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REVIEW www.rsc.

org/softmatter | Soft Matter

Synthesis and applications of emulsion-templated porous materials


Haifei Zhang and Andrew I. Cooper*
Received 22nd February 2005, Accepted 19th April 2005
First published as an Advance Article on the web 27th May 2005
DOI: 10.1039/b502551f

This review describes the use of macroemulsions as templates for the production of porous
materials. We focus on the use of high internal phase emulsions in order to produce
interconnected open porous structures. The review encompasses porous hydrophobic polymers,
hydrophilic polymers, composites, silica, metal oxides, and metals. The potential applications of
these materials are also discussed.

1 Introduction porous materials.4 Polymerisation of both the droplet phase


and the continuous phase results in the production of
Emulsions are heterogeneous mixtures of at least one composites.3,5
immiscible liquid dispersed in another in the form of droplets.1
In most cases, at least one of the liquids will be water or an
aqueous solution. An emulsion is often described as either oil-
in-water (O/W) or water-in-oil (W/O) where the first phase
mentioned refers to the internal (or dispersed) phase.
Generally, emulsions have average droplet sizes of at least
several micrometres and the droplets have a rather broad
size distribution unless special procedures are adopted (e.g.,
fractionation of the emulsion). Emulsions have been investi-
gated extensively for decades and are used in a range of
common practical applications.
In the context of polymer synthesis, emulsions can be used
in three ways (Fig. 1) as templates for the preparation of
colloids, porous materials, and composite materials, respec-
tively. In order to produce colloids, polymerisation takes
place in the dispersed monomer phase, although initiation
tends to occur in monomer-swollen micelles rather than
the larger monomer droplets.2,3 In the case of an O/W
emulsion polymerisation, this process leads to an aqueous
polymer latex. By contrast, polymerisation of the continuous
phase of a concentrated emulsion followed by removal of the
internal phase leads to the formation of emulsion-templated Fig. 1 Schematic representation of polymerisation of an emulsion in
the dispersed phase, continuous phase, and both phases for the
preparation of colloids, porous materials, and composites, respectively.
*aicooper@liv.ac.uk This review focuses on the porous materials.

Haifei Zhang was born in Andrew Cooper received his


Hebei Province, China and PhD in Chemistry from
received his PhD in Chemistry Nottingham University in
in 2001 from the Institute of 1994. His research involves
Chemistry, Chinese Academy polymer synthesis, porous
of Sciences. He is currently materials, nanostructures, and
a Research Associate at supercritical fluids. This work
Liverpool University. His has been supported by EPSRC,
research has involved supercri- BBSRC, the Royal Society,
tical fluids, emulsion templat- the ACS Petroleum Research
ing, and various porous Fund, and by industry.
materials. Professor Cooper is currently
a Royal Society University
Research Fellow at the
Dr Haifei Zhang Professor Andrew Cooper University of Liverpool.

This journal is ß The Royal Society of Chemistry 2005 Soft Matter, 2005, 1, 107–113 | 107
Table 1 Summary of the synthesized emulsion-templated materials
Category Materialsa References

Hydrophobic polymer ST/DVB 10–13,25–27


VBC-ST/DVB 14
ST/DVB with high surface areas 15–18
ST/DVB-based poly(aryl ether 19
sulfone)
poly(styrene-co-alkylmaleimide) 20
ST/DVB containing PCL, PLA, 21–23,61,62
acrylate, organotin
Hydrophilic polymer Cross-linked polyacrylamide 30–34
Cross-linked PHEA and PHMA 32 Fig. 2 (a) A typical SEM image of styrene–divinylbenzene polyHIPE,
Composites Silica-containing composite 35–38
Inorganic oxide/polymer 37,38 scale bar 5 100 mm. Reprinted with permission from ref. 14,E The
Inorganic oxides Silica 36–44,46 Royal Society of Chemistry 2000. (b) An optical microscope image of
Titania and zirconia 37–39,43 monodisperse emulsion-templated polyacrylamide beads, scale bar 5
Alumina 38,39,45 10 mm. Reprinted with permission from ref. 33, E 2002 American
Metal and carbon Gold 47 Chemical Society.
Nickel 63,64
Carbon 49,50,52
a
ST/DVB indicates a polyHIPE polymer composed of the mono- 2. Synthesis of emulsion-templated porous materials
mers ST and DVB, and similarly for other polyHIPEs. Abbrevia-
tions: ST 5 styrene; DVB 5 divinylbenzene; VBC; 5 4-vinylbenzene 2.1. Hydrophobic polymers
chloride; PCL 5 poly(e-caprolactone); PLA 5 poly(lactic acid).
In 1982, researchers at Unilever patented a process for the
preparation of highly porous, cross-linked polymeric materials
There are a number ways to fabricate interconnected porous with a dry density of less than 0.1 g cm23 by polymerising the
structures, for example, by using supercritical fluids,6 gas continuous phase of a HIPE (internal phase at least 90%).10
blowing,7 self-assembled colloidal templates,8 and sacrificial These materials were branded polyHIPE. The system which
polymer templating.9 Emulsion templating is a flexible and has been most extensively studied involves a W/O emulsion
easily controlled method for the fabrication of macroporous containing styrene (ST) and divinylbenzene (DVB) (plus
materials (pore size range 5–100 mm) by polymerising the comonomers and/or porogenic solvents in some cases) as the
continuous phase of a high internal phase emulsion (HIPE) continuous phase. Fig. 2a shows a typical scanning electron
(internal phase volume . 74.05%).4 If a less concentrated microscope (SEM) image of a ST/DVB polyHIPE sample
emulsion is used (internal phase volume , 60%), a more illustrating the emulsion-templated, cellular pore structure.
closed-cell porous structure will be obtained. Materials with Williams et al.11 studied the effect of varying the monomer
closed pores may be useful for sound absorption and as concentration and surfactant level on the openness of the cells
lightweight alloys. Highly interconnected macroporous mate- in the resulting materials. They found that the variation in cell
rials are popular in applications such as separation, catalyst openness was strongly related to the surfactant-to-oil ratio.
support, tissue engineering, and membrane support. A key This research was extended to include oil phases comprised
potential advantage of introducing large macropores is that it of 100% styrene or 100% divinylbenzene.12 The effects of
enhances the mass transport of large molecules, especially in initiator, salt concentration, and the degree of cross-linking
viscous systems. were also investigated. It was found that the highest salt
This review focuses on the preparation of various emulsion- concentrations gave the smallest cells, while the cell sizes were
templated porous materials and their potential applications. insensitive to an increase in monomer concentration. Eight
Table 1 summarizes the range of emulsion-templated materials surfactants and 22 cosurfactants were further studied for their
that has been prepared. Table 2 lists some applications in influence on emulsion stability and pore structure.13 By adding
which emulsion-templated materials have been used. 4-vinylbenzyl chloride (VBC) to the ST/DVB system, the cell

Table 2 Applications of the synthesized emulsion-templated materials


Category Materialsa Applications References

Scaffolds for tissue engineering PCL-ST/DVB Cell growth 22


PLA-ST/DVB Cell growth 23
HA-ST/DVB Osteoblast growth, bone formation 53
Poly-D-lysine-ST/DVB Growth of neurons 54
Emulsion coating Protein release 55
Separation medium ST/DVB sulfonation Modules, filtration test 56
Supports for reactions ST/DVB sulfonation Hydration of cyclohexene 57
ST/DVB sulfonation Ion exchange 58
VBC/DVB amine functionalization CBC scavenger 60
Organotin chloride-ST/DVB Dehalogenation and radical cyclisation 61
Aryl acrylate based ST/DVB Reactive supports 62
Electrodes Porous nickel coating on the cathode 63,64
a
The same abbreviations apply as used in Table 1, and HA 5 hydroxyapatite; CBC 5 4-chlorobenzoyl chloride.

108 | Soft Matter, 2005, 1, 107–113 This journal is ß The Royal Society of Chemistry 2005
size could be changed significantly and it was found that the
average cell size decreased with increasing VBC content.14
The cell size in polyHIPE polymers is typically in the range
5–100 mm with the interconnecting pore size constituting
around 20–50% of the cell diameter.4 PolyHIPE polymers have
high pore volumes (up to 10 cm3 g21) but low surface areas
due to their large pore sizes. By adjusting the level of cross-
linker in the ST/DVB system and by using an inert diluent
(porogen) solvent, a secondary pore structure was generated
within the cell walls of a polyHIPE material, thus leading to a
hierarchical, interconnected pore structure.15 A much higher
surface area of 350 m2 g21 was achieved using this approach.
By using mixtures of porogenic solvents (e.g., chlorobenzene
and 2-chloroethylbenzene), a cellular material with a surface
area of 554 m2 g21 was produced.16 Recently, the morphology Fig. 3 A schematic representation of two methods for preparing
and surface area of ST/DVB polyHIPE foams prepared with porous emulsion-templated beads. (a) O/W/O sedimentation poly-
an oil-phase soluble porogen was investigated in a single merisation to produce large uniform beads (diameter y 2 mm). A
surfactant (Span 80) system17 and in a three-component concentrated O/W emulsion is injected into a hot oil medium and
surfactant (Span 20/dodecyl-benzenesulfonic acid sodium polymerised during sedimentation. (b) O/W/O or W/O/W suspension
salt/cetyltrimethylammonium bromide (CTAB)) system.18 polymerisation for the production of porous emulsion-templated micro-
Other hydrophobic polyHIPEs have been prepared by the spheres. An emulsion (O/W or W/O) is dispersed and polymerised in a
copolymerisation of certain active monomers with the ST/ continuous phase (oil or water) as micrometre-sized droplets.
DVB system. For example, the synthesis of poly(aryl ether
sulfone)19 and poly(styrene-co-alkylmaleimide)20 polyHIPEs and the materials appeared to exhibit quite broad particle size
were reported. The addition of another component or distributions.27
modification to the normal ST/DVB system can endow the
materials with specific properties for various applications (see 2.2. Hydrophilic polymers
also Section 3). Elastomeric polyHIPEs were prepared by Emulsion-templated hydrophilic polymers can be obtained by
polymerisation of an emulsion continuous phase containing sulfonation of the corresponding hydrophobic materials28 or
ST, DVB, and varying amounts of 2-ethylhexyl acrylate or the by the production of highly porous polymers with ionic or
corresponding methacrylate comonomer.21 Because of the polar groups.29 However, there have been comparatively few
highly interconnected macroporous structure, polyHIPEs reports on the preparation of hydrophilic polyHIPE foams
show promise as scaffolds for tissue engineering. PolyHIPE from hydrophilic monomers. From an applications point of
foams containing poly(e-caprolactone) (PCL) were prepared view this is perhaps surprising, especially given the broad range
from PCL macromonomers and either styrene, methyl of porous biomaterials that could be produced from an
methacrylate, or toluene used as an organic diluent.22 A aqueous continuous-phase environment. In order to obtain
similar procedure was adopted to produce polyHIPE foams emulsion-templated hydrophilic polymers, a concentrated oil
containing poly(lactic acid) (PLA).23 Deleuze et al. prepared phase must be emulsified in a continuous aqueous monomer
polyHIPE foams by ring opening metathesis polymerisation solution. For example, in a patent filed by Katagawa,30 porous
of a norbornene derivative using Grubb’s catalyst.24 It was hydrophilic polymeric materials having cavities joined by
claimed that the polymerisation had a living character, such interconnecting pores were produced. To achieve this, an
that the metal–carbene chain end remained active at the end of emulsion was suspended in an oil suspension medium (Fig. 3b),
the preparation and could thus be modified further. and the emulsion droplets were polymerised to produce
Most hydrophobic polyHIPE polymers have been prepared polymeric microbeads.
as monolithic blocks which conform to the shape of the One significant drawback to this approach (and a possible
reaction vessel in which the material is prepared. It is possible reason for the relatively small number of examples) is the large
to convert these porous monoliths into a particulate form volume of organic solvent that must be used to produce porous
by grinding, for example, but this can be an inefficient hydrophilic polymers from an O/W HIPE. Indeed, the volume
and laborious process. In an alternative approach, a W/O/W required in the synthesis may amount to 20 kg organic solvent
suspension polymerisation was performed using a concen- per 1 kg of porous polymer produced, even if one disregards
trated W/O emulsion to prepare discrete spheroidal particles any additional solvents that may be used post-synthesis to
of interconnected cellular foams (Fig. 3b). This approach wash out any residual internal oil phase. We have developed a
was disclosed in a series of patents25 and the resulting method which avoids this problem by using high internal
materials were commercialized by Biopore.26 To achieve this, phase supercritical fluid emulsions.31 For example, super-
ST/DVB W/O emulsions were injected into a stirred aqueous critical CO2 (scCO2) was emulsified in an aqueous solution of
suspension medium which contained a hydrophilic polymer acrylamide (AM) and N,N9-methylene bisacrylamide (MBAM)
as a stabilizer in order to carry out the suspension using a perfluoropolyether ammonium carboxylate (PFPE)
polymerization and to produce beaded materials. The yield surfactant and poly(vinyl alcohol) (PVA) as a cosurfactant
of beads recovered was claimed to be in the range of 65–95% to form a concentrated CO2-in-water (C/W) emulsion.31 The

This journal is ß The Royal Society of Chemistry 2005 Soft Matter, 2005, 1, 107–113 | 109
ratio of CO2 to the aqueous phase was typically 80 : 20 v/v. In 2.3. Organic–inorganic composite materials
the presence of water-soluble initiator, K2S2O8, polymeriza-
Organic–inorganic composites often exhibit enhanced
tion occurred at 60 uC and gelation of the aqueous phase was
thermal stability or additional functionality with respect to
observed. The complete removal of internal phase CO2 was
the equivalent organic materials. It is possible to produce
achieved by simple pressure reduction to produce a highly
porous, emulsion-templated organic–inorganic composites by
porous poly(acrylamide) (PAM) material. This process avoids
a number of methods. For example, methacryloxypropyl-
the use of any organic solvents either in the synthesis or
trimethoxysilane (MPS) was copolymerised with ST and DVB
purification steps. No solvent residues are left in the materials
using free radical initiation in the organic phase of a W/O
which could be advantageous for biological or medical
emulsion. Subsequent hydrolytic condensation of the tri-
applications. As first reported,31 however, the process has a
methoxysilyl groups formed an inorganic polysilsesquioxane
number of disadvantages: in particular, the PFPE surfactant is
network.35 In another method,36 tetraethyl orthosilicate
expensive and non-degradable; the monomer (AM) is toxic;
(TEOS) was first hydrolyzed to obtain TEOS sol. This sol
and the reaction pressure is rather high (300 bar). In a more
was then mixed with an aqueous monomer solution which was
extensive study,32 we addressed these issues by using a redox
used to form an O/W emulsion. Emulsion-templated silica–
co-initiator and inexpensive commercial surfactants (e.g.,
polymer composite beads were produced by a one-step O/W/O
Tween 40) to produce porous polymers at modest tempera-
sedimentation polymerization at 60 uC.36 We have also
tures and pressures (20 uC, 65 bar). In addition to PAM,
reported a more general two-step method whereby emulsion-
poly(hydroxylethyl acrylate) (PHEA) and poly(hydroxyethyl
templated PAM beads are used as scaffolds to produce
methacrylate) (PHMA) were also synthesised.32
inorganic–polymer composite materials by chemical post-
Most emulsion-templated materials have been produced as
modification of the organic material with inorganic reagents.
monolithic blocks11–24,28–32 or in the form of microspheres.30
For example, emulsion-templated polymer–silica37,38 and
We have developed an oil-in-water-in-oil (O/W/O) sedimenta-
polymer–metal oxide37,38 beads were produced in this way.
tion polymerization method to prepare monodisperse, highly
porous polymer beads (Fig. 3a).33 The yield of beads was 100%
2.4. Inorganic oxide porous materials
and the diameter of the beads was typically about 2 mm. These
materials have several advantages over other morphologies In terms of inorganic materials, emulsion-templated silica
such as ease of handling, simple separation from reaction structures have been most widely studied. For example, O/W
mixtures by filtration, and relatively easy removal of the emulsions with an aqueous solution or sol of an inorganic
internal phase of the original emulsions as a result of the precursor in the continuous phase have been gelled to produce
beaded form. To produce these materials, an O/W emulsion porous three-dimensional inorganic oxides.39 Recently, a
(light mineral oil emulsified in an aqueous solution of AM and cationic surfactant CTAB was dissolved in acidified water
MBAM) was injected into a hot oil medium (60 uC) using a and a mixture of 1,3,5-trimethylbenzene (TMB) and TEOS
syringe pump.33 The droplets of the emulsion were poly- was added slowly with stirring.40,41 A white solid was obtained
merised during sedimentation in order to lock in the structure after the sol-gel process which was washed, dried, and then
of the bead. Sedimentation lasted about 10 s: in order to calcined at 650 uC in air. The templated macroporosity was
achieve sufficiently rapid polymerisation, a redox co-initiator ascribed to the natural creaming process that occurred in the
tetramethylethylenediamine (TMEDA) was added to the O/W emulsion.40 The effect of various factors such as the
internal oil phase in addition to the initiator ammonium degree of hydrolysis of TEOS, the condensation of the silica,
persulfate (APS) which was dissolved in the aqueous phase. and the creaming or coalescence of oil or polystyrene particles
Fig. 2b shows an optical microscope image of emulsion- was also investigated.41 In another case, TEOS with surfactant
templated PAM beads prepared by this method. The beads tetradecyltrimethyl ammonium bromide (TTAB) were mixed
are very uniform with a standard deviation in diameter of in an O/W emulsion to produced a hierarchically textured
just 2%. Highly interconnected emulsion-templated pores silica monolith.42 No organic polymers were involved although
were formed which were also open to the bead surface a large quantity of surfactant was used to stabilise the
(average pore size 5 2–15 mm). The beads showed high emulsion (TTAB : TEOS # 3 : 1 by mass).
macropore volumes (.8 cm3 g21 as characterized by mercury Imhof and Pine used an oil-in-formamide emulsion to
intrusion porosimetry).33 We have also developed a com- produce ordered macroporous silica.43 Silica sols were
pressed fluid sedimentation polymerization method to prepare prepared by vigorously mixing silicon tetramethoxide with a
uniform polymer beads by injecting an aqueous monomer mixture of water and formamide acidified to pH 5 2. The
solution into a high-pressure fluid medium (e.g., a mixture emulsion was then fractioned and centrifuged to produce a
of tetrafluoroethane and CO2).34 This process avoids the use monodisperse concentrated emulsion which was templated to
of a non-volatile oil as the sedimentation medium and thus produce ordered macroporous silica. The microstructures of
greatly simplifies production separation and purification. The porous silica prepared from aqueous and nonaqueous emul-
materials produced by this route do not exhibit emulsion- sions were studied in more detail.44 In the case of silicon oil-
templated porosity,34 although in principle one could envisage in-water emulsions, it was found that the emulsion droplets
a C/W/C sedimentation polymerisation method by which it migrated and self-assembled in relatively mobile local regions,
would be possible to synthesise porous emulsion-templated which deteriorated the uniformity of the macropore struc-
beads in the complete absence of any organic solvents or non- ture.44 We have employed polymers to produce macroporous
volatile oils. silica with quite uniform mesopores by using O/W emulsions

110 | Soft Matter, 2005, 1, 107–113 This journal is ß The Royal Society of Chemistry 2005
as templates.36 First, polymer–silica composites were formed, emulsion-templated scaffold, thus avoiding direct contact of
as described above, by O/W/O sedimentation polymerisation. the inorganic precursors with the liquid–liquid emulsion.
Calcination of organic polymer led to a hierarchically porous Typically, an inorganic precursor sol (or solution) is imbibed
silica structure with a high intrusion volume (5.81 cm3 g21) into the scaffold and the targeted inorganic materials are
and a high surface area (421.9 m2 g21).36 The latter arose from then obtained by removing the organic scaffold, usually
the mesopore structure in the material. Fig. 4a shows an SEM by extraction or by calcination. Chmelka et al. used such
image of an emulsion-templated silica material produced by a method to prepare meso/macroporous inorganic oxide
this route. (silica, zirconia, titania) monoliths from polymer foams.37
In general, many inorganic precursors such as metal Macroporous polystyrene foam monoliths were prepared from
alkoxides are highly reactive to water, even towards moisture highly concentrated W/O or O/W emulsions. A self-assembling
in the air. Silica precursors such as TEOS can be hydrolyzed block copolymer/sol–gel mixture was then imbibed into the
under acidic or basic conditions and are relatively tolerant to preformed macroporous foam. Elimination of the organic
water.36,40–44 Other alkoxide precursors are highly reactive agents by solvent extraction or by calcination resulted in a
and this essentially precludes the use of O/W or W/O dual meso/macroporous inorganic material.37 We have used
emulsions. One method to circumvent the problem of uniform emulsion-templated porous polymer beads33 as tem-
precursor reactivity is to use inorganic particles instead of plates to produce various inorganic structures.38 Uniform,
molecular precursors. For example, porous alumina bodies hierarchically porous inorganic beads of silica, alumina, titania
were produced by polymerization and drying polymerizable and zirconia were prepared by simply immersing the polymer
W/O emulsions containing alumina powders.45 The total scaffold beads in an appropriate inorganic precursor solution,
porosity of the alumina bodies increased markedly with the followed by sol-gel condensation in air and subsequent
water content of the W/O emulsion. Binks has reported a calcination of the polymer phase. Fig. 4b–d shows the
simple and effective method for preparing porous silica from emulsion-templated porous structures of alumina, zirconia,
emulsions stabilized by silica particles alone.46 O/W or W/O and titania materials prepared by this method. These
emulsions were stabilized entirely by nanosized silica particles hierarchical structures are composed of mesopores (2–5 nm),
of controlled wettability with excess particles present in the micropores (in the case of silica), and large emulsion-templated
continuous phase. Macroporous silica materials with average macropores of around 5–10 mm. All of the pores in the
pore sizes in the range 5–50 mm were prepared by evaporation structures are highly interconnected.
of the two liquids in the emulsions. Another approach is to
pretreat the inorganic precursors in order to reduce their 2.5. Porous metals and carbon
reactivity. For example, titanium tetraisopropoxide can be
treated with an equimolar amount of the chelating agent 2,4- In principle, emulsion-templated metal or carbon structures
pentanedione.43 This method was employed to prepare could find a range of applications, for example as porous
ordered macroporous titania and zirconia materials using sensors or electrodes. We have found that polyacrylamide
isooctane-formamide emulsions as templates.43 beads can irreversibly adsorb gold nanoparticles from aqueous
An alternative two-step method for producing porous gold sols.47 Based on this finding, emulsion-templated gold
inorganic materials is to use a sacrificial, preformed beads were prepared using gold nanoparticles as building
blocks.47 First, emulsion-templated porous polyacrylamide
beads33 were soaked in a gold nanoparticle sol. The adsorption
of the gold nanoparticles on the polymer surface was con-
firmed by the fact that the red sol was decolourised and the
beads assumed a deep red colour. The polymer–gold compo-
site beads were then soaked in isopropanol, dried in air, and
calcined to produce uniform porous gold beads. Fig. 4e
shows the macroporous structure of a gold bead prepared
by this method. Surprisingly, the emulsion-templated structure
is completely retained, despite the high mass loss that occurs
during calcination. This method is quite versatile; for example,
preliminary results have shown that emulsion-templated
palladium beads can also be produced.48 It is also possible
to control the distribution of the gold nanoparticles in the
metal-polymer composite such that hollow gold beads can be
produced after calcination with an emulsion-templated shell
Fig. 4 Images of PolyHIPE structures of inorganic materials. (a) structure.47
silica, scale bar 5 50 mm, reprinted with permission from ref. 36, E
Porous carbon materials have been prepared by carbonizing
2003 WILEY-VCH Verlag GmbH. (b–d) the structures are, respec-
tively, alumina, zirconia, and titania. Scale bar 5 25 mm. Reprinted
a carbonizable emulsion-templated polymer structure by
with permission from ref. 38, E 2004 American Chemical Society. (e) heating in an inert atmosphere.49 For example, high internal
gold, scale bar 5 5 mm, reprinted with permission from ref. 47, E 2004 phase emulsions of ST and DVB with 0–40% vinylbenzene
WILEY-VCH Verlag GmbH. (f) carbon, scale bar 5 10 mm, reprinted chloride (VBC) in the oil continuous phase were polymerised
with permission from ref. 50, E 2005 Society of Chemical Industry. to give porous polymers.50 These materials were then

This journal is ß The Royal Society of Chemistry 2005 Soft Matter, 2005, 1, 107–113 | 111
sulfonated and carbonized at up to 700 uC to produce require chemical modification or functionalization in order
macroporous carbon monoliths, as shown in Fig. 4f. Porous to fulfil a particular application. For example, a ST/DVB
carbon can also be prepared via a silica templating method, polyHIPE was functionalized with sulfonic groups and
that is, by carbonization of a carbon precursor in the voids of then used as an immobilized catalyst for the hydration of
porous silica and subsequent removal of the silica using HF cyclohexene.57 The reaction mixture was forced through the
or NaOH solution.51,52 Similarly, an interconnected porous pores of the monolith, and flow was enabled without high back
silica with mesopores and macropores was impregnated with pressures due to the large pores in the structure. The kinetics
furfuryl alcohol (FA) by incipient wetness. FA polymerization, of the liquid-phase hydration was measured both in a three-
carbonization and subsequent removal of the silica component phase system and in a two-phase system. This type of
were carried out to produce a carbon monolith possessing a polyHIPE was also modified on its surface by sulfonation.58
hierarchical and interconnected porous structure.52 By incorporating Na+ ions onto the sulfonated surfaces, a
modular form of ion exchange resin was produced which was
3. Applications of emulsion-templated porous capable of effective exchange with metal ions in solution. In
materials single-pass dynamic adsorption tests, the material showed
better column utilization than the equivalent commercial
3.1. Scaffolds and tissue engineering resins.58 Polystyrene polyHIPEs were modified with a wide
The highly interconnected macroporosity of emulsion- variety of functional groups both in a batch method and in a
templated polymers makes them good candidates as scaffolds continuous flow method.59 In the presence of a free-radical
for biological applications such as tissue engineering, provid- initiator, compounds such as HBr and thiols underwent an
ing that an appropriate material is chosen. For example, anti-Markovnikov addition to the residual vinyl groups in the
PolyHIPE foams containing poly(e-caprolactone) (PCL)22 or polystyrene matrix. Other reactions such as hydroboration
poly(lactic acid) (PLA)23 were tested for tissue growth. These with BH3 followed by hydrolysis with H2O2 were also been
studies used whole chicken embryo explants, rat skin explants, investigated.59 Monolithic polymer supports and scavengers
or individual human skin cells. The results showed excellent were prepared by amine functionalization of poly(4-vinyl-
biocompatibility for both types of foam for the duration of benzyl chloride (VBC)-co-divinylbenzene (DVB)) polyHIPE
each experiment. Comparative studies indicated that cells materials.60 The results showed that 4-chlorobenzoyl chloride
adhered more rapidly to PCL-based materials than the PLA- (CBC) was efficiently and rapidly scavenged from solution at
containing counterparts.23 Three groups of ST/DVB ambient temperature.
polyHIPE polymers containing hydroxyapatite (HA), with An organotin chloride catalyst supported on a highly porous
pore sizes of 40, 60 and 100 mm, were evaluated as materials polymer was prepared by polymerisation of a highly concen-
for osteoblast growth and bone formation.53 The results trated reverse emulsion.61 The polymer-supported organotin
demonstrated in vitro cell-polymer compatibility, with osteo- chloride showed good activity and good stability towards
blasts forming multicellular layers on the polymer surface and dehalogenation and radical cyclisation. W/O HIPEs contain-
also migrating to a maximum depth of 1.4 mm inside the ing 4-nitrophenyl acrylate and 2,4,6-trichlorophenyl acrylate
porous matrix. This study showed that osteoblasts seeded onto as reactive monomers were prepared and polymerized to
the polymer demonstrated cellular attachment, proliferation produce highly porous monoliths.62 The monoliths proved
and in-growth, leading to the support of an osteoblastic to be very active toward nucleophiles, and possibilities of
phenotype. In another study, porous ST/DVB polyHIPE functionalizing this polymer support were demonstrated via
matrices were coated with aqueous-based solutions including reactions with amines bearing additional functional groups
poly-D-lysine and laminin.54 The growth of human stem cell- and via the synthesis of an acid chloride derivative.62
derived neurons on these porous matrices was investigated.
These results demonstrated the potential use of solid porous 3.3. Porous electrodes
scaffolds to create three-dimensional environments for cell The preparation of highly porous Ni electrode materials is
growth and differentiation. An emulsion-coating method was
relevant to a number of industrial applications of electro-
developed to release proteins in a controlled way.55 In this
chemical technology. A polyHIPE polymer matrix was used
process, a W/O emulsion generated from an aqueous protein
as a template for the preparation of porous nickel elecro-
solution and an organic polymer solution was forced through a
deposits.63 Ni-mesh electrodes were embedded into a
prefabricated scaffold by applying a vacuum. After solvent
polyHIPE by immersion in the precursor emulsion and
evaporation, a polymer film, containing the protein, was then
subsequent entrapment into the solid porous matrix produced
deposited on the porous scaffold surface. A model protein
by polymerization and drying.63 Immersing the resulted
(lysozyme) could be released in a controlled fashion from
composites into a Ni electroplating bath and passing a direct
these scaffolds.55
current through the two electrodes resulted in the growth of Ni
electrodeposits on the cathode and throughout the polymer
3.2. Reactions and separations
cells and pores. Calcination of the polymer matrix led to a
Because of their highly interconnected porous structures, granular porous Ni coating on the cathode. This method could
emulsion-templated materials can be used as separation be used to grow Ni through the polymer cells and pores.64 The
media56 and as supports for heterogeneous reagents or Ni coating showed an interconnected porous structure with a
catalysts. In the latter case, the porous structure tends to specific surface area of 49.5 m2 g21. The application of

112 | Soft Matter, 2005, 1, 107–113 This journal is ß The Royal Society of Chemistry 2005
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