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Energy Procedia 63 (2014) 2317 2322

GHGT-12

New Poly(Vinylbenzylchloride/Divinylbenzene) Adsorbent for

Carbon Dioxide Adsorption. II. Effect of Amine Functionalization
Chintana Saiwana,*, Pailin Muchana, David deMontignyb, Paitoon Tontiwachwutikulb
a

Petroleum and Petrochemical College, Chulalongkorn University, Bangkok 10330, Thailand

b
Clean Energy Technologies Institute,University of Regina, SK, Canada, S4S 0A2

Abstract
Poly(vinylbenzylchloride/divinylbenzene); by high internal phase emulsion (poly(VBC/DVB)HIPE) was functionalized with
diamines (ethylenediamine, piperazine, aminopiperidine, and imidazole) to improve carbon dioxide adsorption capacity. The
amine group in the poly(VBC/DVB)HIPE was confirmed and quantified by Fourier transform infrared spectroscopy and
elemental analysis. The surface area, pore size, and pore volume of the materials, after being functionalized with amines, were
reduced. The order of the amine loading in the materials was ethylenediamine > piperazine > aminopiperidine > imidazole. The
CO2 adsorption capacities were 2.18, 0.83, 0.66, and 0.39 mmol/g.m2.mol amine for the polyHIPE materials of ethylenediamine,
piperazine, aminopiperidine, and imidazole, respectively.
2013
2014 The
by by
Elsevier
Ltd. Ltd.
This is an open access article under the CC BY-NC-ND license

TheAuthors.
Authors.Published
Published
Elsevier
(http://creativecommons.org/licenses/by-nc-nd/3.0/).
Selection
and peer-review under responsibility of GHGT.
Peer-review under responsibility of the Organizing Committee of GHGT-12
Keywords: Poly(VBC/DVB); polyHIPE; CO2 adsorption; amines; high internal phase polymer; emulsion polymerization

1. Introduction
CO2 adsorption is one of the promising technologies for commercial and industrial applications for removing CO 2
from a gas mixture. Adsorbents typically used are activated carbon [1-3], mesoporous silica [4, 5], zeolite [6, 7], carbon
nanotube [3, 8, 9], and mesoporous molecular sieve [10, 11]. For these adsorbents, the physical adsorption mechanism
plays an important role in the adsorption of CO 2, in which the capacity was dramatically decreased at a moderately high
adsorption temperature [12]. A way to improve the performance of CO2 adsorption is the introduction of amine groups

* Corresponding author. Tel.: +662-218-4137; fax: +662-215-4459.

E-mail address: chintana.sa@chula.ac.th.

1876-6102 2014 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/3.0/).
Peer-review under responsibility of the Organizing Committee of GHGT-12
doi:10.1016/j.egypro.2014.11.251

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Chintana Saiwan et al. / Energy Procedia 63 (2014) 2317 2322

onto the surface of the adsorbent. This modification makes the adsorbent more selective to CO 2 and can be operated at
high temperatures [12].
Zhang et al. [13] improved CO2 adsorption by impregnation of activated carbon with ammonia solution; the
adsorption capacity increased by 28 % when compared to the unmodified material. Lu et al. [14] increased adsorption
efficiency of mesoporous silica by using N-[3-(trimethoxysilyl)propyl]ethylenediamine, which prolonged the cyclic
adsorption properties. Zelenak et al. [15] used different amines, i.e. 3-aminopropyl, 3-(methylamino) propyl, and 3(phenylamino) propyl trialkoxysilane to modify SBA-12 mesoporous silica. It is found that the basicity of the modified
adsorbents affected the adsorption capacity. In addition, the materials used were mostly micropores and mesopores.
When they were loaded with amines, there was a potential blockage of the amine group in the pores as well as a
diffusion limitation of gas in the adsorbents [16]. The use of a larger pore adsorbent may help to promote the transport
of feed gas throughout the adsorbent [17]. He et al. [17] produced a polymer by a technique called high internal phase
emulsion (HIPE), which was further modified with a quaternary ammonium hydroxyl group for CO 2 adsorption.
The previous work [21] prepared poly (vinylbenzylchloride(VBC)/divinylbenzene (DVB)) by the HIPE technique
using an aqueous to oil phase ratio of 90/10. The oil phase consisted of a DVB/VBC volume ratio of 65/35, 20 wt% oil
soluble surfactant mixture, and chloroethylbenzene. The obtained material was preliminarily tested for CO 2 adsorption,
with the CO2 adsorption capacity of 0.106 mmol/g. In this work, increasing CO 2 adsorption by amination of the
polyHIPE material with amine compounds through the chloromethyl group in VBC and nucleophilic substitution
reactions was investigated [18, 19]. Diamines, i.e. ethylenediamine, piperazine, aminopiperidine, and imidazole with
different structures were used. The adsorption capacity of these aminemodified polyHIPE materials and the effect of
the amine structure on the adsorption capacity were investigated.
2. Experiments
2.1 Chemicals and equipment
Monomers used in the oil phase consisted of vinylbenzylchloride (VBC, 90 %) and divinylbenzene (DVB, 65 %) and
were obtained from Aldrich and Merck, respectively. Sorbitanmonooleate (Span 80), and sodium dodecylbenzene
sulfonate, purchased from Aldrich, and cetyltrimethylammonium bromide, from Fluka, were oil soluble surfactants used
as an emulsifier. Porogens used were chloroethylbenzene (99 %) and toluene from Aldrich and Lab Scan (Thailand),
respectively. Potassium persulfate (K2S2O8, 99 %) and calcium chloride dihydrate (CaCl 2.2H2O) were purchased from
Fluka and A.C.S., respectively. Ethanol, N, N-dimethylformamide, and tetrahydrofuran were purchased from Lab Scan,
Thailand. Ethylenediamine (99 %), imidazole (99 %), and piperazine (99 %) were obtained from Merck and 1aminopiperidine (97 %) was obtained from Aldrich. Nitrogen (99.99 %) and ultra-pure helium (99.99 %), carrier gases
for gas chromatograph (GC), air, and premixed gas that contained 4 vol% CO 2 with a nitrogen balance were obtained
from Praxair.
A field emission scanning electron microscope (FE-SEM, Hitachi S-4800) was used to investigate surface
morphology and a Quantachrome/Autosorb 1-MP utilizing the multi-point BET (Brunauer, Emmett, and Teller) method
with N2 adsorption/desorption was used to determine the surface area of the polyHIPE samples. A Fourier transform
infrared spectroscope (FT-IR; Bruker, model Nexus 670) was used to analyze the amination results, and a CHN
elemental analyzer (LECO) was used for quantitative determination of the amines in the polyHIPE material. A GC,
(Agilent Technologies (GC-TCD, model 6890/G1540N) was equipped with a thermal conductivity detector. A GCGaspro (0.32 mm id 60 m l) containing a silica-based stationary phase was used as a chromatographic capillary
column.
2.2 Experimental procedure
The procedure for polyHIPE preparation was described in detail by Saiwan et al. [21]. The optimal condition was 90
vol% water fraction, 20 wt% surfactant mixtures, 65/35 DVB/VBC monomer volume ratio, and chloroethylbenzene
porogen. Dried polyHIPEs were cut to 2 cm piece before functionalization. The functionalization procedure was
adopted from Stefance and Krajnc [20]. Chloride in the polyHIPE sample was determined by the Mohr titration method.
A piece of sample was immersed into an amine solution of N, N-dimethylformamide, in which the molar concentration

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of amines was three times that of chloride in the polyHIPE sample. The functionalization reaction was allowed to take
place at 353 K for 24 h. Then, the modified polyHIPE materials were filtered, washed with N, N-dimethylformamide,
ethanol, and tetrahydrofuran to remove the unreacted amines, and dried in an oven at 333 K overnight.
The amines in the sample were characterized by FT-IR using KBr pellet sample preparation, transmission mode, and
64 scans in the mid IR range from 400 cm-1 to 4000 cm-1 with a deuterated triglycerine sulfate detector to obtain the
FTIR spectra. The elemental composition of the sample was determined at a furnace temperature of 1223 K using
ethylenediamine tetraacetic acid (EDTA) as a standard reference. The surface morphology and surface area of the
sample before and after the amination were determined by FE-SEM and a Quantachrome/Autosorb1-MP, respectively.
The CO2 adsorption was performed following the method described in the previous work [21].
3. Results and discussion
3.1 Amination of polyHIPE
The functionalization of polyHIPE with amines reactants is shown in Figure 1. The chloromethyl group in VBC
provided a good nucleophilic substitution reaction with the amines. The reactions allowed nitrogen in the amines to
react with chloromethyl directly and released chlorine, which reacted with hydrogen in the amines.
H
N

NH2

H 2N

NH2
Ethylenediamine

Ethylenediamine-HIPE
NH

N
HN

Cl

NH

+
HIPE

Piperazine

Piperazine-HIPE
H
N N

H2N N
Aminopiperidine

Aminopiperidine-HIPE
N

HN
N
Imidazole
Imidazole-HIPE

Fig. 1. Amination of ethylenediamine, piperazine, aminopiperidine, and imidazole on poly(VBC?DVB)HIPE by

a nucleophilic substitution reaction at 353 K for 24 h.
The solid materials were characterized by FTIR after the amination. Spectra of all materials and corresponding
polyHIPE references are shown in Figure 2. The polyHIPE spectrum shows C-Cl wagging and C-Cl stretching at 1265
cm-1 and 710 cm-1, respectively, with these two peaks disappearing after amination. In addition, spectra of the amine
modifying polyHIPE materials show the presence of N-H stretching and N-H bending at 3400-3300 cm-1 and 1670 cm-1,
respectively, while the polyHIPE reference does not have these two peaks. The FTIR spectra indicated the reaction
between the amines and chloromethyl groups in polyHIPE.

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Fig. 2. FTIR spectra of polyHIPE reference and amine modifying polyHIPE materials.

The SEM micrographs of the polyHIPE loaded with amines show a pore structure with interconnectivity similar to
the polyHIPE reference material. The CHN analysis determined nitrogen in the sample and the conversion to amines.
The polyHIPE material functionalized with ethylenediamine, piperazine, aminopiperidine, and imidazole contained
2.30, 2.04, 1.86 and 2.04 mmol amine/ gram, respectively, and the BET surface area analysis reported 48, 32, 36, and
133 m2/g, accordingly, compared with the polyHIPE reference (150 m2/g), as shown in Table 1. The highest amine
loading with ethylenediamine indicated that the small molecule of ethylenediamine could better penetrate into the
polyHIPE structure than the cyclic amines. The amination caused the surface area of most materials to decrease, while
also there was a decrease in the pore size and volume related to the reference material. Different types of amines
required different amine loadings on the polyHIPE material due to varying steric hindrance and partial blockage of the
amines in the pores of the polyHIPE. However, the amine-polyHIPE materials still showed an open porous structure
with interconnectivity similar to the polyHPE reference.
Table 1. Surface properties, amine loading, and adsorption capacity of aminemodified polyHIPE adsorbent.
Adsorbent

Surface area
(m2/g)

Pore volume
(10-3m3/kg-1)

Pore size
(10-9m)

polyHIPE

150

0.313

169

Ethylenediamine-HIPE

48

0.127

121

Piperazine-HIPE

32

0.074

104

Aminopiperadine-HIPE

36

0.081

109

Imidazole-HIPE

133

0.309

163

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3.2 CO2 Adsorption

CO2 adsorption of the aminepolyHIPE materials was measured in a dry condition at room temperature and
atmospheric pressure. The surface area of the materials was normalized before calculating the adsorption capacities.
The results showed the adsorption capacities of 2.18, 0.83, 0.66, and 0.39 mmolCO2/g.m2.mol amine for the polyHIPE
materials of ethylenediamine, piperazine, aminopiperidine, and imidazole, respectively. The polyHIPE materials loaded
with amines showed the effect of chemical adsorption as compared to the polyHIPE reference (0.11 mmol/g), which
indicates the physisorption. The highest amine loading of ethylenediamine had the highest CO 2 adsorption capacity,
while the cyclic amines had low adsorption results. The lowest adsorption capacity by imidazolepolyHIPE was
slightly higher than that of the polyHIPE reference. The adsorption capacity was also dependent on the type of amine;
the primary amine of ethylenediamine yielded the highest and the tertiary amine of imidazole showed the lowest
adsorption.
4. Conclusion
The functionalization of the amines in poly(VBC/DVB) to increase CO 2 adsorption reduced the surface area, pore
size and pore volume of the materials; however, the interconnectivity property of the pore structure with was not
affected. The steric hindrance of the amine structure affected amine loading in poly(VBC/DVB). The adsorbent with a
primary and secondary alkylamine could enhance adsorption capacity while the tertiary amine was barely increased at
room temperature and dry atmospheric condition. The ethylenediamine-polyHIPE material exhibited the highest
adsorption capacity among the adsorbents studied.
Acknowledgements
This work was supported by the Royal Golden Jubilee Ph.D Program, and the Rachadaphiseksomphot Endowment
Fund, part of the Strengthen CUs Researchers Project, Chulalongkorn University, Thailand, and the Clean Energy
Technologies Institute, University of Regina, Canada.
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