Reactive & Functional Polymers 68 (2008) 1325–1336

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Reactive & Functional Polymers

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Sulfonation of macroporous poly(styrene-co-divinylbenzene) beads:

Effect of the proportion of isomers on their cation exchange capacity
Claudio A. Toro, Raúl Rodrigo, Jorge Cuellar *
Department of Chemical Engineering, University of Salamanca, Plaza de los Caídos 1-5, 37008 Salamanca, Spain

a r t i c l e i n f o a b s t r a c t

Article history: The influence of the proportions of the meta- and para-isomers of divinylbenzene and eth-
Received 12 March 2008 ylstyrene in the degree of sulfonation of macroporous poly(styrene-co-divinylbenzene)
Received in revised form 16 May 2008 (poly(ST-co-DVB)) beads has been investigated. The first step in this work was the synthe-
Accepted 14 June 2008
sis of poly(ST-co-DVB) beads, with different porous structures, by variation of the propor-
Available online 21 June 2008
tions of cross-linking agent (%DVB) and of the volume fraction of monomers in the organic
phase (Fm) of the polymerization mixture. The next step involved transformation of the
polymeric beads obtained into cation exchange resins by means of hot sulphuric acid treat-
Keywords:
Polymerization
ment. The quantitative extent of the sulfonation reaction was evaluated by measuring the
Sulfonation ion exchange capacity (q) of each type of resin. The Design of Experiments (DOE) method-
Poly(styrene-co-divinylbenzene) beads ology was used to study the effects of %DVB and Fm on q and it was found that only the
Cation exchange resins %DVB factor exerted a significant effect on this parameter, its influence being non-linear
meta-Divinylbenzene and negative. To obtain more reliable results, a new set of experiment was performed in
para-Divinylbenzene which the range of %DVB values was expanded, covering from 25% to 80% DVB. The results
Cation exchange capacity indicated again that the influence of the %DVB factor on q was non-linear and negative;
that is, an increase of %DVB in the synthesis process led to a decrease in q. Since this effect
can be thought to be due to the hindered penetration of the sulfonation mixture into the
very cross-linked gel-type nanoparticles comprising the beads, an attempt was made to
find an interrelationship between the specific surface area (SBET) of each type of bead
and their q, trying to determine whether the sulfonation was merely a surface process.
However, it was found that not only did sulfonation of the surface of the nanoparticles
occur but also that the sulfonation agent penetrated into their interior. Taking these obser-
vations into account, it was suspected that one or more of the isomers present in the com-
mercial DVB polymerize in such a way that their sulfonation is not complete. To check this
possibility, the proportion of the DVB isomers and q were correlated The quantitative rela-
tionship found indicated that the absence of a completely homogeneous sulfonation of
poly(ST-co-DVB) beads seems to be due to an insufficient sulfonation of the benzene rings
of the para-isomers present in commercial DVB.
Ó 2008 Elsevier Ltd. All rights reserved.

1. Introduction recovery and concentration of cations) to their use as

Cation exchange resins are useful in a large number of
applications, ranging from the exchange of cations for dif-
ferent purposes in many industrial and laboratory fields
[1,2] (substitution, elimination, isolation, separation,
* Corresponding author. Tel.: +34 923294479; fax: +34 923294574.
E-mail address: cuellar@usal.es (J. Cuellar).
catalysts [1–7]. However, since each of these applications
has different characteristics, the best performance in each
one of them will only be achieved by using cation exchange
resins with properties suited to the application. The
properties of ion exchange beads, which usually have an
important effect on their performance, are their
structural characteristics and their type and degree of
functionalization.

1381-5148/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.reactfunctpolym.2008.06.010
1326 C.A. Toro et al. / Reactive & Functional Polymers 68 (2008) 1325–1336
Nomenclature
%DVB weight percentage of DVB isomers in the mono-
meric mixture
F Fisher statistic
Fm volume fraction of monomers in the organic
phase
p-value level of experimental significance of the test
q cation exchange capacity (meq/g dry resin)
qm maximum cation exchange capacity (meq/g dry
resin)
^m
q predicted maximum cation exchange capacity
(meq/g dry resin)
SBET specific surface area, calculated from the nitro-
gen adsorption isotherm (m2/g)
t Student statistic
x%DVB coded value of %DVB
Regarding their structural characteristics, ion exchange
resins are usually classified in two groups with major
structural differences: gel and macroreticular resins. Most
cation exchange resins are manufactured from spherical
polymeric beads synthesized by the procedure of suspen-
sion copolymerization [1,2], using styrene (ST) and divinyl-
benzene (DVB) as monomers. DVB is a cross-linking agent
that provides physical strength to the beads. Gel-type res-
ins made from poly(ST-co-DVB) beads usually have a DVB
content below 12% because higher percentages of DVB in-
volve a very low swelling capacity and the rate of the dif-
fusion processes in their interior is slow [3].
Conversely, macroreticular (or macroporous) cation ex-
change resins are synthesized from polymeric beads with a
very high proportion of DVB and, owing to their higher de-
gree of cross-linking, they have higher mechanical and
chemical stability than the gel type. Beads of macroporous
cation exchangers are formed by agglomerated nano-
spheres arranged in groups (affording a porous structure),
their pore size distribution being a function of the synthe-
sis conditions [8–13] of the polymeric matrix. The exis-
tence of permanent pores allows the entrance of very
large molecules, or ions, into the beads and a relatively fast
mass-transfer rate by diffusion into their interior.
With regard to the degree of functionalization, the
transformation of poly(ST-co-DVB) beads into cation ex-
change resins can be accomplished by several methods,
the one most widely used (in the case of strong cation ex-
change resins) involving the sulfonation of polymeric
beads by hot concentrated sulphuric acid [1,14–20]. This
gives rise to an aromatic electrophilic substitution reaction
and sulfonic acid groups are incorporated to the aromatic
rings. The degree of sulfonation, and hence the exchange
capacity, is an important feature of cation exchange resins
because in exchange and catalytic operations [21–23] their
performance depends on this parameter. Cation exchange
capacities, which are usually measured [1] through H+/
Na+ exchange, depend only slightly on the degree of
cross-linking of the polymer. Thus, in the case of polysty-
rene, a mono-sulfonation of each benzene ring in the poly-
mer results in a exchange capacity of about 5.4 meq/(g dry
resin in the H+ form), whereas, for poly(ST-co-DVB) resins
x%DVBxFm coded value of the %DVB  Fm interaction
xFm coded value of Fm
Xm sum of the molar fraction of the meta-isomers
Xm-DVB molar fraction of the m-EVB in the monomeric
mixture
Xm-EVB molar fraction of the m-DVB in the monomeric
mixture
Xp sum of the molar fraction of the para-isomers in
the monomeric mixture
Xp-DVB molar fraction of the p-DVB in the monomeric
mixture
Xp-EVB molar fraction of the p-EVB in the monomeric
mixture
XST molar fraction of styrene in the monomeric
mixture
with 50%, w/w, cross-linking, the exchange capacity should
decrease to approximately 4.7 meq/g owing to the increase
in the molecular weight of the polymeric structural unit.
However, in practice, reported experimental cation ex-
change capacities vary widely and are usually in the
1–5.4 meq/g range, gel-type resins showing the highest
values [22–25], while most macroporous resins have lower
values. Depending on the conditions of the sulfonation
reaction, such as temperature, the degree of cross-linking,
the reaction time and the size of the beads, different ex-
change capacities can be achieved [26–31]. Nevertheless,
the differences between gel and macroporous resins in
the values of this feature cannot always be explained in
terms of the above different conditions of the sulfonation
reaction and neither do they seem to be due to the differ-
ent molecular weight of the polymeric structural unit in
the case of beads with different degrees of cross-linking.
Since a low capacity is usually assumed to be due to a
incomplete sulfonation of the benzene rings caused by hin-
dered diffusion of the sulfonation agent into the beads, sev-
eral studies [22–24,29–31] have attempted to search for a
relationship between the cation exchange capacity of the
resins, or their catalytic activity, and some of the factors re-
lated to their manufacturing process. From the results of
those works it may be deduced that the degree of cross-
linking, the porosity, and the type of DVB isomers do have
some type of influence on the resulting exchange capacity
of cation exchange resins. Despite this, although the useful-
ness of these kinds of materials in principle depends on
their cation exchange capacity, there is lack of quantitative
studies addressing the real effects of such factors.
In light of the above, here we were prompted to seek
quantitative information aimed at facilitating the design
of processes for the synthesis of resins with predetermined
properties. Thus, in this work we report the results of the
synthesis of a set of polymeric beads made with very dif-
ferent structural characteristics, together with the results
concerning their degree of sulfonation. In particular, the
objectives of this research were (a) to determine the fac-
tors, or variables, involved in the process of synthesis of
the polymeric matrix that have a significant effect on the
final cation exchange capacity of the resins, and (b) to find
 C.A. Toro et al. / Reactive & Functional Polymers 68 (2008) 1325–1336
a quantitative interrelationship between those significant
factors and the final cation exchange capacity of the resins
synthesized. Then, the first step in this work was the syn-
thesis of poly(ST-co-DVB) beads, with different porous
structures, by changing the proportions of cross-linking
agent (%DVB) and of the volume fraction of monomers in
the organic phase (Fm) of the polymerization mixture. In
a second step the polymeric beads were transformed into
cation exchange resins by means of hot sulphuric acid
treatment. The degree of sulfonation was evaluated by
measuring the ion exchange capacity (q) of each type of re-
sin. The design of experiments (DOE) methodology was
used to study the effects of %DVB and Fm on q, and some
interrelationships have been obtained through the analysis
of the results by multiple linear regression.
2. Experimental
2.1. Materials
2.1.1. Synthesis of polymeric beads
The monomers to be polymerized were styrene (ST,
99%) and two types of commercial DVB (DVB, containing
55% and 80% DVB isomers respectively, the remainder
being 3- and 4-ethylvinylbenzene), all of which were sup-
plied by Aldrich (Madrid, Spain). The initiator, benzoyl per-
oxide (BPO, 70%, remainder water) was supplied by Aldrich
(Madrid, Spain) and was used as received. The inert diluent
(porogen) was n-heptane (HEP, synthesis grade), obtained
from Panreac (Barcelona, Spain), and the suspension agent
was poly(vinyl alcohol) (PVA, with a weight-average molar
mass of 88,000 and a degree of hydrolysis of 88%) from Ac-
ros Organics (Geel, Belgium). Both were used without fur-
ther purification. Deionised water was employed to
prepare the aqueous solutions.
2.1.2. Sulfonation of the beads
The poly(ST-co-DVB) beads were swollen in dichloro-
methane (DCM) and sulfonated with concentrated (95–
98%) sulphuric acid, supplied by Scharlau (Barcelona,
Spain). Silver sulfate, used as catalyst, was supplied by Pan-
reac (Barcelona, Spain), and was used as received.
2.2. Synthesis of polymeric beads procedure
Macroporous poly(ST-co-DVB) beads were prepared by
the suspension polymerization technique, using HEP as the
porogen. BPO was used as the initiator, and the suspension
agent was PVA. Prior to polymerization, ST and DVB were
first washed with a 10% aqueous NaOH solution to remove
the inhibitor (p-tert-butylcatechol) and then with deion-
ized water until neutralization was achieved. The reaction
was performed in a 500-mL three-necked round-bottomed
jacketed glass reactor fitted with a mechanical stirrer, a
condenser, and a thermometer. To obtain different struc-
tural characteristics, the beads were synthesized from or-
ganic mixtures with the DVB and porogen proportions
shown in Table 1. The details of the polymerization proce-
dure have been reported previously [13]. Most of micro-
particles obtained had a size between 150 and 200 lm.
1327
2.3. Polymeric bead sulfonation procedure
The transformation of the macroporous polymeric
beads into strong cation exchange resins through their sul-
fonation was accomplished following the usual procedure
for the sulfonation [1,14–20] of polystyrene beads: the pre-
cursor macroporous poly(ST-co-DVB) beads were function-
alized to convert them into cation exchange resin in 250-
mL, three-necked, round-bottomed glass reactors
equipped with mechanical stirrers, reflux condensers, and
thermometers. The reactors were loaded with 100 mL of
sulphuric acid (95–98%) and heated to 75 °C in a polyethyl-
ene glycol bath. Then, 0.02 g of silver sulfate, as a catalyst
for the sulfonation reaction, was added to the reactors
and the mixture was stirred to dissolve the solids. Follow-
ing this, a sample of macroporous beads (about 1 g), previ-
ously swollen in DCM (30 ml) for 4 h at room temperature,
was slowly added to the reactor. Since sulfonation pro-
gresses with time, the mixture was kept at 75 °C for suffi-
cient time for a steady value of the cation exchange
capacity to be reached. After the reaction time, the mixture
was sequentially: (a) poured into a beaker placed in a
freezing water bath to quench the reaction; (b) diluted
slowly, by drop-wise addition of deionised water with a
peristaltic pump; (c) vacuum-filtered in a Büchner funnel
to recover the solid products, which were washed with
deionised water to completely remove any possible resid-
ual acid. Finally, the resins were vacuum-dried at 40 °C
overnight. To achieve the maximum degree of sulfonation
under the operation conditions, for each type of micropar-
ticle sulfonation experiments were performed at different
reaction times and the cation exchange capacity was mea-
sured; that is, the sulfonation kinetics were determined.
2.4. Resin characterization
The morphology and topography of the resins before
and after the sulfonation process were studied by scanning
electron microscopy (Zeiss DSM 940 scanning electron
microscope (SEM)). The presence of sulfonic groups on
the polymer surface was also checked by X-ray energy dis-
persive (EDX) analysis.
The quantitative extent of the sulfonation reaction was
evaluated by measurement of the ion exchange capacity of
each resin, using the standard procedure for polystyrene
cation exchange resins [1,20], summarized as follows.
The sulfonated particles were first treated with an excess
amount of 1 N HNO3 to ensure complete loading of the res-
ins in the H+ form. The material was then washed thor-
oughly with deionized water to eliminate the excess of
nitric acid. Then, a known amount of wet particles was
placed in a 250 mL Erlenmeyer flask containing an excess
volume of a 0.1 N NaOH solution, and this was allowed
to stand overnight. Of the supernatant solution, 25 mL
was back-titrated with a 0.1 N H2SO4 solution, using phe-
nolphthalein as indicator, and the exchange capacity (q,
meq/g dry resin) was determined from a mass balance. In
each case, the titrations were repeated three times. The
dry-weight fraction of the wet resins was determined from
the weight loss of the resin samples at 110 °C for 15 h in an
oven.
1328 C.A. Toro et al. / Reactive & Functional Polymers 68 (2008) 1325–1336

Table 1
Experimental design: factor levels, values of the response, and effects

Experiment Factors and interaction Response, qm SBETa

number (meq/ g dry resin) (m2 g1)
%DVB Fm %DVB  Fm
Real values Coded values Real values Coded values Coded values
E1 25 1 0.5 1 1 3.56 100.0
E2 55 1 0.5 1 1 2.38 430.8
E3 25 1 0.7 1 1 3.48 50.3
E4 55 1 0.7 1 1 2.22 342.2
E5 25 1 0.5 1 1 3.62 106.9
E6 55 1 0.5 1 1 2.41 426.2
E7 25 1 0.7 1 1 3.35 53.4
E8 55 1 0.7 1 1 2.50 338.6
E9 40 0 0.6 0 0 2.64 304.8
E10 40 0 0.6 0 0 2.73 292.0
Effects on q 1.125 0.105 0.070
a
Experimental SBET values from García-Diego and Cuellar [13].

2.5. Design and analysis of experiments
The preparation of cation exchange resins requires the
synthesis of polymeric matrices followed by their function-
alization via sulfonation. Since the synthesis conditions
(factors) seem to exert a relevant effect on the final cation
exchange capacity of the resins (response), here the design
of experiments methodology [32,33] was chosen as a first
tool for the development of this work because of its useful-
ness in the determination of the existence of cause–effect
relationships. To apply this methodology, a sequence of
steps must be followed.
2.5.1. Problem identification
Different potential applications of cation exchange res-
ins require the use of resins with appropriate structural
and functional characteristics, the cation exchange capac-
ity being a very important property because of its influence
in operations involving separations and/or catalysis. In this
sense, macroporous cation exchange resins usually have a
low cation exchange capacity in comparison with gel-type
resins, but few studies have been undertaken to elucidate
the cause(s) of this. Accordingly, since the control of this
feature is important, the aim of the present investigation
is to contribute to the understanding of the interrelation-
ships between the factors involved in the processes of
manufacture of these resins and their final cation exchange
capacity, by determining which of the factors, or variables,
brought into play in the manufacture of these resins have
the most relevant effects on the final cation exchange
capacity, and also, by quantifying such effects.
2.5.2. Factor identification
Since in the manufacture of cation exchange resins
there are two clear steps (synthesis of the polymeric ma-
trix and sulfonation), the variables (factors) involved in
each step can affect the final results. While the effects of
temperature, the reaction time and bead size in the sulfo-
nation step can be readily understood, it is in the first step
when the structural characteristics of the beads are
decided, and these structural characteristics appear to af-
fect the final ion exchange capacities in a way hitherto
not fully explained.
Research carried out up to date to determine the influ-
ence of the synthesis conditions on the structural charac-
teristics of the polymeric matrices has indicated that the
main factors with a significant influence are the type and
proportion of porogen and the proportion of cross-linking
agent [13,34]. Factors such the polymerization tempera-
ture and the type and proportion of catalyst have less
effect.
Thus, to obtain beads with different structural charac-
teristics, the weight percentage of DVB isomers in the
monomeric mixture (%DVB, w/w) and the volume fraction
of the monomers in the organic phase, or monomeric frac-
tion, (Fm, v/v), were considered as the factors that should
be varied in order to study their effects on the final cation
exchange capacity.
2.5.3. Level identification
At this stage, it is necessary to select the values (levels)
of the factors at which the experiments are to be run. Since
several earlier works [8–13] have identified the range of
values of the %DVB and Fm that would permit the synthesis
of macroporous beads, the levels for the DVB concentration
and monomeric fraction were chosen within that range.
Thus, the values of %DVB selected were 55% and 25% for
the high and low levels, respectively. Regarding the mono-
meric fraction, Fm, the values were 0.7 and 0.5 for the high
and low level respectively. In principle, it was considered
that these ranges of values were sufficiently wide to unveil
the influence of the structural characteristics in the final
cation exchange capacity of the resins.
The research was initially planned as a bifactorial de-
sign, with only four experiments (experiments E1–E4 in
Table 1). These first four experiments were then replicated
(experiments E5–E8) in order to obtain an estimate of the
experimental error and a more precise estimate of the ef-
fects of the factors on the response. Additionally, two cen-
tre points were also included in the design (experiments
E9 and E10 in Table 1) with a view to checking whether
there was curvature in the effects. The results of this set
of experiments indicated the appropriateness of carrying
out additional experiments. The operation conditions of a
new set of experiments (experiments E11–E22) are given
in Table 2.
 C.A. Toro et al. / Reactive & Functional Polymers 68 (2008) 1325–1336 1329

Table 2
Additional experiments: factor levels and response values

Experiment Factors Response, qm SBET

number (meq/ g dry resin) (m2 g1)
%DVB Fm
Real values Coded values Real values Coded values
E11 25 1 0.6 0 3.71 102.0
E12 25 1 0.6 0 3.62 108.6
E13 30 2/3 0.6 0 3.20 138.4a
E14 30 2/3 0.6 0 3.30 142.7a
E15 40 0 0.5 1 2.74 363.3
E16 40 0 0.5 1 2.81 357.4
E17 55 1 0.6 0 2.38 439.0a
E18 55 1 0.6 0 2.40 434.8a
E19 60 4/3 0.5 1 2.10 ndb
E20 60 4/3 0.5 1 2.04 ndb
E21 80 8/3 0.6 1 1.78 524.1a
E22 80 8/3 0.6 1 1.85 492.1
a
Experimental SBET values from García-Diego and Cuellar [13].
b
Not determined.

2.5.4. Response identification nj  nj;center

xj ¼ ð1Þ
As indicated above, the usefulness of resins in exchange nj;max  nj;center
and catalytic processes often depends on their degree of
where xj are the coded values, and nj, nj,center and nj,max are
sulfonation, which is usually expressed in terms of their
the real, the centre real, and the maximum real values of
cation exchange capacity. Accordingly, this parameter
the range studied for the j factor, respectively.
was chosen as the response to be studied, the objective
The values of the plateau in the sulfonation kinetic
of this being to study the relationships between this
curves (Fig. 3) were taken as the maximum cation ex-
parameter and the operating conditions during bead
change capacity, qm, for each type of resin and these values,
synthesis with a view to contributing to the design of pro-
for all experimental runs carried out, are listed in Tables 1
cesses aimed at the synthesis of resins with predetermined
and 2. The tables also show the values of the specific sur-
properties.
face area, SBET, for each type of bead.

3. Results and discussion

3.3. Effects of synthesis variables on the cation exchange
3.1. SEM and EDX analyses capacity

The morphology and topography of the resins were in-
spected by SEM. The spherical morphology and smooth
topography of the macroporous beads can be seen in the
SEM micrographs shown in Fig. 1.
Complete sulfonation of the inner part of the beads may
be affected by problems of diffusion if the reaction time is
not long enough. In our experiments to check whether the
sulfonation had reached the centre of the beads, some of
them were fractured and examined by dispersive X-ray
analysis (EDX). A SEM micrograph of a halved cation ex-
change bead is shown in Fig. 2a, while Fig. 2b shows the
same particle analyzed by EDX, depicting the homoge-
neous distribution of the points with sulphur. Finally,
Fig. 2c shows the EDX spectrum.
The results for the rest of the beads also indicated that
the sulfonation had reached the centre of the beads.
3.2. Cation exchange capacity
Regarding the effect of the factors on the response, in
order to facilitate the interpretation of the quantitative re-
sults, the levels of the factors were coded, assigning a value
of 1 to the low level and a value of +1 to the high level of
the range studied for each factor, by means of the coding
equation:
From the values of the responses for the first set of
experiments (experiments E1–E10) given in Table 1, the ef-
fects of the factors and their interaction on the cation ex-
change capacity were calculated using the Yates
algorithm [33]. These values are given in the last row of Ta-
ble 1, showing that the %DVB factor has the most impor-
tant effect, followed in importance by the Fm factor, and
finally by the %DVB  Fm interaction. The variations in
the response value, when the factors change from the
low level to high level, are shown in Fig. 4. The factor hav-
ing the straight line with the highest slope is the one with
the greatest effect, while the line with the lowest slope cor-
responds to the factor with the smallest effect. Thus, the ef-
fect of %DVB is the most important and is negative; that is,
the highest value of the response occurs at the lowest level
(25% DVB) of the factor.
This behaviour is also a common experimental finding
in the case of gel-type beads, and is usually explained as
being due to the difficulty encountered by the sulfonation
agent to penetrate into very cross-linked polymeric
structures.
After the effects had been calculated, an analysis of var-
iance (ANOVA) was applied to the experimental results of
qm (experiments 1–10) with a view to establishing the sta-
tistical significance of the influence of the factors, and the
1330 C.A. Toro et al. / Reactive & Functional Polymers 68 (2008) 1325–1336
Fig. 1. SEM micrographs of the macroporous beads from experiment 1 (E1): (a) shape, (b) roughness of the surface and (c) detail of external surface.
existence of curvature in the effects. The results of the AN-
OVA, shown in the Table 3, give the values of the F statis-
tics and their corresponding p-values for each source of
variation studied (factors, interaction, and curvature).
From the values calculated for the F statistics, it may be
concluded that within the range investigated the %DVB is
the only factor that has a significant effect on the response.
Moreover, this influence is not linear because the value of
the F statistics for the curvature is higher than the tabu-
lated value (F0.05,1,5 = 6.61), where 0.05 is the level of sig-
nificance; 1 is the degree of freedom of this source of
variation, and 5 is the degrees of freedom of the error.
Having found from this first set of experiments that
only the %DVB factor had a significant effect on the re-
sponse, its influence being non-linear, it was decided to
perform a new group of experiments with the aim of veri-
fying the non-significance of the effect of the Fm factor and
also of obtaining an empirical model capable of predicting
the values of the response for a broader range of values of
the factors with greater accuracy.
In this new set of experiments, the value of Fm = 0.7
was not used because the microparticles synthesized with
this small proportion of porogen were sometimes found to
be partially agglomerated. Regarding the %DVD factor, its
range of values was expanded, this time covering from
25% to 80% DVB. The new values of both factors are given
in Table 2, and this table also shows the values of the re-
sponse. A graphic plot of the values of the factors in all
the experiments performed in this work is given in Fig. 5.
3.4. Correlation between maximum cation exchange capacity,
qm, and synthesis variables
In this new step, a multiple linear regression analysis
[33,35] was applied to all the values of qm, shown in Tables
1 and 2, to search for a response surface model able to pre-
dict the maximum cation exchange capacity of the resins
as a function of the values of the %DVB and Fm used in
their synthesis, within the range of our experimental
conditions.
 C.A. Toro et al. / Reactive & Functional Polymers 68 (2008) 1325–1336 1331

Fig. 2. Inner structure of the cation exchange resins synthesized from the macroporous poly(ST-co-DVB) beads obtained in experiment 2 (E2): (a) SEM
micrograph of a halved bead, (b) EDX analysis of the same bead, and (c) EDX spectrum.

Fig. 4. Plot of the effects of each factor on the qm response.

Fig. 3. Variation of the cation exchange capacity, q, with the reaction time
for experiments E11(s), E18 (h) and E21 (e).
^m ¼ 2:83  0:609x%DVB  0:0226xFm þ 0:0522x%DVB xFm
q
Taking into account that the curvature was found to be þ 0:099x2%DVB  0:0123x2Fm
significant, in a first attempt a model including quadratic
terms was fitted to the data. R2 ¼ 0:973; R2adj ¼ 0:965 ð2Þ
1332 C.A. Toro et al. / Reactive & Functional Polymers 68 (2008) 1325–1336
Table 3
ANOVA applied to the analysis of the effects
Source of variation Sum of squares
%DVB 2.5313
Fm 0.0220
%DVB  Fm 0.0098
Curvature 0.1040
Error 0.0539
Total 2.7211
Fig. 5. Factors and levels used in the experiments carried out in the (s)
first and (h) second set of experiments. The coded values in this figure
correspond to those used in the multiple linear regression analysis.
^m denotes the predicted value of the cation
In Eq. (2), q
exchange capacity and the terms x%DVB, xFm and x%DVBxFm
represent the coded values of %DVB, Fm, and their interac-
tion, respectively. Likewise, x2%DVB and x2Fm are the coded
quadratic terms that provide the curvature to the model.
The value of the coefficient of multiple determination, R2
of this model is close to 1, indicating that the regression
model fits the experimental data well. However, the ad-
justed coefficient of multiple determination, R2adj , suggests
that non-significant terms could have been included in
the model, because their value is insufficiently close to R2.
To determine the significance of the regression, ANOVA
was applied to the model and the results are summarized
in Table 4. The p-value for the F statistic of the regression
is close to zero, indicating that at least one of the five
regressor variables contributes significantly to this qua-
dratic model.
However, the test for the lack of fit is significant, mean-
ing that this quadratic model is not adequate to explain the
experimental data because the F statistic calculated ex-
ceeds the tabulated value (F0.05,5,11 = 3.20) where 0.05 is
the level of significance; 5 represents the degrees of free-
dom of this source of variation, and 11 refers to the degrees
of freedom of the pure error.
In light of the above, a test of the significance of the
individual regression coefficients was performed. The val-
Degrees of freedom Mean of squares F p-value
1 2.5313 234.59 0.00
1 0.0220 2.04 0.21
1 0.0098 0.91 0.38
1 0.1040 9.64 0.02
5 0.0108 – –
9 – – –
ues of the t statistic and the corresponding p-values are
shown in Table 5.
The regression coefficients are statistically significant,
with a level of significance of 0.05 if the absolute values
of their t statistics are higher than t0.025,16 = 2.47, where
0.025 is the half-value of the level of significance and 16
represents the degrees of freedom of the residual error.
Therefore, since the t statistics for the regression coeffi-
cients of Fm, %DVB  Fm and Fm2 are smaller than 2.47,
the regressor variables xFm, x%DVBxFm, and x2Fm can be elim-
inated from Eq. (2). After these regressor variables had
been eliminated, the experimental data were subjected
again to multiple linear regression analysis and the follow-
ing simplified quadratic model was obtained:
^m ¼ 2:807  0:628x%DVB þ 0:099x2%DVB
q
ð3Þ
R2 ¼ 0:975; R2adj ¼ 0:972
The value of R2 is close to 1, indicating that the regres-
sion model fits the experimental data well. Moreover, in
this case, R2adj is close to R2, meaning that non-significant
terms had not been included in the model. Also, to deter-
mine the significance of the regression, ANOVA was ap-
plied to the model; the results are summarized in Table 6.
The p-value for the F statistic of the regression is
close to zero, indicating that at least one of the two regres-
sor variables contributes significantly to this quadratic
model. Regarding the test for the lack of fit, since the F
statistic calculated does not exceed the tabulated value
(F0.05,3,15 = 3.28) it can be affirmed that the model given
by Eq. (3) fits the experimental data well and that it can
be used to predict qm at any value of the %DVB factor with-
in the range studied. The significance of the individual
regression coefficients was also checked and all of them
were found to be statistically significant.
The final model, represented by Eq. (3), again indicates
that the influence of the %DVB factor on cation exchange
capacities is non-linear and negative; that is, an increase
in the proportion of DVB in synthesis process leads to a de-
crease in the cation exchange capacity of the final resins.
As mentioned in Section 1 of this work, this effect has
been observed in earlier studies [22–24,31]. Poinescu
et al. [31] described the synthesis of cation exchange resins
by sulfonation of poly(ST-co-DVB) beads with SO3 and
studied the influence on the cation exchange capacity of
several reaction parameter (proportion of SO3, degree of
cross-linking of the beads in the range from 1% to 18%,
and the time and temperature of sulfonation) and found
that the higher the %DVB in the beads, the lower the cation
exchange capacity of the resins obtained. Also, the studies
 C.A. Toro et al. / Reactive & Functional Polymers 68 (2008) 1325–1336 1333

Table 4
ANOVA applied to the first quadratic model

Source of variation Sum of squares Degrees of freedom Mean of squares F p-value

Regression 7.8202 5 1.5640 117.21 0.000
Residual error 0.2135 16 0.0133 – –
Lack of fit 0.1436 5 0.0287 4.52 0.017
Pure error 0.0699 11 0.0064 – –
Total 8.0337 21 – – –

Table 5 tion the degree of sulfonation of the beads; they only stud-
Statistical significance of the regression coefficients of the quadratic model ied the exchange capacity, measured by the exchange H+/
given by Eq. (2) Na+, and attempted to explain their findings in terms of
Predictor t p-value the hindered penetration of the ions into highly cross-
linked polymeric structures. The work of Struck and Wid-
Constant 60.42 0.000
%DVB 19.71 0.000 decke [36] also explored the sulfonation of macroporous
Fm 0.62 0.541 poly(ST-co-DVB) beads. In this case, the aim was sulfona-
%DVB  Fm 1.46 0.164 tion of only the surface of the beads. The results were
%DVB2 4.68 0.000
explained in terms of the inhomogeneity of the cross-link-
Fm2 0.23 0.819
ing density; cross-linking density varies within the micro-
t0.025,16 = 2.47. particles, being high at the centre and very low at the
surface. The inhomogeneities were found to depend on
the synthesis parameters; in particular on the proportion
Table 6 of DVB in the copolymer. According to that work, the beads
ANOVA applied to the best quadratic model
really consist of nanoparticles fused together to form
Source of Sum of Degrees of Mean of F p-value agglomerates with spaces between them, forming a porous
variation squares freedom squares network, which affords access of the sulfonation mixture
Regression 7.7595 2 3.8798 347.57 0.000 to the centre of the beads. Thus, the sulfonation occurs first
Residual error 0.2009 18 0.0112 – – on the surface of the nanoparticles located on the outer-
Lack of fit 0.0725 3 0.0242 2.82 0.075
most part of the beads and progresses down the pores into
Pure error 0.1285 15 0.0086 – –
the centre of the beads at a rate that depends on the size of
Total 7.9604 20 – – –
the pores. Once sulfonation of the external surface of the
nanoparticles has been completed, the sulfonation pro-
gresses towards their interior with the reaction time. How-
of Ahmed et al. [24] indicate that the cation exchange ever, in that work no study about the influence of the
capacity of poly(ST-co-DVB) resins decreases when the degree of cross-linking was reported.
beads are manufactured with high proportions of DVB. From these results, it may in principle be concluded
They also found that the exchange capacity depends on that the %DVB has a negative influence on the cation ex-
the porosity of the beads, a maximum being reached when change capacity, although such influence appears to be
porosity is in the 0.3–0.4 ml/g range, owing to the faster modulated by the porosity of the particles. The influence
diffusion of the sulfonating agents through the intercon- of the %DVB has been suggested to be due to the hindered
nected permanent pores in the beads. With a similar end penetration of the sulfonation mixture into the highly
in mind, Coutinho et al. [22,23] synthesized poly(ST-co- cross-linked gel-type nanoparticles comprising the macro-
DVB) cation exchange resins and studied the influence of porous beads. However, although the experimental sulfo-
certain copolymer synthesis parameters in their exchange nation conditions were given in those works, nothing is
capacity and in their catalytic activities. After studying mentioned of studies aimed at determining the minimum
the behaviour of the resins, with different degrees of reaction time necessary to attain beads with the maximum
cross-linking and different types and proportions of poro- cation exchange capacity at the reaction temperature em-
gen agent, those authors found that the resins with the ployed. Nevertheless, taking into account that an insuffi-
highest swelling in water (that is, resins with the lowest cient time of sulfonation affords beads with a capacity
degree of cross-linking) also showed the highest cation ex- lower than the maximum at the reaction temperature, it
change capacity. They explained this assuming that in the is possible that the above conclusions are not correct.
case of the most cross-linked structures there was hin- Accordingly, in order to establish reliable quantitative
dered access (during measurement of the exchange capac- cause-effect relationships we first determined the sulfona-
ity) of the water solution to the sulfonic groups. tion kinetics of all of the particles studied in this work;
Conversely, the resins with the highest proportion of DVB some of them are shown in Fig. 3. As can be observed,
exhibited the highest catalytic activity, which was ex- the shape of the curves varies depending on the %DVB,
plained as being due to the more porous structure of the but in each case a flat plateau (maximum cation exchange
resins made with a high proportion of DVB, thus permit- capacity, qm) can be attained. Additionally, the existence of
ting easier access of the reaction mixture to the active sites. a flat plateau in the kinetic curves indicates that there is no
However, in those works [22,23] the authors failed to men- formation of sulfones with time.
1334 C.A. Toro et al. / Reactive & Functional Polymers 68 (2008) 1325–1336
3.5. Relationship between SBET and the cation exchange
capacity
Since macroporous resins are highly cross-linked, and
since there is a porous network that (as suggested in some
of the works cited above) is used by the sulfonation agent
to penetrate into the interior of the beads, it could be
thought that, owing to the difficult penetration of the sul-
fonation agent into highly cross-linked structures, sulfona-
tion would occur only on the surface of the nanoparticles
forming the beads. Whether this is the case, the degree
of sulfonation should be proportional to the specific sur-
face area (SBET) of the precursor beads (last column in Ta-
bles 1 and 2). To check this, the values of the maximum
cation exchange capacity were plotted vs. the SBET of each
type of bead. As seen in Fig. 6, the higher the SBET, the lower
the exchange capacity, indicating that not only sulfonation
of the surface of the nanoparticles occurs, but that sulfona-
tion also reaches their interior.
Having determined that sulfonation was not merely a
surface process; a second conjecture was that the degree
of penetration of the sulfonation into the nanoparticles
might be a function of the degree of cross-linking of each
of them. This could be possible if it is assumed that the
DVB monomers polymerize first, because they are more
reactive than the styrene monomers. In this case, the core
of the nanoparticles would be formed by highly cross-
linked DVB and the outer region of the nanoparticles
would be made of polystyrene, with only a small degree
of cross-linking, which could be easily sulfonated. If this
is so, the higher the %DVB, the lower the cation exchange
capacity would be. However, such an explanation cannot
be considered adequate because in fact it is possible to ob-
tain ion exchange resins from polymeric beads made with
100% DVB. Although in this latter case it could still be pos-
ited that the nucleus of the DVB nanoparticles would be
more densely cross-linked that their periphery, some
authors, working with gel-type resins [29,30,37], have
attributed the differences in cation exchange capacities to
Fig. 6. Values of qm vs. the SBET of the precursor polymeric beads.
the presence of DVB isomers in the polymerization mix-
ture, and this was the hypothesis explored here.
3.6. Correlation between the proportion of isomers and qm
Commercially available DVB is a mixture of m-divinyl-
benzene (m-DVB) and p-divinylbenzene (p-DVB), together
with a substantial amount of m-ethylvinylbenzene (m-
EVB) and p-ethylvinylbenzene (p-EVB). Table 7 shows the
compositions of the commercial 55% DVB and 80% DVB
used in the present investigation.
Some previous works [29,30] have addressed the sulfo-
nation of gel-type beads made with styrene and with pure
DVB isomers, in which the effect of m-DVB and p-DVB iso-
mers on the kinetics of the polymerization and sulfonation
was studied. In contrast, other authors [38] have only stud-
ied the polymerization kinetics of pure DVB isomers. Thus,
Wiley and Venkatachalam [29,30] synthesized gel-type
cation exchange resins from polystyrene cross-linked (2%,
4% and 8% w/w) with pure m-DVB and pure p-DVB, observ-
ing that the beads made with styrene and p-DVB were sul-
fonated (at 100 °C) faster, and at higher levels, than those
made with the meta-isomer. They concluded that taking
into account the differences in the reactivity ratio values
in the copolymerization of styrene with each isomeric
DVB, the overall effect appears to be that the copolymeri-
zation of styrene with p-DVB will result in a structure with
a tightly cross-linked nucleus to which long chains of
polystyrene are attached and in which much more pure
polystyrene may be imbedded. In comparison, the
poly(ST-m-DVB) copolymer would be expected to have a
structure in which the cross-links are more widely distrib-
uted than in the poly(ST-p-DVB) copolymer, and presum-
ably, less pure polystyrene is formed in the last stages of
the polymerization. Later [37], the same authors reported
that sulfonation kinetics depends on the swelling agent
used, because the swelling agent retained in the beads
probably renders the reaction sites more or less inaccessi-
ble to the sulfonating agent. They found that, when the
beads were swollen in dimethyl sulfoxide or in ethylene
dichloride, the para-cross-linked copolymer was sulfo-
nated more rapidly. Nevertheless, since in those works
only gel-type resins (with very low %DVB) were studied,
the difference in the exchange capacities of resins made
with different isomers was very small.
Moreover, Nyhus et al. [38] carried out a study of the
kinetics of the polymerization of pure m- and p-DVB and
found that m-DVB polymerized at higher rates than
p-DVB in the presence of toluene and 2-ethylhexanoic acid,
the monomer conversion, at the visual gel point, being
higher for p-DVB than for m-DVB.
These results indicate that the rate of polymerization of
each isomer may change, depending on the solvent or
Table 7
Isomeric composition in percentages of the two types of commercial DVB
used in the experimentation
%DVB m-DVB p-DVB m-EVB p-EVB
55 37.52 14.82 37.86 9.81
80 57.36 22.45 12.68 7.51
 C.A. Toro et al. / Reactive & Functional Polymers 68 (2008) 1325–1336 1335

whether styrene is present in the polymerization mixture.
In any case, it appears certain that if the rate of polymeri-
zation of the isomers of DVB and EVB are different and this
difference affords beads and nanoparticles with different
structural characteristics, which in turn leads to different
cation exchange capacities, it should be possible to find a
relationship between the proportion of each type of iso-
mers in the polymerization mixture and the final degree
of sulfonation.
In this sense, taking into account the lack of complete
mono-sulfonation of the benzene rings, our starting
hypothesis was that one or more of the isomers present
in the commercial DVB would polymerize in such a way
that their sulfonation could be incomplete. If this is the
case, by means of the statistical analysis of our results con-
cerning cation exchange capacities it should be possible to
determine which of those isomers, at the reaction temper-
ature, the sulfonation agent was unable to penetrate.
To perform the statistical analysis, as the dependent
variable we used the maximum exchange capacity of each
type of bead, and as independent variables the molar frac-
tions of the different isomers involved in the polymeriza-
tion (Table 8). These were designated: XST, Xm-DVB, Xp-DVB,
Xm-EVB and Xp-EVB. Following this, a multiple linear regres-
sion was performed in search of a suitable correlation
among the values of qm and the molar fractions of all the
compounds. Since in this first attempt the result was not
satisfactory, the molar fractions of the compounds were
grouped in all possible combinations and, in each case, a
linear regression analysis was performed. The best correla-
tion found was as follows:
^m ¼ 3:45  8:91X p þ 2:36X 2ST þ 2:12X 2m
q activated by the two substituents, but is less reactive be-
ð4Þ
R2 ¼ 0:990; R2adj ¼ 0:988
where XP is the sum of the molar fractions of the para-iso-
mers; Xm is the sum of the molar fractions of the meta-iso-
mers, and XST is the molar fraction of styrene.
The value of the coefficient of multiple determination,
R2, is close to 1, indicating a good fit of the regression mod-
el to the data. The R2adj coefficient is very close to R2, which
confirms the absence of non-significant terms in the
model.
In this case, ANOVA was also applied to check the ade-
quacy of the model. The results, shown in Table 9, indicate
that at least one of the variables contributes to the model.
Also, the test for the lack of fit, with a p-value of >0.05 re-
vealed that the model given by Eq. (4) was adequate for the
prediction of the values of the response within the range
(25–80% DVB) of variables studied.
The model represented by Eq (4) indicates that the sul-
fonation of styrene and m-isomers occurs to a similar ex-
tent while, in the case of the p-isomers, the negative
value of the regression coefficient suggests that, at the
operation temperature used here, their sulfonation does
not take place at all, or only does so to a slight extent.
Moreover, this negative value denotes that the presence
of the p-isomers in the polymerization mixture to some ex-
tent prevents the subsequent sulfonation of the styrene
and of the m-isomers.
These results are consistent with the rules concerning
the effects of substituents on the regioselectivity of elec-
trophilic aromatic substitution. In the case of meta-iso-
mers, in the benzene rings there are two alkyl
substituents that are ortho and para directors, whose
directing effects reinforce each other. Thus, sulfonation of
meta-isomers should take place at reinforced positions
which are ortho to one alkyl chain and para to another.
The ortho position between the two alkyl chains is also
cause it is more sterically hindered. Conversely, in the case
of the para-isomers there are no positions with accumu-
lated activating.
Additionally, taking into account that the sulfonation
agent is a polar compound and that the polymeric matrix

Table 8
Molar fraction of the different isomers involved in the polymerization

Experiment XST Xm-DVB Xp-DVB Xm-EVB Xp-EVB Xm Xp q (meq/g dry resin)

E1 0.6015 0.1510 0.0596 0.1492 0.0387 0.3002 0.0983 3.56
E2 0.0000 0.3788 0.1496 0.3745 0.0970 0.7533 0.2466 2.38
E3 0.6015 0.1510 0.0596 0.1492 0.0387 0.3002 0.0983 3.48
E4 0.0000 0.3788 0.1496 0.3745 0.0970 0.7533 0.2466 2.22
E5 0.6015 0.1510 0.0596 0.1492 0.0387 0.3002 0.0983 3.62
E6 0.0000 0.3788 0.1496 0.3745 0.0970 0.7533 0.2466 2.41
E7 0.6015 0.1510 0.0596 0.1492 0.0387 0.3002 0.0983 3.35
E8 0.0000 0.3788 0.1496 0.3745 0.0970 0.7533 0.2466 2.50
E9 0.3205 0.2574 0.1017 0.2545 0.0659 0.5119 0.1676 2.64
E10 0.3205 0.2574 0.1017 0.2545 0.0659 0.5119 0.1676 2.73
E11 0.6015 0.1510 0.0596 0.1492 0.0387 0.3002 0.0983 3.71
E12 0.6015 0.1510 0.0596 0.1492 0.0387 0.3002 0.0983 3.62
E13 0.5118 0.1849 0.0731 0.1829 0.0474 0.3678 0.1205 3.20
E14 0.5118 0.1849 0.0731 0.1829 0.0474 0.3678 0.1205 3.30
E15 0.3205 0.2574 0.1017 0.2545 0.0659 0.5119 0.1676 2.74
E16 0.3205 0.2574 0.1017 0.2545 0.0659 0.5119 0.1676 2.81
E17 0.0000 0.3788 0.1496 0.3745 0.0970 0.7533 0.2466 2.38
E18 0.0000 0.3788 0.1496 0.3745 0.0970 0.7533 0.2466 2.40
E19 0.2943 0.4065 0.1591 0.0880 0.0521 0.4945 0.2112 2.10
E20 0.2943 0.4065 0.1591 0.0880 0.0521 0.4945 0.2112 2.04
E21 0.0000 0.5759 0.2254 0.1248 0.0739 0.7007 0.2993 1.78
E22 0.0000 0.5759 0.2254 0.1248 0.0739 0.7007 0.2993 1.85
1336 C.A. Toro et al. / Reactive & Functional Polymers 68 (2008) 1325–1336
Table 9
ANOVA applied to the best correlation between the values of q and the molar fraction of isomers
Source of variation Sum of squares
Regression 6.2654
Residual error 0.0614
Lack of fit 0.0006
Pure error 0.0608
Total 6.3269
is hydrophobic, penetration of the sulfonation agent into
the polymeric matrix requires – as an a priori condition –
that the matrix must become polar through its sulfonation.
Thus, if the sulfonation of para-isomers did not to take
place, the structures formed with this isomer should be
impermeable to the sulfonation agent, which would not
be able to attack the meta-isomers or the styrene possibly
enclosed in structures surrounded by para-isomers either.
This effect could explain the negative influence of the
para-isomers in the degree of sulfonation of the beads.
The model given by Eq. (4) permits the design of syn-
thesis processes of cation exchange resins with a very
broad range of degrees of sulfonation, which may be very
useful in certain processes. Thus, taking into account that
the affinity of the resins for water depends on the degree
of sulphonation, in some catalytic processes such as esteri-
fications, where one of the reaction products is water, it
could be convenient to use resins with a low degree of sul-
fonation with a view to facilitating the desorption of water.
4. Conclusions
Under the operation conditions used here (75 °C), the
quantitative model obtained indicates that the lack of
completely homogeneous sulfonation of poly(ST-co-DVB)
beads seems to be due to a insufficient sulfonation of
the p-DVB and p-EVB isomers involved in the polymeriza-
tion mixture. These findings are consistent with the
directing effects of the two alkyl substituents in the ben-
zene rings, which in the case of the meta-isomers exert a
reinforcing effect on certain positions of the benzene
rings that facilitates the sulfonation process at those posi-
tions. In contrast, in the case of the para-isomers, the
directing effect of each substituent occurs on different
positions of the benzene rings and hence there would
be no positions with a reinforced effect. Apart from the
lack of sulfonation of para-isomers, the observed negative
effect of the %DVB on the values of q could be explained if
some proportion of the styrene and meta-isomers were
enclosed during the polymerization into structures coated
with non-sulfonated para-isomers. In these cases, since
the para-isomers are non-polar the sulfonation agent
would be unable to penetrate into the interior and the
styrene and meta-isomers enclosed in these structures
would remain unsulfonated.
Acknowledgments
This work was supported financially by the Ministerio
de Educación y Ciencia (MEC, Spain). Furthermore, the
Degrees of freedom Mean of squares F p-value
3 2.0885 475.83 0.000
14 0.0044 – –
1 0.0006 0.13 0.726
13 0.0047 – –
17 – – –
authors thank Banco Santander Central Hispano for schol-
arship granted at one of them.
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