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Inherently reactive polyHIPE material from dicyclopentadienew

Sebastijan Kovačič,a Peter Krajnc*a and Christian Slugovc*b
Received 16th July 2010, Accepted 24th August 2010
DOI: 10.1039/c0cc02610g

A simple formulation of a stable high internal phase emulsion of

dicyclopentadiene which is cured by using properly selected ring
opening metathesis polymerization initiators yields highly
porous monolithic materials with paramount mechanical properties
Published on 10 September 2010 on http://pubs.rsc.org | doi:10.1039/C0CC02610G

and the possibility of easy functionalisation.

Macroporous microcellular polymers are a class of polymeric

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materials with specific morphological features and have a

broad application spectrum. Open cellular morphology of
macroporous polymers can be achieved by high internal phase
emulsion templating. In a high internal phase emulsion the
volume fraction of the internal phase exceeds 74% and can be
used to prepare macroporous monoliths if the continuous
phase contains monomers.1 In that manner, porous polymeric
monoliths with cellular diameters between several and several
hundred mm have been prepared2 and used as scaffolds for
living cells,3 reagent and catalyst support,4 chromatography
media,5 filtration media,6 etc. Mostly radical chain poly-
merisation has so far been used for the production of these
materials, both from water in oil and oil in water emulsions.
A severe drawback of most polyHIPE7 materials is their poor
mechanical properties.
To address this issue, we herein aim at a polyHIPE material Fig. 1 Formulation and cross-linked structure.
based on poly(dicyclopentadiene) (polyDCPD) prepared by
Ring Opening Metathesis Polymerisation (ROMP) of dicyclo- interconnecting pores, excellent mechanical properties and
pentadiene (DCPD). DCPD is a cheap by-product of steam we demonstrate their potential of being functionalized. The
cracking of naphtha and gas oils to ethene and polyDCPD is a critical issue in the preparation of polyHIPE materials is to
tough, rigid, thermoset polymer exhibiting high impact find an emulsion which is stable until the continuous phase is
resistance, high chemical corrosion resistance and high heat cured. For this purpose a formulation composed of 20 vol%
deflection temperature.8 PolyDCPD prepared by ROMP is DCDP in 80 vol% water was investigated. As the surfactant, a
instantly cross-linked via olefin addition and/or olefin metathesis poly(propylene glycol)-block-poly(ethylene glycol)-block-
(cf. Fig. 1),9 thus no additional cross-linker, usually used in poly(propylene glycol) namely Synperonic L121 exhibiting a
polyHIPE preparation protocols, will be necessary. Eventually, very low hydrophilic–lipophilic balance (HLB)11 of only
because polyDCPD is a highly unsaturated polymer network, 0.5 was used. No electrolyte was added to the aqueous phase.
functionalisation of the porous material should be easily This mixture was stirred for 1 h at 400 rpm and then the
feasible. Some efforts of using a high internal phase emulsion initiator [(PCy3)2Cl2Ru(3-phenyl-indenylid-1-ene)] (M1,
and ROMP have been disclosed in the past,10 but attempts PCy3 = tricyclohexylphosphine)12 was added. Curing at room
with DCPD as the monomer were not successful. temperature for 96 h resulted in a monolith (sample A1).
Herein we present polyHIPE materials based on DCPD However, scanning electron microscopy (SEM) revealed a
with open cellular architecture of large pores and smaller porous material with agglomerated particles approx. 2 mm in
size which suggested that the emulsion underwent phase
a separate during curing (cf. Fig. 2). Consequently, emulsions
University of Maribor, Faculty of Chemistry and Chemical
Engineering, Smetanova 17, SI-2000 Maribor, of the same composition were heated to 60 1C (A2) or 80 1C
Slovenia and the Centre of Excellence PoliMaT, Ljubljana, Slovenia. (A3) for 24 h and the resulting monoliths exhibited open
E-mail: peter.krajnc@uni-mb.si cellular structures characterized by a high degree of openness
b
Graz University of Technology, Institute for Chemistry and
Technology of Materials, Stremayrgasse 9, A 8010 Graz, Austria. (Fig. 2). It is to note, that only very low yields of about 15%
E-mail: slugovc@tugraz.at (A2) and 13% (A3) were obtained being accountable for the
w Electronic supplementary information (ESI) available: Experimental thin walls. Presumably, retro Diels–Alder reaction of DCPD
procedures, additional SEM images, FTIR spectra, elemental analysis occurred under these reaction conditions as a competing
data, mechanical properties data, permeability measurements and a
video of a polyHIPE polyDCPD membrane. See DOI: 10.1039/ reaction to ROMP. Generally, a higher temperature is not
c0cc02610g only speeding up the curing reaction but is also decreasing the

7504 Chem. Commun., 2010, 46, 7504–7506 This journal is c The Royal Society of Chemistry 2010

Published on 10 September 2010 on http://pubs.rsc.org | doi:10.1039/C0CC02610G
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Fig. 2 SEM images of polyDCPD monoliths. Reaction conditions: 80% water phase and 20% continuous phase; A1: M1, 20 1C, 96 h; A3: M1,
80 1C, 24 h; B3: M2 80 1C, 24 h; B4: M2 80 1C, 2 h; cross section of a membrane made like B3 (surface on the left hand side); B3 monolith
functionalized with PTMP.
emulsions’ stability resulting in a higher degree of phase
separation. Consequently, the key for obtaining the desired
polyHIPE material is to further speed up the polymerization
reaction by using a faster initiator. For this purpose [(H2IMes)-
(PCy3)Cl2Ru(3-phenyl-indenylid-1-ene)]13 (M2, H2Imes =
N,N-bis(mesityl) 4,5-dihydroimidazol-2-yl) was selected. In
this case, monoliths were obtained in high yields (85%) after
curing for 24 h at 80 1C (B3) or after 2 h curing at 80 1C (B4).
All samples exhibited a typical polyHIPE architecture, with
cavities of approx. 5.5 mm and interconnecting pores of
approx. 1.6 mm in diameter (determined by SEM image
analysis; cf. Fig. 2). The surface area of these samples was
measured by nitrogen adsorption/desorption (BET model).
Relatively low values of approx. 5 m2 g 1 were obtained. Of
particular interest are the mechanical properties of the novel
materials. In the case of samples B3 and B4, tensile tests on
shouldered test bars, made by curing of the emulsion in
proper steel moulds, were performed.14 Young’s moduli for
B3 were in the range of 145 to 159 MPa (tensile stress
sM = 1.44–1.66 MPa; tensile strain eM = 0.9–1.3%) and
those for B4 were slightly lower ranging from 126 to 128 MPa
(sM = 0.99–1.77 MPa; eM = 0.9–2.6%). By all means, the
values should be taken with some precaution because the crack
of the sample occurred in all cases in places were air-bubbles
were trapped in the test bar and it is reasonable, that even
higher E-moduli might be achieved by improving the
sample preparation procedure. The results reveal a significant
improvement when compared to the mechanical properties of
polyHIPEs prepared by free radical polymerization. Young’s
moduli of 3–6 MPa were obtained for typical polyHIPEs,
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while silica particles reinforced materials with Young’s moduli
up to 120 MPa were reported.15
Evaluation of the permeability and flow characteristics was
performed by shaping the monoliths into discs and applying
them as columns in an HPLC system (cf. ESIw).16 Permeability
values of 9.50  10 15 m2 and 4.75  10 15 m2 were obtained
for samples B3 and B4, respectively. In both cases the pressure
drop remained constant for the whole period of time at any
tested flow rate. Furthermore, the back pressure of sample B4
was linearly proportional to the flow rates up to 4 mL min 1.
These findings suggest that there is hardly any change in the
monolith structure due to pressure in this flow regime and
support the data on mechanical properties of the material.
The versatility of the emulsion templating technique was
further demonstrated by the preparation of a 15  15 cm
membrane with open structure of a thickness of 450 mm
(cf. Fig. 2). The relatively low emulsion viscosity and the
improved curing behaviour are particularly advantageous in
this context as it has been demonstrated in the case of classical
radical polymerisation of HIPE that obtaining an open porous
structure on the surface proved to be difficult,17 while in this
case membranes without the surface skin were obtained more
readily.
The chemical characterisation of the polyHIPEs comprised
elemental analysis (EA) and infra red (IR) spectroscopy.
Attenuated total reflection IR spectra obtained from several
positions of a freshly cut monolithic sample immediately after
drying revealed oxidation of polyDCPD, characterized by a
strong CQO absorption band at 1705 cm 1 and broad O–H
absorption band at 3400 cm 1 (cf. Fig. 3) at the outer regions
Chem. Commun., 2010, 46, 7504–7506 7505

Published on 10 September 2010 on http://pubs.rsc.org | doi:10.1039/C0CC02610G
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Fig. 3 FTIR spectra of pure polyDCPD, oxidized polyDCPD and
modified polyDCPD (sample B3a). Insets show two photographs of
monoliths and arrows indicate the places were the ATR-crystal was
placed for the acquisition of the according IR-spectrum.
of the monolith and almost no oxidation in the centre. The
same result can be retrieved by examining the colour of the
samples: oxidized regions appear yellowish, while unoxidized
areas are white (cf. Fig. 3).18 These results are in agreement
with investigations of Mühlebach et al. who studied the role of
an initially formed oxide layer on the surface on the protection
of underlying polyDCPD against further oxidation.19 In this
case, a 140 mm thick sample was oxidized only at its surface
and the amount of oxidation decreased sharply within the first
20 mm.
Examining the elemental composition of the present
samples by elemental analysis, a high amount of oxygen was
found as exemplified by the data for B3 which were C 62.6%,
H 6.4% and O 31.0%, resulting in an empiric sum formula of
C5.2H6.4O1.9. Similar values are found for all samples under
investigation after at least one month of storage under ambient
conditions (cf. ESIw). The high degree of oxidation is due to
the porosity of the material and the thin walls of the scaffold of
about 0.5 mm. This concomitant side reaction most likely
contributes to the favourable mechanical properties mentioned
above and, moreover, it can be exploited for further trans-
formations of the polyHIPE material. This was demonstrated
by reacting the sample B3 with aqueous hydrazine solution.
Elemental analysis and IR spectroscopy revealed a successful
transformation releasing a hydrazone functionalised porous
material. Another way for further functionalisation of the
polyHIPE material is making use of the remaining double
bonds in the material and the thiol–ene reaction.20 For this
purpose, a one pot procedure was developed. The emulsion
was dispensed as described above but additionally a thiol
bearing reagent (pentaerythritol tetrakis(3-mercaptopropionate)
(PTMP)) and a thermal radical starter (azobisisobutyronitrile
(AIBN)) were added. Still the emulsion was stable and curing
with M2 yielded a porous material (cf. Fig. 2). IR spectroscopy
(cf. Fig. 3) and EA revealed successful functionalisation with
the thiol although a rather low sulfur content of only 0.34%
was found. Changing the radical initiator in this one pot
approach from AIBN to potassium persulfate (KPS), the
sulfur content could be approximately doubled to 0.62%
7506 Chem. Commun., 2010, 46, 7504–7506
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(0.11% accounts for the addition of KPS). The scope of this
reaction can be further improved by performing a post
polymerisation functionalisation. In this case sulfur content
as high as 2.27% was obtained. These results clearly demon-
strate the scope of the unsaturation present in the polyHIPE
material for further functionalisation.
In conclusion, a simple formulation of a stable high internal
phase emulsion of DCPD which upon curing using properly
selected ring opening metathesis initiators yields highly porous
monolithic materials is introduced. The resulting polyHIPE
materials exhibit paramount mechanical properties, good
permeability and offer convenient ways for further tailored
functionalisation.
This work was supported by the ÖAD (SI 21/2009), SRA
(BI-AT/09-10-008 and a scholarship to S.K.) and the Austrian
Nano-Initiative (Project 0715 DEVFAB). Robert Saf and
Dorith Meischler are acknowledged for acquiring some SEM
pictures.
Notes and references
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This journal is c The Royal Society of Chemistry 2010