd  tfm  tfs Superscripts
12 12

s polydispersity nW ⲐnN sat conditions of saturation

te characteristic time of the entry of a radical into a * pseudokinetic constant
particle
tf characteristic time of feed Subscripts
tfm characteristic time of the transfer to monomer A monomer A
reaction B monomer B
tfs characteristic time of the transfer to chain transfer C monomer C
agent reaction
0 initial value
tp characteristic time of the propagation reaction
tI characteristic time of the initiator decomposition
reaction Massimo Morbidelli
tt ttcttd Institut für Chemie- und Bioingenieurwissenschaften
ttc characteristic time of the termination by Eidgenössische Technische Hochschule-Zürich
combination reaction Zürich, Switzerland

388 ENCYCLOPAEDIA OF HYDROCARBONS