Polymer 97 (2016) 598e603

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Polymer
journal homepage: www.elsevier.com/locate/polymer

Robust macroporous polymers: Using polyurethane diacrylate as

property defining crosslinker
Qixiang Jiang a, b, 1, Angelika Menner b, *, Alexander Bismarck a, b, **
a
Polymer & Composite Engineering (PaCE) Group, Department of Chemical Engineering, Imperial College London, South Kensington Campus, London, SW7
2AZ, UK
b €hringerstr. 42,
Polymer & Composite Engineering (PaCE) Group, Institute of Materials Chemistry & Research, Faculty of Chemistry, University of Vienna, Wa
A-1090, Vienna, Austria

a r t i c l e i n f o a b s t r a c t

Article history: Polymerised high internal phase emulsions (polyHIPEs) have drawn extensive interest in recent years;
Received 22 March 2016 however, industrial applications do require polyHIPEs to be tough and robust. The mechanical properties
Received in revised form of polyHIPEs can be tuned by copolymerisation of polyurethane diacrylate (PUDA) and styrene. The
24 May 2016
resulting open-porous poly(styrene-co-PUDA)HIPEs were much less brittle and friable when compared
Accepted 26 May 2016
Available online 27 May 2016
to conventional poly(styrene-co-divinylbenzene)HIPEs. Moreover, poly(styrene-co-PUDA)HIPEs have
impact strengths up to 10 times higher than poly(styrene-co-divinylbenzene)HIPEs. The styrene/PUDA
ratio determines the morphology, thermal and mechanical properties of the poly(styrene-co-PUDA)
Keywords:
Polyurethane diacrylate
macroporous polymers. The viscous PUDA promotes the formation of small pores in polyHIPEs. A high
Emulsion templating PUDA content of the copolymer results in a dual glass transition temperature and low mechanical
Impact strengths properties. By using an optimised St/PUDA ratio, we manufactured polyHIPEs with impact strength
similar to that of commercial closed-cell polyurethane foam.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction macroporous polymers, such as porosity, pore size, pore inter-

High internal phase emulsions (HIPEs) refer to emulsions con-
taining more than 74 vol% internal phase [1]. One application of
HIPEs is their use as templates for the synthesis of macroporous
polymers. This route involves making a HIPE containing monomers
in the continuous phase and an inert liquid as internal/dispersed
templating phase. After the polymerisation and purification, mac-
roporous polymers called poly(merised)HIPEs are produced. This
method was first reported by Bartl and von Bonin [2], and has been
further developed over the past 5.5 decades. By tailoring the
formulation of emulsion templates, the properties of the resulting
* Corresponding author. Polymer & Composite Engineering (PaCE) Group, Insti-
tute of Materials Chemistry & Research, Faculty of Chemistry, University of Vienna,
Wa €hringerstr. 42, A-1090, Vienna, Austria.
** Corresponding author. Polymer & Composite Engineering (PaCE) Group,
Department of Chemical Engineering, Imperial College London, South Kensington
Campus, London, SW7 2AZ, UK.
E-mail addresses: angelika.menner@univie.ac.at (A. Menner), alexander.
bismarck@univie.ac.at (A. Bismarck).
1
This work was conducted as part of QJ’s PhD in the Department of Chemical
Engineering at Imperial College London.
connectivity and, therefore, permeability, surface area, and
morphology of the polyHIPEs can be tailored to suit various ap-
plications in/as membrane and separation technologies [3e7],
hydrogen storage [8], catalyst supports [9], electrodes for micro-
batteries [10], oil servicing [11], as low dielectric substrates for use
in the electronics industry [12] and scaffolds for tissue engineering
[13,14].
For a long time poly(styrene-co-divinylbenzene) polyHIPEs
were the most thoroughly studied polyHIPEs [1]. However, they are
extremely brittle and friable, which reduces the number of poten-
tial real-word applications, they can be considered for, dramati-
cally. In order for polyHIPEs to reach their full potential it became
increasingly important to be able to tailor their mechanical per-
formance to the needs of specific applications. We focused on
improving the mechanical properties of emulsion templated mac-
roporous polymers by increasing their foam densities, namely
making polymerised medium internal phase emulsions (poly-
MIPEs) [15,16] and by creating hierarchical pore structures [17,18].
Furthermore, the synthesis of polyHIPE nanocomposites provides
an alternative to improving their mechanical properties. Using
silica particles as functional reinforcement allows to enhance their

http://dx.doi.org/10.1016/j.polymer.2016.05.071
0032-3861/© 2016 Elsevier Ltd. All rights reserved.
 Q. Jiang et al. / Polymer 97 (2016) 598e603
mechanical properties [11,15,19e21]. Incorporating other particles,
such as carbon nanotubes [22,23], titania [24], nanoclay [25] and
magnetic particles [26,27], have also been explored. Emulsion
templated poly(styrene-co-divinylbenzene)/polyurethane inter-
penetrated polymer networks were synthesised by Le pine et al.
[28]. Their elastic moduli were up to 4.3 times higher than those of
macroporous poly(styrene-co-divinylbenzene) controls. An even
higher increase (7 fold) in both, elastic modulus and strength, could
be achieved by impregnating polyHIPEs with furfuryl alcohol fol-
lowed by subsequent curing [29]. By polymerising both the
continuous phase and internal phase of emulsions, polymethacrylic
acid and polydimethyl aminoethyl methacrylate reinforced poly-
HIPEs have been prepared: in this case reinforcement can be
“switched off” by moisture, which resulted in softening the
hydrogels [30].
Besides modifying the morphology and making composites,
preparing polyHIPEs from different monomers was extensively
studied to improve the mechanical properties of polyHIPEs. 1-vinyl-
5-amino tetrazole based polyHIPEs were synthesised, which
possessed higher elastic moduli than poly(styrene-co-
divinylbenzene) polyHIPEs. PolyHIPEs based on dicyclopentadiene
have been prepared via ring-open polymerisation within emulsion
templates [31,32]. The resultant polyH(M)IPEs possessed elastic
moduli ranging from 23 MPa to 300 MPa depending on their
porosity. Yet, the most commonly employed group of monomers
are acrylates as they are solidified by free radical polymerisation,
which is the most widely used polymerisation method in emulsion
templating. A number of acrylates for example, butyl acrylate [33],
ethylhexyl acrlylate and ethylhexyl methacrylate [34], has been
used to improve the mechanical properties of polyHIPEs while
reducing their brittleness. In our previous work, we dramatically
reduced the brittleness of styrene based polyH(M)IPEs simply by
replacing the stiff crosslinker divinylbenzene by the more flexible,
long-chain crosslinker polyethylene glycol dimethacrylate
(PEGDMA) [15,17,20,35]. Pulko et al. [36] prepared bendable poly-
HIPE membranes based on glycidyl methacrylate, ethyleneglycol
dimethacrylate and ethylhexyl methacrylate. Recently, Tunc et al.
[37] reported that polyHIPEs can be tailored from rigid materials to
elastomers by tuning the template composition, i.e. varying the
acrylate/divinylbenzene ratio within emulsion template. Gurevitch
and Silverstein [38] reported polyHIPEs based on stearyl acrylate
and stearyl methacrylate, which possessed shape-memory
properties.
Here we show that polyurethane diacrylate (PUDA), typically
used as coating material, can be copolymerised with styrene within
emulsion templates. We will provide evidence that the high vis-
cosity of PUDA has a profound influence on the structure of the
emulsion templates and, therefore, on the morphology of the
resulting macroporous polymers. Furthermore, we hypothesise
that the presence of PUDA will eliminate the brittleness and
enhance impact resistance as compared to conventional
poly(styrene-co-DVB)HIPEs due to its flexibility and toughness; to
demonstrate this compression and impact tests were carried out.
2. Experiments
2.1. Materials
Styrene (St), divinylbenzene (DVB), ammonium persulfate (APS)
and CaCl2$2H2O were purchased from Sigma-Aldrich (Gillingham,
UK). Polyethylene glycol dimethylacrylate with a molecular weight
of 330 Da (PEGDMA) was kindly supplied by Cognis (Southampton,
UK). Polyurethane diacrylate (PUDA) with a commercial name
Ebecryl 284 (an aliphatic urethane diacrylate diluted with 12% 1, 6-
hexanediol diacrylate, theoretical molecular weight of 1200 Da)
599
was kindly supplied by Cytec (Diegem, Belgium) and the surfactant
Hypermer B246 by Croda (East Yorkshire, UK). All chemicals were
used as received.
2.2. Preparation of polyH(M)IPEs
The emulsification setup consisted of a reactor with a glass
paddle (anchor) rod connected to an overhead stirrer. The contin-
uous and internal phases of emulsion templates were prepared
separately. The internal phase was aqueous solution containing
CaCl2$2H2O as electrolyte and contained APS as initiator. Mono-
mers and surfactant were mixed in the reaction vessel to formulate
the continuous phase, to which the internal phase was added
dropwise while stirring at a speed of 400 rpm. Afterwards, the
emulsions were further stirred at 2000 rpm for 3 min to produce
homogeneous emulsions. These emulsions were transferred into
free-standing polypropylene (Falcon®) tubes and placed in oven
heated to 70
C for 24 h for polymerisation. After polymerisation,
the samples were first washed with water for 24 h and then in
ethanol. The purified samples were dried at 70
C until constant
weight. The formulations of the H(M)IPEs are summarised in
Table 1.
2.3. Characterisation of polyHIPEs
Fracture surfaces of polyH(M)IPEs S1-S9 were investigated by
scanning electron microscopy (SEM, Hitachi S-3400 N, Hitachi High
Technologies, Mannheim, Germany). Prior to the investigation, the
fracture surfaces of the samples were gold coated using an Agar
Auto Sputter Coater (Agar Scientific, Essex, UK) to guarantee suffi-
cient electrical conductivity. The SEM was operated in secondary
electron mode using an electron beam voltage of 15 kV. The images
were further analysed using UTHSCSA software ImageTool. The
diameters of at least 200 pores as well as 200 pore throats were
measured to determine the average pore and pore throat sizes.
The skeletal densities rs of all samples were determined using a
Helium displacement pycnometer (Accupyc 1330, Micrometrics
Ltd., Dunstable, UK). About 0.5 g of polyHIPE were ground into a
powder, weighed and measured. The foam densities rf were
measured using graphite powder displacement pycnometry (Geo-
pyc 1360, Micrometrics Ltd., Dunstable, UK). About 0.1 g of small
polyHIPE fragments were characterised. The porosity (P) was
calculated from the measured densities as follows:
 
rf
P¼ 1 $100% (1)
rs
Mechanical properties of S1-S9 were determined by compres-
sion testing using a Lloyds EZ50 (Lloyds Instruments Ltd, Fareham,
UK) equipped with a 50 kN load cell. Prior to compression testing
the samples were cut into disks with a diameter of about 25 mm
and a height of about 10 mm. The sample disks were compressed
between Teflon-coated compression plates while their stress-strain
curves were recorded. The elastic modulus was determined from
the slope of the initial linear region of the stressestrain curves. The
crush strength was defined as the maximum strength at the end of
the initial linear elastic region (Supplementary data Fig. 1.). At least
six disks per sample were measured.
Charpy impact tests were performed using an Instron Ceast
9050 (Instron GmbH, Darmstadt, Germany) following the standard
EN ISO 179-1-2010. The specimens were cut into
80 mm  10 mm  4 mm and placed on a span with a span length of
62 mm. The pendulum was 166.14 g with an arm of 229.7 mm. The
drop angle of the pendulum was 150
and the energy of the
pendulum was 0.5 J. The impact strength acU (kJ/m2) was calculated
600 Q. Jiang et al. / Polymer 97 (2016) 598e603

Table 1
Poly(styrene-co- PUDA)H(M)IPE formulations.

Continuous phase Internal phase

St/DVB/PEGDMA/PUDA (vol%/vol%/vol%/vol%)a Surfactant B246 (vol%)b APS (mol.%)c Internal phase ratio (vol%)d

S1 50/30/0/0 20 1 75
S2 50/0/30/0 20 1 75
S3 50/0/0/30 20 1 75
S4 56/0/0/33 11 1 75
S5 59/0/0/35 6 1 75
S6 71/0/0/23 6 1 60
S7 59/0/0/35 6 1 60
S8 47/0/0/47 6 1 60
S9 35/0/0/59 6 1 60
a
Monomer volume fraction with respect to continuous phase.
b
Surfactant volume fraction with respect to continuous phase.
c
Initiator molar fraction with respect to molar number of double bonds of the monomers.
d
Internal phase was an aqueous solution of CaCl2$2H2O, the concentration for S2 was 0.544 mol/L, while the concentrations for all other samples was 0.068 mol/L.

as follows: crush strength at break of 4.8 MPa. The poly(styrene-co-PEGDMA)

HIPE S2, however, had a Tg of 131
C, which indicated that PEGDMA
Ec resulted in higher polymer chain mobility than DVB. Even though
acU ¼ $103 (2)
h$b S2 has a much lower elastic modulus (22 MPa) and crush strength
(1.4 MPa) compared to S1; we observed that S2 deformed plasti-
where Ec is the energy (J) adsorbed by breaking the specimen; h
cally (but did not break) when compressed by up to 20% of its
and b are the thickness and width (mm) of the specimen,
original height. This, plus the slightly higher impact strength of S2,
respectively.
indicates that S2 was less brittle than S1, which is consistent with
The thermal properties of the samples were investigated using
our pervious findings [15].
dynamic mechanical thermal analysis (DMTA, RSAG2, TA Instru-
Within the HIPE templates used to prepare the first group of
ment, Eschborn, Germany). Samples with a dimension of
poly(St-co-PUDA)HIPEs (S3-S5) the monomer/crosslinker ratio was
10 mm  10 mm  5 mm were compressed with a frequency of 1 Hz
kept constant while the amount surfactant used to stabilise the
while being heated at a rate of 4
C/min from 25
C to 175
C.
emulsions was varied. In S3’s emulsion template PUDA was used as
the crosslinker instead of the previously used DVB or PEGDMA; all
3. Results and discussion
other components and their ratios as well as the emulsification
conditions were identical to that of S1 and S2. Unsurprisingly, S3
In order to determine the influence of the viscous crosslinker
(77% porosity) and the control polyHIPEs S1 and S2 had similar
PUDA on the morphology and physical properties of styrene based
porosities since the emulsion templates used to make them had
polyHIPEs two control polyHIPEs, poly(styrene-co-DVB) (S1) and
identical internal phase volume ratios. S3 had a skeletal density of
poly(styrene-co-PEGDMA) (S2), were synthesised. The HIPE tem-
1.088 g/cm3 and a foam density of 0.25 g/cm3 (Table 2) and it
plates used to produce S1 and S2 contained 75 vol% internal phase
possessed an open-porous structure (Fig. 1c) with an average pore
and were stabilised by 20 vol% of the surfactant Hypermer B246
size of 1.2 mm and an average pore throat size of 0.4 mm (Table 2).
with respect to the continuous phase volume. Both S1 and S2 have
Since the formulations of S1 - S3 only differed with respect to the
similar skeletal and foam densities (Table 2) resulting in a porosity
crosslinker used, the reduced pore size of S3 compared to that of
of approximately 78% (Table 2). As expected, they possess an open
the control polyHIPEs S1 and S2 must be due to the presence of
porous structure (Fig. 1a) typical for polyHIPEs [39], characterised
PUDA in the HIPE template of S3. PUDA is a very viscous liquid. It,
by an average pore and pore throat size of about 2.8 mm and 0.4 mm
therefore, raised the viscosity of the continuous phase, which
(Table 2), respectively. Although the morphology, densities and
suppressed the tangential interfacial flow of the continuous phase,
porosities of the control polyHIPEs S1 and S2 were very similar,
hence hindering droplet coalescence, resulting in smaller droplets
their thermal and mechanical properties differ significantly. S1 did
[40]. S3 had a Tg of 101
C, which is lower than that of S2. This
not exhibit a glass transition temperature (Tg) within the temper-
indicated that the incorporation of the long chain PUDA increased
ature range from 25
C to 175
C (Fig. 2) due to the high crosslinking
flexibility and reduced the crosslinking density of S3. Surprisingly,
density. Correspondingly, S1 failed in a brittle manner during
S3 had an elastic modulus of 31 MPa and crush strength of 1.8 MPa,
compression testing and had an elastic modulus of 70 MPa and a

Table 2
Skeletal density rs, foam density rf, porosity P, pore dp and pore throat size dpt, elastic modulus E, crush s and impact strength acU of the synthesised polyHIPEs.

rs (g/cm3) rf (g/cm3) P (%) dp (mm) dpt (mm) E (MPa) s (MPa) acU (kJ/m2)

S1 1.080 ± 0.010 0.23 ± 0.01 78 ± 1 2.6 ± 0.8 0.3 ± 0.1 70 ± 4 4.8 ± 0.1 0.24 ± 0.06
S2 1.130 ± 0.006 0.26 ± 0.01 77 ± 1 3±1 0.5 ± 0.2 22 ± 2 1.4 ± 0.1 0.33 ± 0.07
S3 1.088 ± 0.006 0.25 ± 0.01 77 ± 1 1.2 ± 0.3 0.36 ± 0.09 31 ± 8 1.8 ± 0.1 1.0 ± 0.2
S4 1.093 ± 0.003 0.24 ± 0.01 78 ± 1 2.0 ± 0.5 0.4 ± 0.2 59 ± 4 2.9 ± 0.1 1.9 ± 0.6
S5 1.090 ± 0.010 0.23 ± 0.01 79 ± 1 3.3 ± 0.8 0.5 ± 0.2 65 ± 4 3.6 ± 0.3 2.3 ± 0.2
S6a 1.094 ± 0.005 e e 3.7 ± 0.9 0 e e e
S7 1.110 ± 0.007 0.37 ± 0.01 66 ±1 2.7 ± 0.8 0.3 ± 0.1 143 ± 3 7.0 ± 0.3 2.7 ± 0.3
S8 1.122 ± 0.004 0.38 ± 0.01 66 ±1 2.5 ± 0.5 0.3 ± 0.1 111 ± 17 5.0 ± 0.2 1.4 ± 0.5
S9 1.148 ± 0.017 0.39 ± 0.02 66 ±1 2.0 ± 0.4 0.3 ± 0.2 61 ± 9 3.1 ± 0.2 1.0 ± 0.3
a
S6 could not be dried and, therefore, the foam density, porosity, thermal and mechanical properties could not be determined.
 Q. Jiang et al. / Polymer 97 (2016) 598e603 601

Fig. 1. SEM images of poly(St-co-DVB)HIPE, S1 (a); poly(St-co-PEGDMA)HIPE, S2 (b); poly(St-co-PUDA)HIPEs, S3-S5 (cee) and poly(St-co-PUDA)MIPEs, S6-S9 (fei).

strength than that of S1 because the flexibility of the PUDA chains

enhanced the energy adsorption of S3 upon impact. This leads to a
much tougher polyHIPE compared to the poly(Styrene-co-DVB)
HIPE. Furthermore, we compared the friability of the polyHIPEs
by simply using S1 and S3 as chalk to draw lines on a piece of
cardboard: S1 left a clear mark while S3 did not (Fig. 3). This clearly
shows the reduced friableness of S3 than S1.
Lower surfactant concentrations were used for the preparation
of the emulsion templates of S4 and S5 in order to allow for the
formation of larger droplets in the HIPEs and, subsequently, to in-
crease the pore size of the resulting polyHIPEs. The densities and
porosities of S3-S5 are identical within error, which is expected as
the monomer composition and the internal phase volume ratios in
their HIPEs were identical. S4 and S5 possessed also open-porous

Fig. 2. Loss factor tan(d) of poly(St-co-DVB), poly(St-co-PEGDMA) and poly(St-co-

PUDA) polyHIPEs and polyMIPEs.

which are both higher than those of S2. The PUDA crosslinker as
compared to PEGDMA probably provided more flexible joints in the
polymer network, reducing the residual stresses within the mac-
roporous polymers. S3 remained permanently deformed when
compressed to 10% of its original height but did not break; it is
clearly less brittle than S1. The elastic modulus and crush strength
of S3 were lower than those of S1. This was due to the flexibility of
the PUDA chains as well as the lower crosslinking degree in S3. The
latter was a result of the lower PUDA molar concentration than DVB
in the emulsions. However, S3 did have a 3 times higher impact Fig. 3. Using S1, poly(St-co-DVB)HIPEs and S3, poly(PUDA-co-St)HIPEs as chalks to
draw lines: S1 left a white trace while S3 did not.
602 Q. Jiang et al. / Polymer 97 (2016) 598e603
Table 3
Impact strengths of polyHIPEs and rigid polymer foams and composites.
Sample code Sample
S1 Poly(St-co-DVB)HIPE (non-notched)
S5 Poly(St-co-PUDA)HIPE (non-notched)
Commercial rigid polymer foams and compositesa
Un-impregnated rigid polyurethane foam (non-notched)
Un-impregnated rigid polyurethane foam (notched)
Epoxy impregnated rigid polyurethane foam (non-notched)
Polyester impregnated rigid polyurethane foam (non-notched)
Polyvinyl chloride foam with various fillers
a
The samples were selected as they were tested, as same as the polyHIPEs in this work, according to industrial standard EN ISO 179 in their original publications.
structures (Fig. 1 d, e) just like S3: as expected the pore sizes
(Table 2) increased due to the reduction in surfactant concentration
used to stabilise the HIPEs. Although the polyHIPEs S3-S5 have
identical St/PUDA ratios, their Tg increased with decreasing sur-
factant concentration used to stabilise the HIPE templates. Even
after washing, some surfactant will remain in the samples. This
residual surfactant acts as a plasticiser [41]. Since the surfactant
concentration in S5’s HIPE was lower than that in S4’s and S3’s it is
most likely that less surfactant remained in polyHIPE S5 than in S4
and S3, which resulted in a higher Tg. The elastic moduli of S3-S5
increased from 31 MPa over 59 MPae65 MPa and the crush
strengths from 1.8 MPa over 2.9 MPae3.6 MPa (Table 2). Gibson and
Ashby [42] reported that the elastic moduli of porous materials are
solely affected by the porosity of the porous materials. Our finding
that the elastic moduli of our polyHIPEs having identical porosities
increase with increasing pore sizes contradicts this theory. One
explanation could be the decrease in plasticising effect of residual
surfactant in S3 to S5 as discussed above. Moreover, the effect of
pore size on the elastic moduli of the polyHIPEs has been reported
by Maheo et al. [43] and Ceglia et al. [44,45]. The heterogeneous
structure of pore walls (soft pore surface and a rigid core) causes
polyHIPEs with large pores and thus small surface areas to possess
higher elastic moduli. The impact strengths of S3-S5 increased from
1 kJ/m2 to 2.3 kJ/m2, indicating that tougher polyHIPEs were pro-
duced when less surfactant was used to stabilise the emulsion
templates.
In order to investigate the effect of the monomer/crosslinker (St/
PUDA) ratio on the mechanical properties of polyHIPEs, the sur-
factant concentration used to stabilise the HIPE templates was kept
to be 6 vol% while the St/PUDA ratio was varied (Table 1). A high
PUDA fraction (e.g. St/PUDA ¼ 1:1) increased the viscosity of the
continuous phase so dramatically that HIPEs could no longer be
formed. Therefore, a group of MIPEs having an internal phase level
of 60 vol% and a gradually increasing PUDA content was poly-
merised to prepare polyMIPEs S6-S9. PolyMIPE S6, which had the
highest styrene content, was close-celled (Fig. 1f) while polyMIPEs
S7-S9 were highly interconnected macroporous polymers.
Furthermore, the average pore size decreased with increasing
PUDA content from 3.7 mm to 2.0 mm. This indicates that the droplet
size of the emulsion templates decreased with increasing PUDA
fraction, therefore, the increasing viscosity of the continuous HIPE
phase. Since the internal phase volume ratios were kept identical
for S6-S9, the emulsions had to contain gradually more, but smaller,
droplets. This leads to thinner continuous phase films separating
the droplets; the thin liquid films eased the formation of pore
throats during the polymerisation of the emulsions. The skeletal
densities of S6-S9 increased slightly (Table 2) because of the
gradual increase of the PUDA concentration, which has a higher
density than styrene. However, as expected the variation of the St/
PUDA ratios had no influence on the foam densities and porosities
of S7-S9; they are identical within error (Table 2). S7’s Tg was
rf (g/cm3) acU (kJ/m2) Reference
0.23 ± 0.01 0.24 ± 0.06
0.23 ± 0.01 2.3 ± 0.2
0.2 3.955 Ref [48,49]
0.2 0.981 Ref [48,49]
0.2 1.770 Ref [48,49]
0.2 1.754 Ref [48,49]
0.55e0.76 1.67e1.92 Ref [47]
similar to S5’s as identical monomer and surfactant concentrations
were used their emulsion templates. With increasing PUDA con-
centration, S8 and S9 showed broader tan(d) peaks, where a
shoulder on the tan(d) curves appeared at about 80
C for S8 and S9,
while the main tan(d) peaks for both samples shifted to 105
C and
113
C, respectively. This probably indicates a Tg of a PUDA-rich
copolymer (Tg of pure PUDA is 27
C, datasheet of Ebecryl 284)
and a Tg of a St-rich copolymer (Tg of pure St is about 100
Ce110
C
[46]). The mechanical properties of S7 to S9 decreased: the elastic
moduli and crush strengths of S7-S9 decreased from 143 MPa to
61 MPa and from 7.0 MPa to 3.1 MPa, respectively and the impact
strengths from 2.7 kJ/m2 to 1.0 kJ/m2. This was probably due to the
formation of flexible PUDA-rich segments and more rigid St-rich
segments in S8 and S9; the former one reduced the moduli while
the later one did not contribute to the strengths of the samples.
We compare the impact strength of S5, which had the best
mechanical properties among the poly(PUDA-co-St)HIPEs, with
those of other polymer foams reported in the literature in Table 3.
S5 is not only 10 times tougher than poly(styrene-co-DVB)HIPE S1
but it is also superior to polyvinyl chloride foams and close to
commercial rigid polyurethane foams [47e49]. Therefore,
poly(PUDA-co-St)HIPEs could be explored for some real-life appli-
cations, where not only toughness and robustness but also open-
porous structures are required.
4. Conclusion
Polyurethane diacrylate, used as a coating material, was copo-
lymerised with styrene within emulsion templates to produce
macroporous polymers. The high viscosity of PUDA promoted the
formation of small droplets in the emulsion templates and subse-
quently small pores in the polyHIPEs. The pore size of the polyHIPEs
was, therefore, tuneable by tailoring the PUDA concentration. The
copolymerisation of PUDA and styrene did not only reduce the
brittleness and friability of the macroporous polymers, it increased
the toughness by up to 10 times compared to poly(styrene-co-
divinylbenzene)HIPEs. The styrene/PUDA ratio influenced the
thermal and mechanical properties of the macroporous polymers: a
high PUDA concentration led to dual Tg in the polymer and reduced
moduli and impact strengths. An optimised styrene/PUDA ratio
resulted in polyHIPEs with an impact strength of 2.3 kJ/m2, which is
comparable to commercial rigid polyurethane foams.
Acknowledgement
The work was partially supported by the UK Engineering and
Physical Science Research Council (EPSRC) grants EP/D068851/1
and EP/J014974/1, which partially supported AM. We would also
thank QJ’s parents for the financial supporting for his Ph.D at Im-
perial College London. We appreciate the help of the Institute of
Material Science and Technology, Technical University of Vienna for
 Q. Jiang et al. / Polymer 97 (2016) 598e603
the impact test.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.polymer.2016.05.071.
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