120 MICROCELLULAR PLASTICS Vol.

MICROEMULSION POLYMERIZATION
Introduction

The pioneering work on microemulsions was established in the late 1940s (1,2).
Extensive studies on this unique colloidal system were carried out after the 1974
oil crisis. This then led to great interest in free-radical polymerization in vinyl
monomer containing microemulsion. Microemulsion polymerization involves the
propagation reaction of free radicals with vinyl monomer in very fine oil (or wa-
ter) droplets dispersed in the continuous aqueous (or oily) phase. Unlike the
classical emulsion, the transparent or translucent reaction system comprising
microemulsion droplets is thermodynamically stable in nature and these tiny
droplets (1–10 nm in diameter) exhibit an extremely large oil–water interfacial
area (∼105 m2 /dm3 ). Relatively stable polymer particles (∼10 nm in diameter)

Encyclopedia of Polymer Science and Technology. Copyright John Wiley & Sons, Inc. All rights reserved.
Vol. 7 MICROEMULSION POLYMERIZATION 121

consisting of only a few polymer chains per particle are produced and, there-
fore, the resultant polymer molecular weight is very high (106 – 107 g/mol) (3–7).
This cannot be achieved readily by conventional emulsion polymerization (8,9) or
miniemulsion polymerization (10). In addition, the particle nucleation and growth
mechanisms and kinetics associated with microemulsion polymerization are quite
different from those of emulsion and miniemulsion polymerization systems (see
HETEROPHASE POLYMERIZATION). Research interests in microemulsion polymeriza-
tion techniques have grown rapidly since the 1980s because of their potential
applications in the preparation of fine latex particles, ultrahigh molecular weight
water-soluble polymers (flocculants), novel porous materials, polymeric supports
for binding metal ions, conducting polymers, colloidal particles containing various
functional groups for the biomedical field, and transparent colloidal systems for
photochemical and other chemical reactions (5).

Formation and Microstructure of Microemulsion

Considering a colloidal system at constant temperature, volume, and composition,

the change of Helmholtz free energy (dF) for any process undergoing the expansion
of the oil–water interfacial area (dA > 0) can be expressed as

dF/dA= σ − Wdes (1)

where σ is the oil–water interfacial tension and W des is the work of desorption of
surfactant per unit interfacial area. W des is the resultant of various components
such as changes of entropy and surface charge density and molecular interac-
tions between constituents of the interfacial film. When W des is sufficiently large
and σ is extremely small (∼10 − 3 mN/m or lower), dF/dA becomes negative and,
therefore, dF is smaller than zero. Under the circumstances, a spontaneous re-
duction in the average droplet size down to 100 – 101 nm is achieved, thereby
leading to a thermodynamically stable colloidal system (microemulsion). For ex-
ample, a gradual transition from the milky oil-in-water (O/W) emulsion to the
transparent microemulsion and then to the lamellar gel phase can be observed
visually when 1-pentanol (C5 OH, approx. 0.4 g each time) is added successively
to the mixture comprising 100 g of water, 11 g of sodium dodecyl sulfate (SDS),
and 5.92 g of styrene (ST) only with mild mixing at room temperature. Incor-
poration of amphipathic cosurfactant (C5 OH) into the adsorbed layer of anionic
surfactant (SDS) around oil (ST) droplets greatly decreases the electrostatic re-
pulsion force between two surfactant molecules, minimizes σ , and reduces the
persistence length of the interfacial film (ie, enhances the flexibility of the in-
terfacial membrane). All these synergistic factors promote the spontaneous for-
mation of a transparent one-phase microemulsion product that exhibits excellent
fluidity. It should be noted that cosurfactant is not a must in the preparation of
microemulsion.
Figure 1 shows a schematic representation of the pseudo three-component
phase diagram of a surfactant/cosurfactant–oil–water system. Depending on
formulas, fine oil droplets dispersed in the continuous aqueous phase [O/W (or
direct) microemulsion] or fine water droplets dispersed in the continuous oily
122 MICROEMULSION POLYMERIZATION Vol. 7

Surfactant/cosurfactant

50 50
c

a b

Water 50 Oil

Fig. 1. A schematic representation of the pseudo three-phase diagram of

surfactant/cosurfactant–oil–water systems: (a) oil-in-water microemulsion; (b) water-in-oil
microemulsion; (c) bicontinuous structure; (d) lamellar structure; and (e) conventional
two-phase emulsion.

phase [W/O (or inverse) microemulsion] are obtained. The intermediate region
between the O/W microemulsion phase and W/O microemulsion phase is charac-
terized by a bicontinuous structure in which the aqueous and oily microdomains
are interconnected with each other (11,12). Such a middle phase was verified by
the literature data (13). It was shown that the oil–water interfacial layer in the
bicontinuous structure has a zero-mean curvature (ie, it is flat on the average)
and this sponge-like structure is completely disordered. Such a structural aspect
of microemulsion allows the monomer to be incorporated into different phases in
the polymerization system [eg, the dispersed phase (microemulsion droplets), the
continuous phase, or the bicontinuous phase]. This then makes it practical to de-
sign and prepare versatile microemulsion polymers for a variety of applications.
The information on the initial condition of the reaction system (eg, the type of mi-
croemulsion, the dimension of microemulsion droplets, the physical properties of
the oil–water interfacial film, the distance between two droplets, and the viscosity
of microemulsion) is required in order to gain a better understanding of the sub-
sequent polymerization kinetics and mechanisms. For more detailed information
on this subject, please refer to References 3–5,14, and 15.

Microemulsion Polymerization Mechanisms and Kinetics

Significant research efforts have been devoted to the free-radical polymerization

of hydrophobic monomers [eg, ST, methyl methacrylate (MMA), and butyl acry-
late (BA)] in O/W microemulsions. The anionic surfactant SDS in combination
with a short-chain alcohol (eg, C5 OH) as the cosurfactant is the most popular
stabilization package. However, as more polymer forms with the progress of poly-
merization, the increase of free energy as a result of the conformational limita-
tion and/or incompatibility between polymer and cosurfactant results in the in-
stability or turbidity of microemulsion polymer (16). When a cationic surfactant,
Vol. 7 MICROEMULSION POLYMERIZATION 123

dodecyltrimethylammonium bromide (DTAB), was used to stabilize the ST mi-

croemulsion polymerization, eventually no cosurfactant was required to form a
satisfactory microemulsion product (17). It should be noted that the amount of
monomer that can be solubilized within microemulsion droplets is generally quite
low, whereas the levels of surfactant and cosurfactant required to stabilize the
colloidal system are very high in O/W microemulsion products. For example, the
weight percentage of ST does not exceed a few percent, which is much smaller
than that of surfactant/cosurfactant (approx. 15% total) used in microemulsion
polymerization. The acrylic monomer BA can partition into the oil–water interfa-
cial layer to some extent. Therefore, it promotes the formation of microemulsion
in the absence of a typical cosurfactant such as C5 OH (18).
The most widely investigated hydrophilic monomer in the W/O microemul-
sion polymerization is acrylamide (AM). In this case, AM is usually dissolved in
water [50/50 (w/w)] immediately before the preparation of microemulsion because
AM is in powder form. Thus, the resultant polymer particles are swollen with
water and dispersed in the continuous organic medium. These polymer prod-
ucts are widely used for the flocculation of colloidal dispersions, sewage treat-
ment, coatings, adhesives, and enhanced oil recovery (see ACRYLAMIDE POLYMERS).
Just like the hydrophobic monomer BA, AM also tends to migrate toward the
oil–water interfacial layer and it acts as a reactive cosurfactant in the forma-
tion of the W/O microemulsion using toluene as the continuous medium (19,20).
Sodium bis(2-ethylhexyl) sulfosuccinate (AOT) is the anionic surfactant of choice.
The polymerization can be initiated by thermal initiators, photochemical initia-
tors, or γ -radiolysis. The W/O microemulsion polymerization system also suffers
from the drawback that a very high ratio of surfactant to monomer (the ratio of
surfactant to monomer = 2.5–25) is generally required to stabilize this colloidal
system. The basic formulas, characteristics, and kinetic parameters of some rep-
resentative O/W and W/O microemulsion polymerization systems can be found in
References 3–7 and 4 and 5, respectively.
Candau and co-workers (19,21) proposed a mechanistic model for particle nu-
cleation and growth in the W/O microemulsion polymerization system comprising
AOT, AM/water, and toluene. They observed that the diameter of the resultant
latex particles (dp = 20–40 nm) is much larger than that of initial microemulsion
droplets (dm = 6 nm), that is, the final number of latex particles (N p ) is approxi-
mately two to three orders of magnitude smaller than the number of microemul-
sion droplets initially present in the polymerization system (N m ). Furthermore, on
the average, only one polymer chain per particle was obtained. Based on these re-
sults, it was postulated that latex particles are nucleated continuously throughout
the polymerization. This is not the case for the conventional emulsion polymeriza-
tion in which the nucleation of latex particles stops at about 10–20% conversion (9).
The growth of latex particles was attributed to the very limited fraction of initial
microemulsion droplets that can be transformed successfully into latex particles.
The remaining droplets only serve as a reservoir to supply particle nuclei with
monomer and surfactant during the polymerization. The transport of monomer
molecules from microemulsion droplets to latex particles can be achieved either
by molecular diffusion through the continuous organic phase or by the mutual col-
lision between one droplet and one latex particle. Monomer-swollen micelles (ie,
microemulsion droplets) are present throughout the polymerization because of the
124 MICROEMULSION POLYMERIZATION Vol. 7

very high level of surfactant used to stabilize the colloidal system. The probability
for primary radicals generated in the continuous organic phase to enter these mi-
celles with a very large oil–water interfacial area is much higher in comparison
with latex particles. Thus, the nucleation of latex particles is carried into the lat-
ter stage of polymerization and each latex particle is capable of capturing only
one free radical during its lifetime on the average. This particle nucleation mech-
anism was verified experimentally (20). It was shown that N p increases linearly
with monomer conversion. On the other hand, dp remains relatively constant with
the progress of polymerization. Such reaction mechanisms with some minor mod-
ifications may also be adequate for the qualitative description of the nucleation
and growth of latex particles in the O/W microemulsion polymerization.
The O/W microemulsion polymerization system such as SDS/C5 OH–
ST/water has been investigated extensively in the last decade. Representative
studies conducted by Guo and co-workers (22–25) are chosen for discussion here-
inafter. Sodium persulfate (SPS) and 2,2 -azobis(2-methyl butyronitrile) (AMBN)
were used as the water-soluble and oil-soluble initiators, respectively, in their
experiments. The rate of polymerization (Rp ) first increases to a maximum with
the progress of the reaction (Region I, ranging from 0 to 20–25% conversion for
polymerizations initiated by SPS and ranging from 0 to 10–15% conversion for
polymerizations initiated by AMBN) and then decreases toward the end of the re-
action (Region II). A schematic representation of Rp versus conversion (X) profile
for the O/W microemulsion polymerization is shown in Figure 2a. For compari-
son, a typical Rp versus X profile for the conventional emulsion polymerization is
also included in Figure 2b. It should be noted that the constant Rp period, often
observed in conventional emulsion polymerization, is absent from microemulsion
polymerization (Fig. 2). Furthermore, the gel effect [ie, the rapidly increased X
with time (t) owing to the greatly retarded bimolecular termination reaction] is
not experienced in the latter stage of microemulsion polymerization. This is sim-
ply because the resultant latex particles are not large enough (dp = 20–30 nm) to
accommodate more than one free radical therein.
Guo and co-workers (22–25) also showed that the nucleation of latex parti-
cles occurs throughout the polymerization. Microemulsion droplets (ie, monomer-
swollen micelles, dm = 4 nm) are primary loci for the nucleation of latex parti-
cles. However, the nucleation of particle nuclei in the continuous aqueous phase
[homogeneous nucleation (8,9)] and limited flocculation of these particle nuclei
cannot be completely ruled out. The molecular weight of polymer obtained is
very large (1 × 106 – 2 × 106 g/mol) because of the predominant chain trans-
fer of polymeric radicals to monomer inside the growing latex particles. The
resultant monomeric radicals may desorb out of the very small latex particles,
thereby leading to a value of the average number of free radicals per particle
(n) smaller than 0.5. These monomeric radicals in the continuous aqueous phase
may also be reabsorbed by latex particles. A mechanistic model was developed to
simulate the reaction kinetics of the ST microemulsion polymerization. The en-
try rate coefficient of free radicals into microemulsion droplets estimated by this
model is 7 × 105 cm3 /(mol · s), which is several orders of magnitude smaller than
that of radicals into the monomer-swollen polymer particles. This is most likely
due to the condensed interfacial layer of SDS and C5 OH on the microemulsion
droplet surface, which acts as a physical barrier to the incoming radicals. As a
Vol. 7 MICROEMULSION POLYMERIZATION 125

ΙΙ
Ι

Polymerization rate

0 0.5 1
(a)

Ι ΙΙ
Polymerization rate

ΙΙΙ

0 0.5 1
Fractional conversion
(b)

Fig. 2. A schematic representation of the rate of polymerization versus conversion

profile: (a) oil-in-water microemulsion polymerization and (b) conventional emulsion
polymerization.

result, only a small fraction (∼10 − 3 ) of microemulsion droplets initially present

in the reaction system can be successfully converted into latex particles. A sat-
isfactory agreement between the experimental data and model predictions was
achieved. However, the extremely small entry rate coefficient of free radicals into
microemulsion droplets was thought to be physically unreasonable because this
would lead to the greatly enhanced bimolecular termination rate in Guo’s model
(26).
Morgan and co-workers (26) derived the following compact equation for pre-
dicting microemulsion polymerization kinetics.


ln(1 − X) = − f kd [SPS]0 kp [ST]d,0 t2 [ST]0 (2)

The parameter f is the initiator efficiency factor, kd is the initiator decom-

position rate constant, kp is the propagation reaction rate constant, and [ST]d,0
and [ST]0 are the initial monomer concentrations in microemulsion droplets and
in the polymerization system, respectively. This kinetic model was based on the
assumption that (1) all the free radicals generated in the continuous aqueous
126 MICROEMULSION POLYMERIZATION Vol. 7

phase enter microemulsion droplets (ie, particle nucleation loci) and initiate the
polymerization therein, (2) the bimolecular termination reaction in the aqueous
phase is negligible, (3) the entry of radicals into latex particles is insignificant, and
(4) the growing polymeric radical in a latex particle is primarily terminated by
the chain-transfer reaction. According to equation 2, plotting the ln(1 − X) versus
t2 data should result in a straight line with a slope of (−fkd [SPS]0 kp [ST]d,0 /[ST]0 ).
This simple model predicts the behavior of the n-hexyl methacrylate (C6 MA) mi-
croemulsion polymerization reasonably well. In fact, it is the only existing model
that can predict the course of microemulsion polymerization depicted schemat-
ically in Figure 2a. The general validity of this kinetic model was assessed by
several sets of experimental data obtained from the ST microemulsion polymer-
ization, and the poor performance of equation 2 in the high conversion region was
often observed (27–30). Such a discrepancy between the experimental data and
model predictions was attributed to the bimolecular termination and diffusion-
controlled propagation reactions (28).
The technique of pyrene fluorescence intensity measurements was proposed
to study the particle nucleation mechanisms involved in the O/W microemulsion
polymerization (31). The experimental data showed that microemulsion droplets
are the major particle nucleation loci for the polymerization system with the more
hydrophobic ST as the monomer. This is followed by the flocculation of latex parti-
cles with the remaining droplets. In contrast, the polymer reactions taking place
initially in the continuous aqueous phase (homogeneous nucleation) plays an im-
portant role in the MMA microemulsion polymerization.
The feasibility of using a water-insoluble dye to investigate the particle nu-
cleation mechanisms in the ST microemulsion polymerization has been evalu-
ated (30). The parameters chosen for this study include the cosurfactant type
(Ci OH, i = 4, 5, 6), the SPS concentration, and the initiator type [the oil-soluble
2,2 -azobisisobutyronitrile (AIBN) versus water-soluble SPS]. Most of the dye
molecules are solubilized within microemulsion droplets immediately before the
start of polymerization. Dye molecules can be incorporated into latex particles
only when free radicals enter these droplets and successfully convert them into
particle nuclei. Primary particles nucleated in the continuous aqueous phase (ho-
mogeneous nucleation) should not contain any dye because the transport of dye
molecules from droplets or latex particles, across the continuous aqueous phase,
and then into latex particles originating from homogeneous nucleation is prohib-
ited because of the very low water solubility of dye. Thus, the weight percentage
of dye ultimately incorporated into final latex particles (Pdye ) serves as an indica-
tor for the extent of nucleation in microemulsion droplets. The dye content (Pdye )
increases with increasing alkyl chain length of alcohols. Based on these experi-
mental data, it was postulated that the importance of homogeneous nucleation in
decreasing order is C4 OH > C5 OH > C6 OH. Guo and co-workers (22) showed that
N p increases with an increase in the persulfate initiator concentration. This trend
was attributed to the enhanced flux of free radicals into microemulsion droplets. It
was suggested in Reference 30 that the increase of the SPS concentration not only
promotes the capture of radicals by microemulsion droplets but also increases the
probability for oligomeric radicals to precipitate out of the aqueous phase and then
form particle nuclei. The latter effect may override the former, thereby leading to
the decreased Pdye with the SPS concentration.
Vol. 7 MICROEMULSION POLYMERIZATION 127

Chern and Wu (30) also investigated the influence of the oil-soluble initiator
AIBN on the particle nucleation and growth mechanisms in the ST microemulsion
polymerization. Considering the limiting case that the particle nucleation process
is controlled predominantly by the formation of AIBN radicals in the monomer
phase, the value of Pdye should be much larger compared to the ST microemul-
sion polymerization initiated by SPS. However, this is not the case because the bi-
molecular termination reaction between two neighboring AIBN radicals produced
in pair in the very small microemulsion droplets is significant. It was then postu-
lated that the particle nucleation process involves (1) the desorption of one radical
out of the microemulsion droplet containing two AIBN radicals, followed by the
propagation reaction between the remaining AIBN radical and monomer, (2) the
entry of one radical into the microemulsion droplet containing two AIBN radicals,
followed by the bimolecular termination reaction and the subsequent propagation
reaction between the survivor and monomer, or (3) the entry of one radical into
the microemulsion droplet containing no radicals, followed by the propagation
reaction between this radical and monomer therein. For the microemulsion poly-
merization initiated by AIBN, the particle nucleation process is characterized by
a very low efficiency for the initiation reaction. Under the circumstances, a much
higher AIBN concentration is required to give a value of Pdye comparable to that
of the SPS-initiated polymerization.
Kaler and co-workers (26,28,32–36) have contributed a series of papers deal-
ing with the effects of a number of kinetic parameters (eg, the monomer parti-
tioning, bimolecular termination reaction, and diffusion limitation to the prop-
agation reaction) on the reaction kinetics, latex particle size distribution, and
polymer molecular weight distribution in various O/W microemulsion polymer-
ization systems. Analytical expressions based on a mechanistic model were devel-
oped to predict the polymer particle size and molecular weight distributions (32).
These computer simulations were verified by the experimental data obtained from
quasielastic light scattering (QLS) and gel-permeation chromatography (GPC)
(32) and online small-angle neutron scattering (SANS) (33). The results obtained
from SANS also showed that the C6 MA monomer does not swell polymer par-
ticles during microemulsion polymerization (33). Mixed cationic surfactants of
dodecyltrimethylammonium bromide and didodecyldimethylammonium bromide
were used to stabilize this colloidal system. A model based on the latex parti-
cle comprising a polymer core surrounded by a monomer-rich shell is consistent
with the kinetic data, and SANS measurements provided that the concentra-
tion of monomer in the shell is equal to that in the core of the C6 MA-swollen
micelles.
The SANS technique was further adopted to study the partitioning of
monomer between microemulsion droplets and polymer particles for various
monomers (ST, n-butyl methacrylate, t-butyl methacrylate, and C6 MA) (34).
It was found that, during microemulsion polymerization, the partitioning of
monomer is strongly dependent on the composition of microemulsion, especially
on the distance to the phase boundary in the pseudo three-phase diagram of the
surfactant/cosurfactant–oil–water system. For example, the monomer partition-
ing is linear in nature and the concentration of monomer in polymer particles
is quite low if the initial microemulsion composition is far away from the phase
boundary. In contrast, the monomer partitioning is essentially nonlinear and the
128 MICROEMULSION POLYMERIZATION Vol. 7

concentration of monomer in polymer particles is much higher if the initial mi-

croemulsion composition is quite close to the phase boundary. The experimental
data could be interpreted reasonably well by modeling the monomer partitioning
behavior as a competition between the Flory-Huggins bulk polymer free energy
and the Helfrich curvature elastic energy of the surfactant monolayer. The failure
of equation 2 was then attributed to a combined effect of the nonlinear monomer
partitioning, bimolecular termination reaction, and, in some cases, diffusion lim-
itation to the propagation reaction (35). It is also very interesting to note that the
weight-average molecular weight of polystyrene close to 1.5 × 107 g/mol, about
one order of magnitude greater than that controlled by chain transfer to monomer
(∼2 × 106 g/mol), was obtained by the technique of GPC coupled with a multian-
gle laser light scattering detector and a differential refractive index detector (36).
This was attributed to the diffusion-controlled desorption of monomeric radicals
out of latex particles in combination with chain transfer to polymer. Although the
results obtained from these studies made significant progress in this field, fur-
ther research is still required to gain a better understanding of microemulsion
polymerization mechanisms and kinetics.
In addition to the commercially available water-soluble polymers for the
treatment of wastewater (37,38), the incorporation of various functional groups
(eg, OH, COOH, and SO3 H) onto microemulsion polymer particle surfaces
for biomedical applications certainly deserves more attention (39). These func-
tionalized latex particles with a diameter of 20–30 nm exhibit an extremely
large particle surface area and they are especially effective for the adsorp-
tion of proteins, immobilization of enzymes and antibodies, and controlled drug
delivery.
Polymerization in the Continuous or Bicontinuous Phases of
Microemulsion. In an attempt to prepare hydrophobic polymers used to
encapsulate water-soluble materials, W/O microemulsion polymerization sys-
tems were evaluated in the 1980s. For example, the influence of polymerization
within the continuous organic phase (ST and acrylic monomers such as methyl
methacrylate and methyl acrylate) on the regions of stable W/O microemulsion
systems was investigated (16,40–42). It was observed that the formation of
polymer results in serious phase separation during the reaction. Therefore, a
much smaller region of stable microemulsion can be obtained in comparison with
the counterpart in the absence of polymer. These results imply that a recipe
adequate to the preparation of satisfactory microemulsion does not guarantee the
successful transformation of this microemulsion into a unique polymer product.
The factors responsible for this instability problem include changes in the
molecular conformation (the entropy effect) and interactions among constituents
(eg, monomer, polymer, and cosurfactant).
Porous polymeric materials can be prepared by the polymerization of ST
in Winsor I, II, and III microemulsions (43,44). It was found that the porosity of
polymer achieved by polymerization in the bicontinuous phase is higher than that
in the continuous phase of the O/W or W/O microemulsion. This was attributed
to the interconnected microdomains in the bicontinuous phase. In fact, the mi-
crostructure of polymer achieved is closely related to the nature of microemulsion
(45–49). For example, porous polymer with a closed-cell structure (ie, the discrete
Vol. 7 MICROEMULSION POLYMERIZATION 129

water pores are distributed throughout the polymer matrix) is produced when the
polymerization of the W/O microemulsion takes place. In contrast, polymeriza-
tion in the bicontinuous phase results in porous polymer with an open-cell struc-
ture in which water channels are interconnected throughout the polymer matrix.
These results strongly indicate that the morphology of the resultant porous poly-
mer retains the initial structure of microemulsion to some extent. Nevertheless,
the dimension of the resultant porous microdomains (∼103 nm) is much larger
than that of the initial structure of microemulsion (<102 nm) as a consequence
of phase separation with the progress of polymerization. A recent breakthrough
showed that it is possible to produce polymer with a pore size of 50–70 nm, which
is on the order of that of the precursor microemulsion (50). The potential applica-
tions of such a polymerization technique for preparing novel polymeric materials
include microfiltration, separation membranes, polymer blends with a unique mi-
crostructural morphology, and porous microcarriers for the culture of living cells
and enzymes (5). Some other interesting ideas about the preparation of novel
materials include the conductive composite film (51) and microporous silica gel
(52).

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CHORNG-SHYAN CHERN
National Taiwan University of Science and Technology

MICROGELS. See SMART MATERIALS, MICROGELS.

MICROMECHANICAL PROPERTIES. See Volume 3.