Available online at www.sciencedirect.

com

Carbohydrate Polymers 73 (2008) 315–321

www.elsevier.com/locate/carbpol

A multifunctional hydrogel with high conductivity, pH-responsive,

thermo-responsive and release properties from
polyacrylate/polyaniline hybrid
Qunwei Tang, Jihuai Wu *, Jianming Lin
The Key Lab for Functional Materials of Fujian Higher Education, Institute of Material Physical Chemistry, Huaqiao University, 362021 Quanzhou, China

Received 2 November 2007; received in revised form 24 November 2007; accepted 26 November 2007
Available online 5 December 2007

Abstract

Polyacrylate/polyaniline (PAC/PANI) hybrid was synthesized by a two-step aqueous polymerization method, which aniline monomer
was absorbed in the network of polyacrylate and followed by a polymerization reaction between aniline monomers. The PAC/PANI
hydrogel possessed a conductivity of 2.33 mS cm1. A conduction mechanism with charge carriers (protons) hopping along the polyan-
iline chain was suggested. The PAC/PANI hydrogel had predominant pH- and thermo-sensitive properties. The hydrogel showed two
sharp water adsorbed peaks at pH 4–6 and pH > 12. The swelling sensitive temperature of PAC/PANI hydrogel was about 30 °C. PAC/
PANI hydrogel possessed loading and releasing properties. The release obeyed an anomalous mechanism.
Ó 2007 Elsevier Ltd. All rights reserved.

Keywords: Polyacrylate/polyaniline; Conducting hydrogel; pH-responsive swelling; Thermo-responsive swelling; Release property

1. Introduction Wei, MacDiarmid, & Lelkes, 2006; Richter, Howitz, Kuc-

kling, & Arndt, 2004; Siddhantaa & Gangopadhyay, 2005;
Superabsorbent polymers have stronger hydrophilic Wada, Nohara, & Iwakura, 2004; Wu, Lin, & Zhou, 2000;
groups and lightly crosslinked network structure (Wu Wu, Wei, Lin, & Lin, 2003; Wu et al., 2006), it is expected
et al., 2006). Not only it is able to absorb a large amount to prepare a multifunctional superabsorbent material to
of water to form a stable hydrogel, but also the absorbed meet applications requirement by modifying, grafting,
water is hardly removed under some pressure. About three copolymering and other methods.
decades ago (Omidian, Rocca, & Park, 2005), superabsor- Here, polyaniline is integrated with polyacrylate to form
bent polymers were introduced into the agriculture and polyacrylate/polyaniline (PAC/PANI) hybrid and hydro-
diaper industries, and then their applications were extended gel. Polyaniline is a typical conducting polymer. Polyacry-
to other industries where an excellent water holding prop- late is a superabsorbent polymer, its swelling behavior is
erty was prime importance. Recently, many researches sensitive to the pH value and temperature, thus the resulted
focus on the superabsorbent polymer for developing new polyacrylate/polyaniline hydrogel possess conductivity,
applications, such as, conducting materials, sensors and pH- and thermo-sensitivity. Furthermore, the hydrogel
release materials, biomaterials, wave-absorbing materials have porous structure and hydrophilic groups, which
(Abd El-Rehim, 2005; Dispenza, Presti, Belfiore, Spadaro, endows the hydrogel with a controlled release property.
& Piazza, 2006; Ito et al., 2003; Lee & Chen, 2005; Li, Guo, In this way, a multifunctional hydrogel can be obtained,
the multifunctional hydrogel is likely to be used as con-
* ducting materials, sensors, release materials and biomateri-
Corresponding author. Tel.: +86 595 22693899; fax: +86 595
22693999. als (Abd El-Rehim, 2005; Li et al., 2006; Richter et al.,
E-mail address: [email protected] (J. Wu). 2004; Siddhantaa & Gangopadhyay, 2005; Wada et al.,

0144-8617/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbpol.2007.11.036
316 Q. Tang et al. / Carbohydrate Polymers 73 (2008) 315–321

2004). In this paper, polyacrylate/polyaniline hybrid was room temperature. After that, similar to the preparation of
synthesized by two-step aqueous polymerization. Mean- PAC superabsorbent polymer, the intermediate product
while, the pH-responsive swelling, temperature-responsive was filtrated, washed, dried, milled and sifted, finally a
swelling and release property for PAC/PANI hydrogel PAC/PANI hybrid powder thus was obtained.
was investigated.
2.4. The measurement of swelling property of PAC/PANI
2. Experiment
The swelling ratio is the criterion of describing water
2.1. Materials absorption capacity. The measurement of the swelling ratio
of PAC/PANI was conducted by a tea-bag method, and
Acrylic acid monomer (AA) and aniline monomer using distilled water as liquids to be absorbed. The tea bags
(ANI) was reduced distilled prior to use, respectively. used in the method was made of 40 meshes nylon net. The
Potassium hydroxide was used to neutralize acrylic acid weight of the wet nylon net was measured and marked as
monomer and produce potassium acrylate (AC). Potassium Wn. The weight of dry PAC/PANI was marked as Wd.
persulfate (KPS) was purified by recrystallization from 66 After weighing, the test sample was placed into the tea-
wt% ethanol/water solution before being used, which was bag, then the tea-bag with sample inside was suspended
used as a radical initiator for the polymerization reaction and fully immersed into distilled water at 25 °C. After
of polyacrylate (PAC) and polyaniline (PANI). N,N 0 -meth- 24 h, the tea bag was hung in the air for 15 min, and then
ylene bisacrylamide was used as a crosslinker for prepara- the weight of the tea bag including swollen sample was
tion of PAC. measured and marked as Wt. The swelling ratio of PAC/
PANI was calculated according to the follow equation:
2.2. Preparation of polyacrylate superabsorbent polymer ðW t  W d  W n Þ
Swelling ratioðSRÞðg=gÞ ¼ ð1Þ
Wd
Polyacrylate superabsorbent polymer was prepared by
modifying the procedure from reference (Lin, Wu, Yang,
& Pu, 2001; Tang, Lin, & Wu, 2007; Wu, Lin, Li, & Wei, 2.5. The measurement of conductivity of PAC/PANI
2001). A mixed solution of AA monomer, potassium acry- hydrogel
late, crosslinker was made by agitating AA monomer
(15 g), crosslinker (N,N 0 -methylene bisacrylamide, The dry powdered PAC/PANI hybrid of 3 g was
0.006 g), potassium hydroxide (7 g, to partially neutralize immersed in excessive distilled water at room temperature
acrylic acid) in distilled water (15 ml) at ambient tempera- for at least 3 h to reach swelling equilibrium, which resulted
ture. Under a nitrogen atmosphere, the mixture solution in the absorption of water inside of the network of the
was stirred and heated to 80 °C in a water bath for PAC/PANI hybrid and the formation of a semitransparent
15 min, and then the initiator potassium persulfate PAC/PANI hydrogel. The unabsorbed water was removed
(0.15 g) was added, the reaction system was stirred for a by filtrating over a 40-mesh nylon net and hanging up for
few minutes until the polymerization reaction completed. 25 min. The electrical conductivity of the PAC/PANI
A jell-like intermediate product was filtered through What- hydrogel was measured by inserting a Pocket Conductivity
man filter paper No. 54 and then immersed in excess dis- Meter (HANNA8733) in a cylinder containing the PAC/
tilled water to remove any impurities. After vacuum PANI hydrogel of 30 g.
drying at 80 °C for more than 3 h to constant weight,
milled and sifted using a 40-mesh screen, a powdered 2.6. The measurement of pH-sensitive properties of PAC/
PAC superabsorbent polymer thus was obtained. PANI hydrogels

2.3. Preparation of PAC/PANI Buffer solutions with pH 1–14 were used to study the
pH-sensitivity swelling of PAC/PANI hydrogel. The
Using the PAC superabsorbent polymer, a polyacrylate/ desired basic and acidic pHs were adjusted by NaOH and
polyaniline (PAC/PANI) was prepared according to follow- HCl solutions, respectively. The pH values were precisely
ing procedure. Under vigorous agitating, 5 g of PAC super- checked by a pH-meter (Leici/E-201-C, accuracy ± 0.01).
absorbent polymer powdered was immersed in a Then, 0.50 g of dried sample was used for the swelling mea-
predetermined amount ANI aqueous solution at ambient surements in buffers according to the above method
temperature for 30 min, which resulted in the absorption described in Section 2.4.
of ANI monomer inside of the PAC network and the forma-
tion of a swollen sample. The swollen sample was dispersed 2.7. The measurement of temperature-sensitive properties of
in a solution of 100 ml containing a suitable amount of initi- PAC/PANI hydrogel
ator potassium persulfate, which caused an in situ polymer-
ization between ANI monomers and formed PANI inside the The thermo-sensitive swelling of the PAC/PANI hydro-
network of PAC. The polymerization reaction took place at gels under different temperatures was studied in distilled
 Q. Tang et al. / Carbohydrate Polymers 73 (2008) 315–321 317

water in term of swelling ratio as a function of temperature. ring of polyaniline, respectively. The results indicate the
The swelling ratio of PAC/PANI hydrogel was measured formation of PAC/PANI hybrid.
after reaching a measuring temperature for 30 min. About
0.50 g of dried sample was used for measuring the swelling 3.2. Influence of preparation conditions on the conductivity of
ratio of sample according to the above method described hydrogel
in Section 2.4.
A suitable mass ratio of AC to ANI is crucial for the
2.8. Drug loading and release conductivity of PAC/PANI hydrogel. As is shown in
Fig. 2a, with the increase of mass ratio of acrylic acid
The drug loaded and released property was evaluated by monomer to aniline monomer, the conductivity of the
using methylrosaniline chloride as drug target. PAC/PANI hydrogel increases gradually, and then decreases after
dried samples were immersed in the drug target aqueous reaching a highest conductivity of 2.33 mS cm1 with the
solution with different concentrations (0.03, 0.06 and mass ratio of acrylic acid to aniline of 12. Obviously, a
0.10 mg/ml) for 12 h at room temperature. The loaded higher mass ratio of acrylic acid to aniline means lower
and released amount were determined spectrophotometri- concentration of aniline, which causes a polyaniline chain
cally (k = 270 ± 1 nm) with a UV-3100 UV–vis–IR spec- weakening. A lower mass ratio of acrylic acid to aniline
trophotometer (Shimadzu Corporation, Japan). The also cannot absorb enough aniline monomer inside of poly-
regression equation of methylrosaniline chloride solution acrylate network to construct a suited polyaniline chain,
working curve was A = 45.45 c = .022, r = .9994. due to the osmosis character of aniline monomer and poly-
acrylate network. Above two cases cannot form an inter-
2.9. FTIR spectra penetrating network to conduct electrons and bring to
the decrease of conductivity of the hydrogel.
The sample was identified by IR spectroscopy on a Nico- The polyaniline chain is formed inside of the polyacry-
let Impact 410 FTIR spectrophotometer using KBr pellets. late network in aqueous solution system based on the poly-
merization reaction (reactions I and II). The concentration
3. Results and discussion of aniline affects the reaction (II) and the conductivity of
hydrogel. From Fig. 2b, it can be seen that the concentra-
3.1. FTIR spectrum of PAC/PANI hybrid tion of aniline an increase from 0.63 wt% to 1.0 wt% causes
the conductivity to increase, beyond the concentration of
The PAC/PANI hybrid was characterized by FTIR 1.0 wt%, the conductivity decrease.
spectrum. In Fig. 1, the absorption peak at 3331 cm1 crosslinkerþinitiator
belongs to a NAH bending, 2946 cm1 ascribes to a N ðacrylateÞ ƒƒƒƒƒƒƒƒ
ƒ! polyacrylate
first polymerization
ðIÞ
ACH2A stretching, 1710 cm1 attributes to a C@O bend- initiator
ing and 1123 cm1 belongs to a CAH bending of polyacry- N ðanilineÞ þ polyacrylate ƒƒƒƒ! polyacrylate=
second polymerization
late, respectively. The absorption peak at 1565 cm1 is due
to a quinoid ring stretching, 1491 cm1 attributes to ben- polyaniline ðIIÞ
zene ring stretching, 1298 cm1 and 1235 cm1 are stretch-
According to the mass law, a lower aniline concentration
ing vibrations for NAH connecting between benzene ring
causes a slower velocity for the second polymerization
and quinoid ring and between benzene ring and benzene
reaction between aniline monomers, a lower polyaniline
yield, and a lower conductivity. On the other hand, due
to the osmosis character of aniline monomer and polyacry-
50 late network, only part aniline monomers penetrate into
polyacrylate network and polymerize to form polyaniline
40 chain. Under a higher aniline concentration, mostly aniline
Transmittance / %

monomers and oligomer exist outside of polyacrylate net-

30 work, and are washed out in the preparation process. Con-
sequently, higher aniline concentrations do not produce a
higher polyaniline chain density in the network of polyac-
2946

20
3331

rylate and a higher conductivity. In our experiment condi-

765
1491

tions with the aniline monomer concentration of 1.0 wt%,

1710

10
1298
1235

the hydrogel possesses a highest conductivity.

1565

1123

3.3. Conductivity mechanism of the hydrogel

3500 3000 2500 2000 1500 1000 500
Wavenumber / cm-1
Compared the conductivities of the hydorgels and in
Fig. 1. FTIR spectrum of polyacrylate/polyaniline hybrid. their corresponding filtrate liquids in Fig. 2. Obviously,
318 Q. Tang et al. / Carbohydrate Polymers 73 (2008) 315–321

a b 2.2

2.4 hydrogel
hydrogel 2.0 filtrate
filtrate
2.2
1.8

Conductivity (mS/cm)
Conductivity (mS/cm)

2.0
1.6

1.8
1.4

1.6 1.2

1.4 1.0

1.2 0.8
2 3 4 5 6 7 8 0.5 1.0 1.5 2.0 2.5
AA/ANI (g/g) ANI concentration (wt. %)

Fig. 2. Influence of preparation conditions on the conductivity of the hydrogel: (a) The ratio of AA to ANI at ANI concentration = 1.0 wt%; (b) ANI
concentration at ratio of AA to ANI = 8 (Preparation conditions: Mass ratio of KPS to ANI 1.0, react at 20 °C for 6 h).

 
the conductivity of the PAC/PANI hydrogels are higher Ea
rðTÞ ¼ Aexp T ð2Þ
than that of their corresponding filtrate, which suggests R
that the conductivities of hydrogels mainly come from
the polyaniline china (by protons hoping) in the interpene- where Ea is the activation energy, R is the molar gas con-
trating networks structure of PAC/PANI, instead of the stant, A is a constant, and T is absolute temperature.
liquid in hydrogel (by ions hoping) in our conditions. According to the experimental data, the Ea is calculated
On the other hand, from Fig. 2, the conductivity of the as 0.225 eV and the A is 14.88. The Arrhenius behavior
hydrogel evidently depends on the ratio of aniline mono- of conductivity, with an activation energy value of
mer and the concentration of aniline monomer, which 0.225 eV suggests that conduction is due to charge carriers
implies that aniline chain play an important rule in the con- (protons) (Konsta, Daoukaki, Pissis, & Vartzeli, 1999)
ductivity of the hydrogel, in other words, the aniline chain hopping along the polyaniline chain rather than to cooper-
in the interpenetrating networks structure of PAC/PANI ative motions of polymer chains.
govern the conductivity of the hydrogel.
The dependence of temperature on the conductivity of 3.4. Swelling behaviors responding to pH and temperature
the hydrogel shows that the conductivity rises with the
increase of temperature (Fig. 3). The conductivity-temper- The swelling of PAC/PANI hydrogel was investigated at
ature behavior of the PAC/PANI hydrogel can be different pHs ranged from 1.0 to 14.0. The result is shown
described by Arrhenius equation. in Fig. 4a. From Fig. 4a, PAC/PANI do not possess the
maximum of swelling ratio at pH 7, which is different from
the cross-linked polyacrylate that is researched most uni-
versally. This is due to that PAC/PANI is consisted of
2.5 polyacrylate and polyaniline, and polyaniline shows an
ampholyte and alkalescence. The two sharp water absor-
bent peaks can be ascribed to high repulsion of @NH+A
2.0 group on the polyaniline chine in acidic media and
ACOO group on the polyacrylate networks in basic
ln (σ mS/cm)

media. The repulsion action between these groups promote

1.5
the swelling of hydrogel and cause a higher swelling ratio.
Moreover, due to stronger repulsion force between
1.0
ACOO groups than between @NH+A groups, higher
swelling ratio is shown in basic media than in acidic media.
At very acidic condition (pH < 3), a screening effect of
0.5 the counter ions, i.e. Cl, shields the charge of the cations
2.7 2.8 2.9 3.0 3.1 3.2 3.3 3.4 3.5 (ANH+A) and prevents an efficient repulsion (Mahdavi-
1000T -1 (K) -1 nia, Pourjavadi, Hosseinzadeh, & Zohuriaan, 2004). There-
Fig. 3. The conductivity–temperature relationship of hydrogel (prepara- fore, an obviously reduced final absorbency appears.
tion conditions: Mass ratio of AA to ANI 12, mass ratio of KPS to ANI Under this acidic condition, anionic carboxylate groups
1.0, ANI concentration 1.0 wt%, react at 20 °C for 6 h). are protonated, so the polymeric network collapsed. At
 Q. Tang et al. / Carbohydrate Polymers 73 (2008) 315–321 319

a 55
b
50
pH=10.5
50

45
40

40 pH=6.5
SR / g/g

SR / g/g
30
35
pH=1.5
30 20

25
10
20

15 0
0 2 4 6 8 10 12 14 0 10 20 30 40 50
pH Temperature / oC

Fig. 4. Dependence of swelling ratio (SR) of the hydrogel on (a) pH at 25 °C and (b) temperature (Samples prepared conditions was the same as Fig. 3).

about pH 4.5, the carboxylic acid component comes into T > TC, DG > 0, which results in a deswelling and a
action as well. Since the pKa of the aniline monomer is decrease of the hydrogel volume.
about 5.3, its ionization occurs above this value. That Swelling temperature-sensitive property is studied on the
may enhance absorbency. However, in pH range 6–8 closed hydrogel swelling kinetics. Fig. 5 represents the dynamic
with neutrality, most base and acid groups are non-ioniza- swelling behavior of a PAC/PANI hydrogel in water. It
tion, so H-bonding between amine and carboxylic acid or can be found that water uptake depended linearly on t1/2
carboxamide groups may result in a kind of cross-linking (r2 > .99) for all the hydrogels studied, i.e. Fickian behavior
followed by a decreased swelling. With farther increase of is maintained in spite of the swelling of the polymer net-
pH, ionization of carboxylic acid groups happens, and work. The slope for PAC/PANI hydrogels at 5, 25 and
the electrostatic repulsive force between the ACOOK 37 °C is 1.37, 1.23 and 0.46, respectively. Nevertheless,
groups leads to high swelling. Analogous viewpoints were the high values in three cases shows that water molecules
reported in the poly(aspartic acid) (Zhao, Su, Fang, & easily penetrate the free pore volume. Similar phenomena
Tan, 2005) and chitosan-g-poly (AA-co-AAm) systems also were reported in polyquaternium-4 (PQ-4) and poly-
(Konsta et al., 1999). quaternium-10 (PQ-10) systems (Rodriguez, Alvarez-Lore-
nzo, & Concheiro, 2003). The faster swelling velocity
constant for the PAC/PANI hydrogel from the slope at
3.5. Swelling behaviors responding to temperature lower temperature than that at higher temperature suggests
that the swelling depends on the diffusion of water mole-
It is well known that the hydrogels with suitable hydro- cules, and the interaction between the water molecules
philic–hydrophobic balance may exhibit thermosensitivity, and PAC/PANI matrix.
i.e. sharp decrease in volume in aqueous environment
with high temperature. Fig. 4b shows the temperature-
dependant swelling of PAC/PANI hydrogels when media 36
5oC
temperature increases from 5 to 45 °C. It can be seen that 32
the swelling ratio decreases with the increase of tempera- 25oC
ture in the region of 30–45 °C. Swelling behavior of the 28

hydrogel depended on temperature is ascribed to the 24

intramolecular hydrophobic interaction, the H-bonding
SR / g/g

20
with water (Dergunov, Nam, Doldina, & Nurkeeva,
2004), and the porosity (Mahdavinia et al., 2004) of the 16

hydrogel. 37oC
12
From the thermodynamics aspects, the DH that water
8
molecules enter the networks of polymer and cause a
hydrogel swelling is negative due to the formation of 4

hydrogen bond, and DS for the hydrogel swelling is also 0

negative for the formation of cage structures and enhance- 0 2 4 6 8 10 12
Time / hours
ment of the ordered degree of water molecules. According
to DG = DH – TDS, increasing temperature is disadvanta- Fig. 5. Dependence of SR on time at pH of 6.5 (Samples prepared was the
geous for the swelling of hydrogel. If T = TC, DG = 0; same as Fig. 3).
320 Q. Tang et al. / Carbohydrate Polymers 73 (2008) 315–321

a 0.03 mg/mL
b 50

60 37oC
40
0.06 mg/mL 25oC
Cumulative release / %

Cumulative release / %
50

40 30 5oC

30 0.1 mg/mL
20

20

10
10

0 0
0 2 4 6 8 10 0 2 4 6 8 10
Time / hours Time / hours

Fig. 6. Methylrosaniline chloride release (a) under different loaded amount and at 25 °C (b) under different temperature at loaded 0.06 mg/ml (pH at 6.5,
samples prepared was the same as Fig. 3).

3.6. Methylrosaniline chloride loading and releasing by Peppas (Peppas & Ritger, 1987). For a cylindrical geom-
etry, value of n of .45 (or less) is corresponding to a pure Fic-
The PAC/PANI possesses porous structure and the kian diffusion mechanism. Value of n greater than .89
property of semipermeable film (Tang et al., 2007; Wu indicates a relaxation controlled-release mechanism, and n
et al., 2001), which is possible to be used in drug load value between .45 and .89 indicates an anomalous release
and release. Using methylrosaniline chloride with different mechanism. Despite the approximations, it is found that
concentrations as targets, the cumulative release of meth- these relationships could be applied to release data, indicat-
ylrosaniline chloride at different loading amount were mea- ing that the diffusion-based models of Higuchi and Peppas
sured and shown in Fig. 6a. describe drug release from a polymeric system quite well.
The influence of temperature on drug release is shown in According to Eq. (4) and Fig. 6a, the relationship
Fig. 6b, it can be seen that with the increase of temperature, between ln Mt on ln t was made and the result is shown in
the cumulative release amount and release velocity Fig. 7. The diffusional exponent n values for .10, .06 and
increase. This is due to that a higher temperature makes .03 mg/mL are .62, .58 and .46, respectively. Diffusional
a higher kinetic energy of methylrosaniline chloride mole- exponent n values for PAC/PANI hydrogel with different
cule and weakens the interaction between matrix and meth- loading amount between .45 and .89 indicate an anomalous
ylrosaniline chloride molecules. release mechanism, which may be the result of cooperate
Modeling of the controlled release from polymeric effect, including the methylrosaniline chloride concentra-
devices has been the subject of considerable research over tion difference between the exterior and the interior of
the past 25 years (Stephens, Li, Robinsona, Chen, & PAC/PANI hydrogel, and the interaction between meth-
Chang, 2000). Higuchi derived a simple relationship that ylrosaniline chloride and PAC/PANI matrix. The higher
described drug release from a matrix as a function of time
Eq. (3) (Higuchi, 1963).
4.0 0.06 g/L n=0.58
Mt 0.03 g/L n=0.46
¼ kt1=2 ð3Þ 0.10 g/L n=0.62
M 3.6

where Mt and M1 are the masses of drug released when the

3.2
time equals t and 1, respectively. It can be considered that
the release of the drug is linear with the square roots of
ln(Mt)

2.8
time.
Peppas extended the Higuchi model to a more general- 2.4
ized form:
Mt 2.0
¼ ktn ð4Þ
M
1.6
where n is the diffusional exponent. Information about the 3.0 3.5 4.0 4.5 5.0 5.5 6.0
ln[t(min)]
release mechanism can be gained by fitting the release data
(for the first 60% dissolved) and comparing the values of n Fig. 7. The relation of ln Mt–ln t for polyacrylate/polyaniline hydrogel
to the semi-empirical values for various geometries reported with different loading amount.
 Q. Tang et al. / Carbohydrate Polymers 73 (2008) 315–321 321

n value for higher methylrosaniline chloride concentration Ito, K., Chuang, J., Carmen, A. L., Watanabe, T., Ando, N. A., & Yu, G.
indicates that the interaction is enhanced further. (2003). Multiple point adsorption in a heteropolymer gel and the
Tanaka approach to imprinting: Experiment and theory. Progress in
Polymer Science, 28, 1489–1515.
4. Conclusions Konsta, A. A., Daoukaki, D., Pissis, P., & Vartzeli, K. (1999). Hydration
and conductivity studies of polymer–water interactions in polyacryl-
Polyacrylate/polyaniline (PAC/PANI) polymer was pre- amide hydrogels. Solid State Ionics, 125, 235–241.
pared by a two-steps aqueous polymerization. Firstly, the Lee, W. F., & Chen, Y. C. (2005). Effect of intercalated reactive mica on
water absorbency for poly(sodium acrylate) composite superabsor-
polyacrylate superabsorbent polymer was synthesized by bents. European Polymer Journal, 41, 1605–1612.
a routine aqueous polymerization. Secondly, aniline mono- Li, M. Y., Guo, Y., Wei, Y., MacDiarmid, A. G., & Lelkes, P. I. (2006).
mer was absorbed inside of polyacrylate network, then, Electrospinning polyaniline – contained gelatin nanofibers for tissue
PAC/PANI hybrid was prepared by a polymerization reac- engineering applications. Biomaterials, 27, 2705–2715.
tion. When immersed the PAC/PANI hybrid in distilled Lin, J. M., Wu, J. H., Yang, Z. F., & Pu, M. L. (2001). Synthesis and
properties of poly-acrylic acid/mica superabsorbent nanocomposite.
water, a hydrogel with a conductivity of 2.33 mS cm1 Macromolecular Rapid Communications, 22, 422–424.
was obtained. The researches on the conductivity of filtrate Mahdavinia, G. R., Pourjavadi, A., Hosseinzadeh, H., & Zohuriaan,
liquid and the Arrhenius behavior of conductivity of the M. J. (2004). Modified chitosan 4. Superabsorbent hydrogels from
hydrogel suggest that the conduction is due to charge car- poly(acrylic acid-co-acrylamide) grafted chitosan with salt- and
riers (protons) hopping along polyaniline chain. Due to the pH-responsiveness properties. European Polymer Journal, 40,
1399–1407.
bifunctional groups ANHA and ACOOH in PAC/PANI, Omidian, H., Rocca, J. G., & Park, K. (2005). Advances in superporous
the PAC/PANI hydrogel has predominant pH- and hydrogels. Journal of Controlled Release, 102, 3–12.
thermo-sensitive swelling properties. The hydrogel shows Peppas, N., & Ritger, P. L. (1987). A simple equation for description of
two sharp water absorbent peaks at pH 4–6 and pH > 12. solute release I. Fickian and non-fickian release from non-swellable
The sensitive temperature of PAC/PANI hydrogel to swell- devices in the form of slabs, spheres, cylinders or discs. Journal of
Controlled Release, 5, 2–42.
ing is about 30 °C. Based on the porous structure, the Richter, A., Howitz, S., Kuckling, D., & Arndt, K. F. (2004). Influence of
PAC/PANI hydrogel possesses loading and releasing prop- volume phase transition phenomena on the behavior of hydrogel-
erty. Diffusional exponent n values for PAC/PANI hydro- based valves. Sensors and Actuators B, 99, 451–458.
gels between .45 and .89 indicates an anomalous release Rodriguez, R., Alvarez-Lorenzo, C., & Concheiro, A. (2003). Cationic
mechanism, which may be due to the concentration differ- cellulose hydrogels: Kinetics of the cross-linking process and charac-
terization as pH-/ion-sensitive drug delivery systems. Journal of
ence between the exterior and the interior of PAC/PANI Controlled Release, 86, 253–265.
hydrogel, and the interaction between methylrosaniline Siddhantaa, S. K., & Gangopadhyay, R. (2005). Conducting polymer gel:
chloride and PAC/PANI matrix. Formation of a novel semi-IPN from polyaniline and crosslinked
poly(2-acrylamido-2-methyl propanesul) phonicacid. Polymer, 46,
Acknowledgements 2993–3000.
Stephens, D., Li, L., Robinsona, D., Chen, S., & Chang, H. C. (2000).
Investigation of the in vitro release of gentamicin from a polyanhy-
The authors thank for jointly support by the National dride matrix. Journal of Controlled Release, 63, 305–317.
Natural Science Foundation of China (No. 50572030 and Tang, Q. W., Lin, J. M., & Wu, J. H. (2007). Two-steps synthesis of a
No. 50372022), the Key Scientific Technology Program of poly(acrylate-aniline) conducting hydrogel with an interpenetrated
Fujian, China (No. 2005HZ01-4 and No. 2007HZ0001-3), networks structure. Carbohydrate Polymers, 67, 332–336.
Wada, H., Nohara, S., & Iwakura, C. (2004). Electrochemical character-
the Key Project of Chinese Ministry of Education (No. istics of electric double layer capacitor using sulfonated polypropylene
206074) and Specialized Research Fund for the Doctoral separator impregnated with polymer hydrogel electrolyte. Electrochi-
Program of Higher Education (No. 20060385001). mica Acta, 49, 4871–4875.
Wu, J. H., Lan, Z., Wang, D. B., Hao, S. C., Lin, J. M., Yin, S., et al.
(2006). Gel polymer electrolyte based on poly(acrylonitrile-co-styrene)
References and a novel organic iodide salt for quasi-solid state dye-sensitized solar
cell. Electrochimica Acta, 51, 4243–4249.
Abd El-Rehim, H. A. (2005). Swelling of radiation crosslinked acrylam- Wu, J. H., Lin, J. M., Li, G. Q., & Wei, C. R. (2001). Influence of the
ide-based microgels and their potential applications. Radiation Physics hydrophilic group and cross-link density of poly-acrylic acid/mont-
and Chemistry, 74, 111–117. morillonite superabsorbent composite on water absorbency. Polymer
Dergunov, S. A., Nam, I. K., Doldina, M. K., & Nurkeeva, Z. S. (2004). International, 50, 1050–1053.
Swelling behavior of chitosan–polyHEA hydrogels in anionic surfac- Wu, J. H., Lin, J. M., & Zhou, M. (2000). Synthesis and properties of
tant solutions and their thermo-sensitivity. Colloids and Surfaces A, starch–graft–acrylamide/clay superabsorbent composite. Macromolec-
238, 13–18. ular Rapid Communications, 21, 1032–1034.
Dispenza, C., Presti, C. L., Belfiore, C., Spadaro, G., & Piazza, S. (2006). Wu, J. H., Wei, Y. L., Lin, J. M., & Lin, S. B. (2003). Study on starch–
Electrically conducting hydrogel composites made of polyaniline graft–acrylamide/mineral powder superabsorbent composite. Polymer,
nanoparticles and poly(N-vinyl-2-pyrrolidone). Polymer, 47, 961–971. 44, 6513–6520.
Higuchi, T. (1963). Mechanism of sustained-action medication: Theoret- Zhao, Y., Su, H., Fang, L., & Tan, T. (2005). Superabsorbent hydrogels
ical analysis of rater of release of solid drugs dispersed in solid from poly(aspartic acid) with salt-, temperature- and pH-responsive-
matrices. Journal of Pharmaceutical Sciences, 52, 1145–1149. ness properties. Polymer, 46, 5368–5376.