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Synthesis and characterization of Acrylic acid - 2-Hydroxyethyl methacrylate

IPN hydrogels

Article in RSC Advances · September 2015

DOI: 10.1039/C5RA12110H

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RSC Advances
PAPER

Synthesis and characterization of acrylic acid-2-

hydroxyethyl methacrylate IPN hydrogels
Cite this: RSC Adv., 2015, 5, 75870
Rabin Bera, Ayan Dey, Arpan Datta sarma and Debabrata Chakrabarty*

Interpenetrating polymer networks (both full and semi) and ester crosslinked hydrogels have been
synthesized from acrylic acid and 2-hydroxyethyl methacrylate by using various monomer feed
compositions. No crosslinkers have been used in case of ester crosslinked gel, instead the neighboring
13
polymer chains are crosslinked by esterification reaction, which is established by FTIR and C NMR
spectroscopy. Swelling of the hydrogels has been found to be strongly dependent on the pH,
temperature and ionic strength of the medium. The rheological properties of the hydrogels are found to
be dependent on the mode of crosslinking and composition of the gel (only in the case of ester
crosslinked gel) as well. The flexibility of the gel is also dependent on the method of preparation of the
Received 23rd June 2015
Accepted 2nd September 2015
hydrogel. Rheological study in normal force sweep mode reveals the high shape and size regain ability of
the gel. The cryo SEM images show the porous structure of the gels. The hydrogels, especially ester
DOI: 10.1039/c5ra12110h
crosslinked gels, have been found quite effective in the separation of cationic dyes and heavy metal ions
www.rsc.org/advances (copper and iron) from their corresponding aqueous solutions.

case of full IPN, by simultaneous method the monomers and

1. Introduction the crosslinker (either one common for all monomers or
Hydrogels are a special kind of so polymeric materials having different for different monomer) are polymerized and cross-
three-dimensional crosslinked networks that can absorb large linked all at a time.18–20 In case of semi IPN formation by
quantities of water or aqueous solutions without dissolving in simultaneous method, a single crosslinker (which has no
them.1 There are some polymers that can change their structure possibility of any interaction with the second polymer) is used
and eventually their properties in response to physical or chem- for a particular monomer and polymerized simultaneously with
ical changes in the environment, such as pH,2 temperature,3,4 the other monomer such that the rst polymer gets crosslinked
ionic strength, electric eld,5 magnetic eld6 etc. They are known and intermingled with the other linear polymer.21–23 But in case
as intelligent or smart polymers. Environment responsive of sequential method, full IPN hydrogels are prepared by two
hydrogel gains enormous interest in the biomedical elds,7,8 step process. One of the monomers is polymerized and cross-
organic dye and heavy metal ion separation9–13 etc. Recently IPN linked in one step and then the crosslinked polymer I is soaked
hydrogels have gained popularity due to its ability to combine in solution of the other monomer along with its own crosslinker
multicomponent polymer materials without any phase separa- and initiator followed by its polymerization.24,25 Semi IPN
tion, structural rigidity and improved mechanical properties.14 hydrogels are prepared by sequential method in the similar way
Interpenetrating polymer network (IPN) is a blend of two or as that of the full IPN synthesis except using no crosslinker in
more polymers in a network form, at least one of which is the second step of polymerization.26 Semi IPN I is the one in
synthesized and/or crosslinked in the immediate presence of which monomer I is polymerized and crosslinked while the
the others. In case of IPN (full and semi) hydrogels, due to polymer II remain linear. In the semi IPN II the reverse is true
presence of interlocking structures between the polymers, they i.e. polymer I is linear and polymer II is crosslinked.
have more improved mechanical properties, excellent weather Poly(2-hydroxyethyl methacrylate) has some desirable prop-
and creep resistance. The rate or the extent of release or the erties such as its strength, durability, nontoxicity and favorable
adsorption can be controlled by monitoring the extent of tissue compatibility.27,28 The presence of hydrophilic hydroxyl
interpenetration and degree of crosslinking in the IPN and carbonyl groups in the same molecule makes the polymer
system.15–17 water compatible. On the other hand, mechanical strength of
Both the full and semi IPN hydrogels are prepared by the polymer is derived from its hydrophobic backbone part.29
simultaneous and sequential technique of IPN preparation. In Sometimes poly HEMA has been used to enhance the
mechanical strength of other mechanically weak gels.30 But the
main drawback associated with the poly HEMA is its low
Department of Polymer Science & Technology, University of Calcutta, 92, A.P.C. Road, swelling ability. Many researches are being carried out to
Kolkata-700 009, India. E-mail: chakrabarty_deb@yahoo.com; Tel: +91 9830773792

75870 | RSC Adv., 2015, 5, 75870–75880 This journal is © The Royal Society of Chemistry 2015
Paper RSC Advances

increase the hydrogel characteristics (mostly the swelling), as the routine change of the solvent twice a day. The prepared
well as imparting the stimuli responsive character into the poly hydrogel samples were dried by keeping in the oven at the
HEMA gel.31–33 Semi and full IPN hydrogels of HEMA and acrylic temperature of 45–50  C and at certain time intervals the
acid were prepared in the matrix of PVA by Mandal et al.34 samples were weighed. The process was continued till the
Literature survey so far conducted reveals very few reports on constant weight was reached. The gel samples are denoted by
the semi and full IPNs of only neat HEMA and acrylic acid. Most FAH2, FAH6 and FAH10 respectively.
of the articles investigated so far, deal with the acrylic acid- 2.2.2. Semi IPN hydrogel. Crosslinked poly acrylic acid is
HEMA copolymer35 or their IPN with a third polymer.34,36,37 rst prepared by following the above said procedure. Then the
The present work focuses chiey on the crosslinking of both aqueous solution of HEMA and the initiators are absorbed in
poly AAc and poly HEMA for full IPN and only poly AAc for semi the previously synthesized poly acrylic acid gel. MBA is taken as
IPN. In addition to these two types of novel blends, a third and crosslinker in place of EGDMA. MBA crosslink the poly acrylic
an unique method of blending has been followed where acid but the poly HEMA remains uncrosslinked. The gel
simultaneous polymerization of AAc and HEMA and cross- samples are denoted by SAH2, SAH6 and SAH10.
linking of the two polymer networks, through covalent crosslink 2.2.3. Chemical blending/graing and interwinding
(inter molecular) formation by means of esterication reaction through condensation reaction. HEMA and acrylic acid are
between the –COOH group of AAc and –OH group of HEMA has esteried using MSA as catalyst under N2 atmosphere in sealed
been carried out. The properties of all these three types of container for 7 days at 25  C. Aer that the hydrogel formed is
hydrogels (semi IPN of poly AAc/poly HEMA; full IPN of poly taken out, washed using the same procedure applied for the full
AAc/poly HEMA and inter crosslinked poly AAc/poly HEMA) IPN. Thus, the gel is prepared without the use of any crosslinker
have been investigated in terms of swelling efficiencies, but only through esterication reaction between the constitu-
morphology, rheology and applicability in organic dye and ents. The gel samples are denoted by AHE2, AHE6 and AHE10.
heavy metal ion separation and compared thoroughly. For all 2.2.4. For 13C NMR spectroscopy, poly(Mac-HEMA) was
practical purposes such types of studies have been found to be prepared by polymerization of the monomer mixture without
very rare. using any crosslinker. For dye removal study, crosslinked poly
In brief, the objective of the present work is to synthesize acrylic acid and crosslinked poly HEMA were prepared by using
mechanically exible, smart polymeric hydrogels with reason- N,N0 -methylenebisacrylamide (MBA) as crosslinker.
ably good ow characteristic and investigate its effective prop-
erties of dye and heavy metal ion separation from aqueous
solution. 2.3. Characterization
2.3.1. Spectroscopic analysis
2.3.1.1. FTIR study. FTIR measurements of the dried gels
2. Experimental
have been carried out in ATR mode by using FTIR spectropho-
2.1. Materials tometer (Perkin Elmer, Japan) in the range of 4000–600 cm1.
2-Hydroxyethyl methacrylate (Loba Chemie), acrylic acid 2.3.1.2. 13C NMR study. Solid state 13C NMR studies have
(Merck, Darmstadt, Germany), ethyleneglycol dimethacrylate been carried out in JEOL RESONANCE, USA at the eld strength
(EGDMA) (Aldrich), ammonium persulfate (APS) (Merck) and of 400 MHz in order to prove the ester formation through
sodium bisulphite (SBS) (Merck) were used as received. N,N0 - intermolecular condensation between AAc and HEMA. The
methylenebisacrylamide (MBA) (Loba Chemie) was used other experimental parameters are as follows: contact time: 3.5
without further purication. Methane sulphonic acid (MSA) was ms, scans: 1420, X_Resolution: 34.3618 Hz, relaxation delay: 5 s.
purchased from Sigma Aldrich. Buffer capsules were used as 2.3.2. Swelling study. Dried hydrogel samples are allowed
supplied by Merck. Distilled water was used for synthesizing to swell in distilled water at different temperatures and in buffer
hydrogels as well as for swelling. solutions of different pH. The swollen gels are taken out at
certain time intervals, wiped on its surface with tissue paper
and then weighed and the process is repeated until the constant
2.2. Method of hydrogel preparation
weight is reached. Swelling percentage (%) is measured from
2.2.1. Full IPN hydrogel. Measured amounts of HEMA and the following equation:
acrylic acid are taken in a conical ask with measured amount
We  Wd
of water. Aqueous solution of EGDMA as crosslinker of both the Swelling percentage ¼  100% (1)
Wd
polymers formed in situ and APS, SBS as redox initiator are
sequentially added to the said conical ask containing the where We is the weight of the swollen gel and Wd is the weight of
monomers under nitrogen atmosphere. Then the reactant the dry gel.
solution was kept at room temperature (25  C) for 8 hours. The 2.3.3. Morphological study. The scanning electron micro-
molar proportions of the individual reactant are given in graphs of the hydrogel samples in swollen condition are taken
Table 1. The polymer gel formed in each is taken out from the by using cryogenic SEM apparatus, CARL ZEISS EVO18, Special
test tube, washed well by water several times and cut into pieces. edition, Germany. Before up-taking the images, the samples are
The pieces are further subjected to washing by keeping it cryo fractured at 187  C followed by platinum coating with
immersed rst in water and then in methanol for 7 days with coating time of 2 minutes in argon atmosphere at 150 to

This journal is © The Royal Society of Chemistry 2015 RSC Adv., 2015, 5, 75870–75880 | 75871
RSC Advances Paper

Table 1 Composition of the reactant used in hydrogel synthesis

Acrylic acid HEMA MBA EGDMA APS SBS MSA

Hydrogel mol% mol mol% mol mol% mol mol% mol mol% mol mol% mol ml

FAH2 98 0.49 2 0.01 — — 0.1 0.0005 1 0.005 1 0.005 —

FAH6 94 0.47 6 0.03 — — 0.1 0.0005 1 0.005 1 0.005 —
FAH10 90 0.45 10 0.05 — — 0.1 0.0005 1 0.005 1 0.005 —
SAH2 98 0.49 2 0.01 0.1 0.00049 — — 1 0.005 1 0.005 —
SAH6 94 0.47 6 0.03 0.1 0.00049 — — 1 0.005 1 0.005 —
SAH10 90 0.45 10 0.05 0.1 0.00049 — — 1 0.005 1 0.005 —
AHE2 98 0.49 2 0.01 — — — — 1 0.005 1 0.005 0.5
AHE6 94 0.47 6 0.03 — — — — 1 0.005 1 0.005 0.5
AHE10 90 0.45 10 0.05 — — — — 1 0.005 1 0.005 0.5

160  C temperature. Pore size distribution is analyzed using 2.3.5.2. Separation of heavy metal ions. Efficiency of the
the soware “Smart SEM V-05.04.05.00”. poly(AAc-HEMA) hydrogels in separating heavy metal ions is
2.3.4. Rheological study. In order to investigate the determined by keeping 0.5 g of the gel immersed in 25 ml of
mechanical stiffness of the hydrogel, the rheological measure- standard metal ion solution (0.1 mol L1) for 7 days. Then the
ments of the cylindrical hydrogel samples are performed by concentration of the metal ions remaining in the solution is
frequency, stress and normal force sweep test in Anton Paar, UK determined conductometrically from a previously experimented
oscillatory rheometer at 25  C with a parallel plate geometry conductance versus metal ion concentration calibration curve.
(plate diameter ¼ 25 mm, gap ¼ 10 mm) from 100 to 0.1 rad s1 Images are captured using canon powershot A3500.
frequency, 0.1 to 1000 Pa stress and 0 to 5 N normal force
respectively.
2.3.5. Applicability test of the hydrogel 3. Results and discussion
2.3.5.1. Separation of organic dye. To investigate the effi- 3.1. Spectroscopic study
ciency in removal of organic dye (methyl violet and fuchsine)
from aqueous solution, poly(AAc-HEMA) hydrogels (0.5 g) are 3.1.1. FTIR study. Fourier transform infrared (FT-IR) spec-
placed in 25 ml aqueous solutions of dye having strength troscopy in ATR mode has been used to indicate the chemical
50 mg L1 and allowed to reach equilibrium for 7 days at room composition of the different gels under study, any interaction
temperature. Aer that period the concentration of the dye involving the functional groups of HEMA, acrylic acid and their
remaining in the solution is determined spectrometrically by various crosslinkers and shown in Fig. 1(a). The characteristics
using UV spectrophotometer Perkin Elmer USA Lambda 25. absorption peaks of the monomeric units, HEMA, acrylic acid,
Aqueous solution of methyl violet and fuchsine shows the EGDMA and MBA, appear at their usual wave numbers in the
maximum absorption peak at about 585 and 549 nm respec- FTIR spectra of the hydrogel samples. The observed and the
tively. The equilibrium concentration of dye molecules are reference peaks are given in the Table 2, separately for each
determined from the calibration curve obtained with the solu- series of hydrogels.
tions of known concentrations of the dye. In case of the full IPN gels (FAH), the C]O peak of ester is
found to appear at around 1700 cm1 and that of –COOH group

Fig. 1(a) FTIR-ATR spectroscopy of the oven dried hydrogels and (b) 13C NMR spectroscopy of the hydrogels AHE10, poly(acrylic acid-HEMA)
and the corresponding peak assignments.

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Paper RSC Advances

Table 2 FT IR peaks of the hydrogel samples 3.2. Swelling study

Reference Observed Variation in swelling of the hydrogels at different temperatures

Functionality peak (cm1) peak (cm1) occurs due to phase transition controlled by the hydrophilic–
hydrophobic balance of the polymer network. Hydrogels with
FAH C]O of ester 1735–1750 1700
interpenetrating polymer network structure of poly(acrylic acid)
Samples C–O 1000–1300 1017 & 1072
(2 or more bands) as one of the component and with intra-molecular hydrogen
O–H of acid 2500–3300 2930 bonding also undergo a phase transition in water. In this case
O–H of alcohol 3200–3700 3300 the repulsive ionic interaction due to increased ionization at
N–H stretch of amide 3100–3500 — higher temperature controls the vacant space and thus, governs
SAH C]O of ester 1735–1750 1700 the transition temperature.42 Fig. 2(a) shows that the swelling of
samples C–O 1000–1300 1017 & 1072
(2 or more bands) all present poly(AAc-co-HEMA) IPN gels are temperature
O–H of acid 2500–3300 2930 dependent. Swelling of the all hydrogel increases with the
O–H of alcohol 3200–3700 3300 temperature of the medium. The order of equilibrium swelling
N–H stretch of amide 3100–3500 3430 values is identical as that in water at room temperature
AHE C]O of ester 1735–1750 1700
[Fig. 2(a)].
samples C–O 1000–1300 1017 & 1072
(2 or more bands) (sharp peak) Since swelling of acrylic acid based hydrogel is strongly
O–H of acid 2500–3300 2930 inuenced by pH of the medium the measurements of swelling
O–H of alcohol 3200–3700 3300 efficiency of the hydrogels were carried out in different pH
N–H stretch of amide 3100–3500 — medium. The results were collected in Fig. 2(b). In both the
acidic and almost neutral medium the swelling characteristics
of the gels follows a decreasing pattern with increase in HEMA
content for all the full IPN, semi IPN and ester cross-linked
at 1655 cm1.38 There is a probability of formation of hydrogen
chemical blends. In the basic pH range however the swelling
bonding between the C]O group of the ester in HEMA and the
for all the three varieties is much higher. Here also we nd in all
H atom of the –COOH group of AAc unit in the ultimate cross-
the cases of FAH, SAH and AHE that the extent of swelling is
linked structure which might have shied the C]O peaks to the
maximized at the lowest HEMA content under study and grad-
lower value.39,40 O–H peak of the carboxylic acid (–COOH) group
ually decreases with increase in HEMA content. The behavior of
is observed at 2925 cm1. The peaks at around 1017 and 1072
the three systems under swelling at higher pH has been
cm1 are assumed to be due to C–O bond vibration.40 Besides
attempted to explain with some hypothetical models in the
there are two consecutive peaks at around 1390 and 1450 cm1
Fig. 2(c). At higher pH the carboxylic acid (–COOH) group gets
which may be attributed to alkane C–H rocking and bending
completely ionized to form the carboxylates (–COO–) ions. The
respectively.
ionization creates charged blocks in the polymer segments at
In case of the semi IPN samples (SAH) the peaks for C]O,
pH 9.2. This increases inter-chain repulsion in the inter-wind
C–O, O–H and C–H are observed in the similar frequency ranges
polymer matrix which may lead to increase in cell dimensions
as that of the FAH hydrogel samples. There is however, an extra
during swelling. But the phenomenon is suppressed for the
peak for N–H bond at 3430 cm1 which arises from MBA used as
semi IPN and the ester linked gel as well. In case of semi IPN
crosslinker for AAc.
lateral movement of the cross-linked polymer chain may release
Ester crosslinked hydrogels (AHE) also exhibit the similar
the tension created by repulsive interaction of ionized groups.
spectral pattern as those of the FAH samples. The only
For the ester-linked gel the decrease in concentration of
difference in the two spectrums with the others (FAH and
carboxylic acid group lead to complete destruction of strained
SAH) is that the peaks at 1017 and 1072 cm1 are more intense
ionic atmosphere (which is created in case of full IPN). This may
and sharp in case of the AHE samples. It can be rationalized
explain the observed swelling responses in terms of structural
by the formation of new ester linkages and the C–O bonds
point of view. Decrease in concentration of carboxylic acid
which increases the peak intensity corresponding to the C–O
group results in decrease in pH sensitivity as well.
bonds.
To emphasize the effect of HEMA content the equilibrium
3.1.2. 13C NMR study. The crosslinking by esterication
swelling percentage data were plotted in Fig. 2(d) against the
reaction in case of the ester crosslinked gel (AHE system) was
concentration of HEMA used with the assumption that all the
also conrmed by 13C NMR spectroscopy. The investigation was
HEMA was consumed during crosslinking reaction. The
carried out with poly(acrylic acid-HEMA) and one ester cross-
swelling of all the hydrogels under study is however higher than
linked gel (AHE10). It is apparent from the Fig. 1(b) that both
the bare poly HEMA gel. In case of the full IPN the sharp fall in
the spectra contain the similar peaks at around 176, 61, 45, 41,
equilibrium swelling percentage for increase in HEMA content
34 and 19 ppm. The assignment of the peaks is given in
from 2–6% is quite mentionable. With further increase in
Fig. 1(b).41
HEMA content the drop in swelling % occurs slowly. From the
There is an extra peak in the spectrum of AHE10 sample at 53
statistical analysis as given in Table 3 it can be stated that the
ppm. The peak may be attributed to the presence of methylene
standard deviation is minimum in case of the semi IPN
C in the alkyl–oxygen bond of the ester41 which is absent in the
hydrogel when compared to the same values for the full and
copolymer system as shown in the gure.

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Fig. 2 Variation of equilibrium swelling percentage (%) of the hydrogels with the (a) temperature, (b) pH and (d) HEMA content; (c) hypothetical
models to draw structure–property relationship for the three systems during change in pH of the swelling media.

ester crosslinked hydrogel. It might be expected that the effect MSA it may be assumed that crosslinking occurs through the
of hydrophobicity remaining the same, it is the number of cells exible ester linkages to give cellular structure (Scheme 1). The
which predominates in the matrix of the full IPN where both the behavior is well explained by the hypothetical models presented
polymeric networks are completely cross-linked and inter- in the Fig. 2(c).
wined, In case of semi IPN however the PHEMA phase being
linear and a sequential process of IPN formation being followed 3.3. Rheological study
it seldom contributes to the cell formation.
3.3.1. Frequency sweep. Fig. 3(a) shows the storage moduli
In case of gel (AHE) swelling follows decreasing pattern with
of the various gels as functions of angular frequency. All the gels
the increase in HEMA content. As no gel is formed in absence of
under study exhibit a marginal decrease in G0 values as the

Table 3 Equilibrium swelling values and statistical analysis of the hydrogel samples

Equilibrium swelling (%) Statistical values

HEMA content (mol%) FAH SAH AHE Hydrogels Mean (m) Variance (s2) Standard deviation (s)

2 177.4 106.1 61.5 FAH 97.7333 3375.2288 58.0967

6 75.3 81.6 41.1 SAH 87.4333 547.1649 23.3916
10 40.5 74.6 22.6 AHE 41.7333 757.2067 27.5174

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Paper RSC Advances

Scheme 1 Schematic diagram of the reactions occurred during gel formation.

angular frequency decreases. The two full IPN hydrogels exhibit It is quite noteworthy that the storage moduli values always
almost identical pattern with negligible changes in storage remain higher than the loss moduli one. This is the typical
moduli over the entire range of frequency. It may thus, possibly characteristics of gel/hydrogel.43
be inferred that the elastic modulus of the full IPNs are hardly 3.3.2. Yield stress. Low values of yield stress implies higher
dependent on PHEMA content. The semi IPNs under consid- spreadability but lower retention and the vice versa. There are
eration also show similar behavior although their storage different methods in determining the yield stress as discussed
modulus are somewhat lower than those of the full IPN. by Malana et al.44 In the present paper storage modulus have
In case of the ester crosslinked hydrogels, G0 is strongly been plotted as a function of shear stress in which the point of
dependent on the AAc/HEMA copolymer composition. Incre- deection denotes the yield stress of the gel sample according
ment in the HEMA content (from 2 to 10 mole percent) results to the method used by Rajat K. Das et al.45 The yield stress values
in increase in G0 substantially. At higher HEMA concentration, decreases from full IPN samples to semi IPN and further
the possibility of formation of crosslinking by esterication reduces in ester crosslinked hydrogel sample, i.e. the spread-
reaction between the HEMA and the corresponding amount of ability or the exibility is maximum in AHE hydrogel sample
AAc part increases and so the elastic modulus and stiffness also among the three types of gels studied. Hence it can be said that
increases. It supports the assumption of crosslinking by ester- the hydrogels of different exibility can be obtained as needed
ication reaction. by following the different methods of hydrogel synthesis.

Fig. 3 Scanning electron microscopic study and the respective pore size distribution of the (a) full IPN and (b) semi IPN.

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3.3.3. Normal force sweep. In normal force sweep study blends. Wu et al.46 Yeganeh et al.47 and Xu et al.48 pointed out
storage moduli have been measured as function of different that a homogeneous polymer system results a single semi-
normal force in the range 0–5 N in three consecutive cycles and circular arc where as an immiscible or partially miscible blend
it is plotted as function of time in seconds in Fig. 4(a). All the results in two consecutive semicircular arcs. However from the
three type of gels are found to possess good memory effect, i.e. observation of Wu et al.46 it can be said that the distinctions
they have the ability to regain their structure and shape. It is between this two arcs disappear with increase in the miscibility
best understood by the Fig. 4(b) in which G0 at zero normal force or decrease in the phase separation. This may be used for
have been plotted as function of number of cycles. The gure differentiation of IPN and semi IPN system also. It is observed
depicts that the ester crosslinked gels have got almost no from the Fig. 5(a) that both the IPN systems show single clear
change in G0 in three consecutive cycles but it decreases slowly semicircular arc. This clearly emphasizes that no distinct phase
in case of FAH and SAH samples, which means regain ability is separation present between the two polymer system crosslinked
maximum for AHE hydrogels among the three types of hydro- with two different crosslinker at the same time. So this can be
gels studied. taken as a direct proof of IPN formation which only may be the
3.3.4. Cole–Cole plot. Fig. 5(a–c) describe the behavior of reason of such binary polymer system to behave like a homo-
Cole–Cole plot for full IPN, semi IPN and ester crosslinked gel geneous one.
respectively. All the polymer systems are prepared from a binary The semi IPN system [Fig. 5(b)] shows a single semicircular
mixture of two different monomer but crosslinked in three arc but skewed to le. Interfacial tension between the cross-
different ways. It is the general practice to use Cole–Cole plot for linked network of the polymer and the uncrosslinked one may
investigation of the inter phase compatibility of the polymer results such deviations. Single arc clearly indicate a single

Fig. 4 Variation of (a) storage and (c) loss moduli for the gels with the increase in angular frequency; and variation of storage modulus with (b) the
HEMA content and (d) the increase in shear stress (determination of yield stress).

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Paper RSC Advances

Fig. 5 Variation of (a) storage modulus with the normal force for the
gels (up to 3 cycles) and (b) storage modulus at zero normal fore with
the number of cycles of applying force.

distinct phase structure of the binary polymer system. This

intern can be considered as a proof of semi IPN formation in
terms of rheology.
The esterication mediated gel AH2E and AH10E results in
same type of semicircular single arc Cole–Cole plot [Fig. 5(c)].
This indicates a homogeneous crosslinked network system
formed by the crosslinking using esterication reaction. The
results show esterication of HEMA and acrylic acid system
leads to a homophasic network system.

3.4. Morphological study by cryo SEM

Fig. 6(a) and (b) show the cryo SEM images of the hydrogel FAH2 Fig. 6 Cole–Cole plot for (a) full IPN hydrogels, (b) semi-IPN hydro-
gels and (c) ester linked hydrogels with the symmetry parameters at
and SAH2 respectively with individual pore size distribution. Both
the inset of each plot.
the images contain homogeneously distributed multilayered
porous structures. In both the cases the most of the pores are
circular and sometimes it is elliptical of different diameter, though
the mean pore diameter is greater in case of hydrogel FAH2. Pore volume of water or aqueous solution within it compared to SAH
size distribution is seemed to be skewed towards larger pore samples which corroborates the results of the swelling experiment
diameter for the full IPN. The larger multi layered pores in FAH (Fig. 2) discussed earlier. Thus, the gel appears to absorb higher
sample enables the polymer network to absorb and hold greater volume of water in its crosslinked structure.

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Fig. 7 Images regarding the experiment determining removal efficiency of (a) methyl violet, (b) fuchsine, (c) copper (2+) ion and (d) iron (3+) ion
from the aqueous solution of them.

3.5. Applicability test of the gel However the virgin poly AAc gel can absorb only about 30–40%
dye and poly HEMA gel is not at all effective in removal of any
3.5.1. Application in dye removal. All the prepared
dye from its aqueous solution. The percentage of the basic dye
poly(AAc-HEMA) copolymer hydrogels were found to be able to
(methyl violet and fuchsine) removal of the gel varies from 80–
separate dyes from its aqueous solution efficiently [Fig. 7(a–b)].

Table 4 Dye separation valuation of the hydrogels

Removal (%) in methyl violet Removal (%) in fuchsine

Hydrogel Neutral medium Basic medium Neutral medium Basic medium

SAH2 99.2  1.9 99.3  2.0 92.3  1.8 93.3  1.8

SAH6 88.9  1.8 99.9  2.0 93.5  2.1 95.2  2.0
SAH10 80.9  1.6 99.9  2.0 95.3  1.9 95.5  2.0
FAH2 97.8  1.9 99.9  2.0 91.2  1.8 94.2  1.8
FAH6 98.7  2.0 99.8  2.0 93.0  2.0 96.1  2.0
FAH10 98.9  1.8 99.8  1.9 95.2  2.0 97.2  2.0
AHE2 92.1  1.9 99.8  2.0 95.8  2.0 96.8  2.0
AHE6 96.9  2.0 99.8  2.0 93.6  1.9 93.6  1.9
AHE10 96.2  2.0 99.2  1.8 97.8  2.0 96.8  2.0
Poly AAc gel 33.6  2.4 37.2  1.8 30.2  2.3 31.3  2.1
Poly HEMA gel 3.5  0.2 3.2  0.3 2.5  0.8 2.0  0.3

Scheme 2 Structures of the two dye molecules, methyl violet and fuchsine; and schematic representation of their interaction with the polymer
network.

75878 | RSC Adv., 2015, 5, 75870–75880 This journal is © The Royal Society of Chemistry 2015
Paper RSC Advances

Table 5 Cu2+ and Fe3+ metal ion removal by the hydrogels Biswas and Mr Abir Deb of DIC India Limited, Kolkata for
2+ 3+
assistance in FTIR characterization of the samples.
Hydrogel samples Cu removal (%) Fe removal (%)

FAH2 74  3.7 38  1.9 References

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