Desalination 310 (2013) 145150

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Desalination
journal homepage: www.elsevier.com/locate/desal

Modication of poly(glycidyl methacrylate) grafted onto crosslinked PVC with

iminopropylene glycol group and use for removing boron from water
Erdem Yavuz, Yesim Gursel , Bahire Filiz Senkal
Istanbul Technical University, Department of Chemistry, 34469, Maslak, Istanbul, Turkey

H I G H L I G H T S
A new polymeric sorbent with iminopropylene glycol functions was prepared for boron removal.
In the boron uptake experiments were performed depending on different boron concentrations and different pH medium.
Kinetics of boron sorption and regeneration of the polymeric sorbent was investigated.

a r t i c l e

i n f o

Article history:
Received 1 May 2012
Received in revised form 4 July 2012
Accepted 16 July 2012
Available online 28 August 2012
Keywords:
Dehydrochlorinated polyvinyl chloride
Boron removal
ATRP
GMA

a b s t r a c t
Polymer supported coreshell type iminodipropylene glycol functions have been shown to be efcient in
chelation with boric acid and can be used for removal of boric acid at ppm levels. Dehydrochlorinated
poly(vinyl chloride) (DHPVC) polymeric sorbent was synthesized and graft copolymerization of glycidyl
methacrylate(GMA) onto DHPVC was carried out using ATRP method. The epoxy rings in grafted PGMA
reacted with excess of ethylenediamine to give an amine containing sorbent. Reaction of the latter with
glycidol gives corresponding sorbent with iminopropylene glycol functions.
The resulting polymeric sorbent has been demonstrated to be an efcient and regenerable specic sorbent for
removal of boron in parts per million (ppm) levels. Kinetics of boron sorption and regeneration of the polymer
was investigated.
2012 Elsevier B.V. All rights reserved.

1. Introduction
Boron is widely distributed in nature and is naturally found in
minerals, plants, rocks, coal and natural waters. Boron gets released
into the environment through volcanic activity and geothermal
steam. Elemental boron is not found in the environment; in nature,
it is often present in combined forms. Boron compounds are present
in small amounts in seawater (5 mg L 1) and some in mineral
waters.
Boron is also an important micronutrient for animals and human
beings [1], but the range between deciency and excess is very narrow.
The World Health Organization denes boron level of 2.4 mg L 1 as
the non-observed effect level for drinking water. High boron levels in
drinking water can be toxic to human beings [2,3].
For boron removal, main processes that have been studied are:
(1) precipitationcoagulation, (2) reverse osmosis, (3) electro dialysis,
(4) solvent extraction, (5) membrane ltration, and (6) adsorption
(including ion exchange adsorption) [4,5]. Among these methods,
adsorption is a very useful and economical technique at low boron
concentration [4,6].
Corresponding author. Fax: +90 212 2856386.
E-mail addresses: hepuzer@itu.edu.tr (Y. Gursel), bsenkal@itu.edu.tr (B.F. Senkal).
0011-9164/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.desal.2012.07.015

Molecules with three or more hydroxyl functions tend to bind

boric acid tightly by forming either neutral boron ester or borate
complex anion with a proton as counter ion. Since hydroxyl functions
are non-reactive for common metal ions and other species in ordinary
conditions complexation of these types of compounds produces a
means of specic boron binding. Having many vicinal diol functions,
sugar derivatives such as sorbitol and mannitol are preferred as
chelating agents on polymer supports for boron uptake. In accordance
with this principle, poly(styrene)-based resin with N-methylglucamine
functions, emerged in the mid1960s [7], has been reported as
boron-specic sorbent. In the previous works, crosslinked polystyrene sulfonamide with sorbitol functions [8], N-methylglucamine
modied poly(GMA-MMA-DVB) and poly(GMAMMA-DVB) supported
iminodipropylene glycol functions as boron sorbents were synthesized
with high boron loading capacities [9,10].
Linear polymers grafted onto crosslinked polymer resin particles
offer numerous potential applications due to the combination of the
non-solubility resin and the exibility of the graft polymer side chains
as the functional group carrier.
In recent years, surface modication has been of importance to
provide chemicals with desired properties for practical applications,
though many surface modication methods have been developed
[11].

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E. Yavuz et al. / Desalination 310 (2013) 145150

The grafting from method based on atom transfer radical

polymerization (ATRP) technique has been widely used as an efcient
polymerization for preparing well-dened graft copolymers [1216].
Side chains are directly grafted from the backbone via ATRP
initiated by the pendant initiating groups on the backbone polymers.
Commercial halogenated polyolens, such as poly(vinyl chloride)
(PVC), poly(vinylidene uoride) (PVDF), poly(chlorotriuoroethylene)
(PCTFE), and their copolymers are potential ATRP macroinitiators
[17,18].
Graft copolymerization has proved to be a practical method of
overcoming a number of inadequate properties of polyvinyl chloride
(PVC). Chemical modication of the PVC provides more active side
groups at random positions along the length of the polymer chain
to form a multifunctional initiator for grafting reactions. Ghaemy
and Gharaebi [19] have studies on grafting PSt onto DHPVC.
Among the various chemical functional groups, epoxy group is one
of the most important types to be integrated into polymers. This functional group can be modied using various chemical reactions to
introduce different functional properties onto the polymeric surfaces.
They undergo ring opening reaction with various compounds like
amine groups. For this reason, polymers with epoxy groups offer
numerous functionalization possibilities.
In the present work, poly(glycidyl methacrylate) was grafted onto
partially DHPVC by using ATRP method. Epoxy group on the polymeric
sorbent was functionalized via ring opening of epoxide group by using
amine and acid. Ethylenediamine was used to obtain amine containing
polymeric sorbent. Reaction of the latter with glycidol gives corresponding sorbent with iminopropylene glycol functions. The resulting
sorbent has been demonstrated to be an efcient sorbent for removal
of boron. In this study, the kinetics of boron sorption and regeneration
conditions of the sorbent has been investigated.
2. Experimental
2.1. Materials and instruments
2.1.1. Materials
DHPVC has been prepared from PVC powder supplied from SOLVN
S.A. (suspension polymer, with a K value of 64, granule diameter
smaller than 180 m).
Glycidyl methacrylate (GMA) (Fluka), 2,2-bipyridine (Aldrich),
CuBr (Aldrich), ethylenediamine (Fluka), boric acid (Fluka), glycidol
(Aldrich) and all the other chemicals and solvents utilized were
analytical grade commercial products.
2.1.2. Instruments
Perkin Elmer 25 UVvis spectrometer was used for analytical measurements, and spectra of the resins and the sorbed chemicals were
obtained using Thermo FT-IR (with ATR) Fourier Transform Infrared
Spectrum in between wavenumbers of 6504000 cm 1.
2.1.3. Dehydrochlorination of PVC
13.5 g of PVC was dispersed in 100 mL of 10% KOH solution
containing isopropyl alcoholwater. This mixture was reuxed for
10 h. The color of the reaction mixture was changed from colorless to
dark brown during the reaction. Then, degraded PVC was ltered and
washed with excess of water, ethanol, and diethyl ether respectively.
Then, the product was dried under vacuum at room temperature. The
yield of the reaction is 9 g.
The soluble fractions in the degraded PVC were extracted with
tetrahydrofurane (360 mL) by using Soxhlet extractor for 7 h. The
unsoluble part of the product was dried under vacuum.
2.1.4. Determination of chlorine content
To determine the chlorine content 0.2 g of DHPVC was added to
the solution of 4.08 g of NaOH in 20 mL of distilled water. The

mixture was shaken for 24 h in a continuous shaker with 270 rpm.

At the end of the given time, the mixture was heated up to 60 C in
a silicon bath for 2 h to complete the HCl elimination and then cooled
to room temperature and ltered.
Analysis of the chloride ions was performed by the mercuric
thiocyanate method as described in the literature [20]. The chloride
content was found as 3.4 mmol g 1 resin.
2.1.5. Graft copolymerization of poly(GMA) onto DHPVC by ATRP method
Graft polymerization of glycidyl methacrylate was achieved through
chlorine initiation sites on the crosslinked PVC. A typical procedure is as
follows:
0.218 g (1.52 mmol) of CuBr, 0.472 g (3.02 mmol) of the
bipyridine ligand and 10 mL (0.076 mol) glycidyl methacrylate
(GMA) in an under nitrogen were successively put in a three
necked ask equipped with a reux condenser and a nitrogen
inlet.
DHPVC sample (3 g) was added to the ask and the mixture was
heated to 65 C for 16 h. At the end of the reaction period, the
reaction content was poured into 100 mL acetone to remove
homopolymer and the grafted resin was added to 10% of EDTA
solution to remove copper salt. The mixture was ltered and washed
with excess of water (300 mL) and alcohol (50 mL). Vacuum dried
sample weighed 9.0 g.
2.1.6. Determination of epoxy content
The epoxide contents were determined by pyridineHCl method
[21] as follows: 1.6 mL of concentrated HC1 solution (37%) was
added to pyridine and diluted to 100 mL. 20 mL of this solution was
boiled with 0.2015 g of GMA-gPVC polymer sample for 1 h. The
mixture was cooled to room temperature and ltered then 2 mL of
the ltered solution was titrated with 0.1 M NaOH solution. The
epoxy content of the resin was calculated with respect to the differences
between the NaOH consumptions in titrations. The calculated epoxy
content of the resin is 7.7 mmol g1 resin.
2.1.7. Modication of poly(GMA) graft copolymer by ethylenediamine
8 g of GMA-g-PVC was added to 40 mL of ethylenediamine in a
100 mL of ask. The mixture was continuously shaken with a shaker
at room temperature for 24 h, and then it was heated at 90 C in a
thermo stated oil bath for 2 h.
The reaction content was poured into water, ltered and washed
with an excess of water. The product was dried at room temperature
in vacuum 24 h. The yield was 11.0 g.
2.1.8. Determination of amine content
For determination of the amine content, 0.12 g of the polymer
sample was left in contact with 10 ml of HCl (1 M) for 24 h. After
ltration, 2 mL of the ltrate was taken and the acid content of the
solution was determined by titration with 0.10 M NaOH solution in
the presence of phenolphthalein color indicator.
The amine content of the resin was calculated with respect to the
differences between the NaOH consumptions in titrations. A total
amine content of the polymer was calculated as 6.25 mmol g 1
sorbent.
2.1.9. Modication of the amino groups with glycidol
10 g of aminated sorbent was dispersed in 30 mL of DMF. The
mixture was stirred mechanically and 6 mL (0.0904 mol) of glycidol
was added dropwise to the mixture. Stirring was continued for another
24 h at room temperature and this mixture was heated a thermo stated
oil bath for 2 h at 60 C. The mixture was ltered and washed with
excess of water and ethanol respectively. The product was dried at
room temperature under vacuum for 24 h. The yield was 12.7 g.

E. Yavuz et al. / Desalination 310 (2013) 145150

2.1.10. Boron loading capacity of the sorbent

The capacity of the sorbent was determined by batch method as
follows: 0.2 g of the sorbent sample was mixed with 20 mL of
H3BO3 solution (0.485 M) and was stirred for 24 h at room temperature. For the determination of residual boric acid content of the
ltrate, 5 mL of the ltrate was mixed with 10 mL of 0.50 M D-sorbitol
solution and titrated with 0.40 M NaOH solution (using a
microburette) in the presence of phenolphthalein as a color indicator,
as described in the literature [22].
By the difference in initial and nal boric acid contents of the
ltrate, the capacity was calculated as 2.5 mmol g 1 of the resin
sample.
Also, pH depending sorption experiments were performed in the
presence of buffer solutions.

2.1.11. Boron sorption kinetics of the sorbent

Batch kinetic experiment was carried out as follows:
0.2 g of the sorbent was soaked into 5 mL of water and left for 2 h.
Then, 90 mL of H3BO3 solution (9.7 10 4 M) was added to the
wetted sorbents at room temperature. The mixture was stirred
with a magnetic stirring bar. 5 mL of aliquots was taken and transferred to sample-bottles at appropriate time intervals using a lter
paper. Boron contents of the solutions were determined colorimetrically ( = 585 nm) using the carminic acid method) [23].
Concentrationtime plots of the solutions were given in Fig. 2.
2.1.12. Desorption of the boron from loaded sorbent samples
The boron-loaded polymer samples obtained from the capacity
measurements were dried and 0.1 g of each sample was treated
with 30 mL of a 4 M HCl solution for 24 h at room temperature and
then ltered. Boron contents of the ltrates were measured colorimetrically using the carminic acid method.
The ltrated polymer samples were washed with an excess of
water, treated for 30 min with 20 mL of a 0.1 M NaOH solution and
washed again with an excess of water. Using this procedure the
samples were almost boron-free and reusable for the next cycles.
In order to test the boron uptake activities of the regenerated
samples, sorptiondesorption experiments were repeated 5 times.
Additionally, boron loading experiments were repeated, in order to
see a change in the activity of boron sorption.

3. Results and discussion

Thermal dehydrochlorination of commercial PVC was carried out
heating in concentrated NaOH containing isopropanol 80%water
20% mixture for 6 h. This method gave a black product and soluble
polymer fraction was removed by using Soxhlet extraction with THF
(Scheme 1).
Partial dehydrochlorination of PVC generates new double bonds,
and these increase the availability of allylic chlorine atoms in the
backbone. This shows that thermal stability of PVC decreases upon
the increase in dehydrochlorination. Unstable chlorine atoms in PVC
in conjunction with suitable catalyst provide initiation sites for
grafting. Chlorine content of the crosslinked PVC was found as
3.4 mmol g 1 polymer.

Scheme 1. Dehydrochlorination of PVC.

147

In this study, coreshell types of polymers with poly(glycidyl

methacrylate) shells were obtained by ATRP method. Graft polymerization of glycidyl methacrylate can be achieved from chlorine atoms
onto crosslinked PVC (Scheme 2).
In the polymerizations [CuBr]/[L] ratio was chosen as 1/3. The
grafting percentage of PGMA onto crosslinked PVC reached to 200%
for 16 h.
The grafting percentage was determined by calculating the
percentage increase in weight using the following equation:

Grafting Percentage

h

. i
mgf m0 m0  100%

where, m0 and mgf are the weights of the sorbent before and after
grafting, respectively.
Epoxy content of the resin determined by the pyridineHCl method
was found as 7.7 mmol g1 sorbent.
FT-IR spectra of the resulting graft beads (Fig. 1a) represent strong
C\O stretching vibrations at 1726 cm 1, which indicate incorporation of the poly(glycidylmethacrylate) chains. Also, symmetric and
asymmetric vibrations of the epoxy ring are observed at 1247 and
947 cm 1, respectively.
The reaction of epoxy rings in grafted PGMA with excess of
ethylenediamine gives amine containing resin with 6.25 mmol g 1
amine functions.
Modication of the amino groups with equivalent amount of
glycidol, yields iminopropylene glycol functions (Scheme 3).
Fig. 1b shows the FT-IR spectrum of the resulting iminopropylene
glycol modied graft sorbent. The broad band in the 3334 cm 1
indicates OH stretching vibrations in the sorbent.

3.1. Boron sorptions

In the boron uptake experiments were performed depending on
different boron concentrations and different pH medium (Table 1).
Vicinal diol functions incorporated into the polymer structure act
as chelating agent for basic acid, by forming cyclic boron esters.
Boron loading capacity of the sorbent is about 2.50 mmol g 1, in
non-buffered conditions.
Another important point is, that the presence of amino groups is
essential for an efcient boron sorption. In that case, the proton liberated during the formation of the borate ester complex is captured by
the amino group.
In general, the pH of the aqueous solution affects the adsorption
behavior considerably. The equilibrium amounts of boron according
to Table 1, above pH 7, boron sorption capacity increases with
increasing initial pH.

Scheme 2. Synthesis of polymeric sorbent.

148

E. Yavuz et al. / Desalination 310 (2013) 145150

Fig. 1. (a) PGMA grafted DPVC. (b) Iminopropylene glycol modied sorbent.

Scheme 3. Preparation of iminopropylene glycole modied sorbent.

E. Yavuz et al. / Desalination 310 (2013) 145150

450

Table 1
Boron sorption characteristics of the resin at room temperatures.

400

[H3BO3], M

pH

Capacity (mmol g1)

0.485
0.485
0.485
0.485

2.0
4.0
8.0
Non-buffered
(pH 66.5)
Non-buffered
(pH 66.5)
Non-buffered
(pH 66.5)
Non-buffered
(pH 66.5)

1.20
1.76
3.00
2.50

0.121
0.060

350
300

t / qt

0.242

149

1.70

250
200

1.65

150

1.20

100
50
0
0

10

20

30

In aqueous solutions, boric acid acts as a very weak and monobasic

acid:

40

50

60

t (minutes)
Fig. 3. Pseudo-second-order model plots of adsorption of boron on the resin.

BOH3 2H2 OBOH4 H3 O

For this model, the following relation was used for the variation of
adsorbed concentration with respect to time.

where the acid dissociation constant is pKa = 9.25 [24,25].

Below pH 7, boron exists in the form of B(OH)3, where the boron
adsorption amounts are small and above pH 7, on the other hand,
the mole fraction of B(OH)3 decreases, on the other hand, B(OH)4
increases with increasing pH.
According to Table 1, boron sorption capacity increases with
increasing boron concentration.
3.2. Boron sorption kinetics of the resin
Batch kinetic experiments were performed by using highly diluted
boric acid solutions as follows: 0.2 g of the sorbent was wetted
with 5 mL of distilled water for 1 h. 90 mL of boric acid solution
(9.7 10 4 M ) was added to this mixture at room temperature.
While stirring with a magnetic bar, aliquots (2 mL) were taken at
appropriate time intervals and ltered. Residual boron contents of the
ltrates were determined colorimetrically as described above. The
concentrationtime plots were used in Fig. 2.
The kinetics of sorption is an important aspect of the process
control of removal of pollutants.
The Lagergren rst-order rate equation is one of the most widely
used equations for the sorption of solute from a liquid solution [26].


log qeq =qeq qt k1 t =2:303

where k1 is the rate constant of pseudo-rst-order adsorption (min1)

and qeq and qt denote the amounts of adsorption (mg g1) at equilibrium and at time t, respectively. The slopes and intercepts of plots of log
(qeq qt) versus t were used to determine the pseudo-rst-order rate
constant k1 and qeq.
The linear form of the equation describing the adsorption kinetics
by the pseudo-second-order model [27] is as follows:
2

t=qt 1=k2 qe 1=qe t

where qe is the amount of boron adsorbed at equilibrium (mg g1); qt is

the amount of boron adsorbed at time t (mg g1); and k2 is the equilibrium rate constant of pseudo-second-order sorption (g mg1 min1).
The rate parameters k2 and qe can be directly obtained from the
intercept and slope of the plot of t/qt versus t (Fig. 3).
The kinetic values obtained by linear regression are reported in
Table 2. According to experimental and theoretical kinetic data in
Table 2, the experimental results obtained for the adsorption of
boron on the sorbent were found to obey second-order kinetics.

0,00100

3.3. Regeneration of the sorbent

0,00095

Loaded samples were treated with 4 M HCl solution for 1 day at

room temperature. The desorption capacity of the sorbent was
found as 2.0 mmol boron/g resin.
However, second acid treatment gives boron free sorbent. In order
to test boron uptake ability of the regenerated sorbent, loading experiments were repeated at the same conditions. The capacity of the
regenerated sorbent was found to be 2.48 mmol g 1 which is very
close to the original capacity (2.50 mmol g 1).

Concentration, M

0,00090
0,00085
0,00080
0,00075
0,00070

Table 2
Pseudo-rst-order and second-order kinetics for adsorption of boron on the sorbent.

0,00065

First order

0,00060
0

10

20

30

40

time (minute)
Fig. 2. Boron adsorption kinetics of the sorbent.

50

60

Second order

qeq,exp
(mg g1)

k1 102
(min1)

qe
(mg g1)

R2

k2
(g mg1 min1)

qe
(mg g1)

R2

0.155

1.1

0.347

0.734

0.583

0.16

0.998

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E. Yavuz et al. / Desalination 310 (2013) 145150

Scheme 4. Removal of boron with the sorbent.

4. Conclusion
In this work, iminopropylene glycol modied DHPVC polymeric
sorbent was synthesized to prepare an alternative adsorbent for
removal of boron from wastewater (Scheme 4). For this purpose
graft copolymerization of GMA onto DHPVC was carried out using
ATRP method. The epoxy rings in grafted PGMA reacted with excess
of ethylenediamine to give an amine containing sorbent.
Flexibility of the side chains is expected to provide pseudo homogeneous reaction conditions and easy accessibility of the functional
groups involved. It is expected that the adsorbents have the advantage
of mobility of the graft chains in the removal of boron from aqueous
mixtures. The polymeric sorbent has a potential as an adsorbent for
removal of boron from wastewater because it can be used over a
wide pH range.
The desorption capacity of the sorbent was found as 2.0 mmol g1.
Desorption experiment was conducted with regenerated resin again
and the sorbent was desorbed completely.
The results indicated that coreshell type iminopropylene glycol
modied polymeric sorbent demonstrates greater potential for the
boron removal from water.
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