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REACTIVE
&
FUNCTIONAL
Reactive & Functional Polymers 68 (2008) 474–482
POLYMERS
www.elsevier.com/locate/react

Synthesis of a cation-exchange fabric with sulfonate groups

by radiation-induced graft copolymerization from
binary monomer mixtures
Seung Woo Lee a, Yuliya Bondar a,b,*, Do Hung Han a
a
School of Display and Chemical Engineering, Yeungnam University, 214-1 Dae-Dong, Gyeongsan 712-749, South Korea
b
Institute of Environmental Geochemistry, 34A Palladin Avenue, 03142 Kiev, Ukraine

Received 20 June 2007; received in revised form 29 October 2007; accepted 31 October 2007
Available online 6 November 2007

Abstract

Cation-exchange adsorbent based on a nonwoven polypropylene fabric carrying sulfonate functional groups was syn-
thesized by a one-step graft copolymerization of sodium styrenesulfonate and acrylic acid monomers from binary mono-
mer mixtures using the electron beam pre-irradiation method in air. The effect of various polymerization parameters
(absorbed dose, reaction temperature and time, monomer ratio, Mohr’s salt additive) on the degree of grafting was stud-
ied. It was found that the copolymerization process begins with the primary grafting of acrylic acid monomers on the
nonwoven polypropylene fabric and continues by cografting of sodium styrenesulfonate and acrylic acid monomers. Total
ion-exchange capacity and sulfonate group density were evaluated to vary within 3.5–5.5 and 1.0–2.16 mEq/g, correspond-
ingly, for synthesized fabrics with a medium grafting degree (70–220%). These values are similar to those of sulfonated
membranes obtained by radiation-induced graft polymerization of styrene with subsequent sulfonation of polystyrene
chains. The main advantage of the studied approach is a one-step process of synthesis.
Ó 2007 Elsevier Ltd. All rights reserved.

Keywords: Radiation-induced grafting; Electron beam; Polypropylene; Sodium styrenesulfonate; Acrylic acid; Binary monomer mixture

1. Introduction mers available in different forms (films, fibers, res-

Radiation-induced graft polymerization is widely
used to produce high performance chemically active
polymer materials for adsorption and separation
processes on the basis of various commercial poly-
*
Corresponding author. Address: Institute of Environmental
Geochemistry, 34A Palladin Avenue, 03142 Kiev, Ukraine. Tel.:
+38 044 424 9850; fax: +38 044 424 0060.
E-mail address: juliavad@yahoo.com (Y. Bondar).
ins, textiles, powders) [1–4].
Various approaches for synthesizing polymer
adsorbents have been developed, including direct
graft polymerization of vinyl monomers already
containing desirable functional groups, graft copo-
lymerization of two (or more) different types of
monomers onto a polymer backbone, and graft
polymerization of a precursor-monomer that can
be subsequently modified [3–7]. Owing to a limited
number of vinyl monomers with functional groups,

1381-5148/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.reactfunctpolym.2007.10.036
 S.W. Lee et al. / Reactive & Functional Polymers 68 (2008) 474–482
the last two approaches can be considered as the
most promising [8].
For practical purposes the production of cation-
exchange polymer materials bearing strong acid
functional groups, such as sulfonic acid groups, is
an object of intense interest due to their possible
application over a wide pH range [4,9]. Radiation
graft polymerization can be used in different modes
for this purpose: radiation-induced graft polymeri-
zation of styrene with subsequent sulfonation of
polystyrene chains [4,10–12], or immediate radia-
tion-induced grafting of sulfonate group-containing
monomers. The former mode has been successfully
developed for production of proton-exchange
membranes for fuel cells. The latter is under study.
There are a few reports on the immediate radia-
tion-induced grafting of sodium styrenesulfonate
(SSS) – a vinyl monomer with a sulfonate group
[9,13–15]. The first attempts to graft SSS on high-
density polyethylene (HDPE) membrane failed
due to the incompatibility between highly ionized
sulfonic acid groups bordered by a large hydration
sphere and a hydrophobic polymer backbone [13].
To overcome this difficulty the authors used a
two-step process: preliminary grafting of poly-
(acrylic acid) chains to improve hydrophilic
properties of a polymer surface and then graft poly-
merization of SSS after another round of irradia-
tion. The results of SSS grafting on polyethylene
sheets after two low-doses of irradiation are pre-
sented in [14].
In a practical aspect, a one-step grafting process
has some economic advantages. Satoshi et al. [9]
reported a one-step irradiation process that allowed
them to synthesize ion-exchange membranes with
sulfonate groups by graft copolymerization of SSS
in the presence of acrylic acid (AA). However,
despite their initial claims of successfully synthesiz-
ing a polyethylene membrane with an ion-exchange
capacity of 2.5 mEq/g, little data on the peculiarities
of the copolymerization process from binary mono-
mer mixtures as well as SSS monomer grafting were
given in that paper. More extensive information
regarding the grafting of SSS and AA onto HDPE
membranes after one-step irradiation is presented
in [15]. However, the authors did not disclose any
reasons for the graft copolymerization process. In
addition, they gave their results in terms of grafting
degree (a percentage of sample weight increase)
which allows only indirect evaluation of the effi-
ciency of the grafting of both AA and SSS chains,
and forbids any comparison with properties of com-
475
mercially available membranes with sulfonate
groups.
In the present work, we examined how some
experimental parameters (absorbed dose, reaction
temperature and time, monomer ratio and Mohr’s
salt additive) affected grafting of AA and SSS
monomers onto nonwoven polypropylene fabrics
upon irradiation with an electron accelerator in
air. The aim was to find optimal parameters for
the synthesis of cation-exchange fabrics with sulfo-
nate groups. To gain better understanding of the
copolymerization process from binary monomer
mixtures the relationship between grafting degree
and reaction time at 50 and 70 °C was studied and
the FTIR spectra of the appropriate samples were
analyzed. Such an investigation allowed us to find
that the copolymerization process begins with graft-
ing of acrylic acid monomers and continues by
cografting of sodium styrenesulfonate and acrylic
acid monomers. Since the synthesized fabric was a
bi-functional cation-exchanger with two types of
functional groups (carboxylic and sulfonic acid
groups), both total ion-exchange capacity and sulfo-
nate group densities were evaluated. The final
results are represented in terms of density of func-
tional groups (in terms of mEq/g).
2. Experimental
2.1. Materials
Commercial nonwoven polypropylene fabric –
PP (120 g/m2, degree of crystallinity of 65%, thick-
ness of 1 mm, Toray-Saehan Co., Ltd.) was used
for grafting. Reagent grade acrylic acid
(CH2@CHCOOH, Junsei Chemical Co., Ltd.),
sodium styrenesulfonate (CH2@CHC6H4SO3Na,
Tokyo Kasei Kogyo Co., Ltd.), Mohr’s salt
((NH4)2Fe(SO4)2  6H2O, Merck, Germany) were
used as received.
2.2. Method
2.2.1. Graft copolymerization procedure
The pre-irradiation grafting technique was
employed for graft copolymerization of the
SSS + AA monomer mixture. Polypropylene fabric
was irradiated in air at ambient temperature by an
electron beam from an ELV-04 electron beam accel-
erator with an accelerated energy of 1 MeV for dif-
ferent time periods. After irradiation, the PP fabric
was stored at room temperature in a dessicator. The
476 S.W. Lee et al. / Reactive & Functional Polymers 68 (2008) 474–482
irradiated fabric (about of 0.5 g) was weighed and
immersed in 100 ml glass flask with a solution of
AA and SSS monomers in water (AA:SSS = 0.1 M
(7.2 g):0.1M (20.6 g) in 100 ml of water; the total
monomer content was a little less than 2 mol l1)
and Mohr’ salt additive. Then, the flask was purged
by bubbling nitrogen, sealed up, and placed in a
water bath maintained at a constant temperature
for different time periods. When the stipulated time
period was over the grafted PP fabric samples were
removed from the solution, washed thoroughly with
hot distilled water and methanol to remove homo-
polymers and unreacted monomers, and dried in a
vacuum oven at 80 °C until constant weight. The
degree of grafting (DG) was calculated from the
weight gain:
DG% ¼ ½ðW 1  W 0 Þ=W 0   100
where W0 and W1 are the weights (g) of the original
and grafted fabric, respectively.
2.2.2. FTIR analysis
To justify the introduction of functional groups
onto the PP fabric, infrared spectroscopy analysis
was carried out using a FTIR spectrometer (Per-
kin–Elmer, 1725 with a golden gate single reflection
ATR system). The spectra of dried grafted and ori-
ginal samples were measured directly without
treatment.
2.2.3. Ion-exchange characteristics
Total ion-exchange capacity (mEq/g) of the mod-
ified fabric exhibiting the actual number of acidic
functional groups grafted onto the PP trunk was
determined by backward titration experiments.
For this purpose the grafted PP fabric (about
0.5 g) was completely converted to the H+ form
by treatment with an excess solution of 0.1 M HCl
for 12 h. The washed, dried and weighted sample
in the H+ was put into a flask with 20 ml of stan-
dard 0.5 M NaOH solution, stopped down and sha-
ken for about 12 h. Aliquot solutions (2 ml) were
titrated to the phenolphthalein end point with a
standard 0.1 M HCl solution.
Adsorption of Cu2+ ions onto synthesized PP fab-
ric from an aqueous solution (pH  3.8) was inves-
tigated by contacting 0.5 g of grafted PP fabric with
50 ml solution of CuCl2 salt at 22 °C under stirring
(140 rpm). One millilitre solution was collected at
appropriate time intervals for metal ion determina-
tion by using an atomic absorption spectrophotom-
eter (Model UNICAM 989, UK). The quantity of
metal ions adsorbed per gram of dry weight of the
modified PP fabric (mg/g) was calculated by the
following:
Metal ions adsorbed ¼ ðC 0  CÞ  V =W
Where, C0 and C are the Cu2+ ion concentrations in
the solution before and after the incubation period,
respectively (mg/ml); V is the volume of the solution
(ml); W is the weight of the dried adsorbent used
(g). Calculation of sulfonate group density (in terms
of mEq/g) was based on the adsorption text’s results
considering a gram-equivalent value of Cu2+ ions.
3. Results and discussion
3.1. Copolymerization process
When polypropylene fabric is irradiated in air,
mainly hydroperoxides are formed onto the poly-
meric backbone. These hydroperoxides decompose
upon heating to give rise to hydroxyl radicals
(OH) and macroradicals (PPO). Macroradicals
offer a site for grafting, while hydroxyl radicals ini-
tiate undesirable homopolymerization, which usu-
ally leads to a decrease in grafting degree. To
overcome homopolymerization a small amount of
transition metal ions are commonly used as inhibi-
tors [16].
Just as other investigators [13,14] we were unable
to graft SSS monomers onto PP fabric in aqueous
solutions; however copolymerization of SSS with
AA was successfully done. Many factors affect the
radiation grafting process of binary monomer mix-
tures. The ones investigated here, are absorbed
dose, reaction time and temperature, monomer
ratio, and concentration of inhibitor (Mohr’s salt).
3.2. Effect of absorbed dose
The influence of the absorbed dose on the degree
of SSS + AA monomer mixture grafting is pre-
sented in Fig. 1. As it can be seen, the degree of
grafting slowly increases to 40.3 kGy, and then
begins to rise significantly up to 70.5 kGy. The
authors in [15] demonstrated similar nonlinear
behaviors of the DG-absorbed dose in relation to
the monomer molar ratio of AA:SSS = 2:1.
In the FTIR spectra of grafted samples, irradi-
ated with doses less than 40.3 kGy, only a character-
istic band at 1715–1730 cm1 assigned to the –C@O
group of acrylic acid was observed, while the FTIR
 S.W. Lee et al. / Reactive & Functional Polymers 68 (2008) 474–482
Fig. 1. Effect of absorbed dose on the degree of SSS + AA
monomer mixture grafting. Reaction temperature 50 °C, reaction
time 12 h, Mohr’s salt 102 wt%.
spectra of the samples, irradiated with higher doses,
also exhibited characteristic absorption bands
attributed to the SSS group.
In order to clarify some peculiarities of the graft
copolymerization of SSS + AA monomers from
binary monomer mixtures onto the PP fabric sur-
face the degree of graft copolymerization as a func-
tion of time was investigated at 50 and 70 °C, and
the FTIR spectra of the appropriate samples were
analyzed.
3.3. Effect of reaction time
The variation in the degree of monomer mixture
grafting with the reaction time at 50 °C is shown in
Fig. 2 (line 1). The curve of the grafting process con-
sists of a few sections that may denote a stepwise
development of the grafting process. To understand
some of the peculiarities of the grafting process
from binary monomer mixtures, the FTIR spectra
of several modified PP samples were investigated
(Fig. 3).
Three samples with a low degree of grafting
(DG = 2.9%, 7.3%, 8.6%, 17.8%) correspond to
the initial part of the grafting curve (within grafting
time of 10 h). Their FTIR spectra (Fig. 3, spectra
3–6) exhibit a peak at 1715–1730 cm1 due to car-
bonyl stretching absorption of the carboxyl group.
The presence of the above peak indicates the graft-
ing of AA monomers onto the PP fabric. The inten-
sity of this absorption band grows with an increase
in the degree of grafting.
477
Fig. 2. Curves of SSS + AA monomer mixture grafting processes
at 50 °C (1) and 70 °C (2). Absorbed dose 70.5 kGy; Mohr’s salt
102 wt%.
The fourth sample with DG = 73.0% corre-
sponds to the next fast-growing section of the graft-
ing curve (within grafting time of 10–12 h). Its FTIR
spectrum (Fig. 3, spectrum 7) shows the characteris-
tic absorption bands of the sulfonic acid group
(1150 cm1 (asymmetric stretch), 1030 cm1 (sym-
metric stretch), 670 cm1) together with the adsorp-
tion band of the carboxylic group.
The next sample with DG = 98.6% corresponds
to the next middle-growing section of the grafting
curve. Its FTIR spectrum (Fig. 3, spectrum 8) also
shows the characteristic absorption bands of a sul-
fonic acid group together with the adsorption band
of a carboxylic group. Comparing spectra 7 with 8 it
is possible to note the growth of intensity of the
characteristic peaks both for sulfonic acid and of
acrylic acid with an increase in the degree of mono-
mer mixture grafting.
The variation in the degree of monomer mixture
grafting with the reaction time at 70 °C is shown in
Fig. 2 (line 2). The FTIR spectra of studied samples
with a DG less than 32% contain the peak at 1715–
1730 cm1 attributed to the carboxyl group of
acrylic acid. The characteristic peaks of the sulfonic
acid group appear at the FTIR spectra of grafted
samples with higher values of DG. Their intensity
as well as the intensity of the carboxyl group peak
increases with an increase in the grafting degree just
as in the case of grafting at 50 °C.
The above results confirm our assumption of a
stepwise graft copolymerization process: it is obvi-
ous that the process begins with grafting of acrylic
478 S.W. Lee et al. / Reactive & Functional Polymers 68 (2008) 474–482
Fig. 3. IR-spectra of original PP fabric (1); AA-g-PP fabric with DG = 95% (2); AA-SSS-g-PP fabric with DG = 2.9% (3); 7.7% (4); 8.8%
(5); 17.8% (6); 73.0% (7); 98.6% (8). Absorbed dose 70.5 kGy, reaction temperature 50 °C.
acid monomers onto the PP backbone (as the first
step) and then goes on by cografting of SSS and
AA monomers.
A few possible mechanisms of the copolymeriza-
tion process can be considered. First, AA monomers
graft onto the PP backbone via macroradicals
formed during irradiation as discussed above. As a
result, the hydrophilic properties of the PP fabric
improve and SSS monomers can easily diffuse to
the fabric’s surface and also graft directly by the
remaining macroradicals.
This mechanism fits well with conclusions from
authors who studied the two-step process of
SSS + AA monomer mixture grafting [13,14]. For
example, authors [14], when carrying out grafting
of SSS monomers on modified polyethylene-g-AA
sheets with a AA grafting degree of 60%, 80% and
120%, obtained SSS grafting degrees of 4.5%,
15.1%, 17.2%, respectively, after the second irradia-
tion. One can see that the higher degree of AA pre-
grafting results in a higher degree of SSS grafting.
This fact can be ascribed to the improvement of
the hydrophilic properties of the polymer surfaces
[13,14] owing to the grafting of hydrophilic acrylic
acid monomers.
Another mechanism for the copolymerization
process is possible. The process of SSS + AA mono-
mer mixture grafting begins with AA monomer
grafting (as the first stage) and then continues with
the grafting of SSS and AA monomers to the
poly(AA) chains already grafted onto the PP fabric.
We carried out the following test experiment: (1) the
irradiated samples were immersed into an oxygen
free flask with an aqueous solution of Mohr’s salt
(102 wt%) and heated at 50 °C for 12 h; (2) the
AA monomer solution was added to the flask, and
the grafting reaction was allowed to proceed for
5 h at 50 °C. The absence of AA characteristic peaks
in the FTIR spectrum of the control samples indi-
cated that all active species which could initiate
the graft polymerization process, were deactivated
prior to adding of the AA monomers to the flask.
However, to find the intrinsic mechanism of the
copolymerization process additional investigations
are required.
3.4. Effect of monomer ratio
The relation of the degree of SSS + AA mono-
mer mixture grafting and monomer molar ratio in
the reaction solution over the reaction time of 21 h
(the total concentration of monomers in the reac-
tion solution was about 2 mol l1; it was 1 mol l1
for grafting SSS or AA individually) is shown in
 S.W. Lee et al. / Reactive & Functional Polymers 68 (2008) 474–482
Fig. 4. Degree of SSS + AA monomer mixture grafting versus
monomer molar ratio. Absorbed dose 70.5 kGy, reaction tem-
perature 50 °C, reaction time 21 h, Mohr’s salt 102 wt%.
Fig. 4. The highest value of grafting degree is
observed when the molar ratio of AA to SSS in
the grafting solution is 1.0:1.0. The DG value
decreases with a decrease in SSS monomer content
(AA:SSS = 1.5:0.5). The latter can be a consequence
of the increasing reaction solution viscosity owing
to an increase in AA-homopolymer content as com-
pared with the former case. The increase in viscosity
leads eventually to the fall-off of monomer species
diffusion mobility.
A significant decrease in grafting is observed with
an increase in the SSS monomer content in the
grafting solution (AA:SSS = 0.5:1.5) which is
apparently a consequence of the low content of
AA monomers available for grafting. As a result,
the PP fabric surface remains hydrophobic and
SSS monomers cannot be grafted due to the incom-
patibility between highly ionized sulfonic acid
groups with their hydration sphere and hydropho-
bic polymer backbone, as explained earlier in [13].
For the same reason no grafting takes place when
the SSS monomer solution is used alone.
On the other hand, the degree of SSS + AA
monomer mixture grafting may depend on the pH
of the grafting solution. The acidity of the grafting
solution varies from pH < 2 (when grafting occurs
in AA solution) to pH  8 (when grafting occurs
in SSS solution); it is 3  4 when AA:SSS = 1.0:1.0.
The acidity constant value (pKa) of poly(AA) is
about 4.5 [17]. For pH < 4.5, most of the carboxyl
groups are not dissociated and the poly(AA) chains
grafted onto the polymer surface adopt a compact
479
conformation to increase their entropy. For
pH > 4.5, most carboxyl groups are dissociated
and the electrostatic repulsions between the negative
charges bound to the poly(AA) chains (presumably
between charges along the same chain, if the graft-
ing ratio is not too high) leads to an extension of
the poly(AA) chains from the polymer surface.
The extended or semi-extended state of the
poly(AA) chains facilitates diffusion of the SSS spe-
cies to the PP surface. That fact can explain the high
degree of SSS + AA grafting in the equimolar graft-
ing solution.
The reduction in grafting degree in the case of
AA:SSS = 1.5:0.5 in comparison with the above
case can be explained by the likelihood that the
compact conformation of the poly(AA) chains
impedes the diffusion of the SSS species on the PP
surface. The lowest degree of SSS + AA grafting
in the AA:SSS = 0.5:1.5 solution can be due to the
poor pre-modification of the PP fabric by primary
grafting of AA. Perhaps, a high ionic strength of
the solution may also affect the result. When the
poly(AA) chains are in the extended form, the salt
effect is very important since a high ionic strength
solution screens the repulsive electrostatic interac-
tions and thus causes the compaction of grafted
chains [18].
Hereinafter, all experiments are carried out in
monomer molar ratio of 1:1 (at the total concentra-
tion of monomers in mixture about 2 mol l1), as
described in Section 2.2.1.
3.5. Effect of Mohr’s salt additive
The grafting process is usually accompanied by
undesirable homopolymerization from the ther-
modecomposition of hydroperoxides. Some small
amount of transition metal salt is commonly used
to suppress homopolymerization [16]. Metal salts
such as ammonium ferrous sulphate (Mohr’s salt),
ferric chloride, copper chloride and others suppress
homopolymer formation. On the other hand, it is
also known that transition metal ions conduce to
the decomposition of hydroperoxides, thereby lead-
ing to an increase in grafting degree. However, they
can also cause a deactivation of the grafting process
and lead to a decrease in grafting degree when taken
in excess. The superposition of all mentioned cir-
cumstances can lead to both a positive (when DG
is considerably large than DG of the process carried
out without Mohr’s salt) and negative effect under
Mohr’s salt addition. To find a positive effect of a
480 S.W. Lee et al. / Reactive & Functional Polymers 68 (2008) 474–482

transition metal salt on the degree of grafting a set

of thorough experiments must be carried out.
Mohr’s salt was taken as a transition metal salt
additive for our experiments. The influence of
Mohr’s salt on the DG from binary monomer mix-
tures at 50 and 70 °C is presented in Table 1.
The influence of Mohr’s salt additive on the
grafting of AA and SSS from binary monomer mix-
tures at 50 and 70 °C was investigated in [15]. The
authors investigated Mohr’s salt concentration
intervals from 0 to 3  101 wt% with an increment
of 5  102 wt%. They showed that DG reaches
200% without Mohr’s salt additive and then slowly
decreases to 90% when Mohr’s salt is 3  101 wt%
at 50 °C (grafting time was 24 h). An analogous sit-
uation was at 70 °C: DG reaches 320% without Fig. 5. Curves of SSS + AA monomer mixture grafting processes
Mohr’s salt additive and then slowly decreases to at 70 °C with varying contents of Mohr’s salt additive: line 1 –
150% when the Mohr’s salt level is 3  101 wt% without Mohr’s salt and line 2 – with 5  104 wt%.
(grafting time was 24 h). The authors failed to find
a positive influence of Mohr’s salt most likely due
to a wide size of increment (5  102 wt%). for grafting degree, which cannot be achieved with-
We took more narrow size of increment and out Mohr’s salt.
found that the addition of Mohr’s salt to the reac-
tion solution both at 50 and 70 °C (reaction time 3.6. Ion-exchange features
12 h) exhibited an increasing trend of DG up to a
maximum which varied depending on the reaction As a result of radiation-induced graft copolymer-
temperature: it was at a Mohr’s salt content of ization of sodium styrenesulfonate and acrylic acid
103 wt% and a reaction temperature of 50 °C, onto PP fabric, a cation-exchange polymer material
whereas it was at 5  104 wt% at a reaction tem- carrying strong acid sulfonate groups was obtained.
perature of 70 °C. The main specificity of the synthesized fabric is that
The curves of grafting processes at 70° without it is a bi-functional cation-exchanger, carrying two
Mohr’s salt (line 1) and with Mohr’s salt content types of functional groups – both a week acid (car-
of 5  104 wt% (line 2) are presented in Fig. 5. boxylic) and strong acid (sulfonic acid) groups.
As can be seen, the addition of Mohr’s salt causes The total ion-exchange capacity (IEC) of the PP
an increase in the DG and, according to the ten- fabrics synthesized at 70 °C both without Mohr’s
dency of the curves, it reaches the highest values salt and with Mohr’s salt (5  104 wt%) was deter-
mined by a backward titration method. The IEC
value indicates the actual content of the acidic func-
tional groups: both carboxylic and sulfonate. A
Table 1
Effect of Mohr’s salt concentration on the degree of graft relationship between the total IEC (the average
copolymerization at different reaction temperatures between corresponding data of two mentioned
Mohr’s salt content (wt%) Degree of grafting (%) cases) and the DG is shown in Fig. 6. The total
IEC (densities of acidic functional groups) of stud-
SSS + AA monomer mixture
ied fabrics with a medium grafting degree (70–
50 °C 70 °C
180%) vary within 3.5–5.5 mEq/g. This parameter
0 18.6 97.5 is comparable or even higher than that of commer-
104 29.3 107.6
cially available cation-exchangers based on grafted
5  104 86.5 131.9
103 110.0 120.3 textiles [19,20].
5  103 79.7 93.2 In order to determine the contribution of sulfonic
102 82.2 63.8 acid groups to the total IEC a set of batch experi-
101 19.9 36.7 ments towards Cu2+ ions extracted from the
Absorbed dose 70.5 kGy, reaction time – 12 h. aqueous solutions of CuCl2 salt (pH  3.8) was
 S.W. Lee et al. / Reactive & Functional Polymers 68 (2008) 474–482
Fig. 6. Dependence between total ion-exchange capacity and
degree of SSS + AA monomer mixture grafting of the PP fabrics
synthesized at 70 °C without Mohr’s salt (circles) and with
5  104 wt% Mohr’s salt (squares).
performed. Since carboxyl groups of AA weakly
dissociate in the acidic solution, they are not avail-
able for the exchange. In this case only sulfonate
groups, which are highly dissociated and exchange-
able, will adsorb Cu2+ ions.
Sulfonate group density (in terms of mEq/g) was
calculated on the base of adsorption tests taking
into account a gram-equivalent value of Cu2+ ions.
Such evaluation is not exactly quantitative, because
extraction of Cu2+ ions from studied solutions
could occur both due to chemical binding by sulfo-
nate groups and due to physical adsorption. Never-
theless this gives a general idea of the adsorption
properties of synthesized PP fabric.
Cation-exchange PP fabrics synthesized at 70 °C
without Mohr’s salt (line 1) as well as with Mohr’s
salt (line 2) were objects of such investigations.
The calculated densities of sulfonate groups are
denoted in the rectangular frameworks above the
studied samples in Fig. 7.
It can be seen that the density of sulfonate groups
of fabrics with medium grafting degrees (70–155%)
synthesized without Mohr’s salt varies from 1.10
to 1.56 mEq/g. However, the value of fabrics syn-
thesized with Mohr’s salt within the same interval
varies from 0 to 1.57 mEq/g. The latter case reflects
the results of the primary grafting of AA monomers
(0 mEq/g of sulfonate groups) as well as subsequent
cografting of AA + SSS monomers.
It follows from Fig. 7 that the rate of sulfonate
group accumulation in the case of Mohr’s salt addi-
481
Fig. 7. Sulfonate group density (denoted in rectangular frame-
works above a studied sample) calculated for the PP cation-
exchange fabrics synthesized at 70 °C: line 1 – without Mohr’s
salt and line 2 – with 5  104 wt% Mohr’s salt.
tion in comparison with the contrary case is
increased.
The results obtained are of practical significance.
Apparently, to prepare an effective cation-exchan-
ger with a high density of sulfonate groups, it is nec-
essary to take into account the duration of the
reaction time (because of primary grafting of AA
monomers) and Mohr’s salt additive.
It should be noted that the cation-exchange
adsorbents synthesized according to the above
approach have sulfonate group densities similar to
those of sulfonated polymer membranes and textiles
which have been obtained by radiation-induced
graft polymerization of styrene with the subsequent
sulfonation of polystyrene chains (0.5–3.0 mEq/g)
[4,12,20]. The main advantage of the approach pre-
sented above is that it is a one-step process of
synthesis.
4. Conclusion
Radiation-induced graft copolymerization of
sodium styrenesulfonate and acrylic acid monomers
onto nonwoven polypropylene fabrics by electron
beam pre-irradiation was studied. The influence of
grafting parameters, namely, adsorbed dose, time
and temperature of the reaction, monomer molar
ratio, and concentration of Mohr’s salt additive
on the degree of grafting was examined.
The degree of grafting from binary monomer
mixtures is considerably influenced by the adsorp-
482 S.W. Lee et al. / Reactive & Functional Polymers 68 (2008) 474–482
tion dose, monomer molar ratio and concentration
of Mohr’s salt additive in the reaction solution. It
also increases with an increase in grafting time
and temperature.
Copolymerization of acrylic acid and sodium sty-
renesulfonate monomers followed the primary
grafting of acrylic acid monomers. A few possible
mechanisms for the copolymerization process were
considered, however, further experiments are
needed to elucidate the exact mechanism of
copolymerization.
As a result of radiation-induced graft copolymer-
ization of sodium styrenesulfonate and acrylic acid
a cation-exchange PP fabric carrying two types of
functional groups (both a weak acid (carboxylic)
and strong acid (sulfonic acid) groups) was
obtained.
The total ion-exchange capacity of the synthe-
sized fabrics was determined by a backward titra-
tion method. This value, exhibiting the actual
content of acidic functional groups, varied within
3.5–5.5 mEq/g for studied fabrics with a medium
grafting degree (70–180%). The obtained parameter
is comparable or even higher than that of commer-
cially available cation-exchangers based on grafted
textiles.
The values of sulfonate group densities were
determined by adsorption of Cu2+ ions from the
aqueous solutions at low pH. The sulfonate group
density of the synthesized fabrics with medium
grafting degrees (70–220%) varied from 0 to
2.16 mEq/g depending on grafting conditions (reac-
tion time and Mohr’s salt content).
The cation-exchange adsorbents synthesized
according to the above approach had sulfonate
group densities similar to those of sulfonated poly-
mer membranes and textiles which were obtained
by radiation-induced graft polymerization of sty-
rene with the subsequent sulfonation of polystyrene
chains (0.5–3.0 mEq/g).
The main advantage of the methods presented
above is that it is a one-step process for synthesis.
Acknowledgements
This work was financially supported by the Min-
istry of Education and Human Resources Develop-
ment of South Korea (BK21 program) and by the
Yeungnam University Research Grants in 2007,
which are gratefully acknowledged.
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