International Journal of Engineering and Creative Science, Vol 1, No.

1, 2018
www.ijecs.net

Chelating Ion-Exchange and Antimicrobial

Studies of Newly Synthesized Copolymer Resin
Derived From P-Hydroxybenzoic Acid, And
Thiosemicarbazide
Dr.KamlakarNandekar*
*Department of Chemistry, G. H. Raisoni Polytechnic, Nagpur-440028

Abstract: The Copolymer (p-HBTF-I) was synthesized by condensation of p-hydroxybenzoicacid and thiosemicarbazide with
formaldehyde in the presence of 2M HCL as a catalyst at 126 ± 2 0C for 5 hrs. with molar proportion of reactants. The
copolymer (p-HBTF-I) was characterized by elemental analysis, FT-IR, UV-Visible 1H-NMR Spectroscopy. The chelating
ion-exchange property of this polymer was studied for five metal ions viz. Cu (II), Ni (II), Co (II), Zn (II), and Pb (II) ions.
The chelating ion-exchange study was carried out over a wide range of pH, shaking time and in mediaof various ionic
strengths. The copolymer possesses antimicrobial activity for certain bacteria such as B. Subtilis, ,E.Coli, S. Typhi .
Keywords: Synthesis, condensation, ion-exchange, resins.
_____________________________________________________________________________________
*Corresponding Author :Dr. K. A. Nandekar , Email: kamlakar.nandekar@raisoni.net
Ph: 07104-232318, 236102 Fax: 07104-236100 , Mob- 09371228501

_____________________________________________________________________________________________________

I. Introduction exchangers are widely used for the treatment of radioactive

The presence of heavy metals in the environment is a
cause of concern due to their acute and long term toxicity.
Cadmium, Mercury, Iron, Nickel, Lead are the hazardous
metals present in environmental area. The removal of these
metals needs certain technique; Ion-exchange is one of the
powerful techniques for this purpose. Ion-exchange has
attained the status of a unit operation in chemical
industries and has mostly replaced operations like
distillation and other traditional methods of separations.
The heavy metal ion toxicity has increased substantially
because of the use of metal ions as catalyst in various
industries. Many methods such as electrodeposition,
coprecipitation and solid-liquid extraction have been
developed for pre-concentration and removal of metal ions
[1-4]. However, the metal ion removal by chelating ion-
exchange resin using batch equilibration method has
gained rapid acceptance because of its wide variety of
sorbent phases, high degree ofselectivity, high loading
capacity and enhanced hydrophilicity [5-6]. Ion-
20
wastes from nuclear power stations [7-8].
Ion-exchange resins have attracted much interest
in the recent years due to their application in waste water
treatment, metal recovery and for the identification of
specific metal ions [9-10]. Chelating ion-exchange
properties of the resin involving poly [(2, 4-
dihydroxybenzophenone) butylene] and its polychelates
with transition metals are reported [11]. Salicylic acid
andmelamine with formaldehyde copolymer found tohave
higher selectivity for Fe3+, Cu2+ and Ni2+ ionsrather than
Co2+, Zn2+, Cd2+ and Pb2+ ions [12]. Resins synthesized by
condensation of mixtures of phenol or hydroxybenzoic
acid with formaldehyde and various amines have also been
reported [13]. The metal ion uptake capacity increases with
increasing mole proportions of the copolymer synthesized
from substituted benzoic acid [14].
The adsorption behavior of these metal ions are
based on the affinity differences towards the chelating
resins as functions of pH, electrolyte concentrations and
shaking time. The copolymer resin under investigations are
 International Journal of Engineering and Creative Science, Vol 1, No. 1, 2018
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found to be cation exchanger having both ion-exchange

group and chelating group in the same polymer matrix and
the resin can be used selectively for the purpose of
purification of waste water. One of the important
applications of chelating and functional polymers is their
capability to recover metal ions from waste solution.
In this article, we describe the synthesis of a
copolymer derived from p-hydroxybenzoic acid,
thiosemicarbazide and formaldehyde (p-HBTF-I). The
synthesized The metal ion uptake capacity of the
copolymer resin by batch equilibrium method for Co 2+,
Ni2+, Cu2+, Zn2+, and Pb2+ ions in different electrolytes,
pH range and time intervals are also examined and
reported for the first time.The copolymer possesses
antimicrobial activity for certain bacteria such as S.
subtilis, , E. coli, S. typhi have been reported [19].
Copolymer resin is characterized by elemental analysis,
spectral studies (FTIR, 1H NMR ) [15], The surface
features of the copolymer resin are established by SEM.
Fig.1: Suggested structure of p-HBTF-I copolymer
resin
formaldehyde copolymer which might be present along
II-METHOLOGY
with p-HBTF-I copolymer. The yellow color resinous
2.1. Starting materials product wasimmediately removed from the flask as soon
The entire chemical used in the synthesis of various new as reaction period was over and then purified.
copolymer resins were procured from the market and were The copolymer was purified by dissolving in 10% aqueous
analar or Fluka or chemically pure grade. Whenever sodium hydroxide solution, filtered and reprecipitated by
required they were further purified by standard methods gradual drop wise addition of ice cold 1:1 (v/v)
like thin layer chromatography, reprecipitation and concentrated hydrochloric acid / distilled water with
crystallization which are generally used for the analytical constant and rapid stirring to avoid lump formation. The
purification purpose.
process of reprecipitation was repeated twice. The
copolymer sample p-HBTF-I thus obtained was filtered,
2.2. Synthesis of p-HBTF-Icopolymer resin
washed several times with hot water, dried in air,
The new copolymer resin p-HBTF was synthesized by
powdered and kept in vacuum desiccator over silica gel.
condensing p-hydroxybenzoic acid (0.1 mol) and
thiosemicarbazide (0.1 mol) with formaldehyde (0.2 mol) 2.3. Ion-exchange property
in a mol ratio of 1:1:2 in the presence of 2 M 200 ml HCl
The ion-exchange property of the p-HBTF-I copolymer
as a catalyst at 126 0 C ± 2 0 C for 5h, in an oil bath with
resin was determined at three different variations given
occasional shaking, to ensure thorough mixing. The
below.
separated copolymer was washed with hot water and
methanol to remove unreacted starting materials and acid
2.3.1. Determination of metal uptake in thepresence of
monomers.
two different electrolytes and their different
The properly washed resin was dried, powdered and then
concentrations
extracted with diethyl ether and then with petroleum ether
The copolymer sample (25 mg) was suspended in an
to remove p-hydroxybenzoic acid- thiosemicarbazide
electrolyte solution (25 ml) of known concentration. The
pH of the suspension was adjusted to the required value
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using either 0.1 M HNO3 or 0.1 M NaOH. The suspension Where Z (ml) is the difference between actual
was stirred for 24 h at 30ºC. To this suspension 2 ml of 0.1 experimental reading and blank reading; X (mg) is metal
M solution of the metal ion was added and pH was ion in 2 ml ,(0.1 M metal nitrate solution) before uptake;
adjusted to the required value. The mixture was again and Y (mg) is metal ion in 2 ml (0.1 M metal nitrate
stirred at 30ºC for 24 h. The polymer was then filtered off solution) after uptake. By using this equation the uptake of
and washed with distilled water. The filtrate and the various metal ions by resin can be calculated and
washing were collected and then the amount of metal ion expressed in terms of millimols per gram of the
was estimated by titrating against standard EDTA copolymer.
(ethylenediaminetetraacetic acid) at the same pH
(experimental reading). The sameThe same titration has 2.3.2. Estimation of rate of metal ion uptake as a
been carried out without polymer (blank reading). The function of time
amount of metal ion uptake of the polymer was calculated In order to estimate the time required to reach the
from the difference between a blank experiment without state of equilibrium under the given experimental
polymer and the reading in the actual experiments. The conditions, a series of experiments of the type described
experiment was repeated in the presence of several above were carried out, in which the metal ion taken up by
electrolytes .Metal ion, its pH range, buffer and indicator the chelating resins was determined from time to time at
used and colourchange are given in Table 1. 30ºC (in the presence of 25 ml of 1 M NaNO3 solution). It
Table:1Summarised Procedure for EDTA Titration was assumed that, under the given conditions, the state of
equilibrium was established within 24 h. The rate of metal
uptake is expressed as percentage amount of metal ions
Summarised Procedure for EDTA Titration of cation taken up after a certain time related to that at the state of
under investigation equilibrium and it can be defined by the following
Metal pH Indicator Colour relationship:
Buffer used
Ion range used Change
Dil. Fast
Purple
Cu2+ 9-10 HNO3/Dil. Sulphone
to green The percent amount of metal ions taken up at different
NaOH* Black-F
Yellow times is defined as:
2+ Aq.
Ni 7-10 Mureoxide to
NH3/NH4CL
Voilet
Xylenol Red to
CO2+ 6 Hexamine
orange Yellow
Wine Where X is mg of metal ion adsorbed after 1 h and Y is mg
Aq. Eriochrome
Zn2+ 10 red to of metal ion adsorbed after 25 h. Then, by using this
NH3/NH4CL Black-T
blue expression, the amount of metal adsorbed by polymer after
Xylenol Red to specific time intervals was calculated and expressed in
Pb2+ 6 Hexamine
orange Yellow terms of percentage metal ion adsorbed.

2.3.3. Evaluation of the distribution of metal ions at

Note: *No buffer used therefore pH was adjusted by using
either dil. HNO3 or dil. NaOH
The metal ion uptake can be determined as:
22
different pH
The distribution of each of the five metal ions i.e., Co 2+,
Ni2+, Cu2+, Zn2+, and Pb2+ ions between the polymer phase
and the aqueous phase was determined at 30ºC and in the
presence of 1 M NaNO3 solution. The experiments were
carried out as described above at different pH values. The
 International Journal of Engineering and Creative Science, Vol 1, No. 1, 2018
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distribution ratio, D, is defined by the following moiety may be assigned due to sharp band at 2800-3200
relationship. cm-1. The sharp band displayed at 1685-1430 cm-1 may be
due to the stretching vibrations of carbonyl group (C=O) of
both as well as (C=S) moiety . The bands obtained at 1400
– 1200 cm-1 suggest the presence of methylene bridges in
the polymer chain. The weak band appearing at 750 - 780
cm-1 is assigned to C – OH bond. 1, 2, 4, substitution of
aromatic ring is recognized from the bandsappearingat
1279, 1178, 1112, cm-1 respectively[14-15].

Infrared spectra of all the newly synthesized

copolymers resins were scanned at Sophosticated
Analytical Instrument Facility, Punjab University,
Chandigarh in KBr pellet on Perkin Elmer Model 677 IR
spectrophotometer in the region 4000 to 400 cm-1.
Scanning electron micrographs of newly synthesized
copolymer resins have been scanned at Sophisticated
Analytical Instrumentation Facility, STIC, Cochin
university, Cochin.The exact morphology and structure of
copolymer resin sample was investigated by SEM.The
SEM is the ultimate tool for deposits and wear debris
analysis, particle sizing and characterization, failure
analysis, contaminant analysis and metallurgical studies.
Thus by SEM micrographs morphology of the resins
shows the transition between crystalline and amorphous Fig.2: Infra-Red Spectroscopy of p-HBTF-I
nature. When compare to the other resins these copolymer copolymer Resin
resins are more amorphous in nature, hence shows higher
metal ion exchange capacity. 3.2 NMR Spectra:
All the four copolymers viz. p-HBTF-I exhibit singlet
signals in the region 2.3 – 2.8 () ppm which are due to
III- RESULTS AND DISCUSSION: methylene protons of the Ar-CH2-Ar bridges. 1H NMR
spectra of p-HBTF-I copolymers are shown in Fig.3 and
The newly synthesized purified p-HBTF-I copolymer resin show a weak multiple signal (unsaturated pattern) in the
was found to be yellow in color. The copolymer is soluble region 6.5 to 8.5 () ppm that is due to aromatic protons .
in solvents such as DMF, DMSO and THF while insoluble Triplet signal appeared in the region 3.0 to 4.1 () ppm can
in almost all other organic solvents. The melting point of be assigned to amino proton of – C – NH – CS - linkage.
p-HBTF-I copolymer resin is 186 0C and the yield of the Intense signal appeared in the region 3.5 to 4.5 () ppm
copolymer resin was found to be 82 %. may be due to protons of methylenic bridges (CH2) of
polymer chain. Weak signal in the range of 7.5 to 8.2 ()
3.1. Infrared spectra:
ppm is attributed to phenolic –OH proton (intramolecular
A broad band appeared in the region 3500-3200 cm-1 H - bond). A medium singlet peak appeared at 2.5 to 3 ()
may be assigned to the stretching vibrations of phenolic ppm may be assigned to methyl protons of Ar – CO – CH3
hydroxyl (-OH) groups exhibiting intermolecular hydrogen group [14-15].
bonding . The presence of -NH in thiosemicarbazide

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Fig.3: NMR Spectroscopy of p-HBTF-I
copolymer Resin
3.3. Scanning Electron Microscopy (SEM):
The morphology of all the p-HBTF-I resin sample
was investigated by scanning electron micrographs at
different magnification, which is shown in Fig.4. It gives
the information of surface topography and defect in the
structure. The resin spherulites and fringed model. The
spherules are complex polycrystalline formation having as
good as smooth surface. The morphology of resin
copolymer shows also a fringes model of the crystalline
amorphous structure. The extent of crystalline character
depends on the acidic nature of the monomer. But the
photograph shows the fringed and scatted nature having
shallow pits represent the transition between crystalline
and amorphous. The resin exhibits more amorphous
characters with closed packed surface having deep pits.
Thus by SEM micrographs morphology of the resin shows
thetransition between crystalline and amorphous nature.
Fig.4: SEM of p-HBTF-I copolymer Resin
24
3.4. Ion-exchange properties
Batch equilibrium technique developed by De Geiso et al.
[16] was used to study ion-exchange properties of p-
HBTF-I polymer resin. The results of the batch
equilibrium study carried out with the polymer p-HBTF-I
are presented in Tables 1, 2 and 3. Five metal ions Cu2+,
Ni2+, Co2+, Zn2+, and Pb2+ in the formof aqueous metal
nitrate solution were used. The ion-exchange study was
carried out using three experimental variables such as a)
electrolyte and its ionic strength b) uptake time and c) pH
of the aqueous medium. Among these three variables,
twowere kept constant and only onewas varied at a time to
evaluate its effect onmetal uptake of the polymer similar to
the earlier co-workers [17-18].
3.5.1. Effect of electrolyte and its ionic strength on
metal uptake
We examine the influence of chloride, nitrate, chlorate at
various concentrations on the equilibrium of metal – resin
interaction . The amount of metal ions taken up by a given
amount of copolymer depends on the nature and
concentrations of the electrolyte present in the solution.
The results incorporated in Table. 2 shows that in the
presence of nitrate ions, the uptake of Cu2+, Ni2+, Co2+,
Zn2+, and Pb2+ ions increases with increasing
concentrations of the electrolyte. Where as the uptake of
Cu2+, Ni2+, Co2+, Zn2+ and Pb2+ ions decreases with
increasing concentration of the chloride . This may be
explained on the basis of the stability constants of the
complexes with those metal ions.This may be due to the
chloride, ion forming strong chelates with metal ions,
while the other anions i.enitrate form weak chelates. The
position of the metal chelate equilibrium is less influenced
in the presence of nitrate ions than that of chloride ions.
The amount of uptake of Co2+, Zn2+ and Pb2+ ions by the
copolymer under the influence of nitrate is higher than that
of the other metal ions. This may be due to the Co 2+,
Zn2+and Pb2+ ions form weak chelates with the anions of
the nitrate electrolytes [3- 4 ].
The amount of uptake of Cu2+ , Ni2+ , Co2+, Zn2+ and Pb2+
ions by the copolymer under the influence of chloride, ions
is lower for all the metal ions. This may be due to the Cu2+
, Ni2+ , Co2+, Zn2+ and Pb2+ ions form strong chelates with
the anions of the chloride, ions electrolytes. In addition,
the copolymer has more porosity.in its structure they can
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accommodate metal ions of specific size, easily into its 3.5.2. Estimation of the rate of metal ion uptake as a
cavities and acts as a better cation-exchanger . function of time

Table 2: Evaluation of the influence of different To determine the time required to reach the equilibrium,
electrolytes on the uptake of several metal ions a. the rates of ion absorption by p-HBTF-I copolymer resin
samples were measured for Cu2+, Ni2+, Co2+, Zn2+ and Pb2+
Metal Electrolyte Weight of metal ion ions. The term refers to the change with time when they
Conc. (mg)taken up in presence were in contact with the copolymer sample the experiment
Ion
(mole/lit) ofb results, which are shown in table 3. These results indicate
that the time taken for the uptake of the different metal ion
NaNO3 NaCl
at a given stage depended on the nature of the metal ions
2+
Cu 0.01 0.31 0.59 under the given conditions.
0.05 0.38 0.50 The experimental data, which are shown in
0.10 0.47 0.45 Table.3shows that, Cu2+, Ni2+ ions required 6 h for the
0.50 0.57 0.34 establishment of equilibrium [ 1-4] whereas Co2+, Zn2+ and
Pb2+ ions required 5 h for the establishment of
1.00 0.58 0.30
2+
equilibrium. The experimental results revealed that the rate
NI 0.01 0.16 0.43 of metal-ionuptake followed the order of Pb2+ > Co2+> Zn
0.05 0.31 0.31 2+
> Ni 2+> Cu2+ .
0.10 0.39 0.27
0.50 0.47 0.23 Table 3:Percentage of metal ion uptake b at different
time (h)
1.00 0.55 0.16
Metal Percentage of metal ion uptake b at
Co2+ 0.01 0.31 0.43 ion different time (h)
0.05 0.39 0.35 1 2 3 4 5 6
Cu2+ 30 40 51 59 84 89
0.10 0.42 0.28
NI2+ 15 24 33 39.5 56 88.5
0.50 0.54 0.24
2+
1.00 0.66 0.16 Co 37 45 54.5 68 89.5 -
2+
Zn 39 43 50.5 70.5 89.5 -
Zn2+ 0.01 0.17 0.65 2+
Pb 34 45 52.5 77 89.5 -
0.05 0.26 0.52
0.10 0.35 0.35 3.5.3. Distribution ratios of metal ions at different pH
0.50 0.52 0.24
The effect of pH on the amount of metal ion
1.00 0.74 0.17
distributed between the two phases is given in Table 4
Pb2+ 0.01 0.39 1.49 which reveals that the amount of uptake of metal ions by
the resin at equilibrium increases with increasing pH. The
0.05 0.61 1.24
study was carried out up to a definite pH value for the
0.10 0.77 0.97 particular metal ion to prevent hydrolysis of metal ion at
0.50 1.38 0.86 higher pH.
1.00 1.8 0.58 The p-HBTF-I copolymer resin takes up Pb2+ ions
more selectively than the other ions under study at all pH
values. Among the other ions taken up for the study, Cu2+
ions shows selective uptake under moderate pH values.
Further, Ni2+ , Co2+, Zn2+ ions have lower distribution over

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the pH range from 2.5 to 6.5. This can be explained as the
weak stabilization energy of the metal chelates formed
from Ni2+ , Co2+, Zn2+ ions. In the present investigation it
is observed that the order of the distribution of the metal
ions are Pb2+> Cu2+> Ni2+> Zn2+> Co2+.
The diameters for the zone of inhibitions at different
concentration against the test bacteria are given in Table 5.
The standard antibiotic disc (Gentamycine disc 5μg ⁄disc)
inhibited the growth of B. Subtilis by 8-25 mm E. Coli by
18-25 mm, and S. Typhi by 2-25 mm.

Table 4 : Distribution ratio Da of Different Metal Ions

as a Function of pHb
Metal
ion Distribution ratio of metal ion at different pH

2.5 3 3.5 4 5 6 6.5

2+
Cu 9.88 15.69 18.86 26.55 38.10 75.72 168.7 S.Typhi E. ColiB.Subtillus
NI2+
12.5 20.42 31.25 39.13 39.29 54.17 141.3 Fig.8: Antimicrobial screening of p- HBTF-I
2+
copolymer resin.
Co 7.07 10.56 13.33 37.33 51.28 44.44 90.91

Zn2+ 7.41 29.96 55.56 83.33 88.89 98.50 116.6 The results of present antimicrobial assay revealed that
Pb2+ 45.7 59.26 104.3 165.08 466.6 800 1886.4 the p-HBTF-I copolymer showed inhibitory activity
against only B.subtilis, E. coli, S. typhi the tested
4. Antimicrobial Screening of p-HBTF-I copolymer pathogens, suggesting that the presence of
resin. thiosemicarbazide group may enhances antibacterial
Biological assay depends upon a comparison of the activity (Fig. 8). As the p-HBTF-I content increases in the
inhibition of growth of microorganism by measuring the copolymer, the effectiveness of the copolymers to inhibit
concentration of the sample to be examined with the the growth of microorganism increases as expected [19-
known concentration of standard antibiotic. For the 20].
antimicrobial analysis of p-HBTF-I copolymer the agar
diffusion method was employed. During the course of CONCLUSIONS
time, the test solution diffuses and the growth of the • A polymer p-HBTF-I based on the condensation reaction
inoculated microorganisms such as B. subtilis, E. coli, and of p-Hydroxybenzoic acid and thiosemicarbazide with
S. typhi were found to be affected. The activity developed formaldehyde in the presence of acid catalyst was
on the plate was measured by measuring the diameter of prepared.
the inhibited zone in millimetres. The drug gentamycin • The p-HBTF-I resin is a selective chelating cation
was used as the standard for bacteria [19-20]. exchange polymer resin for certain metals.
• The uptake capacities of metal ions by the polymer resin
Table 5: Antimicrobial activities of p- HBTF-Icopolymer were pH dependent.
resin.  The results of present antimicrobial assay revealed that
the p-HBTF-I copolymer showed inhibitory activity
0.0625
Organism 2.0 mg MIC mg against only B.subtilis, E. coli, S. typhi the tested
To 1 mg
pathogens, suggesting that the presence of
B. subtilis - 6 2 thiosemicarbazide group may enhances antibacterial
activity .
E. coli (ETEC) - 7 2
 As the p-HBTF-I content increases in the copolymer, the
S. typhi - 5 2 effectiveness of the copolymers to inhibit the growth of
microorganism increases as expected.

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ACKNOWLEDGEMENT
Authors are thankful to the SAIF, Punjab University,
Chandigarh for carried out spectral analysis, thankful to
BIOGENICS, Hubli (Karnataka) for carried out
antibacterial screening, and also to the SICART,
Vallabhvidyanagar, Gujrat for carried out the thermal
analysis.
[17] Patel. H. J., Patel. M. G., Patel. R. J., Patel. K. H , and
Patel. R. M., Iranian Polymer Journal 17(8), 635-644
(2008).
[18] J. N. Patel., M. B.Dolia, M. B. Patel. R. M. Patel. J. Appl.
Polym. Sci. 100, 439-448 (2006).
[19] E. J. Threlfall., I.S.T. Fisher, L. Ward, H.Tschape
P.Gerner-Smidt, Microb. Drug Resist.,5, 195–199,
(1999).
[20] R. D. Walker, J. F. Prescott, J. D.Baggot ,Iowa State
University Press, 12–26(2000).

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