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Fundamentals of Emulsion Polymerization

Peter A. Lovell* and F. Joseph Schork*

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ABSTRACT: A comprehensive overview of the fundamentals of

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emulsion polymerization and related processes is presented with

the object of providing theoretical and practical understanding to
researchers considering use of these methods for synthesis of
polymer colloids across a wide range of applications. Hence, the
overview has been written for a general scientific audience with no
prior knowledge assumed. Succinct introductions are given to key
topics of background science to assist the reader. Importance is
placed on ensuring mechanistic understanding of these complex
polymerizations and how the processes can be used to create
polymer colloids that have particles with well-defined properties
and morphology. Mathematical equations and associated theory
are given where they enhance understanding and learning and
where they are particularly useful for practical application. Practical guidance also is given for new researchers so that they can begin
using the various processes effectively and in ways that avoid common mistakes.

1. INTRODUCTION and learning and where they are particularly useful for practical
Functional polymer colloids prepared by emulsion polymer- application. Indeed, at several points in the overview, practical
ization have been studied and used in biomedical applications at guidance is given that will help new researchers in this field begin
an increasing pace over the past several decades.1−3 This to use the various processes of particle synthesis effectively and
complex field of research is at the interface of science and in ways that avoid common mistakes.
We begin by giving brief accounts of the origins of emulsion
biochemistry, and the purpose of this paper is to provide a
polymerization and a very simple introduction to important
focused theoretical and practical understanding of the synthesis
features of the process.
of polymer colloids, where appropriate, highlighting features of
1.2. Origins of Emulsion Polymerization. The origins of
particular relevance for researchers in the biomedical field.
emulsion polymerization as a process for performing free-radical
1.1. Scope. This overview discusses the fundamentals of
polymerization reside in attempts by man to imitate the
emulsion polymerization and related processes with the object
production of natural rubber latex by the rubber tree (Hevea
of providing understanding to researchers considering use of
brasiliensis), a challenge that accelerated greatly during World
these methods as tools to create polymer colloids with well-
War II as a consequence of shortages in supply of natural rubber.
defined particle properties and morphology. Importance is
Natural rubber latex is an aqueous dispersion of polyisoprene
placed on ensuring mechanistic understanding of these complex
particles stabilized by proteinaceous surfactants. By analogy, a
polymerizations and how the processes can be controlled and
polymer latex produced by emulsion polymerization is an
used creatively. While the coverage of the fundamentals is
aqueous dispersion of polymer particles stabilized by a colloid
comprehensive and rigorous, the aim is for the overview to be
stabilizer, most commonly a surfactant. In the early days, the
suitable for a general scientific audience. No prior knowledge of
focus was on production of synthetic rubber latexes (e.g.,
this field is assumed and so succinct introductions are given to
styrene−butadiene rubber, SBR), but the versatility of emulsion
key topics of background science, sufficient to enable the reader
polymerization was quickly recognized and led to an extremely
to understand the important concepts of emulsion polymer-
ization and related processes without needing to be distracted by
having to read textbooks or reviews on those topics separately. Special Issue: Polymer Colloids: From Fundamentals
Where considered appropriate, this important background to Application
science is complemented in the main body of the overview by Received: May 19, 2020
more detailed explanations of phenomena that may not be Revised: June 9, 2020
familiar to a wider audience. Mathematical equations and Published: June 16, 2020
associated theory are given where they enhance understanding

© 2020 American Chemical Society https://dx.doi.org/10.1021/acs.biomac.0c00769

4396 Biomacromolecules 2020, 21, 4396−4441
Biomacromolecules
wide range of polymers being produced in this way, including
synthetic elastomers, bulk plastics, and polymer latexes for use in
a vast range of coating applications. Increasingly, emulsion
polymerization is being used to produce functional polymer
colloids for more specialist applications, e.g., for use in the
electronics and biomedical fields.
The extensive use of emulsion polymerization is a direct
consequence of the ease of removing the heat of polymerization,
the low viscosity of the latex at high polymer concentrations, the
ability to control submicron particle size and morphology, and
the ease of separation of the polymer from the latex or, in the
case of coatings applications, the convenience of using the latex
directly. A further, less obvious, but nevertheless important
feature of emulsion polymerization is the ability to achieve
higher rates of polymerization and produce higher molecular
weight polymers in comparison to other methods of free-radical
polymerization. Additionally, over the past several decades,
growing environmental legislation on control of emission of
volatile organic compounds (VOCs) has seen a massive growth
in use of emulsion polymerization to produce latexes for water-
borne coating applications as replacements for solvent-borne
coatings.
1.3. Classical Emulsion Polymerization. In order to
understand the mechanisms by which emulsion polymerization
produces a polymer latex, it is necessary to begin with knowledge
of the most simple form of the process, which starts with
emulsifying monomer (usually relatively insoluble in water) into
an aqueous solution of a surfactant. By applying shear to the
mixture, the monomer is dispersed into droplets of typically
about 10 μm diameter. The droplets are stabilized by adsorption
of surfactant at the monomer−water interface. Additional
surfactant above the critical micelle concentration (CMC) is
contained in micelles, which are spherical aggregates of typically
50−100 surfactant molecules oriented so that their hydrophobic
parts are toward the center of the micelle while the hydrophilic
parts make contact with, or extend into, the aqueous phase. The
micelles become swollen by absorbing molecules of monomer
into their interior and have diameters of about 10 nm.
Polymerization is initiated by adding a water-soluble free-radical
initiator, and as the polymerization proceeds, polymer particles
stabilized by adsorbed surfactant molecules are formed with
diameters (50−500 nm) intermediate to those of micelles and
droplets. As an emulsion polymerization progresses, the main
loci to be considered are the continuous aqueous phase,
monomer droplets, monomer-swollen micelles (if the surfactant
is above CMC), and polymer particles. Most of the polymer in
the final latex is formed by polymerization within the polymer
particles.
The molecular weight of polymer produced in an emulsion
polymerization is normally an order of magnitude greater than
that in a similar homogeneous free-radical polymerization. This
is due to segregation (compartmentalization) of propagating
chains in small particles, coupled with generation of radicals in
the aqueous phase and a consequent increase in the radical
lifetime. In a homogeneous free-radical polymerization, it
usually is necessary to increase the initiator concentration in
order to increase the rate of polymerization, which results in a
higher radical concentration, but this gives rise to more rapid
termination and lower molecular weight (see section 2.2). In
emulsion polymerizations, due to segregation of propagating
chains from each other suppressing bimolecular termination, it is
possible to achieve high rates of polymerization and to produce
high molecular weight polymer in the same polymerization (e.g.,
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by increasing the surfactant concentration to increase the
number of particles); this is a very important feature in
comparison to other methods of performing free-radical
polymerization.
2. FREE-RADICAL POLYMERIZATION
As indicated already, most emulsion polymerizations proceed
via free-radical polymerization, though more controlled radical
polymerization chemistry increasingly is being employed,
particularly for more specialist applications (see sections 5 and
6), and miniemulsion polymerization has opened up further
opportunities, including use of polycondensation and poly-
addition (see section 4.6.2). In presenting the fundamentals,
however, our focus is on free-radical emulsion polymerization
since this provides the foundation for interpreting and
understanding most emulsion polymerizations. For this reason,
we include an overview of the essential features of free-radical
polymerization.
2.1. Chemistry of Free-Radical Polymerization. When
free radicals (R•) are generated from an initiator in the presence
of an unsaturated monomer (generally of structure CH2
CXY), one of those radicals adds to the CC bond to generate a
product radical (R−CH2−CXY•). This new radical is free to
react with another molecule of monomer via the same
mechanism, thereby increasing the chain length by one
monomer unit with the site of the radical moving to the new
chain end. The polymer chain grows rapidly by adding
successive units of monomer in this way (each monomer
addition taking around a millisecond or less) while maintaining
the active radical site at the end of the live (growing) chain. A
chain radical continues to grow until it loses its active radical site
either by a termination reaction with another free radical
(typically by a combination or disproportionation reaction with
another chain radical) or by a chain transfer reaction with
another species present in the polymerization. Hence, this
complex set of reactions is divided into initiation, propagation,
termination, and chain transfer reactions, as shown in the simple
outline in Scheme 1.
The initiator most commonly is an unstable compound of
symmetric structure that decomposes thermally at the reaction
temperature to form two radicals (e.g., benzoyloxy radicals from
benzoyl peroxide), which may undergo rearrangement reactions
(e.g., a benzoyloxy radical can undergo ß-scission to give a
phenyl radical and carbon dioxide) before creating a nascent
chain radical by reacting with monomer. These two steps
constitute initiation, with the rate-determining step being
dissociation of the initiator.
Propagation involves successive addition of monomer
molecules to the chain end. The rate coefficient for propagation
is much higher for very short chains, but quickly reduces as the
number of repeat units increases and, beyond about 5 repeat
units, attains a constant value. In most cases, long chains are
formed with degrees of polymerization ≫100, so it is usual (and
reasonable) to consider the rate coefficient of propagation as a
constant when developing theory. Propagation is essentially
irreversible at temperatures well below the ceiling temperature,
which for the vast majority of monomers is very high (typically
>200 °C) compared to the temperatures employed in most free-
radical polymerizations, including all types of emulsion
polymerization (for which reaction temperature is mostly
limited by the boiling point of water).
Termination occurs by reaction together of two live chain
radicals by either (i) combination (i.e., radical coupling) to form
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Scheme 1. Outline Mechanism of Free-Radical
Polymerizationa
a
I is initiator, i is the number of radicals R• produced from the
initiator (i = 1 or, more commonly, i = 2), M is monomer, P•z is a
chain radical with degree of polymerization z, Pz is a “dead” polymer
molecule with degree of polymerization z, S is solvent, TA is transfer
agent, In is inhibitor, M• and TA• are radicals produced by chain
transfer to monomer and transfer agent, respectively, Q is an inactive
species produced by reaction of a free radical with inhibitor, and ky
represents the rate coefficient for the reaction y.
a dead chain of length equal to the sum of the lengths of the live
chains (combination is dominant in the polymerization of most
monomers) or (ii) disproportionation which results in two dead
chains being formed with lengths equal to those of the live chains
at the instant of their reaction together (a reaction that proceeds
via abstraction of a H-atom by one chain radical end from the
other, which contributes primarily for methacrylates and other
monomers where one substituent, X or Y, is a methyl group).
Invariably, termination is diffusion controlled and the overall
rate coefficient for bimolecular termination, kt, shows a step
change reduction of several orders of magnitude when the
viscosity of the reaction medium reaches the point at which the
mode of diffusion control switches from reaction between short
(highly mobile) chain radicals and (low mobility) long chain
radicals to being between two long chain radicals (both of low
mobility) because the viscosity is too high for fast diffusion of the
short chain radicals. At this point, the rate of polymerization and
degree of polymerization rise rapidly; the effect is known as
autoacceleration or the Trommsdorf f−Norrish ef fect or gel effect.
The term autoacceleration is used since the increases in rate of
polymerization and degree of polymerization lead to a rapid
further increase in viscosity, thereby accelerating the effect.
A propagating chain radical can also be “killed” by chain
transfer to another molecular species, which most commonly
involves abstraction of a single atom (normally a H-atom, but
sometimes a halogen atom), e.g., from a molecule of monomer
or solvent or an added transfer agent. In most cases, the product
radical from these chain transfer reactions will react with
monomer to initiate a new chain. However, if an inhibitor is
added (e.g., hydroquinone), it highly efficiently reacts with all
free radicals present and produces unreactive species that do not
initiate polymerization, effectively stopping polymerization until
it is consumed completely. Chain transfer to monomer is
relatively low for many monomers but high for those with labile
C−H bonds (e.g., vinyl acetate in which abstraction of a H atom
from the ester methyl group gives a radical stabilized by
resonance with the carbonyl group). The extent of chain transfer
to solvents varies massively dependent upon the chemical
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Review
structure of the solvent and increases greatly if the structure
contains easily abstracted atoms (e.g., H-atoms in tertiary, allylic,
and benzylic C−H bonds). Transfer agents are compounds with
high rate coefficients for chain transfer that are included at low
levels to reduce (“control”) the degree of polymerization.
Mercaptans (RS−H) are widely used as transfer agents, but
halogenated compounds (e.g., carbon tetrabromide, CBr3−Br)
also have been used.
If chain transfer to polymer occurs, a branch begins to form on
what was previously a dead polymer chain. Chain transfer to
polymer can proceed intramolecularly which results in short
branches or intermolecularly which results in long branches. The
chemistry and consequences of chain transfer to polymer will be
discussed in much greater detail in section 3.6.
2.2. Kinetics of Homogeneous Free-Radical Polymer-
ization. Free-radical polymerization is characterized by the
formation of high molecular weight polymer early in the reaction
(i.e., at low overall monomer conversions) and the presence of
unreacted monomer even near the completion of the polymer-
ization, which are typical characteristics of a chain polymer-
ization. This is because a single molecule of polymer is initiated
and propagates to the point where it is killed in a time frame of
typically 0.1−10 s. As the reaction progresses, new chains are
initiated, grow, and die in the same way; hence the monomer is
converted progressively into an ever-increasing number of
polymer chains.
For homogeneous free-radical polymerizations, where the
initiator, monomer, and polymer remain in solution throughout
the reaction (either with monomer acting as the “solvent” or as a
solution in an added solvent), analysis of the steady-state
reaction kinetics gives the following equations for the rate of
polymerization (Rp) and the number-average degree of
polymerization (xn̅ ) of the polymer produced4
ij ifk yz
= k pjjj d zzz
j 2k t z
1/2
d[M]
k {
Rp = − [M][I]1/2
dt (1)
1 1 [S ] [TA]
= + C M + CS + C TA
xn̅ (xn̅ )0 [M] [M] (2)
k p[M]
(xn̅ )0 =
(1 + q)(ifkdkt /2)1/2 [I]1/2 (3)
where [I], [M], [S], and [TA] are the concentrations of initiator,
monomer, solvent, and transfer agent, respectively, f is the
initiator efficiency (i.e., the fraction of free radicals from the
initiator that are successful in initiating chains), kt (=ktc + ktd) is
the overall rate coefficient for termination, (xn̅ )0 is the number-
average degree of polymerization in the absence of chain
transfer, CM (=ktrM/kp), CS (=ktrS/kp), and CTA (=ktrTA/kp) are
the transfer constants for chain transfer to monomer, solvent,
and transfer agent, respectively, and q is the fraction of
termination by disproportionation (=ktd/kt). The other terms
are defined in Scheme 1. As described in section 3.6, the effect of
chain transfer to polymer on xn̅ is small because it does not
change the number of live and dead polymer chains and because,
even though the first monomer addition to the resulting chain
radical usually is slower, subsequent propagation of the chain
proceeds as normal.
Hence, in homogeneous free-radical polymerizations, both Rp
and (x̅n)0 can be increased by increasing [M], which is a
maximum in bulk polymerization of the monomer. However, the
initial value of [M] is either fixed or limited by the process
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employed and so [I] is the main parameter for controlling Rp.
Therein lies a dilemma in homogeneous free-radical polymer-
ization because increasing [I] to increase Rp causes a reduction
in (x̅n)0 and since controlling x̅n often is important for
applications, this can place a restriction on the value of Rp that
can be achieved in a given process, dependent on the target value
of x̅n. However, eq 2 shows that chain transfer processes can be
dominant in controlling xn̅ , especially when (xn̅ )0 is high, in
which case this dilemma is reduced. (Note that the measurable
quantity is number-average molecular weight (M̅ n) which for
long chains is related to x̅n by M̅ n = xn̅ M0 where M0 is the
molecular weight of the repeat unit.)
2.2.1. Free-Radical Copolymerization. When two or more
monomers are copolymerized, the composition of the
copolymer will rarely be the same as the composition of the
comonomer mixture because the monomer reactivities will
invariably be different and the more reactive monomer will be
preferentially incorporated into the copolymer chains. The
terminal model is the simplest for prediction of copolymer
composition and assumes that the reactivity of a polymeric
radical is defined only by the end unit and unaffected by the
preceding repeat units. On this basis, there are four propagation
reactions to consider in a binary copolymerization of monomer
A with monomer B, as shown in Scheme 2.
Scheme 2. Terminal Model for Binary Free-Radical
Copolymerizationa
a very high instantaneous overall monomer conversions (most
kpAA and kpBB are the homopropagation rate coefficients, and kpAB
and kpBA are the cross-propagation rate coefficients.
The instantaneous copolymer composition (ignoring stochas-
tic variations) in a homogeneous medium is then given by the
Mayo−Lewis or copolymer equation.4,5
rA f A2 + fA fB
FA =
rA f A2 + 2fA fB + rB fB2 (4)
with rA = k pAA /k pAB and rB = k pBB/k pBA
(5)
where FA is the average instantaneous mole fraction of monomer
A repeat units in the copolymer formed when the mole fractions
of monomers A and B in the copolymerization are fA and f B (=1
− fA), and rA and rB are the monomer reactivity ratios (or simply
“reactivity ratios”), i.e. ratios of the rates of homopropagation to
cross-propagation for each type of chain radical. Since radical
lifetimes in free-radical polymerizations are very short, the
change in values of fA and f B due to preferential reaction of the
more reactive monomer will be negligible during the lifetime of a
propagating copolymer chain and the copolymer equation 4 can
be used to predict FA for that instant in the reaction.
If rA > 1, homopropagation is favored by ∼A•, whereas if rA <
1, cross-propagation is favored by ∼A•. Thus, the values of rA
and rB are very important; not only do they control the
composition of copolymer produced at a given value of fA, they
also control the sequence distribution of repeat units in the
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copolymer chains. The most common scenarios for values of rA
and rB are (i) rA > 1 and rB < 1, in which case FA > fA and, as the
disparity in reactivity ratios increases, the deviation becomes
larger and the copolymer chains contain increasingly long
sequences of A-type repeat units (if rA = 1/rB the sequence
distribution will be random); and (ii) rA < 1 and rB < 1, in which
case both types of chain radical prefer to cross-propagate and
there is an increasing tendency toward alternation of repeat units
in the copolymer chains produced. There are two special cases
for rA and rB values: rA = rB = 1 for which FA = fA for all values of fA
and the sequence of repeat units in the copolymer is random;
and rA = rB = 0, in which case only cross-propagation occurs and
a perfectly alternating copolymer is produced with FA = 0.5 for
all values of fAalthough there are no real systems of these two
types, there are some copolymerizations which approximate to
these behaviors.
Due to one monomer being preferentially consumed, as the
overall monomer conversion increases, the values of fA and f B
will steadily change, giving rise to a continuous change in the
value of FA for the copolymer chains produced as the reaction
progresses. Thus, as conversion increases, fA (and hence FA)
change continuously, which is known as composition drift. This
compositional drift is described by the integrated copolymer
equation.6 For most applications, a specific value of FA is
required, so composition drift is not acceptable. There are three
principal strategies for minimizing or avoiding drift in FA: (i)
stop the reaction at low conversion (typically <5%) to minimize
drift (which still gives some drift and is not attractive for
commercial use because of the need to recover unreacted
monomer); (ii) add the comonomer mixture of composition fA
to the reactor and then feed the more reactive monomer to the
reaction at a rate that compensates for its preferential
consumption and maintains fA constant (not simple to do);
and (iii) keep fA constant by feeding the monomer mixture of
composition fA slowly to the reactor under conditions that give
widely used and referred to as starved conditions).
2.2.2. Further Reading on Free-Radical Polymerization.
Only the essential features of free-radical polymerization have
been described here, sufficient for understanding emulsion
polymerizations, and this has been presented in simple outline
without giving full details, especially in relation to the
mechanistic chemistry and statistical aspects for which far
more complete descriptions may be found in textbooks.4,5
Additionally, more extensive coverage of reactivity ratios for
copolymerization, composition drift, and prediction of sequence
distribution probabilities can be found elsewhere.4,5,7−9
2.3. Homogeneous Polymerization Processes. Free-
radical polymerization may be carried out in various media. Bulk
polymerization is the simplest process, involving only a solution
of initiator in monomer, but although monomers are most often
liquid, the polymer produced is typically a solid. This leads to
problems of removing the polymer from the reactor and, since
most free-radical polymerizations are highly exothermic, the
viscosity of the monomer/polymer solution increases rapidly
with monomer conversion, making it increasingly difficult to
remove the heat of reaction. For these reasons, although bulk
polymerization is used for production of a few commercial
polymers, it is not used widely. In solution polymerization a
solvent (for the initiator, monomer, and polymer) is added to
reduce, to an extent, the viscosity of the polymerizing mass but
brings with it the environmental and health issues associated
with VOCs and reduces the monomer concentration, causing
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proportionate reductions in Rp and (x̅n)0. Additionally, chain
transfer to solvent further reduces xn̅ and isolation of the
polymer involves recovery and recycling of the solvent, which
can add substantially to the cost of the process. Hence, solution
polymerization is used mostly for applications where the
polymer is required to be in solution.
2.4. Dispersed-Phase Polymerization Processes. An
alternative to solution polymerization for reducing the issues
associated with the high viscosities of bulk polymerizations is the
whole realm of dispersed-phase polymerization. In this class of
processes, the liquid monomer is dispersed in a second,
continuous phase, usually water. The viscosity of the dispersion
is controlled to a large extent by the viscosity of the dispersion
medium (see section 7), and so, even at high monomer
conversions, the viscosity remains low, thereby making agitation
easier and aiding removal of the heat of polymerization. The
high thermal conductivity of water makes it a very effective heat
transfer medium, and its high specific heat and large latent heat
of vaporization provide a large safety margin in the event of a
runaway polymerization. In addition, water is plentiful, nontoxic,
environmentally friendly, and inexpensive.
In suspension polymerization a solution of a monomer-soluble
initiator in a water-insoluble monomer is dispersed into droplets
in a continuous aqueous phase by the action of an agitator. Since
little or no surfactant is used, no emulsification takes place; if the
agitation is stopped, the monomer will form a separate bulk
phase, usually above the aqueous phase as most monomers have
densities lower than that of water. The monomer is polymerized
by the initiator within the droplets, which at complete
conversion become polymer beads with approximately the
same size as the original droplets (0.1−2 mm diameter). The
product is readily separated from the aqueous phase, via
filtration or decantation, in the form of macroscopic particles or
beads that are easily washed, dried, and packaged for transport.
Heat transfer is facilitated by the presence of the continuous
aqueous phase and the high total surface area of the droplets.
Low levels of surfactants, sometimes supplemented by low
molecular weight water-soluble polymers, often are dissolved in
the aqueous phase to assist dispersion, and blocking agents, such
as clays or talcs, are used to prevent bead agglomeration. The
loci of polymerization are the monomer droplets. Due to the size
of the droplets, such systems are suspensions rather than
emulsions or stable dispersions. Kinetically, each droplet acts as
a small independent reactor and there is little exchange of
material between the droplets. Since there is no solvent present
at the locus of polymerization, the kinetics of polymerization
within each droplet are those of homogeneous bulk polymer-
ization, i.e., as defined by eqs 1−3. If a water-soluble initiator is
used in a suspension polymerization, very little polymerization
will occur, since few free radicals will reach the locus of
polymerization in the monomer droplets.
If surfactant is included in a suspension polymerization
system, a number of phenomena may occur. If the surfactant is
added in small amounts (below the CMC), the reduction in
interfacial tension between the organic and aqueous phases will
result in smaller monomer droplets, but few other effects will be
seen. If surfactant is added above the CMC and a monomer-
soluble initiator is used, the process is commonly termed a
microsuspension polymerization. Due to the reduced interfacial
tension, droplet diameter (and hence the final polymer bead
diameter) is reduced to approximately 10−40 μm. Little
polymerization takes place in the aqueous phase or in surfactant
micelles swollen with monomer because of the hydrophobic
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nature of the initiator. Microsuspension polymerization may
also employ a low molecular weight polymer as a steric stabilizer
(instead of a surfactant) together with homogenization to
produce the smaller droplet size. The kinetics remain essentially
those of homogeneous bulk free-radical polymerization,
although some submicron particles are often produced since
almost all water-insoluble initiators will partition at least slightly
into the aqueous phase where they can generate particles via
mechanisms of emulsion polymerization. Microsuspension
polymerization is used to produce pressure sensitive adhesives
for repositionable notes and small polymer beads for biomedical
applications.
If the initiator in a microsuspension polymerization
formulation is changed from monomer-soluble to water-soluble,
the kinetics of the polymerization change completely and the
product is not a dispersion of polymer beads but instead is a
colloidally stable polymer latex with a particle diameter that
normally is in the range 50−500 nm. This is emulsion
polymerization in its simplest form, i.e. a free-radical polymer-
ization of a water-insoluble monomer emulsified in water using a
surfactant and polymerized using a water-soluble initiator. The
reaction loci are nanometer-size particles created in situ through
various mechanisms (see section 3.2), and the kinetics are no
longer those of bulk free-radical polymerization because the
small size of the loci of polymerization introduces segregation
effects, e.g., in which termination of propagating polymer chains
is suppressed by the low probability of two propagating chains
existing simultaneously in the same particle. This results in the
formation of higher molecular weight polymer at a high rate of
polymerization (see section 3.3).
If the surfactant concentration in a monomer emulsion is
greatly increased, or if the water-insoluble monomer concen-
tration is greatly reduced, a microemulsion is produced, though
it is normal to include a short-chain alcohol (e.g., butan-1-ol or
pentan-1-ol) to facilitate their preparation. Microemulsions of
monomer are thermodynamically stable systems in which all of
the monomer resides within the micelles. At very high surfactant
concentrations, the surfactant may form a bicontinuous network
rather than discrete micelles. Polymerization of the monomer
within a microemulsion (with water- or monomer-soluble
initiator) is referred to as microemulsion polymerization and
produces polymer latexes with very small diameters (10−100
nm) but has received relatively little attention or use.
In miniemulsion polymerization (see section 4) the monomer
droplet size in the monomer emulsion is reduced sufficiently for
the droplets to become the dominant locus of polymerization.
The product is a colloidally stable polymer latex, as in emulsion
polymerization. However, although the kinetics of miniemulsion
polymerization and the diameter of the final latex particles are
similar to those for emulsion polymerization, it offers
opportunities not possible with normal emulsion polymer-
ization; these will be discussed in detail later.
If the continuous phase is organic, and the dispersed phase is a
water-soluble monomer dissolved in water, the process is termed
an inverse emulsion polymerization and produces dispersions of
concentrated aqueous polymer solutions in the organic medium.
Although not widely used, such polymerizations are very
important in producing polymers for use in cleaning of water
in wastewater treatment plants.
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3. FUNDAMENTALS OF EMULSION
POLYMERIZATION
A simple formulation for an emulsion polymerization is given in
Table 1. After emulsifying the monomer mixture in the aqueous
Table 1. Typical Formulation for Emulsion Polymerization
Component Amount/g
Aqueous phase:
deionized water 230.0
sodium dodecyl sulfate (SDS) 1.1
Monomer mixture:
n-butyl acrylate 50.0
methyl methacrylate 49.0
methacrylic acid 1.0
Initiator solution:
ammonium persulfate 0.4
deionized water 20.0
Total Amount 352.3
phase surfactant solution with agitation, and heating to reaction
temperature, the initiator solution is added to start the
polymerization and agitation continued until completion of
polymerization.
Use of persulfates (−O3SO−OSO3−) as initiators in emulsion
polymerization is widespread because they are cheap, they are
effective in the usual reaction temperature range of 60−95 °C,
and they produce chains with charged end-groups (Px−SO4−)
that can contribute to the surface charge on particles. Redox
initiation systems need to be used when the reaction has to be
carried out at lower temperatures and often involve reduction of
persulfates (e.g., by sulfite ions), so the chain ends again have
charged end groups (Px−SO4− and Px−SO3− from use of the
persulfate-bisulfite redox couple). Since all these initiators give
negatively charged initiating species, it is important to use
anionic surfactants (such as SDS) for providing more substantial
colloidal stability via electrostatic repulsion between particles
(see section 3.1). Some biological applications require positively
charged particles, in which case cationic surfactants (e.g.,
dodecyltrimethylammonium bromide) and initiators that give
cationic initiating species (e.g., 2,2′-azobis(2-methylpropiona-
midine) dihydrochloride) need to be used to provide electro-
static stabilization; the underlying mechanism of emulsion
polymerization is not affected by such changes.
Having established the basic reactants and chemistry of an
emulsion polymerization, we are now in a position to discuss
how the reaction progresses and why it is very different from
homogeneous free-radical polymerization. If performed as
described above, the reaction progresses through three distinct
stages, which were first articulated and interpreted qualitatively
in the seminal paper by Harkins,10 who termed these Intervals I,
II, and III, a terminology that is very helpful and persists today.
The three intervals of an emulsion polymerization are illustrated
in Figure 1. Interval I (typically 0−5% conversion) is the period
during which particles are nucleated and after which the particles
are assumed to remain colloidally stable and simply grow by
further polymerization. Particle nucleation is followed in Interval
II by a period of approximately constant rate of polymerization
in the presence of monomer droplets. Monomer droplets are
absent during Interval III (which typically starts at about 40%
conversion), and the rate of polymerization reduces pro-
gressively as the remaining monomer is consumed.
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Figure 1. The three intervals of emulsion polymerization.
Harkins’ interpretation of the three intervals remains broadly
correct, though his detailed explanation, especially of Interval I,
was incomplete and deficient in several ways. Rather than
present a historical account of how understanding evolved over
several decades, in the subsequent sections we present the
current understanding of emulsion polymerization with the
historical developments rationalized.
Even for the more hydrophobic monomers with very low
water solubilities (such as styrene and n-butyl acrylate),
polymerization begins in the aqueous phase by reaction of an
initiator radical (e.g., the sulfate radical-anion, •OSO3− from
persulfate ions) with monomer dissolved in the aqueous phase
(a fact not recognized until a long time after Harkins’ paper).
The resulting oligomeric chains continue to grow by solution
polymerization in the aqueous phase and have several possible
fates as their length increases. These will be discussed in some
detail in relation to particle nucleation, but first a brief
introduction to factors that control the colloidal stability of
particle dispersions in water will be given.
3.1. Colloidal Stability of Particle Dispersions in Water.
A dispersion of colloidal particles in water would quickly
coagulate in the absence of forces to counteract the van der
Waals attraction between particles. Figure 2 shows schematic
diagrams of the three important ways in which colloidal stability
can be conferred. A simple, descriptive introduction to these
effects is given here, sufficient for understanding colloidal
stability in the context of this review paper; more detailed
understanding is best obtained using textbooks11−15 as a starting
point.
Electrostatic stabilization is the principal mode of colloidal
stability used in emulsion polymerizations. It is achieved by use
of adsorbed ionic surfactant molecules, which bring their
headgroup charge to the surface of particles, as shown in Figure
2(a). The counterions are free to move anywhere in the aqueous
phasethey are attracted to the particle surface by the surface
charges, but also are pulled away from the surface because of
their low concentration at distances far from the surface. The
surface charge and dif f use region of counterions constitute the
electrical double-layer, the extent of which is crucial for colloidal
stability. As particles approach each other closely, the diffuse
regions of counterions overlap, creating a force of repulsion. In
DLVO (Derjaguin, Landau, Verwey, and Overbeek) theory the
sum of the potential energies (V) of electrostatic repulsion and
van der Waals attraction is defined as a function of distance of
separation (h). A typical V(h) versus h curve is shown in Figure
2(a) and has three features: (i) a very deep primary minimum
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Figure 2. Modes of colloidal stability for particle dispersions in water: (a) electrostatic stabilization due to adsorbed ionic surfactant molecules (anionic
shown); (b) steric stabilization due to strongly adsorbed or grafted water-soluble polymer (WSP) chains; and (c) depletion effects arising from WSP
chains dissolved in the aqueous phase. The right-side plots are of total potential energy of interaction (V(h)) versus distance of separation (h) for each
mode of stabilization.
due to dominance of the van der Waals attraction at very small
values of h; (ii) a potential energy maximum (Vmax) at
intermediate h where the electrostatic repulsion is dominant;
and (iii) a weak secondary minimum at larger distances of
separation. Particles may associate weakly (i.e., f locculate) in
ordered arrays at h corresponding to the secondary minimum,
but they are easily disturbed from this order by agitation (if the
particles have a very narrow size distribution, the dispersion will
be iridescent when in the secondary minimum). For reasonable
colloidal stability, Vmax should be greater than 10kT (where k is
the Boltzmann constant and T is absolute temperature). If the
particles gain sufficient energy (e.g., kinetic energy from
agitation), they can overcome the potential energy barrier and
enter the primary minimum from which there is no returnthe
particles become permanently aggregated, which is termed
coagulation. The diffuse region of counterions can be greatly
compressed, and Vmax greatly reduced, by addition of ions to the
aqueous phase (especially multivalent ions), leading to loss of
colloidal stability. Thus, the stability of electrostatically
stabilized particle dispersions is sensitive to the salt content of
the aqueous phase.
Figure 2(b) depicts steric stabilization, which is provided by
complete surface coverage of either strongly adsorbed and/or
chemically bound (i.e., graf ted) water-soluble polymer (WSP)
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chains, which radiate out from the particle surface into the
aqueous phase. In the absence of electrostatic effects, there is no
force of repulsion until the particles approach at distances of
separation close to twice the thickness (δ) of the surface layer of
WSP chains. At h < 2δ, the chains are in contact (i.e., interacting)
and mix or compress each other, all of which is unfavorable
because polymer−water contacts are preferred and the chains
lose configurational (conformational) freedom as they become
concentrated or compressed. Hence, there are both enthalpic
and entropic components to the potential energy of repulsion,
which increases rapidly as h reduces and dominates the V(h)
versus h curve for h < 2δ. If the surface layer is thin (i.e., the WSP
chains are of low molecular weight), a secondary minimum due
to the van der Waals attraction can be present, but this will be
absent if the surface layer is thick. Electrostatic and steric
stabilization can be combined by adsorbing or grafting
polyelectrolyte chains at a particle surface, which is termed
electrosteric stabilization. For both steric and electrosteric
stabilization, it is essential for the chains to be strongly held at
the surface (so grafting is beneficial) and to have complete
surface coverage (bare patches of surface offer no force of
repulsion). In both cases, added electrolytes diminish the quality
of polymer−water interactions and can reduce the magnitude of
the steric repulsion, but the effect is much smaller than for
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Figure 3. Schematic diagram showing scenarios for nucleation in emulsion polymerization. Homogeneous nucleation is represented in (a) and (b),
which show the phases existing at the onset of polymerization and limited coagulation of primary particles, respectively, with surfactant at a
concentration below the CMC. Micellar nucleation is represented in (c) and (d), which show the phases existing at the onset of polymerization and
part way through nucleation, respectively, with surfactant at a concentration above the CMC. Note that homogeneous nucleation can also occur when
the surfactant concentration is above the CMC. Dashed lines for arrows indicate multiple processes of the same kind.

electrostatic stabilization, so steric and electrosteric stabilization
are widely used to increase resistance to the destabilizing effects
of electrolyte additions. Ultimately, if the solvency conditions
are reduced sufficiently, the adsorbed/grafted chains will
collapse back to the surface and the particles can flocculate
because the secondary minimum moves to much smaller h, but
the surface chains still prevent the particle surfaces approaching
close enough to enter the van der Waals primary minimum.
Hence, if the solvency conditions are changed again, the surface
4403
chains will expand and the particles will redisperse into a stable
colloidal form. Thus, steric and electrosteric stabilization can be
used to protect latexes against coagulation.
Depletion ef fects are illustrated in Figure 2(c) and are more
difficult to appreciate because they are caused by WSP chains
that are free in the aqueous phase. There are different
approaches to explaining depletion effects; here we will consider
(in less rigorous terms) the effect of WSP concentration
([WSP]w)note that the actual values at which changes in
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behavior occur are dependent on particle diameter and WSP
molecular weight. A key parameter is the size (δ) of the WSP
chains in the aqueous phase. (δ is used again because, for a given
polymer and molecular weight, it will be similar to the layer
thickness δ for an equivalent adsorbed or grafted chain.) At
“lower” [WSP]w, there is a high probability that particles will
approach to h < δ with no chain between them; the chains are
then excluded from the region between the particles (the region
is depleted of chains), which causes water molecules to move out
to where the polymer chains exist, creating a force of attraction
between the particles. At “higher” [WSP]w, the probability of
particles approaching without a WSP chain between them is
small, so as they approach the chains become concentrated in
the region between them, which is unfavorable (for the same
reasons as in steric stabilization) and creates a force of repulsion
between the particles. This gives rise to V(h) versus h curves that
take the form shown in Figure 2(c) for “bare” particles (which
have no surface charge or adsorbed/grafted WSP chains): (i) an
energy barrier corresponding to Vmax exists at h ≈ δ, and if Vmax >
10kT, depletion stabilization is achieved for h > δ; and (ii) a
primary minimum exists at h < δ where the particles will be
forced to aggregate permanently, which is termed “hard”
depletion f locculation (strictly this is coagulation). Even if the
particles are sterically stabilized (i.e., have an adsorbed/grafted
layer of WSP), depletion effects can occur if WSP chains also
exist in the aqueous phase, but in this case the aggregation at h <
δ is reversible because the adsorbed/grafted chains prevent
direct contact between the particle surfaces; this is termed “sof t”
depletion flocculation (i.e., true flocculation; this is the historic
reason for using the term). The potential energy of attraction
increases as [WSP]w increases (from zero) to a critical value at
which the dispersion is destabilized by depletion effects. As
[WSP]w increases beyond this “lower” critical concentration,
another critical concentration is reached at which the dispersion
becomes stable due to depletion effects. These critical
concentrations reduce as particle diameter and WSP molecular
weight increase. In most latex systems, the concentrations
required for depletion stabilization are too high to be realized in
practice because the free aqueous polymer chains are typically of
low molecular weight. However, depletion flocculation effects
can be observed in latexes that contain aqueous phase WSPs;
e.g., evaporation of water during film formation of a latex-based
coating can trigger depletion flocculation, causing aggregation of
particles that results in loss of gloss in the coating.
3.2. Interval I: Particle Nucleation. There are three
principal mechanisms by which particles are nucleated, which in
order of when they were first recognized and controlled are (i)
micellar nucleation, (ii) homogeneous nucleation, and (iii)
droplet nucleation. All three mechanisms may occur simulta-
neously in a given emulsion polymerization, though one tends to
be dominant dependent upon the monomer, the reaction
formulation, and the reaction conditions. The mechanisms are
described in the following sections with reference to the phases
that exist in the reaction mixture at the beginning of the
emulsion polymerization.
However, before considering nucleation mechanisms in
detail, it is helpful to consider absorption of an oligomeric
radical from the aqueous phase into a spherical locus, such as a
monomer-swollen micelle or latex particle. This is diffusion
controlled and governed by Fick’s first law, leading to the
following equation for the molar rate of absorption16
ρa = 4πDx r[P•x ]w (6)
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where P•x is an oligomeric radical with degree of polymerization
x, Dx is the aqueous-phase diffusion coefficient of P•x , r is the
radius of the spherical locus into which the radical is diffusing,
and [P•x ]w is the aqueous phase concentration of P•x . It also is
pertinent to consider the radical flux per unit area of surface,
Dx [P•x ]w
ρa /A =
r (7)
where A is the surface area of the spherical locus. Thus, small
entities of high surface curvature (such as monomer-swollen
micelles) are far more efficient at capturing oligomeric radicals
than larger entities (such as monomer droplets).
3.2.1. Homogeneous Nucleation. In terms of understanding
nucleation, it is instructive to consider homogeneous nucleation
first, even though it was not the first mechanism of nucleation to
be recognized. This is because the underlying processes involved
in homogeneous nucleation also occur in micellar and droplet
nucleation, though they are not essential to understanding the
essence of those mechanisms, and because it is the only
mechanism of nucleation that can occur in all emulsion
polymerizations, including those performed in the complete
absence of surfactant and monomer droplets. In relation to the
latter comment, surfactant-free emulsion polymerization has
been studied extensively and, although not useful for production
of high solids content latexes, it is useful for making larger
particles (e.g., 500 nm to 1 μm diameter) with narrow particle
size distributions (PSD) and has been exploited for biomedical
applications.
The mechanism of homogeneous nucleation is depicted in
Figure 3(a)−(b) where, for simplicity, we begin by considering a
formulation that has surfactant present at a concentration below
the CMC so that there are no micelles present. In this case, at the
onset of polymerization, as shown in Figure 3(a) there are only
two phases to consider: (i) the aqueous phase containing
molecularly dissolved surfactant, initiator, and a saturation
concentration of monomer and (ii) monomer droplets with a
few surfactant molecules adsorbed at the surface. Radicals
generated in the aqueous phase react with monomer molecules
in the aqueous phase, creating oligomeric radicals that continue
to propagate homogeneously in the aqueous phase and begin to
resemble the structure of a surfactant molecule, with a
hydrophobic tail and a hydrophilic headgroup that usually
carries a charge from the initiator radical, as shown for persulfate
initiation in Figure 3. Hence, as the oligomeric radical grows in
the aqueous phase, it quickly becomes surface active; the degree
of polymerization for surface activity often is referred to as z and
the oligomer as a z-mer.17 The probability of entry into a droplet
is low compared to continued propagation, and so the oligomer
continues to grow in the aqueous phase until it either terminates
(leaving a short water-soluble dead polymer chain in the
aqueous phase) or reaches a critical degree of polymerization
(termed jcrit) at which it becomes insoluble in water. In the latter
case, the propagating oligo-radical then phase separates
(“precipitates”) from the aqueous phase to give a primary
particle that corresponds, at that point, to the collapsed size of
the propagating chain and carries only the single chain-end
charge from the initiator radical, so it is not colloidally stable.
This is the essence of homogeneous nucleation and is shown
schematically in Figure 3(a). In the early development of
homogeneous nucleation theory, it was assumed that a primary
particle would become colloidally stable through rapid
adsorption of surfactant molecules to the surface, such that
every oligomeric radical which attains jcrit becomes a latex
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particle nucleus in which monomer is then absorbed and the
oligomeric radical continues to propagate. In reality, primary
particles have poorly developed hydrophobic interiors (so do
not absorb much monomer) and undergo limited coagulation
with each other until a mature particle nucleus is formed that is
colloidally stable (by virtue of the increased surface charge) and
has a well-developed hydrophobic interior capable of imbibing
an appreciable quantity of monomer.18,19 Adsorption of
surfactant molecules contributes additional surface charge and
reduces the extent of limited coagulation. The process of limited
coagulation, monomer imbibition, and surfactant adsorption
leading to a mature particle nucleus is shown schematically in
Figure 3(b). In the complete absence of surfactant, more
extensive coagulation of primary particles occurs such that the
mature particle nuclei formed are much larger before they
become colloidally stable. This is why surfactant-free emulsion
polymerization produces far fewer particles and consequently
gives rise to large particle sizes.
As Interval I progresses, the already-formed particle nuclei
bring new complexity. The oligomeric radicals growing in the
aqueous phase now have another possibility, namely, entry into
an existing particle nucleus, which is assisted by the high
curvature of the particle nuclei surfaces at this point (in accord
with eq 7) and becomes more likely as the degree of
polymerization of the oligomeric radical increases beyond z. If
an oligomeric radical attains jcrit and precipitates to form a
primary particle, that primary particle may coagulate onto the
surface of an existing particle nucleus, which in effect is another
mode of radical entry into the existing particle nucleus. In both
cases, the oligomeric radical is lost in terms of nucleation. As
more particle nuclei are formed, oligomeric radicals and primary
particles become increasingly likely to be captured by them, and
eventually, when the number of particle nuclei is high enough, all
oligomeric radicals and primary particles become captured. This
marks the end of Interval I for homogeneous nucleation.
Evidence for aqueous phase polymerization was described,
but not explained, by Harkins in his landmark paper.10
Recognition of particle formation through aqueous phase
polymerization was first reported by Priest,20 and homogeneous
nucleation was first described explicitly by Fitch et al.21−23
(based on polymerizations of methyl methacrylate in aqueous
solution). This culminated in a quantitative treatment of
homogeneous nucleation by Fitch and Tsai,24 which was
developed further by Hansen and Ugelstad.16,25 (Hence, the
theory often is referred to as HUFT theory.) More complete
theoretical prediction of the number of latex particles formed by
the end of homogeneous nucleation must take into account
limited coagulation of primary particles and has to balance the
competition between all the possible fates for propagating
oligomeric radicals until the point when the probability of
capture by existing particle nuclei is unity, taking into account
the significance of oligomeric radical surface activity for radical
entry. Hence, theoretical prediction of final particle number for
homogeneous nucleation is complex even for homopolymeriza-
tion and not appropriate for inclusion herethe reader is
referred to the literature for this.16,19,24,25
3.2.2. Micellar Nucleation. Micellar nucleation was proposed
by Harkins10 and has the requirement that the surfactant must
be present at a concentration above its CMC; that is, most of the
surfactant is present in the form of micelles. This is true for the
great majority of emulsion polymerizations performed as batch
processes (see section 3.5.1). In this case, at the onset of
polymerization, the monomer emulsion now comprises three
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phases, as illustrated in Figure 3(c). This adds further
complexity to the fate of oligomeric radicals propagating in
the aqueous phase because they also can be captured by the
monomer-swollen micelles. If the surfactant is present at
concentrations of a few percent by weight of monomer, there
will normally be a very high number concentration of monomer-
swollen micelles (typically 1018−1021 L−1) of small size (around
10 nm diameter). In contrast, the monomer droplets are present
at much lower concentration (typically around 1010−1012 L−1)
and are much larger (around 10 μm diameter). Since the
monomer-swollen micelles have much greater total surface area
(by a factor of at least 100) than the monomer droplets, Harkins
asserted that all oligomeric radicals are captured by the
monomer-swollen micelles, an assertion that becomes even
more compelling when recognizing, from eq 7, that their much
smaller size makes them far more efficient at capturing
oligomeric radicals. Entry into a monomer-swollen micelle is
likely to occur soon after the oligomeric radical becomes a z-mer,
as depicted in Figure 3(c). One of the many important features
recognized and explained by Harkins is that the polymer chains
formed have a much higher degree of polymerization (x̅n ≫
100) than the number of monomer molecules (around 50−100)
present in a monomer-swollen micelle. He rationalized this by
recognizing correctly that the principal role of the monomer
droplets is to serve as monomer reservoirs which supply monomer
to the growing particles by diffusion through the aqueous phase
at a rate that exceeds the rate of polymerization within the newly
created particles. Hence, after a monomer-swollen micelle has
been “hit” by entry of an oligomeric radical, propagation of the
radical continues as normal with an equilibrium concentration of
monomer in the particle nucleus. The surface area of a particle
nucleus increases rapidly in its early stages of growth and
requires more surfactant to maintain colloidal stability. This
additional surfactant comes from monomer-swollen micelles
that have not been hit. Thus, a monomer-swollen micelle has
one of two fates, either (i) become a particle nucleus on being hit
by entry of an oligomeric radical or (ii) disappear by losing its
surfactant and monomer to service the colloidal stability and
growth of already-formed particle nuclei.
The already-formed particle nuclei compete with the
monomer-swollen micelles for capture of the oligomeric
radicals, a situation that is evident from Figure 3(d). As Interval
I progresses, the number of monomer-swollen micelles
decreases and the number of particle nuclei increases, so the
probability for entry of an oligomeric radical into a monomer-
swollen micelle steadily reduces. Eventually all of the monomer-
swollen micelles are just completely consumed, marking the end
of micellar nucleation.
All quantitative theories of micellar nucleation are developed
from balances of the probabilities of aqueous-phase radical entry
into monomer-swollen micelles and existing particles. Smith and
Ewart26 were the first to quantify the Harkins model for
emulsion polymerization and developed a theory to predict the
number concentration of particles per unit volume of aqueous
phase (Nc) at the end of Interval I for two limiting scenarios: (i)
each free radical generated in the aqueous phase gives rise to
entry of a radical into a monomer-swollen micelle, creating a
particle that remains colloidally stable, and (ii) monomer-
swollen micelles and already-formed particles compete for
capture of aqueous phase radicals in proportion to their total
surface areas; that is, they (incorrectly) used collision theory for
entry probability rather than diffusion theory. The end of
particle nucleation was defined as the point at which all the
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Figure 4. Fate of aqueous phase oligomeric radicals in emulsion polymerization. The key to symbols is the same as given in Figure 3. Arrows with
dashed lines indicate multiple aqueous-phase propagation reactions of a growing oligomeric radical with monomer. Dotted lines indicate that all
oligomeric radicals with degrees of polymerization in the range z to jcrit − 1 are capable of entry by diffusion into monomer-swollen micelles and
already-existing particles.
surfactant molecules were adsorbed at particle surfaces, i.e.,
when the total particle surface area Ap = NAaS[S]0, where NA is
the Avogadro constant, as is the surface area occupied by an
adsorbed surfactant molecule (which they assumed to be the
same for monomer-swollen micelles and particles), and [S]0 is
the initial surfactant concentration. For both scenarios of radical
capture, the dependence of Nc on reaction parameters had the
same functional form,
i NAρw yz
Nc = k SEjjjj zz (NAaS[S ]0 )3/5
z
2/5
k υ {
(8)
where kSE has values in the range from 0.37 (when monomer-
swollen micelles and particles compete for radical entry) to 0.53
(when all aqueous-phase radicals enter monomer-swollen
micelles), υ is the volumetric growth rate of particles (assumed
to be independent of particle diameter), and ρw is the molar rate
of radical generation in the aqueous phase.
Dependence of Nc on ρw0.4[S]00.6 was found to be in
reasonable accord with experimental data for emulsion
polymerizations of styrene and a few other monomers of low
water solubility at [S]0 well above the CMC, though predictions
of the value of Nc were not usually accurate, in part because most
of the assumptions inherent in derivation and use of eq 8 are
invalid. In fact, it can be shown27 that micellar nucleation is not a
prerequisite for Nc ∝ ρw0.4[S]00.6 because this dependency results
from the end condition (i.e., Ap = NAaS[S]0) and the assumption
that, once formed, the volume of a particle continues to increase
during Interval I at a fixed rate υ, so it is independent of the
precise mechanism of particle nucleation. It is for this reason that
eq 8 has importance beyond its historical significance in
understanding of micellar nucleation. The vast majority of
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emulsion polymerizations use surfactants (whether or not above
or below the CMC), and eq 8 correctly informs us that Nc can be
expected to increase as ρw and [S]0 increase. Stronger deviations
from Nc ∝ ρw0.4[S]00.6 are observed for monomers of greater
water solubility, because homogeneous nucleation contributes
and may be dominant, and when desorption of radicals out of
particles into the aqueous phase is significant.
3.2.3. Monomer Droplet Nucleation. Entry of oligomeric
radicals into monomer droplets is another mechanism by which
particles can be formed and is termed droplet nucleation. In most
conventional emulsion polymerizations, the monomer droplets
are relatively large and in relatively low number concentration,
so for the reasons discussed in the previous two sections, droplet
nucleation is of minor importance in terms of an effect on the
value of Nc.
If the size of the monomer droplets is reduced sufficiently,
they can compete effectively for capture of oligomeric radicals
and conditions can be achieved under which droplet nucleation
becomes dominant. This was the basis for development of
miniemulsion polymerization (see section 4). A distinguishing
feature of droplet nucleation, as opposed to homogeneous or
micellar nucleation, is the nature of the particle at “birth”.
Monomer droplets that are nucleated into particles by entry of
an oligomeric radical begin as nearly 100% monomer. This is
much higher than for particles formed by homogeneous or
micellar nucleation, which initially contain low monomer
concentrations and then swell to around 50−60% monomer as
they grow during interval I. This fundamental difference can lead
to large differences between miniemulsion and emulsion
polymerizations in terms of radical desorption from particles
and/or termination within particles during Intervals I and II.
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3.2.4. The Balance of Nucleation Mechanisms and Control Table 2. Water Solubilities of Monomers
of Particle Number. Statistically, all three types of particle
Molecular Water Solubility/ Temp/
nucleation can compete and coexist in any emulsion polymer- Monomera Weight mmol L−1 °C Reference
ization, and their contributions must be balanced in theoretical
Acrylonitrile 53.06 1990 60 32
treatments.16,19,25,28−31 However, monomer droplet nucleation
Methyl acrylate 86.09 741 60 32
is normally only significant when the droplet size is small. Since Vinyl acetate 86.09 565 60 32
miniemulsion polymerization is dealt with separately in section 4 Ethyl Acrylate 100.12 233 60 32
and the contribution of droplet nucleation to the value of Nc is Glycidyl 142.15 210 60 32
negligible in the great majority of emulsion polymerizations, methacrylate
only homogeneous nucleation and micellar nucleation will be Methyl methacrylate 100.12 150 50 33
considered here in terms of the factors that control Nc. 4-Methylstyrene 118.18 60.3 60 32
A complete picture of the fate of oligomeric radicals in normal Allyl methacrylate 126.15 50 80 34
emulsions is shown in Figure 4. At any point during its growth in Oct-1-ene 112.21 42.7 60 32
the aqueous phase, an oligomeric radical can enter a monomer- α-Methylstyrene 118.18 8.22 60 32
swollen micelle (if present) to generate a new particle, or it can n-Butyl acrylate 128.17 5.8 80 34
enter an already-existing particle. Alternatively, it may grow to Styrene 104.15 4.3 50 35
jcrit and precipitate to form a primary particle that may enter an n-Butyl methacrylate 142.20 2.5 50 36
existing particle by coagulation or undergo limited coagulation Divinylbenzene 130.19 1.45 60 32
with other primary particles until a colloidally stable particle 2-Ethylhexyl acrylate 184.28 0.971 60 32
nucleus is created. When the already-existing particles are 4-Vinylbenzyl 152.62 0.509 60 32
present in high enough number, they capture all oligomeric chloride
radicals (i.e., the left-side pathway in Figure 4 is completely VeoVa 10 (vinyl 198.31 0.199 60 32
neodecanoate)
dominant) marking the end of nucleation. One further process
iso-Octyl acrylate 184.28 0.176 60 32
shown in Figure 4 is termination of oligomeric radicals in the
iso-Decyl acrylate 212.33 0.133 60 32
aqueous phase before they either undergo an entry event or
tert-Dodecylthiola 202.40 0.036 60 32
attain jcrit. This may be by combination with an initiator radical iso-Bornyl acrylate 208.30 0.0163 60 32
or with another oligomeric radical, which can be significant in 4-tert-butylstyrene 160.26 0.01 25 37
terms of polymerization kinetics in all intervals and, in most Cetyl alcohola 242.44 1.93 × 10−4 35 38
cases, produces a water-soluble, surfactant-like species in the Lauryl methacrylate 254.41 4.71 × 10−5 35 38
aqueous phase. Stearyl methacrylate 338.57 8.24 × 10−6 35 38
There is broad opinion, though often not proven irrefutably, Hexadecanea 226.44 3.88 × 10−6 25 39
that more water-soluble monomers have greater tendency to a
Not monomers, but sometimes used as components in emulsion/
undergo homogeneous nucleation. Monomer water solubility
miniemulsion formulations.
also is an indirect factor in controlling many final latex properties
(e.g., particle morphology and latex rheology; see sections 6 and
7) due to consequences of monomer partitioning between the 3.2.1. At [S]0 > CMC, both homogeneous and micellar
aqueous and particle phases. Hence, for reference, Table 2 shows nucleation can contribute and the complexity of predicting Nc
water solubility data for multiple monomers and other is much greater. For most monomers, there normally is a major
formulation components. (several orders of magnitude) increase in Nc as [S]0 passes from
As stated, there is belief that the higher the water solubility of below to above the CMC, though this transition often is quite
the monomer ([M]w), the higher is the likelihood of broad and not sharp, as might be expected if it was signifying a
homogeneous nucleation in the presence of micelles. This sudden switch from homogeneous to micellar nucleation. When
generalization, however, hides the numerous contributing [S]0 ≫ CMC, it is very likely that micellar nucleation is
factors because, in addition to higher [M]w, several of the dominant for all monomers, so the observed broader transition
more water-soluble monomers also have higher values of kp, so to higher values of Nc in the region of the CMC is indicative of
the rate of propagation of oligomeric radicals in the aqueous both mechanisms of nucleation operating when [S]0 is close to
phase (∝kp[M]w) can be very much higher than for more the CMC, which has been shown to be a realistic possibility by
hydrophobic monomers such as styrene. This is, in part, Gilbert and co-workers.19,40
compensated by the higher value of jcrit for oligomeric radicals The large change in Nc when [S]0 is in the vicinity of the CMC
from more water-soluble monomers, but the bigger factor provides important guidance when designing formulations for
usually is the rate of aqueous phase propagation. Homogeneous latex preparation. Given that the polymerization kinetics and so
nucleation often is presumed to be dominant for monomers with many latex characteristics are dependent on the value of Nc, for
high [M]w (e.g., vinyl acetate and vinyl chloride) and even for reproducibility of preparation, it is clear that surfactants should not
those with moderate [M]w (such as methyl methacrylate and be used at [S]0 close to the CMC.
ethyl acrylate). However, it is very difficult to prove Although [I]0 has a measurable influence on Nc, as is evident
unambiguously which of the two nucleation mechanisms is from the discussion of homogeneous nucleation and eq 8, the
dominant, as has been elegantly explained in the textbook by biggest factors in controlling Nc and latex colloidal stability
Gilbert,19 which also highlights the complexities in attempting to during the polymerization are the selection of surfactant type
predict Nc for real systems. and the value of [S]0. For most emulsion polymerizations,
Clearly, for 0 ≤ [S]0 < CMC, only homogeneous nucleation is however, it is very difficult to predict Nc or colloidal stability with
possible. The value of Nc will normally increase as [I]0 and [S]0 any certainty, so it is usual to develop a formulation by
increase. However, even for the simplest of homopolymeriza- experiment, for which statistical methods of experimental design
tions, accurate prediction of Nc is difficult, as discussed in section often are employed.41−43 The wrong selection of surfactant can
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be quite disastrous in terms of the levels of coagulum produced, Table 3. Calculations Using Eqs 9 and 10 for Seeded
and so it is common to base formulations and choice of Emulsion Polymerizationa
surfactant (or surfactant mixtures) on emulsion polymerizations
(Nc)f/1016
that are known to be satisfactory for the same or similar df/ particles (L dS / mS/g (L % Seed Polymer in
monomers (e.g., taken from the literature, company practice, or WfP nm H2O)−1 nm H2O)−1 Final Particle
intellectual property). 0.500 200 23.87 50 15.6250 1.6
3.2.5. Control of Particle Number Using Seeded Emulsion 0.300 200 10.23 80 27.4286 6.4
Polymerization. In view of the difficulties in predicting 0.100 200 2.65 60 3.0000 2.7
nucleation behavior, strategies for avoiding the uncertainty 0.500 300 7.07 100 37.0370 3.7
around controlling Nc are important. The most effective way of 0.300 300 3.03 50 1.9841 0.5
achieving this is to prepare a large batch of a seed latex and to 0.100 300 0.79
then include a portion of this latex to provide the particle nuclei 0.400 400 1.99 100 10.4167 1.6
in further emulsion polymerizations. If the seed particles are in 0.400 400 1.99 60 2.2500 0.3
sufficient concentration, they will capture all oligomeric radicals 0.200 400 0.75
and thereby eliminate Interval I. Seeding is used commercially to 0.100 400 0.33
achieve greater batch-to-batch reproducibility and is commended for 0.400 500 1.02 100 5.3333 0.8
use in all emulsion polymerizations where control of Nc is important. 0.300 500 0.65
For most applications, there is a particular target final particle 0.100 500 0.17
diameter and final latex polymer content, so it is important to a
For simplicity, ρH2O = 1000 g L−1 and ρP = 1 × 10−21 g nm−3 have
consider whether or not this is realistic for control by seeding.
been used in the calculations. Values of (Nc)f < 1 × 1016 particles (L
Based on historical experimental evidence, with support from H2O)−1 are italicized, and corresponding values of dS, mS, and % seed
theory, 44 a rule-of-thumb guide for having reasonable polymer in final latex particles are not given because seeded control of
confidence that all oligomeric radicals will be captured by the (Nc)f is unlikely to be successful.
seed particles, i.e., for elimination of additional particle
nucleation, is to use a seed particle concentration above 1016 1018−1019 particles (L H2O)−1. The reasons for this are (i) the
particles per liter of aqueous phase ({L H2O}−1). For 100% seed polymer is then a small percentage of the final polymer (as
conversion of monomer and assuming that surfactant and salts evident from Table 3); (ii) the seed latex contributes only a very
(e.g., buffer and residual initiator) contribute negligibly to the small proportion of the total water required (the total water in
total mass of final latex, it is simple to show that the value of Nc the formulation must include the water present from the seed
for the target final latex is given by latex); and (iii) a single batch of seed latex can be used to make
{WfP/(1 − WfP)}ρH O many batches of target latex or many different target latexes.
(Nc)f = 2
particles (L H 2O)−1 Batch-to-batch variation of dS in seed latex preparation is simply
(π /6)df3ρP (9) adjusted for using the calculations described above.
Additional surfactant must be added in a seeded emulsion
where WfP is the mass fraction concentration of polymer in the polymerization to ensure colloidal stability of the seed particles
final latex, ρH2O and ρP are the densities of water (g L−1) and as they grow. In order to eliminate the possibility of micellar
polymer (g nm−3), and df is the final particle diameter (nm). It nucleation, it is important to make sure that the concentration of
also is simple to calculate the mass mS of seed particles of surfactant does not exceed the CMC at any point. When using
diameter dS required more water-soluble monomers, lower rates of radical generation

ji d zy
mS = {WfP/(1 − WfP)}ρH O jjj S zzz g (L H 2O)−1
will also help to reduce the possibility of creating new particles

2 jd z
3

k f{
(10)
Ideally, number-average particle diameters should be used in
these calculations, but in most cases only other average particle
diameters are available, in which case eqs 9 and 10 can still be
used and will be most accurate if the particle size distribution is
narrow. For example, z-average particle diameters measured by
photon correlation spectroscopy are widely used and give
reliable predictions. (See section 3.7 for a discussion of particle
diameter averages and their measurement.)
It is instructive to consider a few scenarios for these
calculations, as presented in Table 3, inspection of which
shows that seeded emulsion polymerization can be very helpful
for controlling Nc when WfP is relatively high (≥0.40) and df ≤
400 nm, which is the situation for most commercial latexes.
However, it also is clear that when WfP is low (≤0.20) and df >
400 nm, it is very difficult to prevent creation of new particles
because Nc is too low to ensure capture of all oligomeric radicals.
Seed latexes are usually prepared at high surfactant
concentrations to have relatively high polymer contents (e.g.,
30−40% polymer by weight of latex) and dS in the range 50−100
nm, which means they have very high values of Nc, typically
4408
by homogeneous nucleation.
Latexes with very large sizes (500 nm to 100 μm diameter) are
best prepared by a series of seeded emulsion polymerizations in
which the latex from each reaction is swollen with just enough
monomer to achieve equilibrium swelling and then polymerized.
For very large particles (diameters >10 μm), coagulation arising
from gravitational forces is a problem, which has been overcome
for production of small volumes of standard narrow PSD
polystyrene latexes by carrying out the polymerizations in
space.45
3.3. Interval II: Particle Growth in the Presence of
Monomer Droplets. The particles created during nucleation
become the loci for polymerization during Interval II (and also
Interval III). It is assumed that the particles remain colloidally
stable as they grow by further polymerization and that secondary
nucleation is absent, such that Nc is constant after Interval I. Key
to understanding Interval II is Harkins’10 recognition that
monomer droplets exist for the complete duration of Interval II and
serve only as reservoirs for supply of monomer to growing latex
particles by diffusion through the aqueous phase at a rate which
exceeds the rate of polymerization within the latex particles (i.e.,
mass transfer of monomer from droplets is fast and exceeds the
rate of chain radical propagation inside a particle). This is now a
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well-established truth and the particles can be considered to be
at equilibrium swelling by monomer throughout Interval II with
few exceptions (e.g., monomers of extremely low water solubility
may not achieve a saturation concentration in the particles due
to very low rates of diffusion). Thus, the factors controlling
swelling of particles by monomer will be considered before
examining the kinetics of polymerization.
3.3.1. Equilibrium Monomer Concentration in Particles.
Measured equilibrium [M]p data for some common monomers
are given in Table 4 and are typical of the values to be expected
for saturation swelling of a homopolymer particle by its
monomer.
Table 4. Saturation Concentration of Monomer in Particles
at 50 °C19
Monomer [M]p / mol L−1 ru / nm
styrene 5.5 47
methyl methacrylate 6.6 34−46
n-butyl methacrylate 3.8 40
n-butyl acrylate 5.0 79
vinyl acetate 7.5 29
Theoretical prediction for equilibrium swelling of particles by
monomer is achieved46 by balancing the favorable free energy of
monomer−polymer mixing against the resistance to swelling
from the unfavorable surface free energy of polymer−water
ij 1 yz ij 2γ VM yz
contact, which when at equilibrium is defined by
ln(1 − ϕp) + jjj1 − zzzϕp + χϕp2 + jjj PW zzzϕp1/3 = 0
j z j ruRT z
k xn̅ { k {
(11)
where ϕp is the volume fraction of polymer in the swollen
particle, x̅n is the number-average degree of polymerization of
the polymer, χ is the Flory−Huggins polymer−solvent
interaction parameter (which can be measured by experiment
or predicted from monomer and repeat unit chemical
structures47), γPW is the polymer−water interfacial tension
(which must be measured or estimated), VM is the partial molar
volume of monomer, ru is the unswollen radius of the particle
(which must be measured), R is the gas constant, and T is
absolute temperature. (Note that the swollen radius was used
originally46 and is given by rswollen = ruϕ−1/3
p .) Equation 11 often
is referred to as the “Morton Equation”, in which it is usual to
assume that 1/xn̅ = 0 because xn̅ invariably is large. The equation
can be solved iteratively to give ϕp from which [M]p can then be
calculated ([M]p = (1− ϕp)ρM/M0 where ρM is the density of the
monomer). The value of [M]p is sensitive to γPW, which for pure
polymer−water contact typically has values in the range 7−32
mN m−1.48 At particle surfaces, γPW is likely to be reduced
significantly by the effects of surfactant and the presence of
monomer dissolved in the aqueous phase. For a given monomer,
if χ and γPW are assumed to be constants, the equation shows that
ϕp is dependent on ru and that ϕp, and hence [M]p, will change as
the particles grow, as illustrated in Figure 5 using values of γPW
that are representative of the range expected at a particle surface.
The Morton Equation predicts that [M]p is highly dependent on
ru when the particles are small (e.g., during Interval I) and that,
although the dependence becomes weaker as ru increases above
50 nm, there is still a slight increase for ru > 150 nm. Hence, the
common presumption that [M]p is constant during Interval II is
an approximation in view of the typical conversions over which
4409
Review
Figure 5. Predicted equilibrium [M]p at 75 °C plotted as a function of ru
for three typical values of γPW (eq 11 was solved iteratively for ϕp to give
[M]p using 1/x̅n = 0 and data for styrene: ρM = 8.7 × 105 g m−3; χ = 0.44;
M0 = 104.15 g mol−1; and VM = M0/ρM).
Interval II occurs; e.g., an Interval II conversion range of 5−40%
would give a 2-fold {(40/5)1/3} increase in ru. Although the
assumption that [M]p is constant throughout Interval II has
support from experimental measurements of [M]p,49 the
conclusions from the Morton Equation are that it will improve
as γPW reduces but in most cases will only be reasonable if ru is
≳50 nm at the end of Interval I.
3.3.2. General Considerations for Polymerization Kinetics
during Interval II. In homogeneous free-radical polymer-
izations, individual chain radicals typically exist for up to, at
most, a few seconds before being killed, but more often have
shorter lifetimes than this. In emulsion polymerizations, chain
radicals are segregated (compartmentalized) into small particles
and have much longer lifetimes. If it is assumed (because the
particles are so small) that termination is instantaneous when a
second chain radical enters a particle containing a single
propagating chain, then the particles can only contain either one
or zero radicals at any given instant in time, so-called zero−one
conditions. This segregation of simultaneously propagating
chains in separate particles is very significant for the kinetics
and is the underlying reason why it is possible to increase both
the rate of polymerization and the degree of polymerization by
increasing Nc.
The rate of polymerization is given by the following quite
general equation (which is applicable during all intervals),
∞
R p = k p[M]p ∑ (iNi /NA)
(12)
i=1
in which kp[M]p is the molar rate of propagation for a chain
radical in a particle, [M]p is the monomer concentration in a
particle, and Ni is the number of particles containing i
simultaneously propagating chain radicals. In view of its very
small volume, it is often assumed that there are severe
restrictions on the number of radicals that can propagate
simultaneously within a particle (i.e., the values of i are limited to
relatively small numbers). This assumption will be discussed
critically later, but for now it will suffice to understand that eq 12
is most appropriate for zero−one conditions.
In their elegant quantification of the Harkins model of
emulsion polymerization, Smith and Ewart26 introduced the
extremely important concept of considering an average particle
that at a particular instant contains the number-average of the
radicals present across all the particles in the reaction, a quantity
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more usually referred to as the average number of radicals per
particle, n̅
∞ ∞ ∞ extremely high values of (x̅n)EP0 mean that termination of a chain
n̅ = ∑ iNi ∑ Ni = ∑ iNi Nc
i=1 i=1 i=1 (13)
ij n yz
Hence, eq 12 can be recast into its more familiar form
R p = k p[M]p jjj ̅ zzzNc
jN z
k A{
(14)
The importance of n̅ cannot be overemphasized because it is
fundamental to understanding the kinetics of emulsion
polymerization. The challenge for Interval II is to predict the
value of n̅. In seeking to do this, Smith and Ewart considered
three cases for the value of n̅ that have remained a firm
foundation for consideration of Interval II ever since and will be
discussed in the following sections. The value of n̅ during
Interval II can easily be determined from experimental data for
Rp, [M]p, and Nc using eq 14, calculations that are now far more
reliable because accurate values of kp measured by pulsed-laser
polymerization are available. 50−54 However, as for Nc,
theoretical prediction of n̅ is complex and challenging. (For
readers who are interested, the complexities have been well
documented and discussed.16,19,40) Before considering the three
Smith−Ewart cases, we will first turn our attention to prediction
of the degree of polymerization.
Under zero−one conditions, the time for which a segregated
chain can propagate in an average particle is equal to the average
time between successive radical entry events (te̅ n), which is given
by
Nc
ten̅ =
ρen NA (15)
where ρen is the total molar rate of radical entry into particles per
unit volume of aqueous phase. For most emulsion polymer-
izations the value of te̅ n falls in the range 1−100 s, which
highlights the significance of compartmentalization. Under these
conditions, in the absence of chain transfer events, it is easy to
predict the number-average degree of polymerization for
emulsion polymerization
k p[M]p Nc
(x ̅ )0EP = k p[M]p ten̅ =
ρen NA (16)
Thus, (x̅n)EP
0 can be increased by reducing ρen (e.g., by reducing
[I]0) or by increasing Nc (e.g., increasing [S]0), or vice versa, as a
result of their effect on te̅ n. Values of kp generally are in the range
from 200 to 40,000 L mol−1 s−1 and for [M]p are around 4−8
mol L−1. Thus, (x̅n)EP 0 typically has a magnitude of about 10 −
4 dt
7
10 , i.e., extremely high. This massively increases the likelihood
that termination of a segregated chain radical will be brought
about by chain transfer events, for which eq 2 is applicable, but in
which all the concentrations are those within a particle. Since
solvents are not used in emulsion polymerizations, only chain
transfer to monomer and transfer agent are relevant
1 1 [TA]p
= + CM + C TA
xn̅ (xn̅ )0EP [M]p (17)
First we will assume that a transfer agent is not present, so only
chain transfer to monomer needs to be considered. Transfer
constants for chain transfer to monomer are quite small for most
monomers (CM is typically in the range 10−4−10−5) and, in
pubs.acs.org/Biomac Review
homogeneous free-radical polymerizations, it often causes only a
relatively small reduction in x̅n compared to (x̅n)0. However, the
radical within a particle is often dominated by chain transfer to
monomer, especially for monomers with high values of kp (such
as acrylates and vinyl acetate). Under these circumstances x̅n →
(CM)−1 and so still remains relatively high (104−105). Hence, in
accord with eq 17, transfer agents often are used at low levels in
emulsion polymerizations to reduce (“control”) x̅n to values
more appropriate to the end application.
Chain transfer to monomer has another very significant effect:
it produces a small, highly mobile, monomeric radical that has
sufficient water solubility to exit the particle. Exit of a monomer
radical brings a noncharged radical species into the aqueous
phase that will not become surface active, just less miscible with
water as it grows until terminating or entering another particle.
Chain transfer to transfer agent within a particle also produces a
small radical of higher mobility than can desorb, though such
radicals are normally much more hydrophobic than a
monomeric radical and so have less tendency to exit (e.g.,
isomers of dodecylthiol are widely used as transfer agents and
give a C12H25S• sulfenyl radical on chain transfer). Finally, there
is a finite probability that, soon after entry, an oligomeric radical
may exit a particle and continue propagating in the aqueous
phase before it enters another particle. Although there are
several possibilities for radical exit, chain transfer to monomer
and exit of the resulting monomer radical is considered to be the
predominant mechanism by which radicals exit particles.
3.3.3. Smith−Ewart Case 1. Smith−Ewart Case 1 is the most
general condition for a zero−one system, which is n̅ ≪ 1. This
was defined because they had the vision to realize that radicals
may exit from a particle and that for Case 1 the rate of radical exit
f rom a particle is much greater than the rate of radical entry into a
particle, which in turn is much greater than the rate of radical
termination in a particle. Under such conditions, at any given
instant, most particles will contain no radicals, some will contain
one radical, and extremely few will contain two or more radicals.
Many emulsion polymerizations are found to proceed under
Case 1 conditions with n̅ < 0.5. This is common: (i) when (x̅n)EP 0
is high (which is normal) and/or CM is high (e.g., allylic
monomers) because chain transfer to monomer is more
prevalent; (ii) when the particles are small (e.g., d < 150 nm)
because this increases the rate of exit; and (iii) when the radical
flux is low (e.g., at low [I]0 and lower reaction temperatures)
because ρen is lower. Theoretical prediction of n̅ for Case 1
conditions is complex and requires solution of the equation
dn ̅
= ρen − ρex
(18)
where ρex is the total rate of radical exit taking into account the
fate of exited radicals. A reliable equation for prediction of ρen
came from the work of Gilbert’s group in what often is referred
to as “Maxwell−Morrison” theory,17 the basis of which is that
surface active z-mer radicals enter (see section 3.2.1); this was a
very important step forward. Several equations for prediction of
ρex have been presented depending on the assumptions about
the fate of exited radicals (e.g., termination in the aqueous phase
or “re-entry” into another particle or multiple exits and re-
entries). The most up-to-date rationale for such treatments has
been presented by Gilbert et al.19,40 One important point to note
is that these theoretical treatments lead to a dependence of n̅
(and hence Rp) on [I]0 as well as several other parameters.
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Biomacromolecules
3.3.4. Smith−Ewart Case 2. Smith−Ewart Case 2 is the most
widely referenced of the three cases because it leads to a simple
prediction that n̅ = 0.5. This is a special case of zero−one
conditions and, in comparison to Case 1 conditions, the only
difference is the assumption that radical desorption is negligible.
Thus, the conditions for Case 2 are instantaneous termination on
entry of a second radical into a particle and a complete absence of
radical exit.
Smith and Ewart carried out a rigorous mathematical analysis
of population balances for Ni over all values of i, leading to
mathematical proof that, under Case 2 conditions, n̅ = 0.5.
However, this is easy to deduce simply by considering an
“average” particle, which will see radical entry events at exactly
equal intervals of te̅ n. Consider a point in time when a radical
enters this average particle, assuming that it does not already
contain a chain radical. Thus, the radical entry event will
instantly initiate a chain radical that will propagate within the
particle for a period of time te̅ n until the next radical enters and
instantly terminates propagation. The average particle now
contains zero radicals again and remains dormant for another
period te̅ n until the next radical entry event initiates a new chain
radical, which will propagate for a period te̅ n until it is terminated
by the next radical entering. Hence, the average particle contains
zero radicals for half the time and one radical for the other half,
from which it is clear that the value of n̅ is 0.5. Another
consequence of the conditions for Case 2 is that n̅ = 0.5
independent of ρen and Nc and that doubling the value of ρen
simply has the effect of doubling the frequency at which the
average particle switches from containing zero to one radical, so
it has no effect on Rp, only on (x̅)EP 0 (which will halve). Under
Case 2 conditions, with n̅ = 0.5, eq 14 takes its most familiar
form.
In the early days of emulsion polymerization, Smith−Ewart
Case 2 was highly celebrated because application of eq 14 to
experimental data gave n̅ values close to 0.5. However, this has
since been shown to have arisen because values of kp available at
that time were inaccurate and when correct values of kp are used,
n̅ only rarely is found to be 0.5, even for styrene emulsion
polymerizations, which had been considered for many years the
classic example of Case 2 kinetics.19 Very high radical fluxes (i.e.,
high values of [I]0 and higher reaction temperatures) will move
an emulsion polymerization toward Case 2 kinetics because
(x̅)EP
0 is reduced, making chain transfer to monomer and exit less
likely. Similarly, monomers (such as styrene) for which kp is
relatively small and CtrM is small will have lower values for (x̅)EP 0
and tend toward Case 2 behavior.
3.3.5. Smith−Ewart Case 3. Smith−Ewart Case 3 corre-
sponds to n̅ > 1. The conditions for Case 3 set out by Smith and
Ewart were that the rate of radical entry is much greater than the
rate of termination, with the presumption that particles are large
enough to accommodate more than one simultaneously propagating
chain radical.
Clearly, Case 3 is more likely to occur in large particles from
which radical exit is less likely. As n̅ increases beyond unity, the
effects of radical segregation are lost and the kinetics eventually
become those for bulk polymerization because termination
becomes rate-controlling instead of radical entry. A better
approach to analyzing Case 3 conditions is described in section
3.3.7.
3.3.6. Alternative Analysis of Particle Growth Conditions. A
theoretical method for probing scenarios during particle growth
was developed by Ugelstad et al.16,55 and makes use of several
parameters together with calculation of n̅ using O’Toole’s
pubs.acs.org/Biomac Review
solution56 of the Smith−Ewart population balance equations.
The analysis has physical inconsistencies but was useful in
reaffirming the Smith−Ewart criteria and providing a
quantitative framework for evaluating some features of emulsion
polymerization that are intuitive and borne out in practice. (i)
Case 1 conditions occur when radical exit is significant, and
more insightfully, under these conditions, increasing the rate of
radical formation in the aqueous phase moves the kinetics
toward Case 2. (ii) Case 2 conditions are possible only when
radical exit is completely absent and the rate of formation of
radicals in the aqueous phase per particle is below the rate of loss
of radicals through bimolecular termination in the particles. (iii)
Case 3 conditions become possible whenever the rate of
formation of radicals in the aqueous phase per particle is above
the rate of loss of radicals through bimolecular termination in the
particles, and the ratio of those rates required to cause a switch
from Case 1 to Case 3 kinetics gets larger as the extent of radical
exit increases.
3.3.7. Zero−One and Pseudobulk Categorization of
Particle Growth Kinetics. Gilbert et al.15,19,40 have shown that
Smith−Ewart Case 3 conditions are part of a more general case
of pseudobulk conditions under which the compartmentalization
of radicals into particles has no effect on the kinetics.
In addition to n̅ > 1, pseudobulk behavior will also occur if
multiple radical exit and re-entry events proceed on a time scale
much shorter than that for bimolecular termination in a particle,
conditions under which n̅ may be very small (e.g., <0.5 and often
≪0.5). In this case, the effects of compartmentalization are lost
because radicals rapidly exchange between particles, so in terms
of kinetics, it is as if the aqueous phase is not there. The kinetics
are then the same as for n̅ > 1. In all cases of pseudobulk
conditions, the value of n̅ is controlled by the usual processes of
radical entry, radical exit, and bimolecular radical termination in
the particles, but this time with the possibility for n̅ to be large.
Under pseudobulk conditions, the value of n̅ is obtained from
solutions to the equation
ij k yz
= ρen − kex n ̅ − 2jjjj t zzzzn ̅ 2
j NAVp z
dn ̅
k {
dt (19)
where kex is the rate coefficient for radical exit and Vp is the
particle volume. The analysis must take into account the effect of
re-entry on kex and diffusion control of bimolecular termination
on kt.
A broader division of particle growth into categories is,
therefore, to use the designations zero−one (which embraces
Smith−Ewart Cases 1 and 2) and pseudobulk (which includes
Smith−Ewart Case 3 as well as the rapid radical exit and re-entry
scenario). Some emulsion polymerizations fall between these
categories and exact analytical solutions for calculation of n̅ are
only possible in the intermediate situation where a particle can
contain either zero, one, or two radicals because two radicals can
exist within a particle, but instant bimolecular termination
occurs when a third radical enters (i.e., 0.5 < n̅ < 1), which is
referred to as zero−one−two conditions. Only under zero-one and
zero-one-two conditions are effects of radical compartmental-
ization observed.
Westmoreland et al.57−61 have performed real-time electron
spin resonance spectroscopy (ESR) of emulsion polymer-
izations, which facilitates measurement of n̅, and revealed that,
for particles with diameters above about 100 nm, n̅ can take very
high values (≫100 and often ≫1000) when [M]p is low, such as
in Interval III or during a starved semibatch emulsion
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polymerization (see section 3.5.2). Even very small particles
with a diameter of 50 nm, which would be expected to show low
values of n̅ due to increased radical exit, were shown to have n̅ in
the range 0.2−0.8 in a starved semibatch process when [M]p is
low. These results indicate that pseudobulk kinetics operate for a
significant proportion of the monomer conversion in most
emulsion polymerizations.
3.4. Interval III: Particle Growth in the Absence of
Monomer Droplets. Interval III begins when the monomer
droplets are just completely depleted by supplying monomer to
the growing polymer particles, i.e., from the point at which
monomer droplets just completely disappear. This typically
corresponds to overall conversions of around 40% in batch
emulsion polymerizations in which, therefore, the majority of
polymer is formed during Interval III.
During Interval III, most of the remaining monomer will
reside within the particles, with a small amount dissolved
molecularly in the aqueous phase. Thus, the particles remain the
principal loci of polymerization and, as conversion increases,
[M]p reduces continuously which, from eq 14, might be
expected to produce a proportionate reduction in Rp, ultimately
to zero when all the monomer is polymerized. However, as
discussed in the previous section, it is common for n̅ to increase
during Interval III as the particle volume increases, compensat-
ing somewhat for the reduction in [M]p, and zero−one and
zero−one−two systems are likely to switch to pseudobulk
conditions at some point, which completely changes the
kinetics. Additionally, chain transfer to polymer becomes more
probable (see section 3.6.1) and effects arising from diffusion
control of propagation and termination in particles can become
highly significant for both Rp and x̅n, as discussed in the following
section. Hence, the kinetics of polymerization during Interval III
are complex.
3.4.1. Effects Arising from Diffusion Control of Propaga-
tion and Termination. The effects of diffusion control on
termination will be considered first. As [M]p reduces during
Interval III, the internal viscosity of the particles increases and,
eventually, may become so high that the termination rate
coefficient, kt, becomes controlled by translational diffusion of
long chain radicals, which is very low in media of high viscosity.
This causes an abrupt, massive reduction in kt and a dramatic
increase in the radical concentration, the consequence of which
is a large increase in Rp and (x̅n)0 for homogeneous free-radical
polymerizations, an effect termed autoacceleration, as discussed
in section 2.1. In emulsion polymerizations, the massive
reduction in kt will change the entry−exit−termination balance
toward higher values of n̅ and pseudobulk kinetics (if the
reaction is not already under those conditions) with consequent
increases in Rp and (x̅n)EP 0 . Thus, autoacceleration often is
observed during Interval III of emulsion polymerizations,
though this is dependent on the monomer: homopolymeriza-
tions of acrylates are particularly susceptible and may even show
evidence of autoacceleration in Interval II; autoacceleration for
methacrylates is substantial, but less than for acrylates, and for
styrene the effect is much smaller. These differences between
monomer classes arise from differences in kp and x̅nthe higher
they are, the more likely is autoacceleration. The effects of
diffusion control of bimolecular termination are accounted for
by Gilbert et al.19,40 in treatment of pseudobulk kinetics.
When the reaction temperature is well below the glass
transition temperature (Tg)4 of the polymer being formed (e.g.,
methyl methacrylate and styrene have homopolymer Tg values
of 105 and 100 °C, respectively), the particle will vitrify (i.e.,
4412
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become glass-like) at very high conversions. If this happens, then
not only are chain radicals immobilized, but diffusion of
monomer to them also becomes much slower and propagation
becomes diffusion controlled, which causes kp to reduce by 1−2
orders of magnitude;62 this sometimes is referred to as the glass
ef fect.
3.5. Emulsion Polymerization Processes. The properties
of polymers prepared by emulsion polymerization are greatly
affected by the process employed, even for the same overall
reaction formulation. In this section, the main factors of
importance are described for each of the three types of process
used. As for all polymerizations, regardless of process, the
reaction must be run under an inert atmosphere because oxygen
can inhibit or retard polymerization and may become
incorporated into the polymer structure as peroxide links. The
reacting mixture must be stirred for the full period of the
polymerization using an appropriate agitator design and speed,
so that good heat removal and good mixing are achieved without
generating too high a shear rate (see section 3.10). As a general
rule, for commercial-scale reactors, an axial flow airfoil impeller
gives low energy consumption and low shear for fluids having
viscosities in the range of most emulsion polymerizations. Radial
flow impellers are often used in emulsion polymerizations at the
laboratory scale, and anchor-type impellers are best for very high
viscosity fluids.
3.5.1. Batch Emulsion Polymerization. This is the simplest
process and involves addition of all reactants to the reactor at the
outset. Usually, the monomer emulsion is prepared and heated
to reaction temperature first. A solution of initiator in monomer
is then added to start the polymerization. Formulations may
include a seed latex in order to eliminate nucleation and get
more reproducible control of particle diameter.
Many academic studies use batch processes, but its industrial
use is limited primarily to synthetic rubber production where
chain transfer to polymer must be suppressed (to suppress
branching and cross-linking) by keeping the monomer
concentration as high as possible. Rates of polymerization can
be very high, making it difficult to remove the heat of
polymerization. Additionally, there is no control of composition
drift in emulsion copolymerizations (see Section 3.9).
3.5.2. Semibatch Emulsion Polymerization. In a semibatch
process, some of the reactants are added to the reactor at the
start and the remainder are fed in a controlled way. Such
processes are highly versatile and are the most widely used of the
three processes. Most commonly, a portion of the water,
initiator, and surfactant and 5−10% of the total monomer are
present in the reactor at the start and allowed to react for a
period of time (often referred to as a “seed” stage) before
metering in the remaining monomer at a controlled rate.
Monomer may be fed to the reactor either directly or as an
emulsion in water (referred to as a “pre-emulsion”), so-called
monomer feed or emulsion feed strategies, the latter being favored
by industry (even though it gives less control) because it tends to
achieve better mixing of the feed into the reaction mixture.
Further quantities of aqueous initiator solution are added,
usually in “shots” at particular times during the reactionfor
reasons of safety, initiator should never be included as part of the
aqueous phase in a pre-emulsion. Since water and surfactant are
essential components of a pre-emulsion, care must be taken in
emulsion feed reactions to allow for the effects this has on
aqueous phase surfactant concentration and on the final latex
polymer content. With monomer-fed reactions, if desired,
additional surfactant can be fed to the reactor as an aqueous
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solution (or even dissolved in the monomer feed when
surfactant and monomer are miscible). For control of final
particle diameter it is necessary to ensure that the additional
surfactant is just sufficient to maintain colloidal stability, but low
enough to prevent formation of new particles, i.e., secondary
nucleation, in which case keeping the aqueous phase surfactant
concentration below the CMC is important since that eliminates
one mode of nucleation.
A very important consideration in semibatch processes is the
rate (RM) at which monomer is fed to the reactor (either directly
or in a pre-emulsion), for which there are two broad scenarios in
relation to the maximum rate of polymerization ({Rp}max) which
is the value of Rp for the reaction when [M]p has its equilibrium
value.
RM > {Rp}max Flooded conditions: monomer is fed to the reactor
faster than it can polymerize and excess monomer builds up to
the point where monomer droplets are formed. The reaction
proceeds much as in a batch process and [M]p has its
equilibrium value.
RM < {Rp}max Starved conditions: monomer is fed to the reactor
slower than it can polymerize and [M]p is well below its
equilibrium value. Instantaneous conversions are very high (the
monomer is consumed rapidly as it enters the reactor) and Rp =
ϕpRM.14,63
Semibatch processes are routinely operated under starved
conditions because it is only then that the full benefits of
monomer feeding can be realized. Although ϕp (and the extent
of starving) is dependent on RM, under these conditions ϕp
typically is at least 0.8, and more usually >0.9, and the period of
monomer feeding is typically 2−4 h. Hence, under starved
conditions, Rp (and the rate of heat removal required) are
controlled by RM. The reaction is effectively in Interval III
throughout the period of monomer feeding, so values of n̅ can be
very high. In their real-time ESR studies of starved emulsion
polymerizations, Westmoreland et al.57,58 showed that there is a
strong dependence of n̅ on particle diameter, with values of n̅ in
the range 0.2−0.8 when dz = 50 nm and 240−29,860 for dz = 500
nm (where dz is the “z-average” particle diameter; see section
3.7). The high value of ϕp also promotes chain transfer to
polymer with significant consequences for the final polymer
molecular weight distribution (MWD) and skeletal structure
(i.e., branching and possibly cross-linking), especially for
polymerizations of monomers such as acrylates and vinyl esters
(see section 3.6.1).
The importance of starved, semibatch emulsion polymer-
ization cannot be overemphasized. In addition to facilitating
simple control of Rp and reactor cooling rate, it also provides
opportunities for elimination of copolymer composition drift
(see section 3.9) and for good control of particle morphology by
feeding different monomer mixtures in succession (see section
6).
3.5.3. Continuous Emulsion Polymerization. In a continu-
ous process, formulation components are fed continuously into
a reactor system from which the product latex is continuously
removed. Such processes are most suited to production of a
single latex in very large volume, though they also have been
used in academic studies of mechanism and kinetics. The
process should operate under steady-state so that it produces
latex of consistent quality. However, oscillations (e.g., of
conversion, particle diameter, etc.) at start-up often are an
issue and can persist for a long time before they disappear. These
often are due to oscillations in aqueous phase surfactant
concentration and nucleation, in which case they can be
pubs.acs.org/Biomac Review
eliminated by using a seed latex as one of the formulation
components.
Emulsion polymerizations can be carried out using many
types of continuous reactor, including a single continuous
stirred-tank reactor (CSTR), multiple CSTRs in series, single-
pass tubular reactors, and multiple-pass tubular reactors (i.e.,
loop reactors). Parameters such as [M]p, Rp, polymer molecular
weight, conversion, copolymer composition, and particle
diameter can be controlled, but PSD and MWD usually are
much broader than for latexes produced by batch and semibatch
processes because of the statistical distribution of reactor
residence times, e.g., one particle may be in the reactor for only a
short time, whereas another may be present for a long time
before leaving. As for batch and semibatch processes, values of n̅
will depend on particle diameter and the polymerization
conditions. CSTR trains consisting of 5 to 15 CSTRs in series
are often used in the emulsion-polymerized rubber facilities.
Some water-based coating polymers are made in loop reactors.
Most other emulsion polymer products are manufactured in
semibatch reactors.64−66
3.6. Effects of Chain Transfer to Polymer. Chain transfer
to polymer leads to branching (and possibly cross-linking) in the
polymer produced and usually is more significant in emulsion
polymerizations than in homogeneous free-radical polymer-
izations. Also, water-soluble polymers are included in for-
mulations for some emulsion polymerizations and can become
grafted to the particles through chain transfer to polymer
reactions. The underlying principles for branching and grafting
are the same and are discussed in the following sections.
3.6.1. Branching and Cross-linking due to Chain Transfer
to Polymer. The mechanisms of chain transfer to polymer were
first established in detail for preparation of low-density
polyethylene (LDPE) by free-radical polymerization at high
temperature, which revealed that the reaction can proceed both
intramolecularly and intermolecularly, as shown schematically in
Figure 6. (Although the typical levels of 3−6 mol % branched
Figure 6. Schematic mechanism of intramolecular and intermolecular
chain transfer to polymer. Propagating chains are red and dead chains
are black. The inset shows the six-membered ring conformation at the
end of the chain radical during intramolecular chain transfer to polymer,
which produces a short branch. Dashed lines for arrows indicate
multiple processes of the same kind.
repeat units in LDPE may not seem high, it actually is very high
in terms of effects on the properties of LDPE4,67 because 1 in
every 17−33 repeat units is branchedLDPE is considered to
be one the most highly branched polymers.)
The intramolecular reaction is most prevalent and typically
proceeds via a 6-membered ring transition state to produce
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Scheme 3. Mechanism of Chain Transfer to Polymer in Acrylate Polymerizationsa

a
Note that although the intermolecular reaction is shown, intramolecular reaction proceeds via the same chemistry, but via a 6-membered ring
transition state at the chain end. Dashed lines for arrows indicate multiple processes of the same kind.

Scheme 4. Mechanisms of Chain Transfer to Polymer in Vinyl Ester Polymerizations (Mechanism (b) Is Dominant)a

a
Note that although the intermolecular reactions are shown, intramolecular reaction proceeds via the same chemistry, but via small ring (5−7
membered) transition states at the chain end. Dashed lines for arrows indicate multiple processes of the same kind.

short-chain branches (typically 4 carbon atoms long), which
disrupt the local polymer chain conformations and have greatest
significance for properties of polymers that crystallize (e.g.,
polyethylene and emulsion copolymers of ethylene with vinyl
acetate) because the short-chain branches disrupt crystallization.
Molecular weight averages (number-, weight-, and z-averages)
are little affected by the intramolecular processes because the
number of chains does not alter and the same chain continues to
propagate much as before. Although intermolecular chain
transfer to polymer is less frequent, it becomes more likely as
conversion increases (i.e., when the polymer concentration is
high, such as in latex particles during emulsion polymerization)
and produces long-chain branches that have a very large effect on
polymer relaxation behavior and so on the physical properties of
amorphous polymers above Tg. In this case, the number of
chains again does not change (so number-average molecular
weight remains largely unaffected), but the originally propagat-
ing chain is killed earlier than normal and the originally dead
chain is reactivated into propagation at the site of H atom
abstraction. This leads to broadening of the MWD and higher
values of weight- and z-average molecular weights. Also, if
termination by combination is dominant, propagating long-
chain branches can couple and thereby create cross-links, again
4414
with major consequences for polymer properties. Hence, with
the exception of crystallizable polymers, the consequences of
intermolecular chain transfer to polymer are much greater in
terms of effects on polymer properties (especially for emulsion
polymers based on acrylates or vinyl esters).
Chain transfer to polymer is negligible in methacrylate
polymerizations due to the lack of an easily abstractable H atom
on the polymer chain. However, in acrylate polymerizations
chain transfer to polymer is significant68−72 and proceeds via
abstraction of H atoms from tertiary C−H bonds at the
substituted backbone carbon atoms, as shown in Scheme 3.
Since steric restrictions on reaction are strong for radicals, the
driving force for chain transfer to polymer is that the product
radical is tertiary and more stable than the normal secondary
propagating radical (both radicals are stabilized by resonance
with the ester CO group). Branching is extensive for acrylates,
typically giving 2−8 mol % branched repeat units (depending, in
part, on the R group), and if acrylate homopolymerizations are
carried out to high conversions, then a high proportion of the
polymer produced will be cross-linked (termed “gel”) due to
termination by coupling of long-chain branches, as depicted in
Figure 6. Acrylates are the main monomer type used in synthesis
of pressure-sensitive adhesive polymers, the properties of which
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Scheme 5. Mechanism Responsible for Synergism in Chain Transfer to Polymer for Vinyl Ester−Acrylate Copolymerizationsa
a
Dashed lines for arrows indicate multiple processes of the same kind.
are very dependent on control of the extent of chain transfer to
polymer.
Scheme 4 shows the two possible mechanisms of chain
transfer to polymer in vinyl ester polymerizations. H-abstraction
from the carbon atom attached to the ester CO group is
dominant to the virtual exclusion of H-abstraction from the
backbone tertiary C−H bond.73,74 Neither the normal
secondary propagating radical nor the tertiary product radical
from backbone H-abstraction is stabilized by resonance (other
than the usual hyperconjugation with H atoms in the preceding
main-chain CH2), but the product radical from side-group H-
abstraction is stabilized by resonance with the ester CO
group, which is the reason why pathway (b) is dominant (even
for vinyl acetate where the product radical from pathway (b) is
primary). Only under starved conditions in emulsion polymer-
ization has pathway (b) been observed,73,74 but even then it was
only to a small extent. For similar temperatures and polymer-
ization conversion profiles, vinyl acetate gives lower levels of
branching (typically 0.2−1 mol % branched repeat units) than
observed for acrylates.
Synergistic effects are observed in copolymerizations. For
example, copolymerization of vinyl acetate with a few mol % of
n-butyl acrylate gives rise to a big increase in branching
compared to homopolymerization of either monomer.75−77 The
reason for this is that the poly(vinyl acetate) chain radical is
highly reactive (i.e., of low stability) and acrylate repeat units
provide labile tertiary C−H bonds for H-abstraction. The
chemistry is shown in Scheme 5 more generally for
copolymerization of a vinyl ester with an acrylate. The converse
also is true, i.e., monomers that give polymeric radicals of high
stability (styrene or methacrylates) will reduce the extent of
branching if included at low levels in an acrylate polymer-
ization.77
In order to understand the principles of how to control the
extent of chain transfer to polymer, it is necessary to examine the
kinetics. Assuming that (i) each chain transfer to polymer H-
abstraction reaction produces a branch (i.e., that monomer
always adds to the product radical), (ii) each propagation event
produces a repeat unit, (iii) the rate coefficient for propagation
from the product radical is smaller than that for the normal
propagating chain radical (known from measurements of kp by
pulsed-laser polymerization54), and (iv) the concentration of
product radicals is much smaller than the concentration of
normal propagating radicals, then it can be shown that the total
mole fraction of branches (f br) is given by
ji k intra zy 1 ji k inter zy [Pr − H]local
fbr = jjjj trP zzzz + jjjj trP zzzz
j k p z [M]local j k p z [M]local
k { k {
(20)
where kintra inter
trP and ktrP are the rate coefficients for intramolecular
and intermolecular chain transfer to polymer, respectively, and
pubs.acs.org/Biomac Review
[M]local and [Pr−H]local are the concentrations of monomer and
abstractable polymer C−H bond, respectively, specifically in the
vicinity of the chain transfer to polymer reaction. The first term
accounts for the intramolecular reaction and the second for
intermolecular reaction. Equation 20 gives helpful direction in
terms of controlling chain transfer to polymer. The rate
coefficient ratios will become smaller as temperature is
decreased because chain transfer to polymer has a higher
activation energy than propagation, e.g. chain transfer to
polymer in acrylate polymerizations is negligible at 0 °C
(which requires redox initiation) and increases progressively to
levels of 2−8 mol % at temperatures of 70−80 °C. The
intramolecular reaction depends on the reciprocal of [M]local and
so is most prevalent when [M]local is small, e.g. in the aqueous
phase of an emulsion polymerization or at high instantaneous
conversions within latex particles. In comparison, the
intermolecular reaction depends on [Pr−H]local/[M]local and
so is strongly promoted at high instantaneous conversions, such
as under starved conditions in a semibatch emulsion polymer-
ization (see section 3.5.2). For these reasons, semibatch
emulsion polymerizations tend to give polymers with higher
levels of branching. As conversion increases toward completion,
both terms will become infinite, but infinite levels of branching
are not observed in practice. Equation 20 fails at very high
conversions because assumption (i) does not hold at very high
conversionsat very low [M]local the product radical is likely to
abstract a H atom from an adjacent chain before it adds
monomer and so the product radical can “hop around” between
chains before it eventually reacts with monomer to create a
branch.
3.6.2. Grafting of Water-Soluble Polymers (WSPs) by Chain
Transfer to Polymer. Emulsion polymerizations designed to
produce latexes for coating applications often include WSPs to
aid colloidal stability (they are then called “protective colloids”, a
poor term but one that is well established) and to assist in
control of latex rheology (see section 7). The WSPs typically are
poly(vinyl alcohol) for latexes used in adhesive applications and
hydroxyethylcellulose for latexes used in paints. The principles
of grafting WSPs to particle surfaces will be discussed generally
first and then exemplified by considering the specific chemistry
for poly(vinyl alcohol) and polysaccharides.
The mechanisms by which WSPs become grafted to the
surface of particles are akin to those described in the previous
section for branching and involve chain transfer to the WSP, as
shown schematically in Figure 7. The first step is H-abstraction
from the WSP in the aqueous phase by either an initiator radical
(usually the sulfate radical-anion) or an oligomeric radical.
Monomer then adds to the product radical, beginning growth of
the graft chain, which propagates until the graft polymer
becomes surface active. The propagating graft polymer may
enter a micelle (thus creating a new particle) or an already-
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Figure 7. Schematic mechanism of grafting of WSPs. The WSP chain is
blue, propagating chains are red, dead chains are black, and monomer
within particles is green. Dashed lines for arrows indicate multiple
processes of the same kind.
existing particle (a radical entry event) or may grow to the point
at which the growing graft chain becomes just too long for
solubility and phase separates to form a primary particle. In each
case, there is a chemical bond linking the original WSP to the
particle surface. Ultimately the particles are covered in attached
WSP chains that radiate out into the aqueous phase; the particles
are referred to as having a “hairy layer”.
Poly(vinyl alcohol) (PVOH) is produced by partial hydrolysis
of poly(vinyl acetate) under conditions that leave a “blocky”
structure (i.e., the residual vinyl acetate repeat units are in
clusters of a few repeat units in sequence) so that they give
stronger adsorption to hydrophobic surfaces; typically, PVOH
with about 18% residual vinyl acetate repeat units is used in
emulsion polymerizations. The mechanisms of grafting in
emulsion polymerizations of vinyl acetate with PVOH are
shown in Scheme 6. Although only present at relatively low
levels, the methyl ester C−H bonds are a major site for grafting,
in part because of the 3× amplification factor of having three
labile C−H bonds per repeat unit, but mostly because of
resonance stabilization of the product radical by the ester CO
group.78 Grafting of PVOH in emulsion polymerization has
been investigated thoroughly.78−81
Grades of hydroxyethylcellulose (HEC) used in emulsion
polymerizations are prepared by ethoxylation of cellulose to give
1.8−3.5 ethylene oxide units per anhydroglucose unit and
degrees of substitution of 0.8−1.8. A series of papers by
Scheme 6. Mechanisms of Grafting of Poly(vinyl alcohol) in Emulsion Polymerizations of Vinyl Acetatea
a
Dashed lines for arrows indicate multiple processes of the same kind.
pubs.acs.org/Biomac Review
Craig82−89 showed convincingly that (directly opposite to
previous popular belief) grafting of HEC is significant with
acrylates and negligible with vinyl acetate. Unlike for PVOH,
degradation of HEC was evident in the absence of monomer
when using persulfate or other peroxy initiators. The
mechanisms put forward by Craig are shown in Scheme 7(a)
but set out in more general terms because the chemistry is
common to all polysaccharides. Propagation from the product
radical for both acrylates and vinyl acetate requires formation of
a less stable secondary radical from the tertiary product radical,
but for acrylates this is more than compensated by resonance
with the acrylate CO group. Although Craig focused on H-
abstraction from the bridge link C atoms, it is easy to show that
grafting and degradation can also proceed via H-abstraction
from any of the ring C atoms, as shown in Scheme 7(b).
Degradation of polysaccharides yields a chain end with a CO
bond and so can be monitored by measuring the reduction in
molecular weight and by appearance of the CO bond (e.g.,
using UV spectroscopy).90 The amount of H-abstraction from
polysaccharide rings reduces significantly if azo initiators are
used, most likely because they give resonance-stabilized tertiary
free radicals.91 Degradation is rapid under normal conditions of
emulsion polymerization with peroxide initiators but is greatly
reduced in the presence of monomer; that is, grafting is much
faster than ß-scission and tends to dominate until the monomer
concentration becomes very low. Thus, it is possible to graft a
high proportion of the polysaccharide chains to particles during
polymerization, but at high conversion when there is very little
monomer present, the grafted polysaccharide chains will then be
degraded and the particles effectively receive a “hair cut”. This
competition between grafting and degradation must be
considered whenever using polysaccharides in emulsion
polymerizations with peroxide initiators.
The kinetics of grafting can be considered in the same way as
for branching. Assuming that (i) each chain transfer to WSP H-
abstraction reaction produces a graft (i.e., that monomer always
adds to the product radical and degradation is absent) and (ii)
each propagation event produces a repeat unit, the ratio of
ij k yz [WSPr‐H]
grafting to propagation frequency (Kgr) is given by
K gr = jjjj trWSP zzzz
j k p z [M]local
k {
local
(21)
where ktrWSP is the rate coefficient for chain transfer to the WSP
and [M]local and [WSPr-H]local are the concentrations of
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Scheme 7. Mechanism of Grafting and Degradation of Polysaccharides in Acrylate and Vinyl Ester Polymerizations Using
Persulfate as Initiatora

a
Dashed lines for arrows indicate multiple processes of the same kind.

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Biomacromolecules
monomer and abstractable WSP C−H bond, respectively,
specif ically in the vicinity of the chain transfer reaction. As for
branching, the rate coefficient ratio will become smaller as
temperature is decreased and so grafting will be reduced by
lowering the reaction temperature. For chain transfer to WSP in
the aqueous phase away from particle surfaces, [WSPr-H]local/
[M]local will be relatively high in most cases because many
monomers have low solubilities in water. (Note, however, that
some monomers do have relatively high water solubilities, e.g.,
vinyl acetate, see Table 2.) For chain transfer to WSP chains that
are grafted (or adsorbed) at the particle surface, [WSPr-H]local/
[M]local is more difficult to predict because it will depend on
surface coverage and effects of the WSP chain conformation at
the interface, though it is very likely that [M]local in the hairy
layer will be higher than in the aqueous phase well away from
particle surfaces. Again, semibatch emulsion polymerizations
operated under starved conditions will tend to give polymers
with higher levels of grafting because [M]local is low at all times
(see section 3.5.2).
3.7. Particle Size Distribution (PSD). Control of particle
diameter is achieved through control of particle nucleation and
growth, as discussed earlier. In this section we are concerned
with the PSD (strictly meaning particle diameter distribution)
and will begin by considering an emulsion polymerization in
which secondary nucleation and particle coagulation do not
occur during Intervals II and III. Under these conditions, all
particles created in Interval I simply grow throughout Intervals II
and III. Particles formed at the start of Interval I will grow for the
full period of Interval I, whereas those formed close to the end of
Interval I will have grown very little by the time nucleation ceases
and Interval II begins. This is the origin of the PSD, which will be
further broadened at the end of Interval I because the nucleated
particles will grow initially at an accelerating rate since [M]p
increases rapidly as particle diameter increases at small sizes (see
section 3.3.1). During Intervals II and III all particles will grow,
but that growth is in mass of polymer per unit time (i.e.,
proportional to volumetric growth rate) which means that a
particle’s diameter grows nonlinearly at an ever-decreasing rate
as the particle gets bigger. Additionally, although eq 6 informs us
that the total radical flux into a particle increases with particle
diameter, the efficiency of radical entry diminishes with particle
growth in accord with eq 7. Hence, for these various reasons, the
PSD is broadest at the end of Interval I and becomes narrower
during Intervals II and III. The breadth of the final PSD is
determined by the relative conversion ranges of Interval I and
Intervals II + III. Therefore, in order to produce latexes with very
narrow PSDs, Interval I must be complete at very low
conversions (<1%), which can be achieved by keeping [S]0
low, though this gives smaller values of Nc and larger particles.
Such conditions have been used very successfully to produce
standard polystyrene latexes with very narrow PSDs and well-
defined particle diameter for use in calibrating instruments for
measurement of particle diameter.
In semibatch emulsion polymerizations operated with
emulsion feeds, nucleation can continue through the feeding
period if the surfactant level in the monomer pre-emulsion is
high, resulting in latexes with small particle diameters and a very
broad particle size distribution. In a semibatch process, creation
of new particles part way through a reaction can be deliberately
triggered by adding a “shot” of surfactant in order to establish
conditions for particle nucleation; such strategies can be used to
achieve bimodal or multimodal PSDs. If secondary nucleation is
avoided by keeping Nc high (>1016 particles (L H2O)−1) and the
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free surfactant concentration low, use of small diameter seed
particles makes it possible to produce latexes with narrow PSDs
by batch or semibatch processes (as is evident from Table 3).
However, in continuous processes (other than single-pass
tubular reactors), the reactor residence time distribution causes
the PSD to be broader, even when seed latexes are used in the
feed.
It is important to note that methods of particle size
measurement are based on different measures of size and give
different particle diameter averages (see the definitions of
common average diameters given in Table 5). For example,
Table 5. Definitions of Common Particle Diameter Averages
Name Symbol Definitiona
number-average diameter d̅n ∑ Nidi
∑ Ni
weight-average diameter d̅w ∑ Nidi4
∑ Nidi3
z-average diameter d̅z ∑ Nidi7
∑ Nidi6
z-average reciprocal diameter (measured by PCS) 1 ∑ Nidi5
()d z ∑ Nidi6
harmonic z-average diameter (from PCS) d̅hz
1/ ( d1 )z
“z-average diameter” (reported by PCS) “d̅z”
jij ∑ Nidi zyz
= d̅hz
j ∑ Ni z
surface-average diameter d̅s 1/2
k {
2
jij ∑ Nidi zyz
j ∑ Ni z
volume-average diameter d̅v 1/3
k {
3
a
Ni is the number of particles of diameter di
photon correlation spectroscopy (PCS, a type of dynamic light
scattering, DLS) is an absolute method that is very popular, due
to its simplicity and relatively low cost, but gives the harmonic z-
average particle diameter (often incorrectly referred to simply as
the “z-average diameter”) which is heavily weighted to larger
particles, so is most useful when the PSD is narrow.92,93 The
hydrodynamic size is measured by PCS, which includes any
surface species, such as grafted WSP chains, or other molecules
that move with the particle (e.g., adsorbed layers plus ions and
water hydration sheaths). PCS instruments often interpolate the
full PSD curve, but these are based on assumptions about the
distribution and are not very reliable94,95 and a numerically
significant population of small particles may go completely
undetected. In contrast, transmission electron microscopy
(TEM) gives the dry particle diameter with any surface layers
collapsed and requires calibration, but if enough particles are
analyzed it can give a measure of the PSD from which any
average can be calculated. TEM of soft polymer particles,
however, can give major errors because the particles flatten into
“pancakes” during analysis unless the samples are either made
rigid by chemical treatment (e.g., with phosphotungstic acid) or
held at temperatures well below Tg both before and during
analysis. Also, some polymers (e.g., homopolymers of
methacrylates) degrade easily in the electron beam and will
shrink in size during the analysis. Another criticism of TEM is
that, even if a few thousand particles are measured, only a tiny
fraction of the population is being analyzed. High-speed
centrifugation, hydrodynamic chromatography, and field-flow
fractionation are able to give the full PSD of hydrodynamic size.
These methods are powerful and make it possible to detect small
populations of particles (especially important for detecting the
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presence of a small population of very small or very large
particles) and can resolve multiple peaks in the PSD. More
details of the merits and limitations of the various methods for
measurement of particle size and PSD can be found else-
where.13−15
3.8. Molecular Weight Distribution (MWD). Under
zero−one conditions with low values of n̅ (<0.1) as a
consequence of chain radical termination being dominated by
chain transfer to monomer, the instantaneous polymer MWD
will have the form of the most probable distribution (for which
M̅ w/M̅ n = 2, where M̅ w and M̅ n are the weight- and number-
average molecular weights, respectively) as for any polymer-
ization in which termination is by chain transfer to monomer.4,5
This also will be true, regardless of the value of n̅, if a transfer
agent is included and chain transfer to transfer agent dominates
termination of the chain radicals. Under pseudobulk conditions,
the instantaneous polymer MWD will also be the most probable
distribution unless termination is dominated by combination, in
which case the MWD will be narrower (M̅ w/M̅ n = 1.5).4,5
Smith−Ewart Case 2 conditions are special in that the
polymer MWD will then be closely linked to the PSD because it
will be determined by the variation in actual times between
radical entry events for each particle, which will be influenced by
particle diameter in accord with eq 6.
As discussed in section 3.6.1, chain transfer to polymer has no
significant effect on M̅ n. However, intermolecular chain transfer
to polymer increases M̅ w (and higher molecular weight averages)
and may also lead to formation of cross-linked polymer of
(theoretically) infinite molecular weight. Thus, intermolecular
chain transfer to polymer often has a major effect of broadening
the polymer MWD, which can be profound during the final 10%
of conversion.
In all cases, the predicted form of the MWD is for a given
instant in time and so polymer MWD will invariably become
broader as conversion increases, even in the absence of
intermolecular chain transfer to polymer. The integrated form
of the MWD can be found in ref 6.
3.9. Emulsion Copolymerization. Most emulsion poly-
merizations involve copolymerization of two or more mono-
mers, so it is essential to understand the differences in
comparison to homogeneous free-radical polymerizations. The
Copolymer Equation 4 was derived for polymerization in
homogeneous media (e.g., solution) but can be applied to
emulsion copolymerizations provided that local monomer
concentrations are used because each monomer will partition
differently between the aqueous and particle phases. For
example, if monomer A is significantly more water-soluble
than monomer B, the mole fractions of monomer in the aqueous
and particle phases will differ from the total mole fractions as
follows: f aqueous
A > f total
A > f particle
A and f aqueous
B < f total
B < f particle
B .
(The ratio of phase volumes is an increasingly important factor
in determining these values as the difference in monomer water
solubilities increases.) In a batch emulsion polymerization,
oligomeric radicals in the aqueous phase will have a higher
proportion of repeat units from monomer A, and the copolymer
formed in the particles will have a composition that is lower in
monomer A repeat units, than is predicted from f total A . The
deviations from predictions made using total mole fractions can
be enormous when using highly water-soluble monomers, such
as acrylic acid or acrylamide, which will be predominantly found
in the aqueous phase with only a small amount in the particles.
As the overall conversion increases there will also be
composition drift, which when combined with the effects of
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monomer partitioning, can have a major effect on the kinetics of
polymerization, the progress of the reaction, and the properties
of both the final polymer and latex when using a batch process.
For example, copolymers prepared by batch emulsion
copolymerization of monomers with large differences in
reactivity ratios often show evidence of macroscopic hetero-
geneity, such as the presence of two glass transitions because
copolymer formed early in the reaction is of a composition that
is not compatible with the copolymer formed late in the reaction,
which leads to their phase separation within the particles.96,97
Semibatch processes operated under flooded conditions
proceed much as in the equivalent batch process and show
effects of monomer partitioning and composition drift with
conversion. However, when operated under starved conditions, a
semibatch process produces copolymer of uniform composition that is
equal to the feed composition. By feeding a monomer mixture with
the desired copolymer composition under starved conditions,
for which little unreacted monomer exits in the reactor, a
pseudo-steady-state is achieved under which the copolymer
composition is equal to the feed composition (i.e., FA =
fA).14,15,96,97 Hence, unlike in batch or flooded semibatch
processes, particles of highly uniform composition can be
produced with only the small amount of copolymer formed early
in the reaction (when the pseudo-steady-state is being attained)
and late in the reaction (after complete addition of the feed)
being subject to composition drift. This is extremely significant
and another major advantage of starved semibatch processes,
which is why such processes are used extensively for commercial
production of latexes and in control of particle morphology (see
section 6). They also are simple to perform in practice, unlike
other strategies for achieving uniform copolymer composition
(such as adjustment of individual monomer feed rates using real-
time analysis-feedback loops or optimal monomer addition rate
profiling).
Continuous processes allow for control of copolymer
composition within the constraints of the conversion because
partitioning effects and composition drift will occur across the
range of conversion achieved in the reactor.
When a highly water-soluble monomer is included as a
comonomer, it is likely that water-soluble copolymer will be
formed in the aqueous phase, i.e., that termination of
propagating radicals may take place in the aqueous phase. The
efficiency of radical entry is reduced and there will be a buildup
of low molecular weight WSP in the aqueous phase. Control of
the extent to which this happens is important as it can have
serious consequences for colloidal stability because the WSP
chains can cause coagulation of the latex particles by depletion
effects (see section 3.1). Even if depletion effects are not serious,
the WSP will increase the aqueous phase viscosity and affect
latex rheology (see section 7). Monomers with carboxylic acid
groups (e.g., acrylic acid and methacrylic acid) are widely used at
low levels (e.g., 1−5 mol %) with the objective of increasing
colloidal stability of the final latex through postpolymerization
neutralization of the acid groups in copolymer chains located at
particle surfaces. During polymerization, it is imperative to
ensure the acid groups are in protonated form by controlling the
aqueous phase pH (ideally at pH ≤ 4, i.e., corresponding to the
acid group pKa) because at higher pH a significant proportion of
the acid groups will be ionized and the ionized monomer will be
present only in the aqueous phase, which accentuates the
problems associated with WSP formation.98 Conductometric
titrations of the latexes produced facilitate measurement of the
proportions of acid groups present (i) in the aqueous phase, (ii)
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near the particle surface, and (iii) buried in the particles.99 This
is very useful in assessing the effects of process variables and
comonomer composition. Starved semibatch processes enable
more of the acid monomer repeat units to be incorporated into
copolymer in the particles.98,99 When using acrylic acid,
regardless of the process employed, the majority of acid groups
are found near the particle surface with some in aqueous phase
copolymer. By comparison, methacrylic acid is more hydro-
phobic and has lower solubility in water, so it is much more
useful for incorporating acid groups more deeply into particles.99
(In this respect, it is notable that, in protonated form, unlike
poly(acrylic acid), which is very soluble in water, poly-
(methacrylic acid) has limited solubility in water.)
3.10. Colloidal Stability. The colloidal stability of
monomer emulsions depends on a number of factors. The first
is Ostwald ripening. This is a diffusional mechanism of instability
in which smaller droplets shrink while large droplets grow (via
diffusion across the aqueous phase) in order to reduce the
overall interfacial free energy of the system. If the monomer is
even slightly soluble in the continuous aqueous phase (and most
monomers are; see Table 2), monomer will, over time, diffuse
from the smaller monomer droplets into the larger ones. This
results in a lower interfacial area (and interfacial energy), since
the loss of interfacial area of the smaller droplets is larger than
the gain in interfacial area of the larger ones. The reduction in
interfacial energy is the driving force for Ostwald ripening. This
results ultimately in complete phase separation into a monomer
layer and an aqueous layer, which invariably will be the lower
layer because monomers typically have densities below that of
water. This is not often a problem for emulsion polymerization
where the monomer droplets are relatively large, and the
emulsion is stirred before and during polymerization. The
second mode of instability is Stokes Law separation in which,
driven by gravitational forces and the difference in densities
between the monomer droplets and the aqueous phase, the
monomer droplets float to the surface (cream) and form a
separate monomer layer. This too is not usually a problem in
emulsion polymerization because the monomer emulsion is
stirred. Hence, during emulsion polymerizations, the main issue
of concern is the colloidal stability of latex particles.
Although the latex particles could become colloidally unstable
by either of the modes described above, they are not normally a
contributing factor in particle stability. Much bigger influences
on colloidal stability come from effects of: (i) surface charge and
extent of the electrical double-layer of ions near the particle
surface; (ii) water-soluble copolymer; and (iii) the shear rate
imparted by the agitator in the reactor. The particles can
undergo flocculation and/or coagulation with each other (see
section 3.1). Flocculation is reversible with stirring and so is not
evident during polymerization, while coagulation is irreversible
and gives rise to deposits of polymer on the reactor surfaces, on
the stirrer blades, and in the form of large particle aggregates
dispersed in the latex (often referred to as “grit”). Coagulum
formation in commercial processes can be tolerated, but only at
very low levels and, even then, preferably as grit that can be
filtered from the product latex because down-time for reactor
cleaning is a major cost. For academic studies, small amounts of
coagulum (up to 1−2% of total polymer) are acceptable because
there is usually only a small effect on the target latex properties.
Coagulation can be reduced by use of an appropriate surfactant
and surfactant level, feeding surfactant during the polymer-
ization in order to maintain an adequate surface coverage on the
polymer particles. This may include ionic surfactants (to provide
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electrostatic stabilization) and/or nonionic surfactants (to
provide steric stabilization). Loss of colloidal stability can be
driven by excessive shear, i.e., by giving the particles enough
kinetic energy to overcome the energy barrier to coagulation.
Hence, although a high level of agitation (shear) might be used
for monomer emulsification, the rate of agitation during the
polymerization should be only high enough to facilitate good
mixing and heat transfer (removal of the heat of reaction) during
polymerization. Good mixing is essential for several reasons
besides ensuring uniform heat transfer. Aqueous initiator
solutions typically have a high enough salt concentration to
cause latex coagulation, so addition of initiator shots during
polymerization must be done with very good mixing to minimize
this. (In general, addition of salts is to be avoided (especially
multivalent ions) because electrostatic stabilization is very
susceptible to failure in their presence at low−moderate
concentrations.) Feeding monomer onto the surface of the
reacting mixture in a semibatch process is bad practice that in the
worst case scenario, will lead to pools of monomer at the surface
in which bulk polymerization is possible and results in large
amounts of coagulum. Hence, monomer is best fed directly into
the reacting mixture at a position low enough in the reactor that
the feed always is below the surface. In all cases, reactor feeds
should go to points in the reactor where there is the greatest
shear.
Bulk polymerization in monomer droplets is another factor
that can contribute to coagulum.100 As discussed in section
3.2.3, with the exception of miniemulsion polymerization, entry
of oligomeric radicals into monomer droplets is negligible in
terms of nucleation and polymerization kinetics. However, the
effect of this can be significant in terms of latex stability and the
formation of coagulum. Since some (and possibly all) droplets in
an emulsion are likely to absorb radicals during the course of the
reaction, those droplets cannot disappear completely but instead
shrink to a point where they have no excess monomer, relative to
the particles. The large particles formed in this way will have
poor colloidal stability and promote coagulation. This issue is
avoided by using a starved semibatch process because excess
monomer in the form of droplets is never present.
Significant research has gone into developing methods for
preventing migration of surfactants away from particle surfaces
and has embraced use of modified initiators, monomers and
transfer agents that carry surfactant groups as part of their
structure (termed inisurfs, surf mers, and transurfs, respec-
tively).101−105 In each case, the surfactant group becomes
chemically attached to the polymer during polymerization and
so cannot migrate, which not only improves colloidal stability
but also has the additional benefit of preventing surfactant
migration to the substrate interface and surface of films cast from
the latexes. Inisurfs and transurfs can only give surfactant groups
at chain ends, so are not as effective or versatile as surfmers,
which can be used to incorporate much higher, controlled
numbers of surfactant groups per chain. Hence, surfmers have
been most widely studied and used. In order to ensure control of
surfmer incorporation, starved semibatch processes are
preferred, though this can lead to some surfactant groups
being buried within the particle.
Where latex shear stability is important for the end application
(e.g., high-speed coating of paper), it is usual to add more
surfactant to the latex after polymerization is complete. The
broader subject of latex stability has been well-discussed by El-
Aasser and co-workers106,107 and more widely in textbooks.13−15
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Figure 8. Schematic diagram showing the mechanism of nucleation in miniemulsion polymerization: (a) shows the phases existing at the onset of
polymerization in which there is a complete absence of micelles and a low concentration of molecularly dissolved surfactant; and (b) shows the phases
existing part way through nucleation.
3.11. Detailed Theory and Mathematical Modeling.
Mathematical equations have been included in this paper where
they are directly useful and/or assist in understanding. All of the
equations relating to polymerization kinetics are instantaneous;
that is, they apply to a specific instant in time when
concentrations have specific values that, in many cases, are
transient and change during the polymerization. Integration of
the kinetics equations is nontrivial and usually requires
assumptions that some concentrations do not change
significantly. The equations resulting from such integrations
have been collated by Schork.6 In addition, readers interested in
learning about more complete theoretical treatments of
emulsion polymerization will find textbooks and reviews a
good starting point.14,15,19,40
Comprehensive mathematical modeling of an emulsion
polymerization process can be done but must include
population balances over PSD, polymer chain length distribu-
tion, distribution of radicals per particle, copolymer composition
distribution, and copolymer sequence distribution. Details of
such models also are beyond the scope of this review, but some
examples may be found in the literature.108−116
4. MINIEMULSION POLYMERIZATION
The mechanisms of conventional emulsion and miniemulsion
polymerizations, although related, are in some ways significantly
different. As discussed in section 3.2.4, particle nucleation in
conventional ab initio (unseeded) batch emulsion polymer-
izations can be irreproducible, which is the reason why emulsion
polymerizations are often seeded with polymer particles of
known size and concentration, prepared specifically for use as
seed particles. Miniemulsion polymerization provides a different
approach to control of particle nucleation. In an ideal
miniemulsion polymerization, the nucleation of one droplet
results in the formation of one particle of approximately equal
surface area, in which case nucleation of a particle by entry into a
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droplet has little effect on the competition for radicals. This is
not so with conventional emulsions since both homogeneous
and micellar nucleation result in a large shift in the surface area
from micelles to particles as the particles are created and grow.
Here we present an introduction to the important features and
benefits of miniemulsion polymerization. An in-depth dis-
cussion is given by Schork et al.117
4.1. Mechanism of Miniemulsion Polymerization.
Miniemulsion polymerization was first reported by Ugelstad,
Vanderhoff, and El-Aasser in 1973.118 It involves the use of an
effective surfactant/costabilizer system to produce very small
(0.08−0.30 μm) monomer droplets. The droplet interfacial area
in these systems is very large, and most of the surfactant is
adsorbed at the droplet surfaces with the free aqueous-phase
surfactant concentration well below the CMC, so micelles are
absent. As for conventional emulsion polymerizations, it is
normal to use water-soluble initiators, such as persulfates. Figure
8 illustrates the mechanism of nucleation in miniemulsion
polymerization and may be contrasted with Figures 3 and 4. The
first thing to note in comparing these figures, is that the
mechanism of miniemulsion polymerization is significantly less
complex. Particle nucleation is via entry of oligomeric radicals
into miniemulsion monomer droplets because micelles are not
present and because there is insufficient free surfactant available
to stabilize any primary particles formed by homogeneous
nucleation in the aqueous phase. The fate of primary particles is,
therefore, simply to coagulate onto and enter miniemulsion
droplets. Ideally, all the droplets are hit by radicals and become
latex particles. Thus, the reaction proceeds by polymerization of
the monomer in the miniemulsion droplets and there is no true
Interval II.
In conventional emulsion polymerization, homogeneous and
micellar nucleation dominate. This is because the very large size
of the monomer droplets and their low total interfacial area
make them ineffective in competing for entry of radicals. As
discussed in sections 3.2.3 and 3.10, droplet nucleation takes
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place in emulsion polymerization, but it is generally considered
to be insignificant in terms of kinetics and only important in
terms of its undesirable potential for promoting coagulum
formation. The underlying principle for miniemulsion polymer-
ization is that if the monomer droplet size can be reduced to
below 0.5 μm, two phenomena will occur. First, the droplets will
be able to compete successfully for water-borne radicals due to
their smaller diameter and increased interfacial area. Second, the
reduction in droplet size will result in a huge increase in droplet
interfacial area that requires a monolayer of surfactant to remain
colloidally stable. When preparing a miniemulsion for a given
formulation, the surfactant necessary to support the much larger
interfacial area comes from breakup of surfactant micelles. In a
properly formulated miniemulsion, all micelles will be sacrificed
to adsorption at the droplet interfaces. Thus, the small
miniemulsion droplets cause the depletion of micelles to the
point of exclusion, leaving droplet nucleation as the dominant
particle nucleation process.
4.2. Preparation of Miniemulsions. Miniemulsions are
produced by the combination of a high shear rate, to break up
the starting emulsion into submicron monomer droplets, and a
surfactant/costabilizer system to provide colloidal stability and
retard monomer diffusion from the final submicron monomer
droplets. Both are necessary to effect the reduction in droplet
diameter. High shear is provided by a sonicator or a mechanical
homogenizer. The surfactant is necessary to retard droplet
coalescence caused by stirring, Brownian motion, or Stokes law
creaming or settling. When a monomer emulsion is subjected to
high shear, small droplets will result and there will be a statistical
distribution of droplet sizes. The costabilizer (referred to in
earlier works as a cosurfactant or hydrophobe) prevents Ostwald
ripening119 (see section 3.10). If Ostwald ripening is allowed to
continue unchecked, the droplet sizes will become large enough
for creaming to occur in a matter of seconds to minutes; for
example, Jannson120 has shown that, in the absence of
costabilizer, Ostwald ripening occurs in unagitated systems on
a time scale of seconds.
A costabilizer dissolved in the monomer functions to prevent
Ostwald ripening by retarding monomer diffusion from the
smaller droplets to the larger. Costabilizers need to be highly
insoluble in the aqueous phase (so that they will not diffuse out
of the droplets) and highly soluble in the monomer. Under these
conditions, diffusion of monomer out of the smaller droplets
results in an increase in the concentration of the costabilizer in
those particles (since, by definition, costabilizers are too
insoluble in the aqueous phase to leave the droplet). The
increase in free energy associated with this concentration of the
costabilizer balances the decrease in free energy due to the
reduced interfacial area caused by Ostwald ripening, and at some
point, ripening stops. The thermodynamics are essentially the
same as for equilibrium swelling of particles by monomer (see
section 3.3.1), but in this case the components are monomer and
costabilizer. Hence, the Morton Equation 11 is modified by
replacing: (i) the identifiers “P” by “C” (for costabilizer) with
consequent changes to the identities of the variables and
parameters; and (ii) 1/x̅n by the ratio of monomer to costabilizer
molar volumes. The equation has been extended by Ugelstad121
to droplets containing three components (monomer, polymer,
and costabilizer).
4.2.1. Costabilizers. Since all costabilizers have a very low but
finite water-solubility, in their presence Ostwald ripening will
proceed, but on a time scale of months, which is unimportant in
relation to the time scale of polymerization, which is minutes to
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hours. Miniemulsions have been shown to remain stable for six
months or more. In the original miniemulsion polymerization
paper,118 El-Aasser and co-workers showed that a costabilizer
could be used to stabilize small monomer droplets, making them
competitive as sites for particle nucleation. The earliest
costabilizer used by El-Aasser and co-workers was cetyl
alcohol,118 which has a water solubility ≈1.9 × 10−4 mmol L−1
at 35 °C.38 The use of hexadecane (water solubility ≈3.9 × 10−6
mmol L−1 at 35 °C39) followed shortly after this.30 Both cetyl
alcohol and hexadecane suffer from the fact that they are too
high in molecular weight to be easily removed from the final
latex but are volatile enough that they add to the VOC loading of
the product and, therefore, are not entirely desirable. Hence,
alternatives have been sought.
Highly water-insoluble monomers, such as lauryl methacry-
late122 and other highly hydrophobic monomers,123 as well as
highly hydrophobic, monomer-soluble initiators124 and chain
transfer agents (e.g., tert-dodecylthiol) have been used as
reactive costabilizers. Polymeric costabilizer has been used as
well.125 Use of polymer costabilizers will not give thermody-
namic stability by completely eliminating Ostwald ripening but
can slow monomer diffusion and, more importantly, enhance
radical entry into particles126 to the point where significant
droplet nucleation can take place before Oswald ripening
destroys the monomer droplet distribution. Polymeric costabil-
izers have major advantages in that they are totally innocuous in
the polymeric product and can give greater efficiency of
conversion of droplets into particles, as discussed in the
following section.
4.3. Control of Nucleation in Miniemulsion Polymer-
ization. Miniemulsion polymerization is distinct from emulsion
polymerization in that the predominant mode of particle
nucleation is droplet nucleation. This does not mean, however,
that all droplets are nucleated and become polymer particles. As
in an emulsion polymerization, miniemulsion droplets that are
not nucleated serve as monomer reservoirs for the polymer
particles. Reimers and Schork127 have shown that, for their
formulations (using 4 wt % poly(methyl methacrylate) as
costabilizer), the particle number is independent of the level of
initiator. This is often taken as evidence of droplet nucleation
efficiency near 100%. Miller et al.126,128,129 have reported that
when cetyl alcohol is used as the costabilizer in conjunction with
preformed polymer (1 wt %) in the monomer miniemulsion
droplets, enhanced nucleation is observed (i.e., a higher
proportion of droplets are converted to particles) due to
enhanced radical entry into droplets, with a resultant increase in
the rate of polymerization. They also found that the number of
particles is independent of initiator concentration, again
implying a droplet nucleation efficiency near 100%, while
without preformed polymer in the droplets the nucleation
efficiency may be less than 20%.
One of the initial concerns about miniemulsion polymer-
ization was that it would produce very broad PSDs. Landfester
and Schork130 report PSDs for multiple formulations in which
the PSDs are equal to or only slightly greater than those of
equivalent conventional emulsion polymerizations.
Reimers and Schork have shown that, in comparison to
nucleation in conventional emulsion polymerization, mini-
emulsion droplet nucleation can be very much more robust to
effects of rates of initiation or levels of residual inhibitor in the
monomer mixture.127 They were able to develop miniemulsions
in which the particle number was essentially independent of
initiator flux over a wide range of operating conditions.
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4.4. Miniemulsion Copolymerization. Since all the
monomer is present in the miniemulsion droplets at the start
of polymerization, composition drift can be expected and is
observed in miniemulsion copolymerizations, as evident from
studies of copolymerization of vinyl acetate with n-butyl
acrylate131 for which the reactivity ratios are quite different,
with vinyl acetate being much less reactive (rVAc = 0.04; rBA =
5.596). Monomer partitioning again has an influence on the
copolymerization and, for this example, accentuates the
differences in monomer reactivity because vinyl acetate is far
more soluble in water than is n-butyl acrylate (see Table 2). Due
to this, the mole fraction of vinyl acetate in the locus of
copolymerization, i.e., the droplets, is lower than its value for the
total comonomer mixture. Hence, the copolymer molecules
produced within nucleated miniemulsion droplets have a high
proportion of n-butyl acrylate repeat units at lower overall
monomer conversions and a steadily increasing proportion of
vinyl acetate repeat units as the overall conversion increases.
There also can be unusual effects in miniemulsion
copolymerization, as observed when the less reactive monomer
has very low solubility in water. This is exemplified here for
copolymerization of vinyl stearate with methyl methacrylate by
batch emulsion and miniemulsion copolymerization,132 data
from which are shown in Figure 9. In this case, the conventional
Figure 9. Cumulative mole fraction of vinyl stearate repeat units in the
copolymer (F̅ VSt) as a function of fractional conversion of total
monomer (Ctotal) for copolymerization of vinyl stearate with methyl
methacrylate132 at total f VSt = 0.034. Experimental data are shown for a
conventional batch emulsion copolymerization (□) and a mini-
emulsion copolymerization (●). The solid line is the theoretical
curve based on integration of the Copolymer Equation 4 using the
homogeneous copolymerization reactivity ratios: vinyl stearate (rVSt =
0.02) with methyl methacrylate (rMMA = 2.35).
emulsion copolymerization gives a lower vinyl stearate
incorporation (compared to prediction using the Copolymer
Equation 4) early in the reaction, presumably because of
limitations on vinyl stearate transport, which is slow to diffuse
from monomer droplets due to its very low aqueous phase
concentration, or to differences in swelling capability between
the monomers (vinyl stearate is much less soluble in the aqueous
phase, and with three times the molecular weight, provides the
same volume fraction as methyl methacrylate with one-third the
mole fraction). The miniemulsion copolymerization, however,
gives higher vinyl stearate incorporation (compared to
prediction) because some of the methyl methacrylate is
dissolved in the aqueous phase, while virtually none of the
vinyl stearate is, thereby increasing the mole fraction of vinyl
stearate in the miniemulsion droplets compared to its value for
the total comonomer mixture.
4.5. Colloidal Stability of Latexes Prepared by
Miniemulsion Polymerization. Prior to polymerization, as
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described in section 4.2, miniemulsions must be protected
against Ostwald ripening. After miniemulsion polymerization,
the latexes obtained have been shown to exhibit increased shear
stability compared to latex of similar composition and particle
size prepared by conventional emulsion polymerization.100 This
is thought to be due to the conventional latex containing a very
small fraction of large particles derived from monomer droplet
nucleation (see section 3.10). This is not a factor in
miniemulsion polymerization and the lack of a tail of very
large particles in the PSD imparts greater shear stability.
When miniemulsion polymerization is used to carry out
controlled radical polymerizations (see section 5), the presence
of a very large concentration of short oligomers early in the
polymerization is thought to cause an Ostwald ripening
instability known as superswelling.133
4.6. Advantages and Exploitation of Miniemulsion
Polymerizations. In general, miniemulsion polymerization
provides a number of advantages over conventional emulsion
polymerization. These include increased latex shear stability,
very reproducible particle nucleation (under conditions where
droplet nucleation efficiency is near 1), and, potentially, the lack
of monomer transport limitations. In addition, miniemulsion
polymerization retains the important advantages of emulsion
polymerization, namely: high molecular weight polymer is
produced at high rates of polymerization with an absence of
VOCs at complete monomer conversion (provided that
nonvolatile costabilizers are used).
An attractive feature of miniemulsion polymerization is that
transport of monomer through the aqueous phase is not
required, so it is possible to prepare latexes from very highly
water-insoluble monomers with ease. Other examples where the
special features of miniemulsion polymerization are used to
advantage include the preparation of hybrid materials from
existing polymers, making use of grafting during polymerization
(see section 6.3), the nanoencapsulation of drugs, pigments, and
other particulate materials (section 6.4), and, increasingly,
carrying out controlled radical polymerizations (section 5.1).
There are disadvantages of miniemulsion polymerization that
have been impediments to its adoption for industrial processes.
The first is inertia and an unwillingness to modify existing
successful products and processes. The second is the thought
that it adds complexity and cost to the process. It is true that one
must invest in homogenization (miniemulsification) equipment,
but the cost of this is relatively insignificant in comparison with
the overall capital cost of a polymerization reactor. Standard
industrial homogenizers can be used, minimizing the costs of
design and eliminating custom manufacture. There also is a
misconception that the energy cost associated with mini-
emulsification will add significantly to the cost of manufacture.
However, the energy cost of miniemulsification can be
calculated and is only of the same order of magnitude as the
energy cost of heating the polymerization reactor contents from
ambient to polymerization temperature. There is a legitimate
concern that the use of hexadecane or other costabilizers adds
VOC to the product. This can be obviated by employing a
polymeric costabilizer (see section 4.2.1) Finally, there are
questions about the stability of the miniemulsion, but this should
not be a concern if an effective costabilizer is used, especially if a
low level of polymer is employed (see section 4.3). All of these
concerns become less significant when one is considering a low
volume, high value added biomedical or biomolecular
application.
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Scheme 8. Principal Categories and Types of CRP
4.6.1. Inverse Miniemulsion Polymerization. An inverse
miniemulsion is a miniemulsion in which the continuous and
dispersed phases of a conventional miniemulsion are in-
verted.134 Inverse miniemulsion polymerization is especially
useful for producing hydrophilic polymers, nanostructured
polymers, encapsulated organic/inorganic materials, and
biodegradable polymers.135
4.6.2. Step Polymerization in Miniemulsions. While
miniemulsion polymerization is predominantly applied to free
radical monomers, step polymerization in miniemulsions has
been reported. The obvious problem is that step polymer-
izations involving loss of water as a condensation product
(polycondensations) are equilibrium reactions, and the presence
of large amounts of water around the miniemulsion droplets/
particles will limit the extent of reaction and consequently (for
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step polymerization kinetics) the molecular weight. Landfester
and co-workers136 have succeeded in synthesis of polyesters in
miniemulsion. They report that the extent of esterification is
independent of particle size but strongly dependent on the
hydrophobicity of the monomers (and hence the water
concentration inside the particles). Pascual et al.137 have
prepared polyesters in miniemulsion, both by polycondensation
and ring opening polymerization. Landfester and co-workers
have reported preparation of high molecular weight polyur-
ethanes in miniemulsion.138−140 This is significant since the
isocyanate monomers used in polyurethane synthesis are
sensitive to water. They also demonstrate one-pot synthesis of
polystyrene/polyurethane and poly(butyl acrylate)/polyur-
ethane hybrids by miniemulsion polymerization.
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5. CONTROLLED RADICAL POLYMERIZATION (CRP)
In the last 30 years, chemistries that achieve “quasi-living” radical
polymerization have been developed. They all have the same
essential feature, which is that the propagating radical is trapped
reversibly and released only for short periods of chain growth
before being trapped again. Increasing the ratio of rate of
trapping to rate of propagation will give rise to better control and
a narrower MWD. However, termination is not eliminated, it is
simply reduced to being an event of very low probability
compared to the radical trapping reaction. Thus, the term
“living” strictly is not appropriate. The IUPAC terminology is
reversible-deactivation radical polymerization,141 which accurately
reflects the mechanism of chain growth, but the alternative term
controlled radical polymerization (CRP) has now become widely
adopted and will be used here.
In CRPs, at a given instant in time, a large fraction of the active
chains are in their dormant form, which releases the chain radical
for short bursts of propagation before it is deactivated again. In
this way, active chains can grow for the entirety of the
polymerization, though many will suffer a true termination
reaction at some point. Since termination is bimolecular, it can
be made completely negligible by keeping the steady-state “free”
radical concentration extremely low, but this has the
consequence of giving very low Rp. Hence, a compromise has
to be reached between control and Rp. Nevertheless, it is possible
to produce homopolymers and statistical copolymers with
relatively narrow MWDs (M̅ w/M̅ n < 1.5, often <1.2) and, more
significantly, to synthesize block copolymers of all kinds with
well-defined block lengths, in each case with the associated
advantages of radical polymerization, i.e., being simple to carry
out at moderate temperatures, and for most monomers at
atmospheric pressure, and applicable to a very large number of
monomers that, mostly, copolymerize well with each other
(unlike anionic living polymerization4,5). Hence, methods of
controlled radical polymerization have generated a lot of interest
and research activity.
Here we will introduce the basic chemistry for the three types
of CRP that have been most widely studied for use in emulsion
and miniemulsion polymerizations, but not in great detail
because the literature in this field is vast and there are many
reviews, of which some are cited here.142−149 There are
essentially two categories of CRP (see Scheme 8): (i) reversible
radical trapping and (ii) rapid, reversible chain transfer.
In nitroxide-mediated radical polymerization (NMP) the
trapping agent is a nitroxide. NMP is suitable for styrene and
acrylates but fails to give control of methacrylate homopolyme-
rizations because the nitroxide abstracts a H atom from
monomer at the allylic CH3 group.142,146 The chemical
structures of some nitroxides that are effective in controlling
NMP are shown in Scheme 8. The rate of dissociation of the
terminal C−ON (alkoxyamine) bond is controlled largely by the
structure of the nitroxide and the temperature. Conventional
free-radical initiators can be used in conjunction with the
nitroxide for initiation, but it is best to use alkoxyamines (e.g.,
styrl derivatives of the nitroxide) as initiators, since the number
of chains is then controlled directly. TEMPO was the first
nitroxide to be widely used, but is only suitable for NMP of
styrene, usually at 125−130 °C, for which styrene thermal self-
initiation is substantial and reduces control.142,146,150 TIPNO
was a major improvement on TEMPO, giving good control with
styrene and acrylates at temperatures around 110−120 °C, for
which thermal initiation of styrene is reduced but still significant.
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SG1 is a newer nitroxide that gives good control for styrene,
acrylates, and acrylic acid at temperatures as low as 90 °C and is
water-soluble, so it has found use in emulsion and miniemulsion
polymerization.146,151 More recently, a new nitroxide (TITNO)
designed to be hydrophobic and work at lower temperatures has
been developed that gives excellent control of styrene NMP at
70 °C (for which thermal initiation is negligible) and of n-butyl
acrylate NMP at 90 °C.152 Control in NMP necessarily requires
very low “free” radical concentrations and so NMP is slow. The
degree of control usually reduces at higher conversions and so it
is difficult to achieve very high conversions. Hence, although a
lot of research on NMP has been done, including emulsion and
miniemulsion NMP, it is not so attractive for commercial use.
Atom-transfer radical polymerization (ATRP) belongs to the
same CRP category as NMP but is capable of controlling
polymerization of a wider range of monomers, including styrene,
methacrylates, acrylates and vinylpyridine, though acidic
protons cannot be tolerated (so acrylic and methacrylic acid
must be used in their fully ionized form). In ATRP, a halide atom
(typically Br or Cl) is exchanged reversibly between the “free”
chain radical and the oxidized form of a catalytic amount of
transition metal compound (often Cu2+) that is complexed,
usually by coordination with tertiary amine ligands. Initiation is
achieved using an alkyl halide (e.g., methyl 2-bromoproprionate
for styrene and acrylates or ethyl 2-bromoisobutyrate for
acrylates and methacrylates), which controls the number of
chains produced, and a complexed transition metal “activator”
(e.g., CuBr). ATRP has been used to synthesize many different
types of block copolymer architecture (from diblock to
multiblock and star block shapes), but as for NMP, ARTP is
slow because the “free” radical concentration must be kept very
low to minimize bimolecular termination. Removal of the toxic
transition metal and its ligand at the end of polymerization is an
issue that is particularly acute for emulsion and miniemulsion
ATRP because it is very difficult to extract these from the latex
produced.
Reversible-addition−f ragmentation chain-transfer polymeriza-
tion (RAFT) is essentially a small perturbation of a conventional
free-radical polymerization in which an extremely efficient,
reversible chain transfer agent (the RAFT agent) is added and
normal free-radical initiator is used. Provided that an
appropriate RAFT agent is used, it is applicable to the full
range of monomers. The exchange of chain radicals at the RAFT
end-group is extremely fast compared to bimolecular termi-
nation and must be fast compared to propagation to achieve a
narrow MWD (requiring exchange transfer constants, CRAFT >
10). The most widely used class of RAFT agents are
dithiobenzoates (as illustrated in Scheme 8), which are suitable
for use with styrene, acrylates, methacrylates, acrylic acid,
methacrylic acid, acrylamides, and vinylpyridine. Monomers of
lower reactivity (e.g., vinyl acetate) require less active RAFT
agents, such xanthates and dithiocarbamates. The reaction of
initiator radicals with the RAFT agent generates the radical R•
which then initiates a new chain that is made dormant by chain
transfer to another molecule of RAFT agent, thereby releasing
another R• radical to initiate another chain, and so on. Hence,
the number of chains should be controlled by the amount of
RAFT agent provided that the rate of radical generation from the
initiator is low. On this basis, the moles of dead chains produced
by bimolecular termination is directly related to the moles of
dissociated initiator. Thus, the initiator to RAFT agent ratio
must be kept low. This criterion is especially important in the
preparation of block copolymers, but again leads to low Rp. Since
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RAFT is very similar to free-radical polymerization with a
normal chain transfer agent, it is particularly suited to use in
emulsion and miniemulsion polymerization. The main dis-
advantages of RAFT are that the use of sulfur compounds can
lead to problems with odor and to discoloration of the polymer.
5.1. Emulsion and Miniemulsion CRP. The attraction for
carrying out CRPs in emulsion and miniemulsion is the same as
that already discussed for free-radical polymerization. In
comparison, CRP opens up the possibility of producing latexes
containing polymers with narrow MWDs or block copolymers of
well-defined architecture.4,5,14 Narrow MWDs are not necessary
for most applications and can have negative effects; for example,
for pressure-sensitive adhesives, a broad MWD is desirable
because low molecular weight chains provide increased tack and
interfacial adhesion, whereas high molecular weight chains
promote cohesion of the polymer. Thus, it is the unique
properties of block copolymers,4 in particular, that have driven
the considerable interest in exploring both emulsion and
miniemulsion CRP. Naturally, in order to understand how to
control these polymerizations in emulsion and miniemulsion,
much of the research has concerned homopolymerizations.
Because the majority of chains are kept in a dormant, yet
active state throughout a CRP, the sequence distribution in
copolymer chains produced by continuous CRP of a mixture of
two monomers is dependent on the type of reactor used and, in
particular, on the reactor residence time distribution. For
instance, a continuous stirred-tank reactor will produce
copolymer chains with a uniform sequence distribution, whereas
a plug-flow reactor will produce chains with a tapered sequence
distribution that is richer in repeat units from the more reactive
monomer at one chain end and richer in repeat units from the
less reactive monomer at the other chain end. Thus, a reactor
system can be designed, based purely on the various reactor
types available, to produce different combinations of repeat unit
blocks and gradients within each copolymer chain.153−155 This
also is true for emulsion and miniemulsion CRP.
Besides the obvious need to assess water-sensitivity of the
controlling agents, partitioning is the most important consid-
eration for transferring CRP from a homogeneous medium to a
heterogeneous medium. The main effects are easy to predict. If
the controlling agent(s) are highly soluble in water, good control
is not possible because most of the controlling agent will be in
the aqueous phase, whereas the majority of polymerization will
take place in the particles. If the controlling agent(s) have low
water solubility and are dissolved in the monomer, better control
is possible, but CRP will then be possible in all loci, including
monomer droplets, which can lead to bimodal MWDs and, more
significantly, large amounts of coagulum. Hence, batch emulsion
polymerization is not well suited to CRPs, and it is more effective
to use preswollen seed particles to carry out emulsion CRPs.
Problems associated with partitioning of controlling agents
are significant for NMP, but far more limiting for ATRP.
Because miniemulsion droplets constitute a self-contained
nanoreactor, they are more attractive for use in carrying out
both NMP and ATRP. Miniemulsion NMP has been used very
effectively to control homopolymerizations and to produce
block copolymers, albeit at low Rp, especially successfully with
SG1 as the nitroxide.156−159 However, even in miniemulsion,
ATRP is only possible if the ligands have very low water
solubility so that the transition metal activator is held in the
monomer/polymer phase. Additionally, all anionic and many
cationic surfactants interact with the activator and cannot be
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used, limiting greatly the choice of surfactant and restricting the
choice mostly to nonionic surfactants.
In comparison to NMP and ATRP, RAFT is far better suited
to being carried out in emulsion and miniemulsion and has been
used very successfully with the usual water-soluble initiators
(such as persulfate), though choice of surfactant can be
important. For the reasons described earlier, hydrophobic
RAFT agents are preferred in emulsion RAFT but must have
sufficient water solubility to ensure transport of the RAFT agent
to particles, even when using a seeded, starved semibatch
process. There is strong evidence for exit of the small radical R•
released by reaction with the RAFT agent, and partitioning of
these radicals between the phases can have a significant effect on
the control achieved and Rp. Nevertheless, a major advantage of
RAFT is that as a chain grows within a particle, it soon attains a
degree of polymerization at which the released polymeric radical
is too hydrophobic to exit the particle; in contrast, with NMP
and ATRP, the identity of the released species (T• in Scheme
8(a)) does not change and always is small, so its tendency to exit
or partition into the aqueous phase remains the same
throughout the polymerization. Oligomeric z-mer radicals
entering a particle from the aqueous phase may instantly
exchange with a dormant species and, if CtrRAFT is very high, will
undergo several exchanges before the released z-meric radical
reacts with monomer; this provides time for the z-meric radical
to exit the particle again, an effect that is thought to contribute to
reduction in Rp. A simple way to reduce problems associated
with exit of radicals is to use larger particles, which is best
achieved using seed particles. Hence, it is possible to prepare
homopolymers and block copolymers with relatively narrow
MWDs in a predictable way using emulsion RAFT. Mini-
emulsion RAFT has obvious attractions in terms of both the
larger size of the droplets, which should help reduce effects from
exit of radicals, and the lack of need for transport of RAFT agent
through the aqueous phase, which (at least in theory) should
make the reactions more predictable.
An interesting use of RAFT160−162 and NMP163,164 has been
to first create short chains of neutralized (meth)acrylic acid
homopolymer or copolymer by homogeneous aqueous
polymerization and then feed in a hydrophobic monomer to
grow these chains, which soon become surfactant-like and
micellize. Further polymerization of the chains in the micelles
produces particle nuclei that with further polymerization grow
into latex particles. The resulting particles are electrosterically
stabilized by the first-stage neutralized (meth)acrylic acid repeat
unit containing polymer, which is directly chemically linked to
their surface. Hence, surfactant-free latexes are produced in
which migration of the stabilizing moiety is not possible; this is
an advantage for coatings formulated from the latex. An
extension to this concept, which has been applied to ATRP,
NMP, and RAFT, is to use initiating species that are amphiphilic
and provide the chains for steric or electrosteric stabilization of
the particles produced by polymerization from an aqueous
solution.165−168
Another development has been the use of inverse
miniemulsion CRPs to create microgels and very specific
molecular structures in WSPs.135,169−172
An excellent review of the use of CRP in dispersed systems for
biological applications has very recently been published and is
essential reading for anyone interested in biomedical applica-
tions of polymer colloids.3
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6. PARTICLE MORPHOLOGY
One of the most important features of emulsion and
miniemulsion polymerization is the ability to produce particles
with specific surface characteristics (e.g., reactive surface
functional groups) and/or internal morphology (e.g., core−
shell or multiphase structure) relatively easily, though not as
simply as might first be thought. Some of the achievable particle
morphologies are illustrated in Figure 10, and routes to their
preparation are discussed in the following sections.
Figure 10. Diagrams of cross-sectional areas through the equators of
particles illustrating some of the particle morphologies that have been
achieved by methods of emulsion and miniemulsion polymerization.
The letter designations for the polymer phases do not indicate the order
in which the polymers were formed, but only that they are different,
immiscible polymers.
6.1. Morphology of Apparently “Homogeneous”
Particles. Latex particles produced by emulsion or mini-
emulsion polymerization of a single monomer always have a
morphology that cannot be ignored because the particle surfaces
are distinctly different from the particle interior due to surface
colloid stabilizing groups/molecules (e.g., adsorbed surfactant
and/or adsorbed/grafted WSP chains) and surface charges from
polymer end-groups (e.g., sulfate end-groups from persulfate
initiation). Ionic polymer end-groups can contribute signifi-
cantly to the surface charge and are the only source of colloidal
stability in narrow PSD latexes prepared by surfactant-free
emulsion polymerization. However, because sulfate end-groups
slowly hydrolyze to hydroxyl groups, the colloidal stability may
reduce over time.
There are indications from real-time ESR studies during batch
and starved semibatch emulsion polymerizations that polymer
chains are formed near to the particle surface,60,61 and
theoretical modeling supports this observation.173 Hence,
particles may have an internal morphology in terms of the
radial distribution of molecular weight, and possibly branching,
within an apparently homogeneous particle. The extent to which
an entering radical has access to the full volume of a particle is
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very important for control of particle morphology, as discussed
in section 6.2.2.
6.2. Core−Shell and Other Particle Morphologies. Due
to the very low entropy of mixing, polymers of even only slightly
different structure are usually immiscible with each other.4 This
makes it possible to produce core−shell and multiphase particles
by emulsion polymerization, a feature that has been used
extensively to advantage by academia and industry. For many
applications, this is key to delivering novel materials and to
enhancing end-use performance. In crude terms, a core−shell
particle could be created by completely polymerizing one
monomer or comonomer mixture first and then adding a
different monomer or comonomer mixture to complete the
polymerization, so-called sequential feeding. However, the
outcome is rarely simple because the internal morphology is
controlled by the thermodynamics of the system and the
mobility of chains.
6.2.1. Thermodynamic Control of Particle Morphology. If
sequential feeding is used in an emulsion polymerization under
conditions whereby the polymer chains have complete mobility,
the resulting particle morphology will be controlled by
equilibrium thermodynamics. Hence, the morphology with
minimum free energy will be obtained and is controlled by the
polymer−polymer and polymer−water interfacial tensions. It is
relatively straightforward to predict the overall free energy
(GPM) for a given particle morphology174,175
G PM = ∑ γi− jAi− j
i−j (22)
where γi−j and Ai−j are the interfacial tension and area of interface
“i−j”, respectively. The challenges are to obtain reliable values
for the polymerA−polymerB, polymerA−water, and poly-
merB−water interfacial tensions and to survey all conceivable
morphologies in order determine which specific morphology has
the lowest free energy. The issues have been discussed by
Sundberg and co-workers.48,176,177 Provided that the interfacial
tensions are known, eq 22 can give quite good predictions of
morphology when the chains have complete translational
freedom. The idealized core−shell structure shown in Figure
10(a) is an example of a simple equilibrium morphology that is
produced if polymer A is significantly more hydrophilic than
polymer B, such that γPA‑W ≪ γPB‑W. In the absence of cross-
linking, the morphology obtained under conditions that
facilitate equilibrium thermodynamics should be the same
regardless of which polymer is formed first. This gives rise to the
term inverse core−shell when a core−shell morphology is
obtained in which the first-formed polymer is present as a
shell surrounding a core of second-formed polymer in the final
particles. If γPA‑W and γPB‑W are similar, the equilibrium
morphology during polymerization may be different from the
final prediction because monomer will influence the values of
γPA‑W and γPB‑W and reduce the value of γPA−PB; these effects will
change according to the monomer(s) present at a given time and
as conversion increases. If γPA‑W ≈ γPB‑W ≳ γPA‑PB, then both
polymers will prefer to be at the surface and lobed morphologies
will be formed, like those depicted in Figure 10(b)−(c). The
value of γPA−PB can be reduced significantly if grafting of polymer
A to polymer B occurs (e.g., due to chain transfer to polymer),
which can lead to multiple inclusions of smaller domains of the
polymer with the higher polymer−water interfacial tension, such
as shown in Figure 10(d)−(e). The effect of surfactant and even
initiator end-groups on the interfacial tensions can be significant,
so the equilibrium morphology may change if they are changed.
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Figure 11. Representation of the Sundberg−Stubbs decision map187 for prediction of particle morphology (adapted from the content of Figure 1 in
Progress in Organic Coatings, vol. 61, J. M. Stubbs and D. C. Sundberg, “The Dynamics of Morphology Development in Multiphase Latex Particles”, pp
156−165, Copyright (2008), with permission from Elsevier).
The equilibrium particle morphology can also be sensitive to
postadditions of surfactant because this will reduce both γPA‑W
and γPB‑W, thereby making the contribution from the polymer−
polymer interface more important; this can result in changes of
morphology over time if chain mobility is low, but still possible.
6.2.2. Effects of Chain Mobility on Particle Morphology.
Although equilibrium morphologies can be obtained, the chains
often do not have sufficient mobility to achieve this and more
complex morphologies are obtained. Furthermore, if the desired
particle morphology does not correspond to the equilibrium
morphology, then it is essential to reduce chain mobility in order
to control the phase structure within the particles. These effects
will now be discussed. The work of Sundberg and co-workers in
this area is seminal48,178−188 and will be followed here in
descriptive (rather than mathematical) terms in order to convey
the important concepts.
There are two chain mobility factors to consider, the mobility
of an entering oligomeric radical and the mobility of the polymer
chains already present in the particle. Chain mobility depends
strongly on: (i) x̅n (when x̅n ≳ 100, the diffusion coefficient of a
chain is proportional to x2n); (ii) temperature (chains are
essentially immobile below Tg); and (iii) cross-linking (a chain
in a network polymer can change its local conformation within
the network if above Tg, but cannot undergo translational
movement). Thus, restriction of chain mobility can be used to
achieve nonequilibrium particle morphologies and often is
important when preparing particles of controlled structure.
Sundberg et al.180 proposed a model that examined non-
equilibrium particle morphology in terms of penetration of
oligomeric radicals and monomer into a particle. Monomer
diffusion is relatively fast, even in highly viscous media such as
polymers at temperatures ≳Tg. In this context, for most of the
polymerization, the polymer Tg will be significantly lower than
that of the pure polymer due to plasticization by the monomer
present in the particles. Given that polymerization temperatures
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are typically 70−95 °C and the highest pure polymer Tg values
normally encountered are for poly(methyl methacrylate) and
polystyrene (both having Tg ≈ 100 °C), in most cases the
monomer-swollen polymer in the particles will be above Tg.
Even under starved conditions with higher Tg polymers, it was
found that monomer molecules are easily capable of penetrating
the particles fully. Thus, the key parameters determining
nonequilibrium particle morphology are those relating to
chain mobility.
Based on many years of observations and theoretical
experience, Sundberg and Stubbs187 produced a decision tree
for bespoke software that predicts morphology in terms of the
extent of penetration into a particle by entering oligomeric
radicals and the extent of phase separation/consolidation
(which is dependent on the mobility of the already-formed
polymer chains), taking into account thermodynamic effects
where chain mobility facilitates this. A slight adaptation of their
decision tree is shown in Figure 11a series of questions are
asked, the answers to which eventually lead to the most likely
type of final particle morphology. Its qualitative use requires
approximate knowledge of (i) the difference between γPA‑W and
γPB‑W (which can often be assessed simply based on differences
in polymer hydrophilicity, e.g., it is reasonable to assume that
γPB‑W < γPA‑W if polymer B is more hydrophilic than polymer B);
(ii) polymer Tg under reaction conditions (easy to estimate
approximately) in comparison to reaction temperature; and (iii)
whether or not polymer A and polymer B are miscible (to which
the answer invariably is no if the polymer chains have x̅n > 100).
Hence, it is usual to assume that the two polymers will be
immiscible, but also to recognize that oligomeric radicals are
likely to remain miscible with the preformed polymer until they
reach a critical value of x̅n at which they will phase separate if
chain mobility is sufficient.
6.2.3. Experimental Strategies for Controlling Particle
Morphology. The principle of using sequential monomer
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feeds to produce multiphase particles is simple, but as indicated
in the previous section, the desired morphology will be obtained
only by selecting the correct conditions. Thus, the Sundberg−
Stubbs decision tree is very helpful when planning the
formulation, process, and reaction conditions for preparation
of a particular particle morphology. There are, however, two
other factors that are of paramount importance when seeking to
control morphology: (i) controlled particle growth in the
absence of secondary nucleation or particle coagulation; and (ii)
a relatively narrow PSD. These factors will be considered first
before going on to give some examples of the application of the
decision tree to selecting a process and reaction conditions.
As discussed in section 3.2.5, for controlled particle growth Nc
must be high enough to ensure capture of all oligomeric radicals
(and primary particles, if formed), a rule-of-thumb guide for
which is to ensure that Nc > 1016 particles (L H2O)−1. Surfactant
concentration during particle growth must be kept low, just high
enough to maintain colloidal stability, but not so high that it
encourages secondary nucleation of second-stage polymer
particles (hence, it is helpful to ensure that the free surfactant
concentration in the aqueous phase is kept well below the CMC
to eliminate the possibility of micellar nucleationthis can be
tested by measuring the surface tension of samples removed
from the latex during the reaction). A narrow PSD is necessary to
get well-defined particle morphology because smaller particles
are more efficient at capturing oligomeric radicals (see section
3.2) and because particle diameter is proportional to the cube
root of particle mass (i.e., the diameter of a small particle
increases more rapidly with a given increase in particle mass).
Consider the example of a system that produces an ideal core−
shell morphologyif the first-stage polymer PSD is broad, then
the smallest particles are likely to form thicker second-stage
polymer shells and the largest polymer particles are likely to form
thin shells, with a multitude of different possibilities in between.
Thus, a broad first-stage polymer PSD will give rise to core−shell
particles for which there is a distribution of shell thicknesses
superimposed on the broad PSD.
Use of either a reliable seed stage that gives particles with a
narrow PSD or (better) a preformed seed latex with a narrow
PSD are the best ways to satisfy the criteria for controlling
particle morphology. It always is wise to check that the particles
are growing in the required way during the second-stage
polymerization by sampling the reaction to measure the mass of
polymer produced and the particle diameter, which is easily and
quickly done using PCS (which is fine for narrow PSDs). This
enables calculation of the total number of particles in the reactor
(whatever its size)
total
mpolymer
Ntotal =
ρP (π /6)d3 (23)
where mtotal
polymer is the total mass of polymer in the reactor at the
time of sampling (e.g., calculated from the total mass added to
the reactor and the measured latex solids content, adjusted for
presence of other nonvolatiles), ρP is the polymer density (which
usually can be assumed equal for the two polymers without too
much error), and d is the (unswollen) particle diameter for the
sample. Use of the swollen diameter measured by PCS leads to
low values of Ntotal, but if the instantaneous conversion is high,
the error is relatively small and it can be used; the value of Ntotal
calculated using the PCS value of d will come back to its accurate
value at the end of polymerization when monomer conversion is
complete. Alternatively, the PCS d can be adjusted approx-
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imately to account for swelling since the amount of unreacted
monomer can be calculated from the conversion. The reason for
needing to calculate Ntotal is that during semibatch processes
more water and monomer are added to the reactor and so the
value of Nc can change even if there is controlled growth of the
particles, whereas Ntotal will be constant. If Ntotal is increasing
during the reaction, secondary nucleation is occurring or if it is
decreasing, limited coagulation has happened; in either case,
control of morphology is either poor or absent. Thus, it is
necessary to monitor Ntotal in order to have confidence that a
controlled morphology can be achieved or to direct the changes
in formulation or reaction conditions needed to achieve
constant Ntotal. Provided that particle growth is controlled and
PSD is narrow, it is possible to use sequential feeding to produce
particles with multiple layers of polymers, similar to that shown
in Figure 10(g).
Although it is a prerequisite for controlling morphology,
simply establishing that Ntotal is constant is not sufficient because
it only confirms that the particles were grown and gives no
indication of the internal particle structure. Hence, methods for
examining particle morphology are needed. Most commonly,
this is achieved by TEM or atomic force microscopy (AFM) of
microtomed sections of particles embedded in a matrix (e.g., a
cast film or dispersed in another polymer). Examining the
surface of a film or blend is not satisfactory because the surface
can be different from the bulk; films should be sectioned across
their thickness, perpendicular to the plane of the film. For
analysis by TEM, selective staining agents need to be used to
provide contrast between the phases. Ruthenium tetroxide is the
most versatile staining agent and will stain many different
polymers, but at different rates which allows for contrast to be
developed.189 (Historically, osmium tetroxide was used but is
only effective in staining polymers with olefinic CC bonds.) In
many cases, there is a difference in stiffness between the phases,
so AFM phase contrast imaging is effective in revealing the
different phases, but where the difference is not sufficient, newer
instruments are able to use the probe to simultaneously probe
the surface and record infrared spectra of the surface at sufficient
resolution to reveal phases of different chemical structure. When
analyzing TEM or AFM images from microtomed sections, it is
important to realize that particles may have been sectioned at
any point from their pole to their equator.
We can now come back to discussing use of the Sundberg−
Stubbs decision tree. We will assume a narrow PSD polymer A
first-stage and that controlled particle growth of the polymer A
particles is achieved by formation of polymer B (i.e., as in Figure
11).
The ability of an entering oligo-B radical to penetrate into
polymer A depends on the physical state of polymer A under
reaction conditions. The Tg of pure polymer A (obtained from
the literature, measured or predicted from composition if it is a
copolymer47) is important, but will be reduced somewhat during
polymerization due to plasticization by monomer in the
particles. For example, if polymer A is poly(methyl meth-
acrylate) (PMMA, Tg ≈ 105 °C) and the reaction is run under
starved semibatch conditions at 70 °C, it is likely that oligo-B
radicals will not penetrate and instead polymerize near the
particle surface. If you want to create a shell of hydrophobic
poly[(n-butyl acrylate)-stat-styrene] (PBA-S, with composition
giving a Tg ≈ 10 °C, i.e., ≪ reaction temperature), the best that
can be achieved is a less coherent lobed outer layer because,
although the more hydrophobic PBA-S is formed at the particle
surface, it has the mobility to rearrange in order to minimize its
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contact with water and expose some of the underlying PMMA to
make contact with water (for which there is a thermodynamic
driving force). However, if a shell of polystyrene (Tg ≈ 100 °C)
was desired, then a core−shell morphology would be obtained
because the polystyrene chains are constrained to formation on
the surface and do not have the mobility to reorganize; in this
case the “nonequilibrium” core−shell structure will result.
Clearly, it should be straightforward to create a PMMA shell
over polystyrene first-stage particles (equivalent to the
equilibrium morphology) because γPA‑W will be greater than
γPB‑W. In both the examples of achieving core−shell morphology,
the surface of the shell may be nodular (raspberry-like, as in
Figure 10(f)) rather than smooth because polymer B has very
little mobility.
The second main route through the decision tree occurs if
pure polymer A Tg < reaction temperature, in which case the
entering oligo-B radical will be able to penetrate the polymer A
particle to a large extent, though its ability to do so will diminish
as it grows inside the particle and will become more dependent
on the volume fraction of monomer in the particle, since dilution
by monomer will reduce the internal viscosity in the particle.
When the chain radical has become long enough to entangle
with the already-formed polymer chains, the active end will
move by reaction dif f usion (i.e., by propagation) only. However,
as discussed in section 3.3.2, termination is usually dominated by
chain transfer to monomer, which produces a small radical that
initiates a new chain with high initial mobility (this will also be
the case if chain transfer agent is included). Hence, when radical
penetration is possible, formation of polymer B can take place
much deeper into the particle than the distance penetrated by
the entering oligo-B radical. This deeper penetration has been
demonstrated.180 For example, this scenario would occur when
using poly(n-butyl methacrylate) (PBMA, Tg ≈ 36 °C) as the
first-stage polymer. The question then becomes whether or not
phase separation is possible, which also depends on the mobility
of the already-formed chains. If a highly starved semibatch
process is used at 70 °C, then the volume fraction of monomer in
the particles will be low, so polymer mobility will also be low due
to the high internal viscosity. Regardless of the choice for
polymer B, it is likely that phase separation will be restricted
because the propagating chains will become entangled with the
existing chains within the extremely viscous particle interior and
chains will find it difficult to aggregate to form well-defined
phases. This will give rise to a metastable molecular mixture with
either a radial distribution or a more uniform distribution of the
two polymers, depending on the extent to which chain radicals
penetrate into the particle. In order to facilitate phase separation,
the internal viscosity needs to be reduced, which can be achieved
by operating the reaction under less starved conditions, e.g., by
feeding the monomer faster, in which case phase separation
becomes possible to give small phase domains and then, as the
steady-state [M]p increases toward its equilibrium value, phase
consolidation becomes possible. In order to achieve an
equilibrium core−shell morphology, where the more hydro-
philic polymer forms the shell, there must be relatively high
polymer chain mobility, which normally is possible only when
reaction is run under flooded semibatch conditions or as a batch
polymerization. Hence, when seeking to grow a more hydro-
philic polymer shell onto the surface of a low Tg hydrophobic
particle, the decision tree indicates that it is necessary to use fully
swollen particles and a batch process, which is possible for
homopolymerizations, but would give rise to copolymer
composition drift in a second-stage copolymerization. Similarly,
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the decision tree indicates that a core−shell particle with a low
Tg hydrophilic core and a shell of hydrophobic polymer cannot
be achieved. Additionally, in order to eliminate copolymer
composition drift, starved semibatch processes must be used
when producing copolymer phases. Hence, for preparation of
particles with well-defined shells surrounding low Tg first-stage
particles, other constraints on chain mobility must be
introduced.
Copolymerization with cross-linking monomers (i.e., mono-
mers with more than one CC bond) leads to branching in the
copolymer and, ultimately, to cross-linking of the copolymer. As
stated earlier, cross-linking stops translational movement of
chains (chain mobility ceases when a chain becomes part of a
network). Hence, cross-linking can be used to restrict chain
mobility. The question becomes, how far does an entering oligo-
B radical penetrate before it becomes immobilized by branches
or cross-links? Sundberg and Stubbs studied this for a low Tg
(≈40 °C) hydrophilic first-stage copolymer and a hydrophobic
second-stage copolymer of higher Tg (≈70 °C) using ethylene
dimethacrylate (EGDMA) at different levels as a cross-linking
monomer in the second-stage comonomer mixture.186 They
found that EGDMA had little effect on the morphology and
interpreted this as being due to radical penetration taking place
faster than branching/cross-linking of the chain radicals could
reduce radical penetration. However, theoretical prediction and
practical observations showed that when the first stage polymer
is cross-linked, even at relatively low levels, then penetration of
the first-stage polymer by an entering oligo-B radical is greatly
restricted and nonequilibrium core−shell morphologies can be
produced.178,179
An alternative strategy that works in overcoming the
limitations highlighted by the decision tree is to use graftlinking
monomers, which have two or more CC bonds of very
different reactivity, an example being allyl methacrylate (ALMA)
where the allyl CC bonds are of low reactivity.190 By using
ALMA (at levels of 1−2 mol % in the comonomer mixture) in a
preceding phase (i.e., synthesis of polymer A for a two-phase
system), that phase will be very lightly cross-linked (eliminating
polymer A chain mobility) and will contain a significant
proportion of ALMA repeat units with unreacted allyl CC
bonds. If the second-stage monomer mixture is added under
starved semibatch conditions, an oligo-B radical will have lower
mobility in the cross-linked polymer A phase and will react with
some of the allyl CC bonds, immediately switching it to
movement by reaction diffusion only. Thus, entering oligo-B
radicals have much lower penetration into the particle and
polymer B will be formed mostly near the surface of the polymer
A first-stage particle. This strategy has been used successfully to
prepare multilayer particles for toughening of PMMA (as well as
other thermoplastics), e.g., particles with a core of hydrophobic
low Tg polymer and a shell of hydrophilic high Tg polymer or
particles with a core of hydrophilic high Tg polymer, a second
layer of hydrophobic low Tg polymer and an outer shell of
hydrophilic high Tg polymer, or even particles with a core of
hydrophobic low Tg polymer, a second layer of hydrophilic high
Tg polymer, a third layer of hydrophobic low Tg polymer, and an
outer shell of hydrophilic high Tg polymer.191−195 Hence,
graftlinking monomers like ALMA are widely used in synthesis
of commercial multilayer particle latexes. The grafting between
the polymers also has the advantage of providing strong
interfaces between the layers, which is crucial when the particles
are being used for enhancing mechanical properties. It is, of
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course, not necessary to use a graftlinking monomer in synthesis
of the outer shell of polymer.
Particle morphologies rarely have the idealized core−shell
structures shown in diagrams like those in Figures 10 and 11.
There invariably are microdomains of one polymer in the other
polymer phase, and incoherent lobe-like layers are quite
common, including lobe-like internal layers within multilayer
particles. In fact, distinct layers with thicknesses of 10−15 nm
are extremely difficult to achieve because the interphase regions
are typically of this thickness. Fortunately, in most cases, the
morphology does not need to be perfect to deliver the desired
effect. Hence, a pragmatic view about achieving a particular
morphology is sufficient and, in terms of end applications,
achievement of enough structuring to deliver the desired effect is
the most important factor.
Radial distributions like that shown in Figure 11 are best
achieved by changing copolymer composition radially within the
particle, rather than by having a metastable molecular mixture of
homopolymers. This is readily achieved using power-feed starved
semibatch processes98,196 in which two monomer supply tanks
are used to feed monomer to the reactorthe first tank feeds
monomer B into a second stirred tank containing monomer A,
and the mixture of monomers from this second tank is fed to the
reactor. Thus, the comonomer mixture being fed into the reactor
has an ever-increasing proportion of monomer B. Provided that
particle growth is controlled, under these conditions radial
distributions of copolymer composition can be achieved because
the particles grow in small increments with the instantaneous
copolymer composition reflecting the composition of the
comonomer mixture entering the reactor at that point.
As should be evident from the discussion, preparation of
core−shell or other layered particle morphologies is done using
emulsion polymerization processes. Miniemulsion polymer-
ization can be used to prepare the first-stage polymer particles,
allowing advantage to be taken of its lack of need for monomer
diffusion through the aqueous phase and the ease with which
other materials can be encapsulated into particles (see sections
6.3 and 6.4), but the broader PSD does limit the precision to
which particle morphology can be controlled in subsequent
particle growth stages.
A quite different approach to creating core−shell types of
particles is the use of heterocoagulation. In this case, for example,
large particles with positive surface charge are added slowly to a
latex of much smaller particles stabilized by negative surface
charges; the opposite scenario of adding large negatively charged
particles to small positively charged particles also works. The
particles of opposite surface charge attract each other and so the
small particles deposit onto the surface of the large particles.
Provided that this is done carefully to avoid coagulation (which
is the reason for adding the large particle latex to the small
particle latex), it is possible to completely cover the surface of the
large particles and change their surface charge to that of the small
particles. This gives morphologies such as that shown in Figure
10(h) from which core−shell particles can be produced by
heating the latex to a temperature above the Tg of the small
particles to give them the chain mobility to coalesce with each
other to create a coherent shell.197,198 Morphologies similar to
Figure 10(h) can also be obtained by using Pickering stabilizers
(charged particles) instead of surfactants to provide colloidal
stability in miniemulsion polymerization.199
6.2.4. Particles with Chemical Functionality. Particles with
chemical functionality are important for control of latex
rheology, cross-linkable coatings and for more specialized
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applications, particularly biomedical applications. Usually,
chemical functionality is provided using f unctional monomers
that have the functional group of interest, which very often is
polar. Hence, in many cases, the monomers used to provide
chemical functionality have relatively high water solubilities and
partition strongly into the aqueous phase. For this reason, they
can only be used at low levels (typically <10 mol %). A large
number of functional groups have been incorporated into latex
particles or attached to latex particle surfaces, including
poly(ethylene glycol) chains (useful for providing steric
stabilization and for masking particles in biomedical applica-
tions)200,201 and complex functionalities (e.g., antibodies) for
latexes used in medical diagnostics;1,2 it also is possible to create
core−shell particles with molecular imprints in the shells for
diagnostic purposes,202−204 as depicted in Figure 10(k). A
review of each of these areas is beyond the scope of this paper, so
instead we focus on general principles for their incorporation.
The first consideration is the tolerance of the functional group to
free radicals and to the oxidizing effects of the usual peroxide-
based initiators. Many groups are quite tolerant, e.g., carboxylic
acid, hydroxyl, epoxide, alkylamine, sulfonic acid, alkyne,
hydroxyethylsulfonyl, and oxazoline groups all can be
incorporated by copolymerization with a monomer containing
the functional group. However, sometimes it is necessary to
attach functional groups to preformed latex particles, a topic that
will be discussed at the end of this section and is most relevant
for specialist applications where the additional cost of doing this
can be justified (e.g., in the biomedical field).
The principles for controlling the location of hydrophilic
repeat units have already been discussed in section 3.9 with
regard to use of acrylic acid and methacrylic acid for providing
carboxylic acid groups at the surface of latex particles. Hence, if
the functional monomer is very water-soluble, formation of
some functional WSP is inevitable. For more specialized
applications (e.g., biomedical) this can be an issue, in which
case the latex needs to be dialyzed with a membrane of high
porosity in order to remove the WSP chains from the latex
aqueous phase or more generally cleaned.205 In less critical
applications, e.g. latexes for coatings, this can be tolerated if the
WSP reacts chemically during film formation to become part of
the polymer matrix. For example, diacetone acrylamide
(DAAM) is widely used to provide ketone side groups for
cross-linking during film formation by reaction with the amine
groups of adipic acid dihydrazide (ADH), which is added to the
latex after its preparation.206 Even if a significant amount of
DAAM-containing WSP is present, the DAAM groups present
as copolymer repeat units in the particles react with the DAAM-
containing WSP, which then becomes cross-linked with the
particles during film formation. More hydrophobic functional
monomers will be more easily incorporated in the copolymer
particles and may become buried; if they are required only to be
near the surface, then they should be included in the final part of
the monomer mixture fed to the reactor. If designing a new
functional monomer, its ability to copolymerize well must be
borne in mind, e.g., acrylate, methacrylate, or styrenic
monomers are far better than vinylic or allylic monomers; 1,2-
substituted CC bonds are to be completely avoided because
they generally do not polymerize. Additionally, the presence of
weak bonds (e.g., allylic or benzylic C−H bonds, C−Br bonds,
and S−H bonds) that are susceptible to atom abstraction must
be avoided in order to prevent chain transfer to the functional
monomer severely limiting x̅n.
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An alternative approach for achieving surface functionality is
to use postreaction attachment, for which click reactions have
been used successfully. For example, dialyzed latexes with alkyne
surface groups will undergo the Huisgen click reaction with
azide groups on a functional compound to efficiently attach the
functional compound to the particle surface;207 the reverse
strategy also is possible.208 These reactions are limited to dilute
latexes because of the need for catalysis by copper(I) salts, so are
suitable only for high-cost applications.
Another type of functional particle are responsive microgels,
which are cross-linked particles of hydrophilic polymers that
swell considerably with a change in conditions, e.g., local pH or
temperature. They can be prepared by normal emulsion or
miniemulsion polymerization using a cross-linking comonomer
with reaction conditions under which the polymer is insoluble in
water, so that cross-linked particles are formed. They are termed
microgels because the particles are submicron size cross-linked
(i.e., network) polymers which, therefore, cannot dissolve, only
swell. The key to achieving responsive behavior is to use
functional monomers in their synthesis that confer sensitivity to
their environment. For example, a microgel containing high
levels of methacrylic acid repeat units (prepared at low pH to
ensure their incorporation into the particles; see section 3.9) will
respond to a change of aqueous phase pH from 4 to 10 by
expanding greatly due to neutralization of the carboxylic acid
groups, which then have a high affinity for water and charge
repulsion between each other.209 Another example are microgels
prepared by emulsion polymerization using N-isopropylacryla-
mide (NIPAM) cross-linked with methylene bis(acrylamide) at
temperatures above 50 °C.210 Poly(NIPAM) has a phase
transition (LCST) in aqueous media at 32 °Cbelow this
temperature it is soluble in water, but above this temperature it
loses its associated water molecules and is insoluble. Hence,
poly(NIPAM) microgels will expand greatly on cooling from 35
°C down to 30 °C, a sharp transition which can be used to
release molecules trapped in the microgel. For all types of
microgel, expansion of the microgel particles is constrained by
the cross-links, so the final swollen diameter will depend on the
degree of cross-linking. Poly(NIPAM) also has been grown from
the surface of polystyrene particles using a method of controlled
radical polymerization, thus making the particles sensitive to
temperature.211,212
6.3. Hybrid Miniemulsion Polymerization. The absence
of monomer transport across the aqueous phase is a feature of
miniemulsion polymerization that makes it especially useful in
the synthesis of hybrid materials, where one of the materials is
insoluble in water but is soluble in monomer. For instance,
alkyd-acrylic hybrid particles have been synthesized in which a
preformed alkyd is dissolved in an acrylate comonomer mixture
and then miniemulsion polymerized.213−217 Crucially, the
acrylate polymerizes in the intimate presence of the alkyd
resin, so that graft copolymers are formed which stabilize the
morphology. Attempts to produce such hybrids by conventional
emulsion polymerization fail because, as monomer diffuses out
of the monomer droplets to the latex particles, the alkyd in the
droplets becomes concentrated and eventually forms large,
unstable particles that coagulate and bring about loss of latex
stability; in addition there is no possibility for grafting (since the
alkyd is never at the locus of polymerization). Similar hybrids
incorporating polyurethanes,218−220 polyesters,213 and other
polymers,221,222 as well as inorganic223,224 materials, have been
reported. (See the review by Guyot et al.225).
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In cases where one wishes to create an aqueous dispersion of a
pre-existing polymer that cannot be produced by miniemulsion
polymerization, it is possible to dissolve the polymer in a solvent
(more volatile than, and of low, but finite, solubility in, water),
create a miniemulsion by conventional techniques, and then
carefully evaporate the solvent under controlled vacuum to
create a dispersion of the polymer.
6.4. Nanoencapsulation. Encapsulation of organic com-
pounds (e.g., drugs, dyes, perfumes) can be useful for prevention
of their diffusion or for slow release. Encapsulation of inorganic
compounds is of benefit for achieving good dispersion (e.g.,
pigments, clays) or to give the particle special characteristics
(e.g., iron oxide makes the particles respond to magnetic fields).
The principles of hybrid miniemulsion polymerization can be
applied to encapsulation of organic compounds or inorganic
compounds into latex particles. The compound needs to be
dissolved or dispersed in the monomer prior to miniemulsifi-
cation. Subsequent polymerization then encapsulates the
compound provided that it does not phase separate from the
particles during polymerization. For example, encapsulation of
titanium dioxide (TiO2) particles via miniemulsion polymer-
ization has been described by El-Aasser and co-workers.226−229
When encapsulating inorganic hydrophilic materials via
miniemulsion polymerization, it is often necessary to pretreat
the inorganic surface to make it more hydrophobic and allow
dispersion within the monomer droplets.230−232 If this is not
done, the resulting particles are often “armored” (like Pickering
emulsions) with the inorganic particles residing on the surface
(rather than the interior) of the particles. However, this is not
always necessary for emulsion polymerization, particularly with
clays, which are naturally hydrophilic, and tend to exfoliate in an
aqueous medium. After varying degrees of edge modification
(functionalization to make the surface more hydrophobic) the
clay particles and adsorbed surfactant can form hemimicelles,
which act as sites for polymerization, and the clay can be
effectively encapsulated.233
The interest in encapsulation of TiO2 is to ensure its uniform
dispersion in paints or plastic materials. In addition to use of
miniemulsion polymerization, TiO2 has been encapsulated in
particles by other methods, including heterocoagulation.
However, the most effective method was developed by Hawkett
et al. making use of RAFT.234 In this method, a low molecular
weight statistical copolymer of n-butyl acrylate and acrylic acid
(PBA-AA) is prepared by RAFT and then dissolved in an
aqueous sodium hydroxide solution at pH 5.5−8, thus
neutralizing the carboxylic acid groups. The TiO2 particles are
dispersed into this solution by milling or sonication, the PBA-AA
adsorbing to the TiO2 particle surfaces because at the pH values
used its surface is either neutral or positively charged. A water-
soluble azo initiator is added and a new comonomer mixture fed
into the reactor (e.g., methyl methacrylate and n-butyl acrylate),
which copolymerizes from the RAFT end-caps of the PB-AA,
creating a block copolymer that ultimately surrounds and
encapsulates the TiO2 particles. In this way very high efficiencies
of encapsulation of TiO2 particles have been achieved, similar to
that in Figure 10(l). The use of statistical (“random”) PBA-AA is
critical to the success because these chains have no tendency to
form micelles (if micelles of chain-extended PA-AA did form, the
RAFT end-groups would be present in them and so the micelles
would become the locus of polymerization, not the surface of the
TiO2 particles). Efficient encapsulation of phthalocyanine blue
pigment also was achieved in this way.234
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Exfoliated clay nanocomposites were first developed in the
late 1980s by Toyota, who first used them to increase the
modulus of nylon-6.235 Individual clay platelets have two major
benefits if dispersed uniformly in a coating or plastics material:
(i) they act as reinforcements and stiffen the matrix; and (ii) they
provide excellent barriers to vapor or oxygen transmission when
aligned perpendicular to the direction of flow. These benefits
can only be realized if the clay platelets can be uniformly
dispersed. Hence, there has been great interest in encapsulating
individual clay platelets in polymer particles by several methods,
including emulsion polymerization on the clay surface. By far the
most successful method has been an adaptation of the Hawkett
et al. RAFT method for encapsulating titanium dioxide.236 This
has facilitated highly efficient encapsulation of individual clay
platelets, similar to that shown in Figure 10(m).
Several methods have been used to encapsulate iron oxide
particles for diagnostic applications, including creating a shell
over ferrofluid droplets by methods of emulsion polymer-
ization237 and encapsulation by miniemulsion polymeriza-
tion.238 This gives particle morphologies like that depicted in
Figure 10(p). Hawkett et al.239 have recently used their RAFT
methodology to encapsulate clusters of a few tiny (<10 nm) iron
oxide particles for use in cell labeling.
In other work, carbon black encapsulation by emulsion
polymerization240 and miniemulsion polymerization241 has
been demonstrated. Luo et al.242 have encapsulated aqueous
solutions (potentially containing various therapeutics) via
inverse miniemulsion polymerization.
One of the reasons for interest in poly(NIPAM) is that its
LCST is close to human body temperature, which raises the
possibility of encapsulating a therapeutic drug within a
poly(NIPAM) microgel for highly localized delivery in warmed
tissue if the LCST could be raised sufficiently. This has been
achieved243 by controlling its tacticity4,5 using a specially
designed RAFT agent (to give a LCST of 37.6 °C).
Unfortunately, due to differences in the solubilities of NIPAM
and the RAFT agent, miniemulsion polymerization of this
system has not been realized.
6.5. Hollow Particles. Hollow particles, of the type depicted
in Figure 10(i), have found an important application as organic
opacifiers for water-borne coatings that can replace the inorganic
pigments (such as TiO2) normally used for this purpose. This
highly innovative, clever technology was first developed by
Rohm & Haas (now part of Dow Chemical)244 and is marketed
under the trade name “Ropaque”. The principle for preparation
of the hollow particles is as follows. The first stage involves
preparation of a latex of lightly cross-linked carboxylic acid
containing copolymer particles (e.g., 15−30 wt % methacrylic
acid) at controlled pH to ensure the acid groups are protonated
so that particles can be formed. In the second stage, the first-
stage particles are grown with a completely coherent shell of a
high Tg copolymer (e.g., Tshell
g of 80−95 °C) that contains a
much lower level of carboxylic acid groups (e.g., 1−5 wt %
methacrylic acid), just sufficient to make the shell permeable to
aqueous base. In the third stage, the core−shell latex is heated to
a temperature ≳ Tshellg and an aqueous base (e.g., ammonium
hydroxide) is added which is able to diffuse through the shell to
neutralize the acid groups of the core copolymer. This causes the
core to swell significantly (for the reasons described for acid-
containing microgels in section 6.2.4) such that the shell is
inflated and the whole particle becomes much bigger. The
swollen core−shell morphology is then locked in place by
cooling the latex to a temperature well below Tshell
g (so the shell is
pubs.acs.org/Biomac Review
then rigid). The final latex is blended with a film-forming latex to
create a coating formulation, which when cast or painted into a
film loses water by evaporation, including the water from inside
the swollen core−shell particles. Since the shell remains rigid,
the loss of water from the swollen core eventually leads to
mechanical failure of the core copolymer and it collapses to the
inner wall of the shell. When the coating is fully dry, these hollow
particles (ultimately filled with air that has diffused into the film)
are embedded in a matrix of the film-forming polymer, which
typically has a refractive index of 1.4−1.5, so the hollow particles
cause light scattering and the film is made opaque. The opacity
depends on the concentration of the hollow particles and their
size, which is tuned to maximize light scattering.
Using the principles of the Rohm & Hass process, Hawkett et
al.245 have adapted their RAFT method for encapsulation of
TiO2 particles to produce what they call nanorattles, which in
application have a morphology like that in Figure 10(n). In this
case, the TiO2 particles are dispersed in an aqueous solution of
PBA-AA RAFT copolymer in protonated form, which surrounds
individual TiO2 particles. The PBA-AA encapsulated TiO2
particles are then coated with a shell of high Tg copolymer in
the next stage by RAFT-controlled chain extension of the PBA-
AA copolymer. The next step follows the Rohm and Haas
approach. The dispersion is heated to a temperature ≳ Tshell g and
an aqueous base is added, which diffuses through the shell to
neutralize the acid groups of the inner PBA-AA copolymer,
causing it to swell considerably and inflate the shell. In a third
stage, the inflated shell is grown to greater thickness by
polymerization of divinylbenzene, before cooling the dispersion
to room temperature, which makes the (now thicker) shell rigid
because it is well below Tshellg . Individual encapsulated TiO2
particles are now each within a swollen PBA-AA inner phase
surrounded by a rigid shell, locking the swollen morphology in
place. When these particles are blended with a film-forming latex
and coated, the swollen inner PBA-AA will fracture due to loss of
water and will collapse onto either the inside of the shell and/or
onto the surface of the encapsulated TiO2 particle. This leaves a
void within which there is a single TiO2 particle, hence the name
nanorattle. The significance of this is that the refractive index
difference is not just between the void (i.e., air) and the matrix
polymer, but also between the void and TiO2, which has a high
refractive index of 2.8. Hence, the nanorattles give much greater
light scattering and opacity.
Very large hollow particles of polystyrene with diameters of
6−8 μm and narrow PSDs have been formed by using a porous
glass emulsification technique to create large droplets of styrene
containing hexadecane and then polymerizing the droplets,
during which the polystyrene phase separates to form a shell.246
A very unusual type of “hollow” particle, termed a parachute
morphology because of its appearance (see Figure 10(j)) results
from polymerization of monomer within the walls of vesicles.247
Polymerization takes place within the walls of the vesicle, but
mostly occurs at a single point; the final vesicle is delicate and
filled with aqueous phase.
7. LATEX RHEOLOGY
As is true for most complex fluids, the rheology of polymer
latexes is generally non-Newtonian, and so viscosity can only be
reported at a given shear rate. At low shear rates, the viscosity is
high and then drops markedly as the shear rate increases and the
latex transitions from a relatively disordered state to a relatively
ordered state. At even higher shear rates, disorder is induced
again, and the measured viscosity increases. Within a given
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Biomacromolecules
intermediate range of shear rates, the viscosity is a function of
several properties of the latex, e.g., in decreasing order of
importance: aqueous continuous phase viscosity, dispersed-
phase particle volume fraction, average particle size, and PSD.
The Krieger−Doherty Equation248 for viscosity of an aqueous
dispersion of impermeable spheres is most commonly used to
ÅÄÅ ÑÉÑ−2.5ϕmax
interpret latex viscosity
ÅÅ jij ϕdp zyzÑÑÑ
Å
= ηaq ÅÅÅ1 − jjj zÑ
j ϕmax zzzÑÑÑÑ
ÅÅ
ÅÇ k {ÑÖ
ηdisp
(24)
where ηdisp and ηaq are the viscosities of the dispersion and
aqueous continuous phase, respectively, ϕdp is the volume
fraction of impermeable spheres (dispersed phase), and ϕmax is
the maximum possible volume fraction of the spheres (which
depends on the particle packing). The equation is applicable for
all values of ϕdp up to ϕmax. For latexes, the value of ϕdp is for the
hydrodynamic particle, including all species that move with the
particle. The equation shows that the most important factor
determining the viscosity of a latex is the aqueous phase
viscosity, which can be greatly increased by the presence of
water-soluble polymers added to enhance colloidal stability or
produced during polymerization or added post reaction to
facilitate greater control of latex rheology (see section 3.6.2).
The second most important factor is the dispersed-phase
volume fraction ϕp and as its value approaches ϕmax (=0.74 for
hexagonal close packing of monodisperse particles), the latex
viscosity rises rapidly; the latex then becomes like a semisolid
gel.
The PSD is important in that a latex with a broad PSD will
have a much lower viscosity than one with a narrow PSD at the
same dispersed-phase volume fraction. This is due to the fact
that small particles can fit into the interstices between large ones,
such that a higher dispersed-phase volume fraction can be
achieved for a given viscosity. This is the basis for producing
multimodal PSD latexes that have manageable viscosities at very
high polymer contents, up to 70−80 wt % (see section 3.7).
Several factors can alter the effective dispersed-phase volume
fraction and, therefore, latex viscosity. Carboxylated latexes have
particles with surface carboxylic acid groups (e.g., from
copolymerization with methacrylic acid), which when neutral-
ized with added base will cause the particles to swell due to
charge repulsion between the ionized acid groups and their high
affinity for water. Swelling of the particles increases the effective
dispersed-phase volume fraction and so increases the latex
viscosity−the effect can be large if the latex has a high dispersed-
phase volume fraction before neutralization. A latex containing
particles with a thick electrical double layer on the surface will
have a higher viscosity than one with a thin electrical double
layer (e.g., compressed by added salts, see section 3.1). This is
because the effective dispersed-phase volume fraction includes
any species (in this case, counterions) that move with the
particle. Finally, if a latex has nonspherical particles, its viscosity
will be higher than that of a latex of spherical particles with the
same dispersed-phase volume fraction because, as the non-
spherical particles rotate, they sweep out a hydrodynamic
volume that is larger than their actual volume, resulting is an
apparent increase in dispersed-phase volume fraction.
8. SUMMARY
A comprehensive overview of the fundamentals of emulsion
polymerization and related processes has been presented with
pubs.acs.org/Biomac Review
the object of providing new researchers to this field with the
necessary theoretical and practical understanding to begin using
the various processes effectively and creatively in ways that avoid
common mistakes. The overview has been written for a general
scientific audience with no prior knowledge assumed. It balances
coverage of mechanistic and theoretical understanding, with
sufficient insight into the opportunities for exploitation of the
multitude of types and sizes of colloidal particles that can be
created by these processes, to provide readers from any
background with the necessary foundation to realize the
opportunities this opens in their research.
Some of the key messages are (i) these processes are complex
and a good understanding of the mechanisms operating is
essential to controlling them; (ii) the idealized (and most widely
presented) explanation of emulsion polymerization set out by
Harkins, Smith, and Ewart, while a good starting point, rarely is
observed in practice; (iii) there is a need to understand the
conditions under which the three mechanisms of particle
nucleation operate; (iv) the related concepts of segregation
(compartmentalization) of propagating radicals into submicron
size particles and the average number of radicals per particle (n̅)
are crucial to understanding and deliver the unusual kinetics
associated with these methods of polymerization; (v) the time
between radical entry events into particles is long (typically 1−
100 s) and is the reason why it is possible to achieve high rates of
polymerization and high molecular weights when n̅ ≤ 1 and why
chain transfer to monomer often dominates the killing of
propagation; (vi) it is important to recognize that monomer
water solubility has major effects on kinetics, including effects on
particle nucleation and the effects of differential partitioning of
monomers in copolymerizations between the aqueous, mono-
mer droplet, and particle phases; (vii) in practical applications,
the uncertainties of nucleation are best eliminated by using seed
latexes or miniemulsion polymerization with polymeric
costabilizers; (viii) preparing particles with a narrow particle
size distribution requires the use of emulsion polymerization
with either seed latexes or constraint of particle nucleation to the
first few percent conversion of monomer, and then achieving
controlled particle growth without secondary nucleation or
limited coagulation of the particles; (ix) in most practical uses of
emulsion polymerization, semibatch processes run under
starved conditions are necessary to achieve control of copolymer
composition and particle morphology; (x) chain transfer to
polymer will be very significant in acrylate and vinyl ester
homopolymerizations when the concentration of monomer in
the particles is low (i.e., interval III and starved polymerizations)
leading to branching and possible cross-linking; (xi) grafting of
water-soluble polymers (WSPs) to particle surfaces is possible
via chain transfer to WSP chains in the aqueous phase, but
grafted polysaccharide chains will undergo rapid degradation
when monomer concentration is very low if using peroxy
initiators; (xii) control of particle morphology requires careful
design and control of reaction conditions, for which the ground
rules are well established; (xiii) great opportunities exist for
creating novel materials, including functional particles, hybrid
particles, hollow particles, and encapsulation of other substances
into polymer particles using emulsion and miniemulsion
polymerization and methods of controlled radical polymer-
ization; (xiv) all the equations for reaction kinetics presented in
this overview are instantaneous, so apply only at a particular
instant in time for the local (not overall) concentrations and
values of rate parameters existing at that moment in the locus for
which the equation applies.
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Biomacromolecules pubs.acs.org/Biomac Review

The list just given may be considered long, but it is only a ϕp volume fraction of polymer in a particle
starting point and reflects the complexities of the processes. reversible-addition−fragmentation chain-transfer pol-
Together with deeper reading, it will be a good check list for RAFT ymerization
those new to the field when planning how to use these extremely Rp rate of polymerization
versatile methods for preparation of polymer colloids. The [S]0 initial concentration of surfactant per unit volume of
opportunities for innovation are enormous and will be delivered water
most effectively through understanding and control of these [TA]p concentration of transfer agent in the particles
complex polymerization processes, which is the principal Tg glass transition temperature
purpose of this overview. WSP water-soluble polymer

■ AUTHOR INFORMATION
Corresponding Authors
Peter A. Lovell − Department of Materials, School of Natural
Sciences, The University of Manchester, Manchester M13 9PL,
United Kingdom; orcid.org/0000-0002-5544-9185;
Email: pete.lovell@manchester.ac.uk
F. Joseph Schork − School of Chemical and Biomolecular
Engineering, Georgia Institute of Technology, Atlanta, Georgia
30332-0100, United States; orcid.org/0000-0001-8963-
7152; Email: joseph.schork@chbe.gatech.edu
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.biomac.0c00769
Notes
The authors declare no competing financial interest.
x̅n
(x̅n)0
number-average degree of polymerization
number-average degree of polymerization in the
absence of chain transfer for homogeneous free-radical
polymerization
(x̅n)EP
0 number-average degree of polymerization in the
absence of chain transfer for emulsion polymerization
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