Swelling equilibria and procion blue HERD dye adsorption studies of 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate-based polymeric gels prepared by photoinitiated cationic polymerization

Article abstract of DOI:10.14233/ajchem.2013.14610

In this study, superswelling behaviour of two different cross-linked polymer of 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexane- carboxylate (EEC) monomer was investigated. The cross-linked polymer of EEC i.e., (PEEC) and EEC with cyclohexene end-functio

Full text of DOI:10.14233/ajchem.2013.14610

Asian Journal of Chemistry; Vol. 25, No. 14 (2013), 7793-7797
http://dx.doi.org/10.14233/ajchem.2013.14610
Swelling Equilibria and Procion Blue HERD Dye Adsorption Studies of
3,4-Epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate-Based
Polymeric Gels Prepared by Photoinitiated Cationic Polymerization
1,*
2
2
2
E. SAHIN , M. DEGIRMECI , F. SEMDINOGLU and N. GENLI
1Department of Chemistry, Faculty of Science, Dokuz Eylul University, Buca 35160, Izmir, Turkey
2Department of Chemistry, Faculty of Science and Arts, University of Harran, Sanliurfa, Turkey
*Corresponding author: Fax: +90 2323014188; Tel: +90 2323019507; E-mail: elif.sahin@deu.edu.tr
(Received: 24 September 2012; Accepted: 15 July 2013)
AJC-13810
In this study, superswelling behaviour of two different cross-linked polymer of 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane-
carboxylate (EEC) monomer was investigated. The cross-linked polymer of EEC i.e., (PEEC) and EEC with cyclohexene end-functional
polystyrene macromonomer (PEEC-co-PSt) were prepared by photoinitiated cationic polymerization using diphenyliodonium salt (PhI2+).
The per cent swelling, equilibrium swelling, initial rate of swelling, swelling rate of constant and diffusion constant values were evaluated
for PEEC and PEEC-co-PSt gel systems in dimethyl sulfoxide. PEEC and PEEC-co-PSt gels were swollen in the range 878-999 % in
DMSO. The adsorption of procion blue HERD dye onto PEEC and PEEC-co-PSt in DMSO solution was investigated. The equilibrium
adsorption data on reactive dye on PEEC and PEEC-co-PSt were analyzed by Langmuir and Freundlich models. The maximum adsorption
capacity (qm) has been found to be 556 mg/g for PEEC and 714 mg/g for PEEC-co-PSt gels.
Key Words: Swelling, Dye adsorption, Photoinitiated cationic homopolymerization, Copolymerization.
studied radiation induced acrylamide based hydogels to
analyze the adsorption of proteins, pharmaceuticals, cationic
dyes and heavy metal ions11. Unlike the others, we used
photoinitiated cationic (co)polymerization in this study12.
Synthetic dyes have been extensively used in many
industries such as textile, leather tanning, paper production,
food technology, photoelectrochemical cells, hair colourings,
biomaterial in medicine, pharmaceutical and veterinary indus-
tries etc.13-15.A number of textile dyes, known as reactive dyes,
have been used to purify proteins. Selection of the supporting
matrix or gel is the first important consideration in dye-affinity
systems. There are several methods for immobilization of dye
molecules onto the supporting matrix or gel. The adsorption
should carefully be optimized to design a successful separation.
The aim of this study is to investigate the swelling prop-
erties and adsorption characteristics of gels. Dynamic swell-
ing studies are important for swelling characterization of poly-
meric gel systems. These swelling properties are of particular
importance in textile industry, biomaterial in medicine, pharma-
ceutical and veterinary industries.
INTRODUCTION
Crosslinking polymer chains result in polymer networks
called gels. Gels do not dissolve but swell/shrink (i.e., change
their volume) in contact with liquid phases. This behaviour is
responsible for many applications for example in drug delivery
systems, molecular separation applications, biomedical devices
such as artificial muscles, gel based sensors and display devices,
adsorbents1-3. The swelling behaviours of crosslinking
polymetric gel may cause its volume to change which is the
macro exhibition of its conformational change of the macro-
molecular chain. Therefore, research on the swelling behaviours
of crosslinking polymeric gels may reveal the interaction of
microscopic molecules, conformational relationship of the
macromolecular chain and flowing process of liquid infiltration
and exudation4,5, which is of important value to deeply under-
stand the mechanism of the gel.
Crosslinking polymer can be synthesized via various
methods including anionic, cationic, radical polymerizations
and chemical modifications of polymer ends6. In recent years,
a bulk of research has been focused on the characterization
and swelling behaviour of gels prepared by simultaneous free
radical copolymerization and crosslinking in the presence of
an initiator and a crosslinking agent7-10. Saraydin et al. have
EXPERIMENTAL
Styrene (Fluka) was distilled over calcium hydride and
stored in a refrigerator under nitrogen before use. The

7794 Sahin et al.
Asian J. Chem.
compounds 3-cyclohexene-1-methanol (Aldrich), 2-bromo-
propanoyl bromide (Aldrich), 3-chloroperoxybenzoic acid
(Aldrich) and sodium bicarbonate (Merck) were used as
received. The compound 3,4-epoxycyclohexylmethyl-3',4'-
epoxycyclohexanecarboxylate (EEC) was commercially
obtained from Ciba Specialty Chemicals and used as received
without further purification. Dichloromethane (Lab-scan),
dimethyl sulfoxide (Merck), pyridine (Lab-Scan), diphenyl-
(5.95 × 10-3 mol/L). The tubes were degassed with nitrogen
prior to irradiation by a merry-go-round type photoreactor
equipped with 16 lamps emitting light nominally at λ = 300
nm and a cooling system. At the end of the reaction, cross-
linked polymers were filtered, dried and weighed.
Experiments of swelling and diffusion: The swelling
behaviours of dried gels were carried out by immersion in
DMSO at 25 ºC in a water bath to measure the parameters of
diffusion and swelling. Swollen gels removed from the DMSO
at regular intervals were dried superficially with filter paper,
weighted and placed in the same bath again. Swollen gels
weighted by an electronic balance (Sertorious CP 224S). The
measurements were continued until a constant weight was
reached for each sample.
–
iodonium hexafluorophosphate (Ph2I+PF6 ) (Fluka), CuBr
(Aldrich), 2,2'-bipyridine (Merck) and all other solvents and
chemicals were used as received. Swelling work was made at
room temperature and room atmosphere with DMSO. In the
adsorption part of this study, procion blue HERD (Aldrich)
was used.
Polymerization procedure: Cyclohexene oxide end-
functional macromonomer of polystyrene (CHO-PSt) was
synthesized by atom transfer radical polymerization (ATRP)
method. In Scheme-I (Table-1), syntheses of CHO-PSt as well
as the characteristic of the investigated polymer are given. The
details of polymerization conditions and characterization
processes were currently available from a previous article16.
Adsorption studies: The equilibrium adsorption isotherm
was determined using batch studies. Samples, consisting of a
portion (0.1 g) of the adsorbent material gel and various initial
dye concentrations 20-200 mg/L, were poured into the conical
reaction flask. The time required to reach equilibrium as
determined in equilibrium studies was 24 h. The effect of the
adsorption isotherm was determined by examining the series
of isotherms at 30 ºC. The sample, 0.1 g of dry gel, was trans-
ferred into 50 mL of the synthetic DMSO solutions of the dye
and allowed to equilibrate for 24 h at 30 ºC. The influences of
PSt content in the superswelling gels were investigated for
adsorption of dye onto PEEC and PEEC-co-PSt gels. Spectro-
photometric method was applied to dye solutions. Spectro-
photometric measurements were taken using a Shimadzu UV
1601 model UV-visible spectrophotometer at ambient tempe-
rature. The absorbances of these solutions were read at 650
nm. DMSO was chosen as the reference. The equilibrium
concentrations of the reactive dye solutions were determined
by means of precalibrated scales.
O
O
Br
OH
Br
O
Pyridine
Br
Br
+
CH-Br
1
O
O
Br
O
O
3-chloroperoxybenzoic acid
O
CH-Br
CHO-Br
2
O
O
Br
Br
RESULTS AND DISCUSSION
O
O
n Styrene
O
n
O
CuBr/bpy
110 oC, in bulk
Preparation of PEEC and PEEC-co-PSt cross-linked
polymers: Photoinitiated cationic polymerization of 3,4-
epoxycyclohexylmethyl-3',4'-epoxy- cyclohexanecarboxylate
(EEC) with and without cyclohexene oxide end-functional
macromonomer of polystyrene (CHO-PSt) was performed in
CH2Cl2 at room temperature using diphenyliodonium salt
(PhI2+) as a cationic photoinitiator. EEC can ultimately form
cross-linked networks with and without CHO-PSt upon irra-
diation in the presence of PhI2+ due to the two epoxy groups
present in the structure. The overall reactions for synthesis of
PEEC and PEEC-co-PSt are depicted in Scheme-II.
Swelling measurements in DMSO: Equilibrium swell-
ing experiments were carried out to investigate the swelling
properties of the materials which were prepared using the
various preparation methods. Dry gels were weighed and then
immersed in DMSO at 30 ºC. Swollen gels were removed from
DMSO at predetermined intervals, blotted dry and weighed
in air. The percentage swelling (or mass swelling) is the most
important parameter about swelling studies. The percentage
swelling (S %) was calculated using the following equation17:
CHO-Br
CHO-PSt
3
Scheme-I: Preparation of cyclohexene oxide end-functional
macromonomer of polystyrene (CHO-PSt)
TABLE-1
SYNTHESIS OF CHO END-FUNCTIONAL MACROMONOMERS
OF PSt BY ATRPa USING CHO-Br AS INITIATOR
[I] × 10-2
(mol/l)
Time Conversion
Mn
Mn H
Mn theo
1490
Mw/Mn
1.27
b
(min)
(%)
GPC
NMR
28.9
90
39
1590
1920
aTemperature 110 ºC, [St]0 = 8.75 mol/L (in bulk), [I]: [CuBr]:[Bpy] =
1:1:3, b Determined by GPC according to PSt standards.
Photoinitiated cationic polymerization method was applied
to prepare cross-linked polymers. Photopolymerizations were
carried out in CH2Cl2 solution. In the preparation of PEEC the
monomer 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclo-
hexanecarboxylate (EEC) (5.95 × 10-3 mol/L) and the cationic
photoinitiator diphenyliodonium hexafluorophosphate
(Ph2I+PF6–) (5 × 10-3 mol/L) were placed in a quartz tube. The
cationic photoinitiator Ph2I+PF6 (5 × 10-3 mol/L) and the
macromonomer CHO-PSt (100 g/L) were placed in another
quartz tube to prepare PEEC-co-PSt the monomer (EEC)
–
(W0 − W )
t
S (%) =
×100
(1)
W0

Vol. 25, No. 14 (2013) Adsorption Studies of 3,4-Epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate-Based Polymeric Gels 7795
O
global. From a system design viewpoint, a lumped analysis of
swelling rates is thus sufficient to the practical operation. A
simple kinetic analysis is a second order equation in the form
of
-
Ph2I+PF6
O
C
O
O
PEEC Cross-linked polymer
hν, 300 nm
EEC
4
dS
O
O
C
= k2,S(Seq − S)
(2)
Br
dt
O
O
n
O
O
O
+
where k2,S is the rate constant of swelling and Seq (or Seq %)
denotes the swelling per cent at equilibrium. After definite
integration by applying the initial conditions S = 0 at t = 0 and
S = S at t = t, eqn. 2 becomes
EEC
CHO-PSt
Ph2I+PF6
-
hν, 300 nm
PEEC-co-PSt Cross-linked polymer
t
= A + Bt
(3)
5
S
Scheme-II: Preparation of PEEC and PEEC-co-PSt cross-linked polymers
whereA is reciprocal of initial swelling rate r0 or 1/k2,SS2eq and
B = 1/Seq is inverse of the degree of swelling at equilibrium
form18. To test the kinetics model, t/S versus t graphs are plotted
and representative graphs are illustrated in Fig. 2. The calcu-
lated kinetic parameters are tabulated in Table-2.
where Wt is the mass of the swollen gel at time t and W0 is the
mass of the dry gel at time 0.
The DMSO intake of initially dried gels was observed for
a prolonged duration of time. Swelling isotherms of PEEC
and PEEC-co-PSt gel are plotted as shown in Fig. 1. It can be
seen that the swelling (S) % increases with time until a certain
point, when it becomes constant. This value of S % may be
named ''equilibrium'' swelling (Seq %). The values of Seq % of
PEEC and PEEC-co-PSt gel are 878 and 999 % (Table-2).
The effects of crosslinker are important in preparing of PEEC-
co-PSt. The reason behind this behaviour may be the molecular
structure of crosslinkers. That is the reason PSt is behaving as
crosslinkers.
2.5
2.0
1.5
1.0
0.5
0
PEEC
PEEC-co-PSt
000
500
1000
Time (min)
1500
2000
Fig. 2. Swelling kinetics curves of PEEC and PEEC-co-PSt gel in DMSO
solutions
100000
80000
60000
40000
As can be seen from Table-2, the swelling rate constant is
decreased in PEEC-co-PSt copolymer. This is plausible for
the network to enhance with the extent of PSt polymeric groups
in structure.
Diffusion: The swelling curves of PEEC and PEEC-co-
PSt gels in DMSO were used to calculate a certain diffusion
characteristics. The following equation was used to determine
20000
PEEC-co-PSt
PEEC
the nature of diffusion of DMSO into gels19,20
F = ktn
.
(4)
0
4000
540.
1040
Time (min)
1540
2040
where F denotes the amount of DMSO diffused into the gel at
time, t is infinite time (at equilibrium), k is a constant related to
the structure of the network and the exponent ‘n’is a numerical
value to determine the type of diffusion. For a cylindrical
shapes, n ≤ 0.50 corresponds to Fickian diffusion, whereas
0.50 < n < 1.00 to indicate diffusion is non-Fickian. Eqn. 4
was applied to various stages of swelling. Plots of ln F against
ln t yielded straight lines from which the exponent's n and k
were calculated from the slope and intercept of the lines given
in Table-3 both for PEEC and PEEC-co-PSt gel systems in
DMSO. It can be clearly seen from the table that the values of
the diffusion exponent, falling in the range from 0.27 to 0.29
are lower than 0.50. Hence, the diffusion of DMSO into PEEC
and PEEC-co-PSt gels were assumed to be Fickian in character.
Table-4 also demonstrates that diffusion of DMSO is higher
at PEEC-co-PSt because of the PSt higher cross-linking density.
Equilibrium isotherms for reactive dye adsorption on
PEEC and PEEC-co-PSt gels: Adsorption isotherm data on
Fig. 1. Swelling isotherms of PEEC and PEEC-co-PSt gels
TABLE-2
SWELLING KINETICS PARAMETERS OF PEEC
AND PEEC-co-PSt GEL SYSTEMS IN DMSO
Swelling rate
Theoretical
equilibrium
swelling, Seq %
max; gDMSO/ggel
Initial swelling
rate, r (dS/dt)0;
gDMSO/ggel (min)
constant, k2,S
105; ggel/gDMSO
(min)
×
PEEC
0.10
0.08
1.18
1.30
909
1000
PEEC-co-PSt
Swelling kinetics: In order to examine the controlling
mechanism of the swelling processes, several kinetic models
are used to test experimental data. The large number and array
of different chemical groups on the PEEC and PEEC-co-PSt
gel chains imply that there are many types of polymer-solvent
interactions. It is probable that any kinetics is likely to be

7796 Sahin et al.
Asian J. Chem.
TABLE-3
isotherm allows an expression encompassing the surface
heterogeneity and the exponential distribution of active sites
and their energies. This isotherm does not estimate any satu-
ration of the sorbent surface; thus infinite surface coverage is
predicted, indicating physisorption on the surface.
DIFFUSION CHARACTERISTICS OF PEEC
AND PEEC-co-PSt GEL IN DMSO
n
k × 102
PEEC
PEEC-co-PSt
0.29
0.27
1.15
1.40
The correlation of the experimental adsorption data with
a number of adsorption models was undertaken to gain an
understanding of the adsorption behaviour and the hetero-
geneity of the adsorbent surface. The Langmuir equation can
be represented as follows24:
TABLE-4
MODEL PARAMETERS OBTAINED FROM
FITTING THE EXPERIMENTAL EQUILIBRIUM
DATA WITH ISOTHERM MODELS
Langmuir isotherm
Freundlich isotherm constants
r2 r2
KF
constants
q
m ⋅KL ⋅Ce
qe =
KL × 10-5
1.82
Qm
RL
n
(5)
1+ KL.Ce
PEEC
PEEC-
co-PSt
556 0.9995 0.9994 5.5 6.7 0.8963
714 0.9965 0.9992 5.6 5.4 0.8646
where Ce (mg/L) is the equilibrium concentration of dye in
solution; qe (mg/g) is the surface concentration of dye at equili-
brium; qm (mg/g) is the amount of dye adsorbed at complete
monolayer coverage; KL (L/mg) is a constant that relates to
the energy of adsorption. The linearized Langmuir equation
is represented as follows:
1.12
the reactive dyes are illustrated in Fig. 3. The shape of the
isotherms indicates L2-behaviour according to Giles and Smith
classification21. In L2-type isotherms, adsorption of solute on
the adsorbent proceeds until a monolayer is established, with
the formation of more than one layer not being possible. The
shape of isotherm presented in Fig. 3 is indicative of high
affinity between the sorbent surface and the reactive dye
molecules. The adsorbent effectively removes the dye at low
initial concentrations; at higher concentrations the isotherms
reach a maximum capacity as indicated by the plateau of the
data. Most reported adsorption isotherms of reactive dyes were
1
1
1
=
+
(6)
qe qm KL.qm.Ce
The values of qm and KL were calculated from the slope
and intercept of the straight lines of the plot 1/Ce versus 1/qe.
The essential characteristic of the Langmuir isotherm can be
expressed in terms of a dimensionless equilibrium parameter,
such as the separation factor (or) equilibrium factor (RL) used
in the following equation:
of L2-type isotherm22,23
.
1
PEEC-co-PSt
PEEC
RL
=
(7)
1+ KL.Ce
700
This parameter indicates that isotherm will shape accor-
ding to the following adsorption characteristics: RL > 1
unfavourable; RL = 1 corresponds to linear; 0 < RL < 1 is
favourable and RL = 0 is irreversible as given in Table-4. It can
be seen that the adsorption of Procion Blue HERD onto PEEC
and PEEC-co-PSt gels will be favourable. The correlation of
the dye adsorption data with the Langmuir isotherm model
was high, with r2 values of 0.9994 and 0.9992 for PEEC and
PEEC-co-PSt gel, respectively.
500
300
00
The Freundlich model can take the following form:
100
200
300
Ce (mg/L)
1/n
(8)
qe = KF.Ce
Fig. 3. Adsorption isotherms of reactive dyes. Mass of gel: 0.025 g; volume
of solution: 25 cm3; temperature: 25 ºC. Points: experimental data;
lines: Langmuir model
where KF [mg/g (L/mg/)n] represents the adsorption capacity
when dye equilibrium concentration (Ce) equals 1 with n
being the degree of dependence of adsorption on equilibrium
concentration. The model parameters (as obtained from linear-
regression analysis) and correlation coefficients (r2) are
presented in Table-4.
Accordingly, the anionic reactive dye molecules favourably
adsorb on the gel surface with low competition from solvent
molecules, with this adsorption process continuing until the
surface concentration reaches a maximum value. In addition,
multilayers of adsorbate failed to form due to the electrostatic
repulsion between adsorbed molecules and those in solution.
Langmuir and Freundlich equilibrium isotherm models:
The experimental data were applied to the Langmuir, Freundlich
isotherm model. The Langmuir model assumes chemisorption
on a set of well defined localized sorption sites, having the
same sorption energies independent of surface coverage and
no interaction between adsorbed molecules. Langmuir isotherm
assumes monolayer coverage of sorbate onto sorbent. Freundlich
ln KF
ln qe =
(9)
(1/ n)lnCe
Various constants associated with the isotherm are the
intercept, which is roughly an indicator of sorption capacity
(KF) and the slope (1/n), being the sorption intensity. The values
are given in Table-4. The Freundlich isotherm has been illus-
trated to be a special case of heterogeneous surface energies
but it can be easily extended to this case. It has been stated25,26
that the magnitude of the exponent 1/n gives an indication of

Vol. 25, No. 14 (2013) Adsorption Studies of 3,4-Epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate-Based Polymeric Gels 7797
the favorability and capacity of the adsorbent/adsorbate
system. Values where n > 1 represent favorable adsorption
conditions. In most cases the exponent falling in the interval
1 < n < 10 shows beneficial adsorption.
to be reasonably high at PEEC-co-PSt for adsorption of Procion
Blue HERD. The values of dimensionless equilibrium para-
meters like the separation factor (RL) indicate the favorability
of the process described in the present study. We demonstrate
that the Langmuir and Freundlich models can provide adequate
representations of the data used in this study to describe dye
sorption onto PEEC and PEEC-co-PSt gels at equilibrium,
rendering a better fit. Hence the data reported here are quite
useful to produce some substances to be used in pharmaceutical,
environmental and biomedical applications, or in the applications
of immobilized biologically active molecules. The results also
showed that the PEEC and PEEC-co-PSt gels being useful as
adsorbent for the DMSO pollutants such as reactive dyes, an
important problem encountered in the biomedical and pharma-
ceutical industries.
The values for qm, KL, KF and n are summarized in Table-
4. The analyses of correlation coefficients showed that
Langmuir isotherm provided the best fit of experimental
adsorption data (RL > 0.99). The fact that the Langmuir
isotherm fits the experimental data very well may be due to
the homogeneous distribution of active sites onto the PEEC
and PEEC-co-PSt, since the Langmuir equation assumes that
the surface is homogenous. Thus, Langmuir model was chosen
to interpret procion blue HERD dye adsorption by PEEC and
PEEC-co-PSt.
The maximum adsorption capacity observed for PEEC-
co-PSt (714 mg/g) was almost 1.3 times greater than that of
PEEC (556 mg/g). Maximum adsorption capacities of PEEC
increased with content of polystyrene.
ACKNOWLEDGEMENTS
The authors thank Harran University, the Scientific Re-
search Council (HÜBAK) for financial support.
The parameter KF is a Freundlich constant that indicates
the adsorption capacity of an adsorbent and is a constant which
shows the strength of the relationship between adsorbate and
adsorbent26. The value KF of PEEC and PEEC-co-PSt for
procion blue HERD dye is ca. 5.5 (L/g). It is generally accepted
that the values of n in the range of 1-10 represent good
adsorption. In the present work, the exponent n was in the
range from 1-10, indicating favorable adsorption. The results
given in Table-4 show that the adsorption of procion blue
HERD dye onto PEEC-co-PSt is favorable.
PEEC and PEEC-co-PSt gels are new materials as an
adsorbent. It is important to point out that the results obtained
from adsorption studies, based on a number of experiments,
have shown that each polymeric sample and derivatives have
their own adsorption features, which relate to crosslinking
degree.
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Conclusion
In this study, PEEC and PEEC-co-PSt cross-linked polymers
were prepared via photoinitiated cationic polymerization.
Photoinitiation of cationic polymerizations can be efficiently
achieved using EEC with and without CHO-PSt co-monomer
by aid of the iodonium salt at 300 nm. Gels were prepared in
DMSO and swollen to equilibrium in DMSO. Gel systems
swelled in the range 878-999 %. Equilibrium swelling data
were used to determine swelling parameters such as swelling
exponent, swelling coefficients and diffusional behaviour of
DMSO of the gel systems. Gels were of the type a Fickian
diffusion character. It was seen that swelling of PEEC-co-PSt
gel increased with contents of polystyrene. The second part of
this study has shown that PEEC and PEEC-co-PSt adsorb the
reactive dye, being the procion blue HERD. Langmuir model
suitably fitted in the present system shows the formation of a
monolayer covering of the adsorbate at the outer space of the
adsorbent. The Freundlich model was used to analyze the
isotherm. The monolayer adsorption capacity was determined