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Synthesis and investigation of swelling behavior of new agar based superabsorbent hydrogel as a candidate for agrochemical delivery - Springer
Original Paper
(1) Polymer Research Laboratory, Department of Chemistry, Sharif University of Technology, P.O. Box 113659516, Tehran, Iran
Ali Pourjavadi
Email: purjavad@sharif.edu
Received: 28 October 2008
Accepted: 27 January 2009
Published online: 25 February 2009
Abstract
In this investigation a new type of superabsorbent hydrogel based on agar was prepared, and
the effect of the feed ratio of some components (acrylic acid, MBA, APS and agar) on the
swelling capacity of the hydrogel was systematically studied. Maximum water absorbency of
the optimized final product was found to be 1,100g/g in distilled water. The structure of the
hydrogel was characterized by FT-IR method and morphology of the samples was examined
by scanning electron microscopy (SEM). Swelling properties of optimized hydrogel sample in
different swelling mediums were investigated. The optimum hydrogel were also loaded with
potassium nitrate and its potential for controlled release of potassium was investigated by
measuring conductivity in various conditions.
Keywords Agar Acrylic acid Hydrogel Swelling behavior Potassium nitrate
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Introduction
Polymer networks consist of long macromolecular chains cross-linked with each other by
chemical or physical bonding. Polymer networks swollen in a liquid are called polymer gels.
Hydrogels are polymer gels, which swell extensively in water. The most common hydrogels are
polyelectrolyte gels: their high degree of swelling in water is due to the exerting osmotic
pressure of counter ions. Such gels can acquire up to several hundredweight parts of water per
one part of a dry polymer [1]. Considerable attention has been devoted to the preparation and
application of responsive hydrogels for medical and pharmaceutical fields particularly as
stimuli-sensitive drug delivery [24].
Stimuli-responsive hydrogels undergo a substantial volume change when an environmental
factor such as temperature, pH, or ionic strength is altered. The volume phase transition is
caused by a change in the hydrogels water content. Hydrogels have attracted attention
because of both potential and demonstrated utility of this behavior in a variety of applications
ranging from flow controllers in microfluidic devices to sorbents [57]. Conventional
application of agrochemicals results in ground water contamination. Thus, we need a more
controlled application of agrochemicals to reduce amounts of active ingredients without
diminishing efficiency. The replacement of conventional agrochemical formulations by
controlled release systems not only helps to avoid treatment with excess amounts of active
substances, but also offers the most suitable technical solution in special fields of application.
On the other hand, hydrogels of natural polymers, especially polysaccharides, have recently
found widespread applications because of their unique advantages. Polysaccharides are, in
general, non-toxic, biocompatible, biodegradable and abundant [8, 9].
Hydrogels can be prepared by simultaneous copolymerization and crosslinking of one or more
monofunctional and one multifunctional monomer or by crosslinking of a homopolymer or
copolymer in solution [10, 11]. Hydrogel properties depend strongly on the degree of
crosslinking, the chemical composition of the polymer chains, and the interactions of
network and surrounding liquid.
Agar (Scheme 1) is an alternating copolymer of 3-linked -D-galactopyranose and 4-linked
3,6-anhydro--L-galactopyranose residues. Agar is the most hydrophobic polysaccharide
with the strongest tendency to gel formation that melts at about 40C. Agar forms hydrogels
via intermolecular aggregations prompted by thermal changes [12]. Due to its
biocompatibility, it has generally been used as a cell immobilization matrix, drug delivery
vehicle, or dental impression material [13, 14].
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Scheme 1
Proposed mechanistic pathway for synthesis of the agar-g-poly (AA-co-AMPS) hydrogel
The purpose of this paper is to synthesize agar-g-poly (acrylic acid-co-2-acrylamido-2methylpropanesulfonic acid) hydrogel. The effect of reaction variables affecting on water
absorbency of the composite and swelling behavior in various solvents, salt and pH solutions
was investigated. The absorbency under load (AUL) of optimized hydrogel was determined by
using an AUL tester [15] in various applied pressures. Dynamic swelling kinetics of the
hydrogel was also determined. Finally, we investigated the release of KNO3 from the optimum
hydrogel as models of ionic fertilizer.
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Instrumental analysis
The infrared spectra of hydrogel were recorded by ABB Bomem MB-100 FTIR
spectrophotometer (Canada). The dried sample was ground with dried KBr powder and
compressed into a disc, and then was subjected to analysis. In order to prevent the
morphology of hydrogels, the dried samples were coated with gold under reduced pressure and
their scanning electron micrographs were obtained using a Philips (XL30) scanning electron
microscope.
Hydrogel synthesis
In a 200 mL flask, fitted with a mechanical stirrer (Heidolph RZR 2021, 200 rpm), is placed
40 mL of water and variable amounts (0.51.5 g) of agar and the mixture is stirred at 100C
until a clear solution is obtained. Then the reaction flask is cooled until the temperature of
the mixture reaches to 85C. The mixture is heated in a water bath preset at 85C. Then,
appropriate amounts of 2-acrylamido-2-methylpropanesulfonic acid (AMPS, 0.5 g),
partially neutralized acrylic acid (AA, 47 g), and N, N'-methylene bisacrylamide (MBA,
0.030.09 g) in 10 mL H2O were added. After 5 min, ammonium persulfate (APS, 0.03
0.09 g) in 5 mL H2O was added. After 1015 min obtained gel was cooled at room
temperature and poured to excess non solvent ethanol (200 mL) and remained for 3 h to
dewater. Then, ethanol was decanted and the product cut into small pieces. Again, 200 mL
fresh ethanol was added and the composite remained for 48 h. Finally, the filtered gel was
dried in oven at 50C for 24 h. After grinding, the powdered composite hydrogel was stored
away from moisture, heat and light.
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ES(g/g ) =
W2 W1
W1
(1)
Where, W 2 and W 1 are the weights of swollen hydrogel and dry hydrogel in grams,
respectively.
pH sensitivity
pH-responsiveness of the hydrogel was investigated in terms of swelling and deswelling of the
final product at two basic (pH 8.0) and acidic (pH 2.0) solutions, respectively. Swelling
capacity of the hydrogels at each pH was measured according to Eq. (1) at consecutive time
intervals.
Swelling kinetics
Hydrogel sample (4060 mesh, 0.10 g) was poured into a weighed tea bag and immersed in
250 mL distilled water. At consecutive time intervals, the water absorbency of the sample was
measured.
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(2,068 and 4,137 Pa)) to the dry hydrogel sample particles. Then, 0.9% NaCl solution was
added so that the liquid level was equal to the height of the sintered glass filter. Whole of the
set was covered to prevent surface evaporation and probable change in the saline
concentration. At consecutive time intervals, the water absorbency of the hydrogel was
measured. After 2 h, the swollen particles were weighed again, and AUL was calculated
according to Eq. (1).
Loading of KNO3
The dry gel was put into a solution of KNO3 and leave to swell for 2 h. The swollen gels were
dried at 50C. The % loading was calculated by the following equation:
(2)
where m 1 and m 0 are the weights of loaded gel and dry gel, respectively.
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FT-IR spectroscopy was used to confirm the chemical structure of hydrogel. The FT-IR
spectra of agar, poly (AA-co-AMPS) and synthesized hydrogel were shown in Fig. 1ac. The
broad band at 3,2003,500 cm1 is due to stretching of these hydroxyl groups. FTIR
spectrum of the hydrogel [Fig. 1(c)] represents several new peaks. The bands observed at 512,
630 and 1,400 cm1 can be attributed to sulfonate group of AMPS, bands at 1,545 and
1,710 cm1 is due to stretching of carboxylate and carboxylic acid groups, respectively. The
small peak at ~930 cm1 is due to the 3,6-anhydro--L-galactopyranose unites. The band
observed at ~890 cm1 is due to the unsubstituted D-galactopyranose unites. Finally the
peak observed at ~1,646 cm1 that is related to of agar is the characteristic absorption band of
polysaccharides.
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Fig. 1
FTIR spectra of a agar, b poly (AA-co-AMPS), c synthesized hydrogel, d loaded hydrogel and e unloaded
hydrogel
Also the IR transmittance spectra of unloaded (a) and loaded (b) hydrogels are presented in
Fig. 1de. The spectra confirm the presence of KNO3 as evident from vibrational frequency of
nitrate ion at 1,384 cm1.
SEM images of hydrogel are shown in Fig. 2. It is obvious from this Figure; the hydrogel has a
porous structure. It is supposed that these pores are the regions of water permeation and
interaction sites of external stimuli with the hydrophilic groups of the graft copolymers.
Fig. 2
SEM photographs of the optimized superabsorbent hydrogel (Agar 1 g, NU 40%, AA 1.26 mol/L, AMPS
0.044 mol/L, APS 0.0024 mol/L, and MBA 0.006 mol/L, 85C). a 10,000 and b 20,000
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0.0060 mol/L of MBA. At the lower than this amount, the formation of very loosely
crosslinked networks, resulting in highly swollen hydrogels with very low gel strength. Higher
crosslinker concentration produces more crosslinked points in polymeric chains and increases
the extent of crosslinking of the polymer network, which results in less swelling when it is
brought into contact with the solvent.
Fig. 3
Dependency of swelling of the hydrogel vs. the crosslinker concentration employed in the polymerization
process. Reaction conditions: Agar 1 g, NU 40%, AA 1.26 mol/L, AMPS 0.044 mol/L, and APS
0.0040 mol/L, 85C
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Fig. 4
Dependency of swelling of the hydrogel vs. the initiator concentration employed in the polymerization
process. Reaction conditions: Agar 1 g, NU 40%, AA 1.26 mol/L, AMPS 0.044 mol/L, and MBA
0.006 mol/L, 85 C
Effect of AA concentration
The effect of AA concentration on the swelling capacity of the hydrogel was studied by
varying the AA concentration from 0.76 to 2.02 mol/L (Fig. 5). Maximum swelling
(1,100g/g) was obtained at 1.26 mol/L of AA concentration. Enhanced acrylic acid
concentration increases the diffusion of AA molecules into the agar backbone that
consequently causes an increase in water absorbency. In addition, higher AA content
enhanced the hydrophilicity of the hydrogel that it caused a stronger affinity for more
absorption of water. The swelling decrease after the maximum may be attributed to (a)
preferential homopolymerization over graft copolymerization, (b) increase in viscosity of the
medium which hinders the movement of free radicals and monomer molecules, (c) the
enhanced chance of chain transfer to monomer molecules and (d) non-neutralized acid
groups of grafted and non-grafted polyacrylic acid chains.
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Fig. 5
Dependency of swelling of the hydrogel vs. the monomer (AA) concentration employed in the
polymerization process. Reaction conditions: Agar 1 g, NU 40%, APS 0.0024 mol/L, AMPS 0.044 mol/L,
and MBA 0.006 mol/L, 85C
Fig. 6
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Dependency of swelling of the hydroegl vs. agar weight employed in the polymerization process. Reaction
conditions: NU 40%, AA 1.26 mol/L, APS 0.0024 mol/L, AMPS 0.044 mol/L, and MBA 0.006 mol/L, 85C
Fig. 7
Swelling capacity variation of the optimized hydrogel in saline solutions with various concentrations
The effect of cation type (cations with different charge) on swelling behavior is shown in
Fig. 8. In the case of salt solutions with multivalent cations, ionic crosslinking causes an
appreciable decrease in swelling capacity. Therefore, the absorbency for the hydrogel in the
studied salt solutions is in the order of monovalent>divalent>trivalent cations. Similar results
have been reported in similar previous studies [20, 21].
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Fig. 8
Swelling capacity of the optimized hydrogel in different chloride salt solutions (0.15 M)
Hm/(V 1 2 ) = ( 1 2 )
(3)
where H m is the enthalpy change on mixing of a polymer and a solvent, V is the whole
volume of the solution, 1 and 2 are the volume fractions for the solvent and the polymer,
1 and 2 are the solubility parameters for the solvent and the polymer, respectively.
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Fig. 9
Sensitivity of the optimized hydrogel swelled in different solventwater media with varied composition
It can be concluded from this equation that to dissolve a polymer in a solvent, the values
must be close to each other. As swelling absorbency of the superabsorbent hydrogels in water
is maximum, the value of water (23.4 (cal/cm3)1/2) can be regarded as the solubility
parameter of it. The solubility parameter for solvent-water mixtures ( mix ) can be calculated
using following eq. (4)
mix = 1 1 + 2 2
(4)
where 1 and 2 are the volume fraction, and 1 and 2 are the solubility parameters of the
two solvents.
It can be seen from Table 1 that with increasing of mix values toward 23.4, the hydrogel can
be highly swollen as in pure water. In other words, the swelling capacity of the hydrogel in the
solventwater mixture will be close to that in pure water if mix is close to water . A similar
observation is recently reported by Zohuriaan-Mehr and co-workers [23].
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Table 1
Solubility parameters for solvents [22]. Symbols and mix [(cal/cm3)1/2] are the solubility parameters for
the solvent and the solventwater mixture, respectively
Solvent
(or mix)a
Acetone
9.9
2-propanol
11.5
Ethanol
12.7
Water
23.4
1,100
20.19
571
19.83
495
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repulsion among similarly charged COO- and -SO 3 - groups along the macromolecular
chains. This causes extensive swelling of the hydrogel as indicated by higher water uptake of
value of the gel. The swelling-loss in the highly basic solutions may be attributed to the
charge screening effect of excess Na+ in the swelling media, which, in turn, shields the
carboxylate and sulfonate anions and prevents effective anion-anion repulsion.
Fig. 10
Effect of pH of solutions on swelling capacity of the hydrogel
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Fig. 11
Onoff switching behavior as reversible pulsatile swelling (pH8) and deswelling (pH2) of the optimized
hydrogel
Swelling kinetics
Figure 12(a) represented the dynamic swelling behavior of optimized hydrogel sample with
certain particle sizes (4060 mesh) in water. The samples swelled rapidly and reached
equilibrium within about 25 min. Power law behaviors were obvious from Fig. 12(a). The
initial swelling rate can be calculated using Voigt-based equation (Eq. (5)) [28].
/
S t = S e (1 et )
(5)
where S t (g/g) is swelling at time t, S e (g/g) is equilibrium swelling; t(min) is time for
swelling S t , and (min) stand for the "rate parameter". To find the rate parameter for
superabsorbent sample, Ln[1-S t /S e ] versus time (t) was plotted [Fig. 12(b)]. The slope of
the line passing the point zero and the point of 60% fractional swelling was determined (slope
=l/, gives the rate parameter). Therefore, the rate parameter for the superabsorbent
composite was found to be 2.1 min in distilled water.
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Fig. 12
Representative swelling kinetics of the optimized hydrogel with certain particle sizes (4060 mesh) (a), and
the rate parameter (s) calculating graph (b)
Fig. 13
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Fig. 14
Influence of loading on the release rate of KNO3
Table 2
Loading condition, loading percent and release percent after 24 h
Entry
% load
% release after 24 h
0.1 M
44.6%
78%
0.5 M
83.7%
67%
1M
132.6%
47%
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release of potassium nitrates loaded near the surfaces of the hydrogel. This figure clearly
indicates that the release in highly basic or acidic solutions is low but in pH=5.7 maximum of
released is observed. This can be explained by this fact that the active agent in the hydrogel
could be released as a result of the hydrogel volume change. According to the Fig. 10, the
maximum swelling of hydrogel is in pH~6 and according to the Fig. 15, maximum release is
in pH=5.7. This result indicates that the higher swelling ratios of the hydrogel create larger
surface areas to diffuse the KNO3.
Fig. 15
Effect of pH on KNO3 release
Conclusion
In the present study, we prepared a novel superabsorbent hydrogel by simultaneous graft
copolymerization of AA and AMPS onto agar. Crosslinking graft copolymerization of AA
and AMPS onto agar was performed in an aqueous medium using a persulfate initiator and a
bifunctional hydrophilic crosslinker. Variations in the reaction parameters affecting the
ultimate swelling capacity of the final product optimized the synthesis of superabsorbent
hydrogel. The maximum water absorbency (1,100g/g) was achieved under the optimum
conditions, which were found to be AA 1.26 mol/L, AMPS 0.044 mol/L, MBA
0.0060 mol/L, APS 0.0024 mol/L, neutralization percent 40%,agar weight 0.5 g, and at a
reaction temperature of 85C. Swelling measurement of the optimized hydrogel in different
salt solutions showed appreciable swelling capacity in comparison with our previous works.
Moreover, the synthesized hydrogel exhibited high sensitivity to pH. Furthermore, the
absorbency under load (AUL) of optimized hydrogel was investigated at various applied
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pressures. Dynamic swelling kinetics of the hydrogel was also determined. Therefore, this
hydrogel may be considered as an excellent candidate for different applications in the future.
Finally, the dry hydrogel loaded with potassium nitrate swells in aqueous medium releasing
the salt entrapped within the matrix. The release rate was related to pH and KNO3 percent
loading of hydrogels. Therefore, this hydrogel may be considered as a candidate for fertilizer
delivery in agriculture.
We express our appreciation to Hamid Salimi (Ph.D student of Sharif University) for his
patient and unflagging assistance.
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