J Porous Mater (2012) 19:189–194

DOI 10.1007/s10934-011-9459-8

Organic acid catalyzed synthesis of 5-methylresorcinol based

organic aerogels in acetonitrile
Anna-Liisa Peikolainen • Olga Volobujeva •

Riina Aav • Mai Uibu • Mihkel Koel

Published online: 12 February 2011

Ó Springer Science+Business Media, LLC 2011

Abstract A method of preparing 5-methylresorcinol and 1 Introduction

formaldehyde based organic aerogels in non-aqueous
media with a benzoic acid derivative as a catalyst is being Organic aerogels are precursors for the preparation of
proposed in this paper. Here acetonitrile is used as a sol- carbon aerogels, which are highly nanoporous materials
vent that allows direct drying with carbon dioxide over the with large specific surface areas. Their porous structure of
supercritical state without the need for a solvent exchange. interconnected pores allows them to be used as adsorptive
The acidic properties of 2,6-dihydroxy-4-methyl benzoic materials [1–3]; when doped with precious metal, carbon
acid promote the reaction of sol–gel polymerization, and at aerogels become catalyst carriers [4–6] and can be used as
the same time it takes part in the reaction as a co-monomer electrodes for electrical double-layer capacitors [7, 8] and
and influences the nanostructure of the material. The fuel cells [9, 10]. Carbon aerogels are electrically con-
evolution of the polymer was monitored using nuclear ductive and can be used as electrodes for electrical actua-
magnetic resonance spectroscopy and the structure of the tors [11].
resulting organic aerogels depending on the molar ratio of Well known is an organic aerogel preparation method
5-methylresorcinol to 2,6-dihydroxy-4-methyl benzoic described by Pekala [12], by which aerogels were prepared
acid was studied by nitrogen adsorption–desorption mea- from resorcinol–formaldehyde gels that were formed in
surements, scanning electron microscopy and infrared basic aqueous solution and dried by supercritical CO2
spectrometry. extraction. Before the extraction water, which is poorly
miscible with CO2, was exchanged for acetone prior to
Keywords Aerogel  Organic aerogel  drying. There are a few examples where, in order to sim-
5-methylresorcinol  2,6-dihydroxy-4-methyl benzoic acid  plify the procedure, CO2 miscible alcohols have been used
Supercritical drying  Oil-shale as solvents for gel formation [13, 14].
Mulik et al. have synthesized aerogels from resorcinol–
formaldehyde under acid conditions (HCl) in acetonitrile. In
their experiments, acetonitrile was exchanged for acetone
prior to supercritical CO2 drying. [15] Recently, the same
A.-L. Peikolainen (&)  R. Aav  M. Koel group replaced HCl with hydrated metal ions as Brønsted
Department of Chemistry, Tallinn University of Technology, acids for the catalysis of the resorcinol–formaldehyde
Akadeemia tee 15, 12618 Tallinn, Estonia gelation in acetonitrile/ethanol, resulting in interpenetrating
e-mail: annnaliiisa@gmail.com
networks of metal oxides and resorcinol–formaldehyde
O. Volobujeva [16]. The mixed-gels were again solvent-exchanged with
Department of Materials Science, Tallinn University acetone, however, this work is conceptually analogous to
of Technology, Ehitajate tee 5, 19086 Tallinn, Estonia the incorporation of the catalyst to the gel reported here. In
accord with the study of A.W. Francis on phase equilibria of
M. Uibu
Laboratory of Inorganic Materials, Tallinn University ternary systems with liquid carbon dioxide, acetonitrile and
of Technology, Ehitajate tee 5, 19086 Tallinn, Estonia water [17], it is possible directly to apply CO2 extraction to

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the gel that contains acetonitrile. This has been done by processing industry and were obtained from Carboshale
Willey et al. [18], who, in order to dry the humic acid gel, OÜ, Estonia. Formaldehyde, 37 wt% solution in water
replaced the original solvent (water) in the gel by acetoni- (stabilized with 10–15% of methanol), was purchased from
trile prior to supercritical CO2 drying. Sigma–Aldrich. Acetonitrile, HPLC grade, came from
In our previous studies we have been concentrated on Rathburn Chemicals Ltd., Germany.
using 5-methylresorcinol (5-MR) for aerogel preparation The supercritical extraction system with a double clamp
[5, 19] where we have been successful in synthesizing the autoclave, 100 ml in volume, was constructed by NWA
gels in water and in methanol in the presence of inorganic Analytische Meßgeräte GmbH, Germany. CO2 (99.8%)
base catalysts. The scope of this work was to develop a was obtained from AS Eesti AGA.
simple and fast procedure for producing aerogels from
5-MR in acetonitrile (ACN)—a solvent that does not
2.2 Analysis techniques
require solvent exchange prior to drying. In order to pre-
vent inorganic impurities an organic catalyst was desired.
Infrared (IR) measurements were performed with a Spec-
Acetic acid [20], oxalic acid and para-toluenesulfonic acid
trum BX FT-IR System (Perkin Elmer) in the 4,000 to
[21] have been used in aqueous systems as catalysts for
400 cm-1 range by the KBr disk method. Nuclear magnetic
aerogel preparation earlier. Here we propose a different
resonance (NMR) spectra were recorded on a Bruker 800
efficient acidic organic catalyst, 2,6-dihydroxy-4-methyl
Avance III NMR spectrometer. Solvent peaks of CD3CN in
benzoic acid (dHMBA). dHMBA has a very similar 13
C (118.69 ppm) and 1H (1.94 ppm) NMR were used as
molecular structure to the monomer, 5-MR, and for this
chemical shift references. The morphology of the materials
reason we expected that that derivative of benzoic acid,
was determined using a Zeiss ULTRA 55 high resolution
besides being a catalyst, would also take part in the sol–gel
scanning electron microscope (SEM), and nitrogen
polycondensation as a co-monomer. Therefore, dHMBA
adsorption analyses were performed using a Sorptometer
would get incorporated in the aerogel backbone and it
KELVIN 1042 built by Costech International. Helium was
would not have to be removed after gelation, thus elimi-
used as a carrier gas, nitrogen as the adsorptive gas. The
nating any need for time-consuming post-gelation washes.
specific surface area (SBET) was calculated according to the
To confirm this hypothesis, NMR spectra were gradually
Brunauer-Emmet-Teller theory. Shrinkage was calculated
recorded during the gelation process. The amount of cat-
as a decrease in the cross-sectional area of the cylindrical
alyst in the sol has been found to be very important in
gel monolith during drying (Eq. 1).
tailoring the structure of the resulting gel: an increase in the
amount of the catalyst in the sol leads to smaller gel par- Agel  AOA
Shrinkage; % ¼  100 ð1Þ
ticles, smaller pores and a larger specific surface area [22– Agel
25]. To test the influence of the 5-MR/dHMBA ratio on gel Agel and AOA are the cross-sectional areas of the gel and
formation and on the morphology of the resulting aerogel the corresponding aerogel, respectively.
material, a series of organic aerogels from 5-MR and
dHMBA were synthesized.
Also benzoic acid and alternative hydroxy derivatives of 2.3 Aerogel preparation
benzoic acid such as 4-hydroxybenzoic acid, 2,5-dihy-
droxybenzoic acid and 2,6-dihydroxybenzoic acid were Appropriate amounts of the aromatic precursors 5-MR and
tested as potential catalysts for gel preparation. A dHMBA were dissolved in acetonitrile, and a formalde-
homogenous gel was obtained when dHMBA or 2,6- hyde solution (in water) was added subsequently. The
dihydroxybenzoic acid was used. Our further study was molar ratio of aromatic monomers to formaldehyde (FA)
focused on the use of dHMBA because it led to substan- was fixed at 0.5 and the molar ratio of the solvent (H2O in
tially faster gelation compared to 2,6-dihydroxybenzoic FA solution and ACN) to the aromatic monomers was kept
acid. at 50. The molar ratio of 5-MR to dHMBA was varied from
90 and 10 mol% (indicated as 90/10) to 25 and 75 mol%
(indicated as 25/75) of the total molar amount of aromatic
monomers in the sol, respectively. Sol–gel polycondensa-
2 Experiment tion occurred at 25 °C within 3 h, depending on the com-
position of the sol. Gel formation was affirmed by tilting
2.1 Materials the sol-filled test tube 45° while observing the movement
of the surface of the sol.
5-Methylresorcinol (99.6%) and 2,6-dihydroxy-4-methyl After aging the gel a minimum of 24 h, it was removed
benzoic acid ([99%) are by-products of the local oil shale from the test tube and placed directly into the autoclave,

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where the drying of the material resulted in an organic At lower dHMBA concentrations (10–25%) the speed of
aerogel. An optimized three-step process was followed for polycondensation increased as the amount of catalyst
drying. First, the gel was introduced to liquid CO2 at a (dHMBA) was increased. At the same time, the increased
pressure of 200 bars at 25 °C for 20 min to fill the pores of amount of co-monomer (dHMBA) with two available
the gel with liquid CO2 and mix it with ACN. The exit reaction sites slows the formation of a solid cross-linked
valve of the autoclave was then opened and the internal network. This effect could be noticed when the amount of
pressure reduced to 100 bars, allowing the liquid CO2 to dHMBA was increased from 25 to 40%. From 40% of
flow through the gel at a constant 100 bars at 25 °C for 2 h dHMBA the rate of gelation again increased which may be
to replace the mixture of CO2 and ACN with CO2. After related to the formation of a different type of polymer
replacement, the temperature inside the autoclave was structure (shown below). The gel formation time as low as
raised to 45 °C and supercritical CO2 extraction (SCE) was 97 min was achieved when the amount of dHMBA
carried out for 2 h. The extraction was completed by de- exceeded the amount of 5-MR three times.
pressurising the autoclave to atmospheric pressure, and The function of dHMBA as a monomer was tested by
then lowering the temperature in the autoclave to ambient preparing a sol from dHMBA with FA in ACN without
temperature. 5-MR in the mixture. A transparent yellow sol turned
opaque in 1 h, but did not lead to the further formation of a
solid gel network. This is probably because of the bifunc-
3 Results and discussion tionality of dHMBA: it is able to form a linear polymer but
not a three-dimensional network. The sample was dried
The correlation between the ratio of 5-MR to dHMBA and under ambient conditions and the remaining solid was then
the morphology of the resulting aerogel is complicated due analysed by IR spectrometry. In Fig. 2, the IR spectrum of
to the dual role of dHMBA in the system. A detailed the sample is compared to the spectrum of the gel from
mechanism of electrophilic aromatic substitution on res- 5-MR and FA in water prepared according to a formula
orcinol is being proposed by Mulik et al. [15]. Under acidic described by Pérez-Caballero et al. [26].
conditions, the mechanism of polymer formation starts At wavenumbers 1470 and 2930 cm-1, the absorption of
with protonation of formaldehyde followed by nucleophilic C–H bonds from methylene bridges can be recognized, and
attack by the p-system of aromatic monomer. Reactive the absorption at 1110 cm-1 corresponds probably to C–O
positions of the aromatic ring are the 2-, 4- and 6- positions bending vibrations of formaldehyde condensation products
in the case of the 5-MR ring, and the 3- and 5- ring posi- such as polymethylene glycol, hemiformal etc. [27], how-
tions in the case of dHMBA due to the electronic properties ever, in the case of base-catalyzed 5-MR-FA aerogel the
of the substituents. This substitution leads to the formation absorption could as well correspond to C–O from the
of hydroxymethylated monomers. Further condensation of methylene ether bridge linking the aromatic rings[28].
the hydroxymethyl group with an unsubstituted site in the The absorption bands at 1680 cm-1 and 1200 cm-1 indi-
aromatic ring results in CH2 bridge formation between the cate the C=O and C–O bonds from carboxyl group of
aromatic monomers [15]. dHMBA, which are also present in the spectrum of pure
The dual behaviour of dHMBA can be seen from the dHMBA (Fig. 3).
effect of the 5-MR/dHMBA ratio on the gel formation time The evolution of gel formation was monitored using
(Fig. 1). NMR spectroscopy to confirm that dHMBA is a

Fig. 1 Gel formation time at different %5-MR/%dHMBA ratios at

25 ± 1 °C (the exact value of %dHMBA is depicted next to each data
point) Fig. 2 IR spectra of 5-MR-FA and dHMBA-FA polymers

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higher frequency (173 ppm) than its parent acid. These

signals can be attributed to newly formed carboxylic acids,
which are intermediates of polymerization and the ester
formation was not observed.
The same can be deduced from the 1H NMR spectra
(Fig. 5). All monomer peaks disappear within 2 h. It can
also be followed that the acidity of the solution phase
decreases during the reaction, as resonating frequency of
protic hydrogens (a broad singlet) decreases from 4.3
(6 min) to 3.4 ppm (120 min). On the spectrum recorded
before adding an aqueous solution of FA, the signals of
hydrogens H30 and H50 are overlapping with a signal from
protic hydrogens (6.4 ppm). The signals at 4.6–4.9 and 3.3
Fig. 3 IR spectrum of raw dHMBA
and 3.4 correspond to hydrogens from FA and methanol
polycondensates.
bifunctional molecule and that polymerization does not These results are in a good agreement with the gel
occur via the carboxyl group. A sample with a 5-MR/ formation time data. Also, faster consumption of 5-MR
dHMBA molar% ratio of 50/50 was used. (Fig. 4) The than dHMBA can be followed on 13C and 1H spectra,
spectra indicated as 0 min (13C,1H) were measured before which is due to the deactivating influence of carboxyl
adding FA solution to the sample, and the subsequent group of dHMBA in aromatic substitution.
spectra were recorded during 142 (13C NMR) and 120 Measurements of nitrogen sorption on organic aerogels
(1H NMR) minutes after the addition of FA. The poly- showed that an increase in the amount of catalyst increases
merization proceeded during the NMR measurements. The the specific surface area of the material and the total vol-
formation of new compounds can be seen after the addition ume of the pores only in the limited range of the dHMBA
of FA and the disappearance of all aromatic signals within concentration. The largest specific surface area and the
2 h, only intermediates of the sol formation could be largest total pore volume, 600 m2/g and 800 mm3/g,
recorded in solution phase. The new signals on the spectra respectively, were achieved at 5-MR/dHMBA ratio of
between 83–95 and 50–57 ppm are from FA solution and 75/25 as can clearly be seen in Fig. 6. There were no
can be attributed to condensation products of FA and micropores (pores with diameter less than 2 nm) in 5-MR-
methanol. On the 13C NMR spectra, the new signals of dHMBA-FA organic aerogels.
esters were expected to appear in the area of lower fre- On SEM micrographs (Fig. 7), it can be seen that the
quency than a signal of carboxylic carbon in parent acid morphology of the materials at ratios 75/25 and 25/75 are
(\172 ppm). completely different. When the amount of 5-MR prevails,
On the enlargement of the spectral fragment recorded the structure of the aerogel is composed of uniform
after 35 min can be seen that the only new signals corre- spherical clusters (diameters 24–25 nm), which is similar
sponding to the carboxylic carbons were resonating at to that of 5-MR-FA aerogels prepared in basic aqueous

Fig. 4 a 13C NMR spectra of 5-MR-dHMBA-FA sol in CD3CN recorded during142 min after the addition of FA, b enlargement of the spectra
recorded 35 min after the addition of FA; 200 scans per spectrum (201 MHz)

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Fig. 5 1H NMR spectra of

5-MR-dHMBA-FA sol in
CD3CN recorded during
120 min after the addition of
FA; 4 scans per spectrum
(800 MHz)

and 25/75 appears to be similar. The strings of clusters are

longer with a higher amount of dHMBA, and the mac-
ropores are larger. Although the yellow colour of the sols
intensified when the percentage of dHMBA was increased,
all the gels in the examined range were transparent and
equally bright orange in colour. After drying, the trans-
parency remained to some extent, while aerogels with a
higher percentage of 5-MR were darker than those with a
higher percentage of dHMBA, the colour ranging from
dark red to bright orange, respectively.
The densities of the materials correspond with the
Fig. 6 Specific surface area (SBET) and total volume of pores (Vtot)
of aerogels with different ratios of %5-MR/%dHMBA (the exact results of SEM analysis: by increasing the percentage of
value of %dHMBA is depicted next to the data point) dHMBA in the sol, increasingly large macropores form in
the gel and a material with a lower density is achieved
(Fig. 8). Increasing macroporosity facilitates easy removal
solvent [5]. Increasing the percentage of dHMBA led to the of the solvent from the gel leading to smaller shrinkage of
presence of large macropores due to the formation of the material during drying. However, from 5-MR/dHMBA
strings of clusters. The strings of clusters with a broad size ratio of 30/70 the density and shrinkage started to increase
distribution can already be observed at a 5-MR/dHMBA which is most likely due to increasingly tenuous network
ratio of 60/40 which correlates well with the results of gel which is not supporting the overall shape of the monolith
formation time measurements. At 25/75, the cluster size sufficiently. Aerogels become brittle. Along with the vol-
distribution is again quite uniform, with diameters of ume decrease during drying, the density of the aerogel
approximately 15 nm. The morphology of aerogels 50/50 increases.

Fig. 7 SEM micrographs of aerogels prepared at different 5-MR/dHMBA ratios

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Acknowledgments The authors would like to thank Tiiu Kailas for 25. J. Shen, J. Hou, Y. Guo, H. Xue, G. Wu, B. Zhou, J. Sol-Gel Sci.
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