Short Communication

Journal of Chemical Engineering of Japan, Vol. 37, No. 6, pp. 804807, 2004

Preparation of Thermosensitive Microgel Adsorbent for Quick

Adsorption of Heavy Metal Ions by a Temperature Change
Ryoichi K ANAZAWA, Kazuya M ORI,
Hideaki TOKUYAMA and Shuji SAKOHARA
Department of Chemical Engineering,
Graduate School of Engineering, Hiroshima University,
4-1, Kagamiyama 1, Higashi-Hiroshima-shi,
Hiroshima 739-8527, Japan

Keywords: Adsorbent, Heavy Metal Ion, Molecular Imprinting, Thermosensitive Gel, Polymerizable Surfactant
A thermosensitive microgel adsorbent, which adsorbs and desorbs a specific heavy metal ion by the
temperature swing, was developed. The microgels was prepared by the emulsion polymerization using
anionic polymerizable surfactant. N-Isopropylacrylamide (NIPA) and N-(4-vinyl)benzyl ethylenediamine
were used as the primary monomer and the chelating monomer, respectively. In the preparation, the
molecular imprinting technique using Cu(II) ions as a target heavy metal ion was adopted. The
thermosensitive microgel adsorbents were dispersed stably even if the temperature of the suspension
exceeded the transition temperature of poly(NIPA), and Cu(II) ions were adsorbed quickly in response
to the temperature change.

Introduction
In the previous paper (Kanazawa et al., 2003b),
we proposed a novel gel adsorbent, which adsorbs and
desorbs heavy metal ions repeatedly by the temperature swing. Such a gel adsorbent was prepared by
copolymerizing N-isopropylacrylamide (NIPA) with
the chelating monomer using the molecular imprinting technique. NIPA is well known as a representative
monomer for the preparation of thermosensitive gels.
Thermosensitive gels swell below the transition temperature in water, while shrink above the transition temperature because of the transition to the hydrophobicity.
The transition temperature of NIPA gel is about 32C
(Ito, 1989). In the previous work, N-(4-vinyl)benzyl
ethylenediamine (Vb-EDA) was prepared as a chelating
monomer, and was copolymerized with NIPA in the
presence of Cu(II) ions as a target heavy metal ion.
The adsorption amount of Cu(II) ions on the imprinted
gel depended on the temperature and the maximum adsorption amount was observed at a specific temperature where the size of gel network corresponds to that
memorized in the preparation of gel. The gel adsorbed
and desorbed repeatedly by the temperature swing.
Furthermore, the gel adsorbed Cu(II) ions selectively.
Figure 1 shows schematically the mechanism of adsorption and desorption by the temperature change.
In the separation process, the adsorption rate is
Received on November 14, 2003. Correspondence concerning
this article should be addressed to S. Sakohara (E-mail address:
sakohara@hiroshima-u.ac.jp).

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an important factor. However, it took almost 100 hours

to attain the equilibrium adsorption amount in the previous work, in which the gel powder prepared by grinding the dried bulk gel was used. The size of dried gel
powder was widely distributed from several tens to
several hundreds micrometers, and these gels swelled
and shrank within several minutes in response to the
temperature change, for example between 10 and 35C.
Although the gel was relatively small and shrank
quickly in response to the temperature change, the adsorption rate was quite small. Such a small adsorption
rate is considered due to the facts that the
thermosensitive powder gels scarcely disperse above
the transition temperature because of the hydrophobic
interaction, and that the diffusion of Cu(II) ions into
the gel is obstructed by the skin layer of the shrunk
polymer network formed by the rapid increase in temperature, in other words, the dense part of the polymer
network on the surface of gel particles (Park and
Hoffman, 1994).
To alleviate such a problem, we tried to prepare
the thermosensitive microgel adsorbent, which can disperse in an aqueous solution above the transition temperature. The various methods for the preparation of
microgel, such as the precipitation polymerization
(Pelton and Chibante, 1986) and the emulsion polymerization (McPee et al., 1993; Ito et al., 1999), are
known. The emulsion polymerization in the presence
of a polymerizable surfactant is also an effective
method to produce the suspension containing highly
concentrated stable microgels (Kanazawa et al.,
2003a).
Copyright 2004 The Society of Chemical Engineers, Japan

Table 1

Synthesis conditions of microgels

[mol/m3 ]

Monomer

N-Isopropylacrylamide (NIPA)
Chelate (complex of Vb-EDA and Cu(II)

250500
03.6

Cross-linker

N,N-Methylenebisacrylamide (MBAA)

12.525

Surfactant

SE-10

0.951.8

Accelerator

N,N,N,N-Tetramethylethylenediamine

2.55

Initiator

Ammonium peroxodisulfate

2.55

solvent, water; temperature, 50C

Fig. 1

Schematic figure of adsorption and desorption of

Cu(II) ions by a temperature change for NIPA-co(Vb-EDA) gel

Fig. 2

Chemical structure of an anionic polymerizable surfactant, SE-10

In this work, the microgel adsorbent was prepared

by the emulsion polymerization in the presence of a
polymerizable surfactant, and the adsorption rate of
Cu(II) ions on such microgel adsorbents was examined.
1.

Experimental

1.1 Preparation of microgel adsorbent

N-Isopropylacrylamide (NIPA, Kohjin Co. Ltd.)
of the primary monomer was purified by
recrystallization from hexane. The chelating monomer,
N-(4-vinyl)benzyl-ethylenediamine (Vb-EDA) and its
complex with Cu(II) ions were prepared according to
the method developed by Lu et al. (2000). The procedures are shown elsewhere (Kanazawa et al., 2003b).
As a polymerizable surfactant, an anionic surfactant
of commercial grade, SE-10N (Asahi Denka Co., Ltd.)
was used. The chemical structure is shown in Figure
2. N,N-Methylenebisacrylamide (MBAA) was used as
a cross-linker agent. N,N,N,N-Tetramethylethylenediamine and ammonium peroxodisulfate were used as
the polymerization accelerator and initiator, respectively.
The polymerization procedure was basically the
same as those in our previous work (Kanazawa et al.,
2003a). The polymerization was performed in water at
50C under the nitrogen atmosphere for 2 hours. The
preparation conditions are summarized in Table 1. The

suspension containing the formed microgels was

dialyzed with a cellulose tubular membrane (Cellu Sep
T3, Membrane Filtration Product, Inc.) in water and
in 1 mol/dm3 HCl aqueous solution to remove the residual monomers and the imprinted Cu(II) ions, respectively. After that the suspension was dried in a drying
oven at 50C. The suspension of NIPA microgels was
also prepared by the same method without chelating
monomers.
1.2 Adsorption experiments
The adsorption experiments were performed as
follows: Dried microgels of 0.075 g were added to
0.02 dm3 of a copper perchlorate aqueous solution containing the desired amount of Cu(II) ions in a test tube.
The tube was shaken in a water bath of 10C for 1 day
to swell the gel. After that, the tube was transferred to
a thermostat bath controlled at 50C to adsorb Cu(II)
ions. This time is set to t = 0. Where it took about 5
minutes to increase the temperature of the suspension
including the microgels from 10 to 50C. The concentration of Cu(II) ions in the solution were measured at
the desired time intervals by inductively coupled
plasma atomic emission spectroscopy (ICP, SPS3000,
Seiko Instrument Inc.). The sample solution was obtained by removing the microgels from the solution
with a filter syringe (0.2 m PP, Whatman Inc.).
1.3 Measurement of swelling diameter of microgel
The size distribution and an average diameter of
disperse microgels were measured by a laser diffraction particle size analyzer (SLAD-300V, Shimadzu Co.)
under the controlled temperature.
2.

Results and Discussion

2.1 Effect of the Vb-EDA content on diameter of

imprinted microgel
A pale colored suspension was obtained by the
emulsion polymerization using the polymerizable surfactant, SE-10N. Figure 3 shows the effect of the VbEDA content in the imprinted microgels on the number
base average diameter of dispersed microgels. The
measurements were performed at 35C. The microgels
were prepared with NIPA of 500 mol/m 3, MBAA of

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Fig. 3

Effect of temperature on the number base average

diameter of imprinted microgels

Fig. 5

Time course of the adsorption amount of Cu(II) ions

on the imprinted microgel

Effect of the Vb-EDA content in the imprinted

microgels on the number base average diameter of
dispersed microgels

25 mol/m3 and Cu(Vb-EDA) 2 of various concentrations. Where Cu(Vb-EDA) 2 represents the complex of
the chelating monomers, Vb-EDA, and a Cu(II) ion.
The average diameter of microgels increased with an
increasing concentration of chelating monomers and
approached to a constant value. The increase in the average diameter of microgels is probably due to the aggregation of microgels caused by neutralization of
the electric charge of the polymerizable surfactant with
the chelating complex. By increasing the concentration of the chelating complex above 2.4 mol/m3 the
formation of precipitate was observed. The result
shown in Figure 3 was obtained by removing such precipitates.
The inset in Figure 3 shows an example of the
particle size distributions. The distribution was obtained with a sample which did not contain the precipitates mentioned above. It is known that the size
distribution of particles prepared by emulsion polymerization using the polymerizable surfactant was relatively wide (Kanazawa et al., 2003a).
2.2 Temperature dependence of particle size
Figure 4 shows the temperature dependence of
the number base average diameter of imprinted
microgels. The sample microgels were prepared with
NIPA of 250 mol/m 3, MBAA of 12.5 mol/m 3 and
Cu(Vb-EDA)2 of 3.0 mol/m3. It was observed that the
microgels were suspended stably even if the temperature of the suspension exceeded the transition temperature of poly(NIPA), about 32C. The average diameter
of the microgel decreased with an increasing suspension temperature, and was kept constant above 35C
which is very close to the transition temperature of
poly(NIPA). The gel diameter in such a shrunk state

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Fig. 4

corresponds to that prepared by the emulsion polymerization at 50C. From this result and our previous
work (Kanazawa et al., 2003b), it can be considered
that the complex structure of Vb-EDA and Cu(II) ions
engraved in the microgels appears above 35C. In other
words, the maximum adsorption amount of Cu(II) ions
can be obtained above 35C.
2.3 Temperature dependence of the adsorption
amount of Cu(II) ions and the adsorption rate
Figure 5 shows the time course of the adsorption
amount of Cu(II) ions on the imprinted microgels. The
sample microgels were prepared with NIPA of 500
mol/m 3, MBAA of 25 mol/m 3 and Cu(Vb-EDA) 2 of
3.4 mol/m3. This preparation condition was selected to
synthesize relatively large gel particles.
The microgels were swollen previously at 10C
in the solution containing Cu(II) ions, and then the temperature of the solution was increased to 50C as mentioned in Section 1.2. At the swelling state of 10C,

JOURNAL OF CHEMICAL ENGINEERING OF JAPAN

the adsorption amount of Cu(II) ions was very small,

about 0.1 mg-Cu/g-dry gel, while at the shrinking state
of 50C, the adsorption amount of Cu(II) ions was
about 2.5 mg-Cu/g-dry gel. This result supports the
consideration that the complex structure of Vb-EDA
and Cu(II) ions engraved in the microgels appears
above 35C.
The time required to attain the equilibrium
amount was about 100 minutes. It can be said that the
adsorption rate was very large compared with that reported in our previous work, in which it took more than
100 hours as mentioned above. The main reason is considered due to the fact that the microgel adsorbents prepared with the polymerizable surfactant keep the dispersed state even if the temperature of the suspension
exceeds above the transition temperature of
poly(NIPA). The effect of the formation of a skin layer
by the rapid increase of temperature on the adsorption
rate and the handling of such small particles in practical use should be investigated further.
Conclusion
Thermosensitive N-isopropylacrylamide microgel
adsorbent was prepared by emulsion polymerization
using an anionic polymerizable surfactant and the molecular imprinting technique using Cu(II) ions as a target ion. Although the diameter of the microgel was
dependent on the content of the chelating monomer,
N-(4-vinyl)benzyl-ethylenediamine, the microgels
were suspended stably even if the temperature of the
suspension exceeded the transition temperature of
poly(NIPA). The adsorption amount of Cu(II) ions on

VOL. 37 NO. 6 2004

the microgels at the shrinking state of 50C, where the

gel network size was the same as that in the preparation of gel, was quite large compared with that at the
swollen state of 10C, and Cu(II) ions were adsorbed
very quickly by the temperature change as expected.
Acknowledgment
The authors would like to acknowledge the support of the
Grant-in-Aid for Scientific Research from JSPS (Japan Society for
the Promotion of Science) (Grant No. 14550750).
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(1999)
Kanazawa, R., S. Sakohara and S. Ito; Synthesis of Thermosensitive
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