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STUDIES ON POLY(ACRYLATE)S
CONTAINING PENDANT LIGAND WITH
8-HYDROXY QUINOLINE AZO COMPOUND
AND THEIR DIVALENT METAL COMPLEXES
BY
S. VIJAYALAKSHMI
A thesis submitted to the
PONDICHERRY UNIVERSITY
in partial fulfilment of the requirements
for the award of the degree of
DOCTOR OF PHILOSOPHY
in
CHEMISTRY
DEPARTMENT OF CHEMISTRY
PONDICHERRY ENGINEERING COLLEGE
PUDUCHERRY-605 014
MAY 2008

BONAFIDE CERTIFICATE
Certified that this thesis titled 'STUDIES ON
POLY(ACRYLATE)S CONTAINING PENDANT LIGAND WITH 8-
HYDROXY QUINOLINE AU) COMPOUND AND THEIR DIVALENT
METAL COMPLEXES' is the bonafide work of Mrs. S. Vijayalaksbmi
who carried out the research under my supervision. Certified further, that to
the best of my knowledge the work reported herein does not form part of any
other thesis or dissertation on the basis of which a degree or award was
conferred on an earlier occasion on this or any other candidate.
Place : Puducherry
Date : ab. C ' a@
Dr. S. SUBRAMANIAN
Supervisor
Professor & Head
Department of Chemistry
Pondicherry Engineering College
Puducheny 605014

DECLARATION
I hereby declare that the thesis entitled "STUDIES ON
POLY(ACRYLATE)S CONTAlNlNG PENDANT LlGAND WlTH 8-
HYDROXY QUINOLINE AZO COMPOUND AND THEIR DIVALENT
METAL COMPLEXESn submitted to Pondichcny University for the award of
Doctor of Philosophy is a record of original and independent research work done by
me under the supervision of Dr. S. SUBRAMANIAN, Professor & Head,
Department of Chemistry, Pondicheny Engineering College, Puduchcny.
Place: Puducheny
Date: 26-05-2008
S ~r[~C/;Icdlvc
(S. VIJAYALAKSHMI)

ABSTRACT
8-Hydroxy-5-azoquinoline phenylacrylate, 8-Hydroxy-5-
azoquinoline phenylmethacrylate, wm prepared by reacting
acryloyVmethacryloyl chloride with 8-Hydroxy-5-azoquinoline hydroxy
benzene. 8-Hydroxy-5-azoquinoline phenol formaldehyde was prepared by
condensing equimolar amount of 8-Hydroxy-5-azoquinoline hydroxy
benzene with formaldehyde in the presence of oxalic acid. 8-Hydroxy-5-
azoquinoline phenylacrylate/methacrylate formaldehyde macro monomers
were prepared by reacting acryloyl/methacryloyl chloride with 8-Hydroxy-5-
azoquinoline phenol formaldehyde. These monomers and macro monomers
were characterized by elemental analysis, IR and 'H-NMR spectroscopy.
The monomers and macro monomers were polymerized in DMF
medium using benzoyl peroxide as free radical initiator. The DMF solution of
the polymers containing a few drops of ammonia on treatment with aqueous
solution of Cu(II)Mi(II) ions gave the corresponding metal complexes:
poly(8H5AQPA)-Cu(II)/Ni(II), poly(8HSAQPMA)-Cu(II)/Ni(II),
poly(SH5AQP-F)-Cu(II)Mi(II), poly(8H5AQPA-F)-Cu(II)/Ni(II), and
poly(8H5AQPMA-F)-Cu(II)/Ni(II). Characterization of the polymers and
polymer-metal complexes were carried out.
The polymers were soluble in THF, DMF, DMAc, and DMSO
whereas insoluble in common organic solvents like benzene, toluene, acetone
and methanol. GPC data reveals that the molecular weight (Gw) of the
polymers is moderately high of the order of 3.72 x lo4 - 3.96 x 10~.~lemental

analysis values and 'H NMR signals an in good agreement with expected
structure of the polymers.
The IR-spectra of polymers exhibit broad bands around
3400-3000cm.' due to the intramolecular hydrogen bonded -OH
stretching,1730cm'' due to the C=O group of ester. In the case of Cu(I1)
complex, the broad band is absent due to the involvement of phenolic -OH
group in co-ordination with the metal. However, in the case of nickel complex
there is a strong absorption around 3500cm-I which does not disappear even
when the sample was heated at 150°c.~his band, therefore, has to be due to
water molecules taking part along with Ni(I1) ions during co-ordination. The
medium intense band around 1150cm"due to esteric C-0 and the band at
1570cm" is due to N=N stretching. The band around 550cm-' and 725cm"
corresponds to M-0 and M-N vibrations respectively.
The X-ray diffraction and DSC studies indicate the polymers to be
amorphous, while their metal complexes crystalline. From thermo gravimetric
analysis, it is observed that the initial decomposition (10%) for polymers is
around 100'~ and the metal complexes around 400°c, indicating superior
thermal stability of the latter to the former.
From elemental analysis it is observed that the metal ion to polymer
ligand ratio is 1:2. Diffuse reflectance studies gave bands at 14,150cm" and at
22,000crn.' for Cu(I1) and three bands 9,000,15,500, 25,225cm-I for Ni(I1)
complexes. Further evidence for the above is provided by magnetic moment
measurements 1.75 and 3.86B.M. It is noted that the above results go hand in

hand with the FT-IR data already discussed pertaming to the structure of the
complexes.
The electrical conductivity measurements reveal that polymer metal
complexes behave as insulator.
The metal ion uptake studies for all the polymers were canied out at
different pH and with different electrolytes. All the polymers have good
metal ion uptake properties.
Taking poly(8H5AQPA)-Cu(II)/Ni(II) complexes as model,
application studies were carried out. Both Cu(I1) and Ni(I1) complexes
catalyze hydrolysis of ethyl acetate to ethanol and acetic acid as well as
initiate the polymerization of N-vinyl pyrrolidone.
Cu(I1) polymer-metal complex catalyze the oxidation of cyclohexanol
to cyclohexanone in the presence of Hz02. Ni(I1) polymer-metal complex
gave negative result in this aspect. Cu(I1) and Ni(I1) were treated with 7M
HCI. These results in dechelation giving the parent polymers without any
degradation. The regenerated polymer on treatment with the metal ions forms
the complexes. The reproducibility of the above was established by repeating
the sequence several times. Thus polymerlmetal complex recyclability is
ascertained along with the stability of the polymers in acidic conditions.

ACKNOWLEDGEMENT
I wish to express my deep sense of gratitude to
Dr. S. Subramanian, Professor & Head, Department of Chemistry,
Pondicheny Engineering College, Puducheny for supervising my research
work with utmost zeal and for his useful discussions concerning the same. He
was continuous source of inspirationthroughout the tenure of the programme.
My heartfelt and profound thanks goes to Dr. T. Kaliyappan,
Assistant professor, Department of Chemistry, Pondicherry Engineering
College for his useful discussions, and constant encouragement through out
the course which can not be explained by words.
I sincerely thank Doctoral Committee members Dr. G.
Vaidyanathan Professor in Physics, P.E.C. and Dr. Bidhu Bhushan Das,
Reader in Chemistry, Pondicheny University for their useful suggestions
during the course.
My thanks are also due to my husband Mr. R Sounderarajan and
my son S. Raghu Raman for their co-operation during the period of research.
I would also like to express my sincere thanks to staff members of
Chemistry Department Dr. S. Balasubramaniam, Dr. P. Sankar, Dr. S.
Rnjagopan, Dr.(Mrs). A.B. Manjubhashini, Mr. R Sagayam, Mr. S.
Muniappan and research scholars especially to R Sankar, R Srldarane, V.
Genapathy, P. Kandasamy, V. Jayalakshmi and M. Saaidaran for their
ready assistance, whenever needed.
v-e-r"l--'
(S. '. VIJA ALAKSHMI)

TABLE OF CONTENTS
CHAPTER No. TITLE PACE No.
ABSTRACT
LIST OF TABLES
LIST OF FIGURES
LIST OF ABBREVIATIONS
1. INTRODUCTION 1
1.1 CLASSIFICATION OF POLYMER-
METAL COMPLEXES 3
1.2 STRUCTURE AND REACTIVITY 13
1.3 POLYMER- METAL COMPLEXES-
A SURVEY 14
1.4 APPLICATIONS OF POLYMER-
METAL COMPLEXES 41
1.5 PHYSIC0 CHEMICAL PROPERTIES 58
1.6 CHARACTERISATION OF FUNCTIONALISED
POLYMERS AND THEIR METAL
COMPLEXES 74
1.7 SCOPE AND OBJECTIVES 78
2. EXPERIMENTAL 80
2.1 MATERIALS 80
2.2 PURIFICATION OF CHEMICALS 80
2.3 PREPARATION OF 8-HYDROXY-5-
AZOQUINOLINE HYDROXY BENZENE 82
iv
x
xii
mi

CHAPTER No. TITLE PAGE No.
2.4 ACRYLOYL CHLORIDE
2.5 METHACRYLOYL CHLORIDE
2.6 MONOMER SYNTHESIS
2.7 POLYMERISATION
2.8 PREPARATION OF POLYMER-METAL
COMPLEXES IN DMF MEDIUM
2.9 CHARACTERIZATION
2.10 APPLICATION STUDIES
3. RESULTS AND DISCUSSION
3.1 SYNTHESIS OF MONOMERS
3.2 SYNTHESIS OF MACROMONOMERS
3.3 CHARACTERISATION OF MONOMERS
AND MACROMONOMERS
3.4 SYNTHESIS OF POLYMERS
3.5 PREPARATION OF POLYMER-METAL
COMPLEXES
3.6 CHARACTERISATION OF POLYMER
AND POLYMER-METAL COMPLEXES
3.7 STRUCTURE OF POLYMER-METAL
COMPLEXES
3.8 ELECTRICAL CONDUCTIVITY
3.9 APPLICATION STUDIES
4. SUMMARY AND CONCLUSION
REFERENCES
LIST OF PUBLICATIONS

LIST OF TABLES
TABLE No. TITLE PAGE No.
Resins for the extraction of metals from natural
water system
Analytical methodology for the separation of
selected metal ions using functionalized
chelating resins
Physico-chemical characteristics of monomers
Yield of the polymers I-V
Yield of the polymer-metal complexes Ia-Vb
Solubility parameters of polymers I-V
Intrinsic viscosity and molecular weights of
polymers I-V
Elemental analysis data of polymers I-V
Elemental analysis data of polymer-metal
complexes Ia-Vb
IR spectral data of polymer and polymer-metal
complexes
'H-NMR spectral data of polymers I-V
T, and TGA of polymer and polymer-metal
complexes I-IIIb
T, and TGA of polymer and polymer-metal
complexes IV-Vb
Magnetic moment of polymer-metal complexes
Ia-Vb
Conductivity of polymer-metal complexes Ia-Vb

TABLE No. TITLE PAGE No.
Percentage metal uptake of polymers at
different pH
Percentage metal uptake of poly(8HSAQPA)
with different electrolytes
Percentage metal uptake of poly(8HSAQPM.4)
with different electrolytes
Percentage metal uptake of poly(8HSAQP-F) with
different electrolytes
Percentage metal uptake of poly(BH5AQPA-F) with
different electrolytes
Percentage metal uptake of Poly(8HSAQPMA-F)
with different electrolytes
Elemental analysis data of polymer-metal complexes
la and Ib
Magnetic moment, diffuse reflectance spectral data
of polymer-metal complexes Ia and Ib

LIST OF FIGURES
FIGURE No. TITLE PAGE No.
Synthesis of 8-hydroxy-5-azoquinolinehydroxy
benzene 94
Preparation of (meth)acrylate monomers 94
Preparation of formaldehyde resin 95
Synthesis of macromonomers and polymers 96
Synthesis of polymers 97
Synthesis of polymer-metal complexes 101
Viscometric results of polymers 105
IR spectra of poly(8HSAQPA)(a),
poly(8HSAQPA) -Cu(II)@) and poly(8HSAQPA)
-Ni(II)(c) 110
IR spectra of poly(8HSAQPMA)(a),
poly(lH5AQPMA) -Cu(II)@) and
poly(8HSAQPMA)-Ni(II)(c) 11 1
IR spectra of poly(lHSAQPF)(a),
poly(8HSAQPF)-Cu(I1) 112
@)and poly(8HSAQPF)-Ni(II)(c)
IR spectra of poly(BHSAQPAF)(a),
poly(8HSAQPAF) Cu(Il)(b) and
poly(8HSAQPAF)-Ni(II)(c)
IR spectra of poly(8HSAQPMAF)(a),
poly(SH5AQPMAF)-Cu(II)(b) and
poly(8HSAQPMAF)-Ni(II)(c)
'H-NMR spectrum of poly(lH5AQPA)

FIGURE No. TITLE PAGE No.
'H-NMR spectrum of poly(8HSAQPMA)
'H-NMR spectrum of poly(8HSAQPF)
'H-NMR spectrum of poly(8HSAQPAF)
'H-NMR spectrum of poly(8HSAQPMAF)
DSC curves of poly(BHSAQPA)(a),
poly((8HSAQPA)-Cu(II)(b) and
poly(SH5AQPA)-Ni(II)(c)
DSC curves of poly(BHSAQPMA)(a),
poly(8HSAQPMA)-Cu(n)Cb) and
poly(8H5AQPMA)-Ni(U)(c)
DSC curves of poly(SHSAQPF)(a),
poly(8H5AQPF)-Cu(II)@) and
poly(8HSAQPF)-Ni(II)(c)
DSC curves of poly(SHSAQPAF)(a),
poly(8HSAQPAF)-Cu(II)(b) and
poly(8HSAQPAF)-Ni(II)(c)
DSC curves of poly(8HSAQPMAF)(a),
poly(8H5AQPMAF)-Cu(II)(b) and
poly(8HSAQPMAF)-Ni(II)(c)
TGA curves of poly(8HSAQPA)
(a), poly(8H5AQPA)-Cu(II)(b) and
poly(8H5AQPA)-Ni(II)(c)
TGA curves of poly(8HSAQPMA)
(a),poly(8HSAQPMA)-Cu(II)(b) and
poly(8H5AQPMA)-Ni(II)(c)
TGA curves of poly(8H5AQPF)
(a),poly(8H5AQPF)-Cu(II)(b) and
poly(8HSAQPF)-Ni(II)(c)

FIGURE No. TITLE
TGA curves of poly(BHSAQPAFXa),
poly(8H5AQPAF)-Cu(II)@) and
poly(8H5AQPAF)-Ni(1IXc)
TGA curves of poly(8HSAQPMAF) (a),
poly(8H5AQPMAF)-Cu(II)@)
and poly(8HSAQPMAF)-Ni(II)(c)
DRS spectra of poly(8H5AQPA)-Cu(I1)
(a) and poly(8HSAQPA)-Ni(I1) @)
DRS spectra of poly(8H5AQPM~)-Cu(I1)
(a) and poly(8HSAQPMA)-Ni(I1) @)
DRS spectra of poly(8HSAQPF)-Cu(I1)
(a) and poly(lH5AQPF)-Ni(1I) (b)
DRS spectra of poly(8HSAQPAF)-Cu(I1)
(a) and poly(8HSAQPAF)-Ni(I1) (b)
DRS spectra of poly(8HSAQPMAF)-Cu(I1)
(a) and poly(8HSAQPMAF)-Ni(I1) (b)
X-ray diffiactogram of poly(dH5AQPA)
(a), poly(8H5AQPA)-Cu(II)(b) and
poly(8HSAQPA)-Ni(II)(c)
X-ray diffractogram of poly(BH5AQPMA)
(a), poly(8HSAQPMA)-Cu(II)(b) and
poly(8HSAQPMA)-Ni(II)(c)
X-ray diffractogram of poly(8HSAQPF)
(a), poly(8H5AQPF)-Cu(II)(b) and
poly(8H5AQPF)-Ni(lI)(c)
xiv
PAGE No.

FIGURE No. TITLE PAGE No.
X-ray dihctogram of poly(8HSAQPAF)(a),
poly(8HSAQPAF)-Cu(II)(b)and
poly(8HSAQPAF)-Ni(II)(c)
X-ray diffractogram of poly(8HSAQPMAF)(a),
poly(8HSAQPMAF)Cu(II)(b) and
poly(8HSAQPMAF)-Ni(II)(c)
Structure of polymer- metal complexes
Percentage metal uptake of poly(8HSAQPA)
at different pH
Percentage metal uptake of poly(8HSAQPMA)
at different pH
Percentage metal uptake of poly(8HSAQPF)
at different pH
Percentage metal uptake of poly(8HSAQPAF)
at different pH
Percentage metal uptake of poly(8HSAQPMAF)
at different pH
Metal uptake in different contact time for the
polymer poly(8HSAQPA)
Structure of polymer-metal complexes

a.u
AO
ATA-SG
B.P.0
BM
CCl4
cnl-'
Oc
6
DMAc
DMF
DMG
DMSO
DRS
DVB
EMK
g
hr
PM
mg
min
ml
mm
mmol
NDSA
NIBABN
NVC
LIST OF ABBREVIATIONS
- Arbitrary units
- Angstromunit
- Aurin Tricarboxylic Acid-Silica Gel
- Benzoyl peroxide
- Bohr magneton
- Carbon tetrachloride
- Per centimeter
- Degree centigrade
- Delta
- Dimethylacetamide
- N,N-Dimethylformamide
- Dimethylglyoxime
- Dimethyl sulfoxide
- Diffise Reflectance Spectroscopy
- Divinylbenzene
- Ethyl methyl ketone
- Gram
- Hour
- Magnetic moment
- Milligram
- Minute
- Millilitre
- Millimeter
- Millimole
- 2-Naphthol-3,6-Disulphonic
Acid
- N-isobutyloyl -L-asparagine
- N-Vinyl Carbazole
xvi

OCA
PAN
PAOS
PLH
PLL
PNMABN
PVP
SEM
SSA
THR
X
XPS
- Octanoic Acid
- Pyridylazo-naphthol
- Polflamino-organosilane)
- Poly(L-histidine)
- Poly(L-lysine)
- Poly(N-methacryloyl-L-aspmpine)
- Poly(Viny1pyridine)
- Scanning Electron Microscope
- Sulphosalicylicacid
- 4-(2-thiazolylazo) resorcinol
- Chi
- X-ray Photo Electron Spectroscopy

CHAPTER 1
INTRODUCTION
Polymer science has emerged as active discipline of materials
science. This field impinges on areas of commodity, engineering and
speciality polymers thereby stimulating interest all over the globe in
exploiting newer domains. One such branch that has emerged is polymermetal
complexes comprising an organic polymer containing co-ordinating
sites, complexed with metals. This is of relatively recent origin and an
interdisciplinary approach taking into its fold areas viz; chemistry,
metallurgy, environmental and material sciences.
A co-ordination compound may be defined as a compound
containing a central metal atom or ion to which are attached molecules or ions
whose number usually exceeds the number corresponding to the oxidation
number or valency of the central atom or ion. The groups that are bound to the
central metal atom or ion in a symmetrically oriented fashion through coordinate
or co-ordinate covalent bond are called ligands. For a long time, the
co-ordination compounds were considered as a rare and special class but
subsequently have become versatile.
The chemistry of co-ordination compounds is at present undergoing
rapid development in diverse disciplines. The impetus for progress in this area
has resulted from its many biological applications. Metal chelates play an
essential role in the chemistry of living matter viz; chlorophyll's (Mg(I1)
complex) and haemoglobin (Fe(I1) complex) (Vernon and Seely 1966). A

large number of metal proteins and other metal complexes of biological
importance have been studied.
Apart from biological field, co-ordination compounds play an
essential role in chemical industries. For instance in 1963, the Nobel Prize in
chemistry was awarded jointly to K.Zeigler of the Max Plank institute in
Germany and G.Natta of the University of Milan in Italy, for developing a
new metal complex catalyst containing aluminium and titanium. This catalyst
revolutionized in the polymer synthesis.
Work on co-ordination complexes has revealed that heterogeneous
systems possess more economical potentials and advantages over
homogeneous systems. Polymer-metal complexes belong to the former case.
The high molecular weight polymer-metal complexes work as storage houses
for solar energy. Efficient chemical conversion in storage of solar energy will
be difficult with the homogeneous systems. Molecular design using a
heterogeneous system would therefore be important. Fundamental research on
the photoreaction in the micro heterogeneous environment provided by the
polymer has been reported (Mathur et al 1980).
Metalloenzyme is a kind of polymer-metal complex present in
nature, where metal ions are surrounded by a giant protein molecule of
definite three dimensional structures. A typical example of such a
metalloenzyme whose structure has been determined is plastocyanin (a kind
of blue-copper protein) (Coleman et al 1978). In plastocyanin the copper ion
shows a distorted tetrahedral structure and is co-ordinated by methionine's
sulfur atom which is not normal in usual low molecular weight metal
complexes. This abnormal co-ordination behaviour and the hydrophobic
environment around the copper ion brought by giant protein molecule cause
unusual redox behaviour of the copper ion. Generally, the protein in
metalloenzyme not only decides the chemical structure, but also causes an

allosteric effect through conformational change of its polymer chain. In order
to throw light upon the effect on the protein surrounding the metal ion,
intensive studies of the structure and catalytic activity of synthetic polymer
metal complexes were initiated.
Polymer-metal complexes have been of interest to many researchers
during the past three decades in the light of their potential applications in
diversified fields like, organic synthesis (Samuelsonl963),waste water
treatment (Bolto 1980), hydrometallurgy (Vernon 1976), polymer drug grafts
(Ramirez and Andrade 1974), recovery of trace metal ions (Coleman 1975)
and nuclear chemistry (Schmuckler 1965). In addition, they are also used as
models for enzymes (Banazak et a1 1965 and Palumbo et al 1978).
A polymer-metal complex is composed of synthetic polymer and
metal ions, wherein the metal ions are bound to the polymer ligand by a
co-ordinate bond. A polymer ligand contains anchoring sites like nitrogen,
oxygen or sulfur obtained either by polymerization of monomer possessing
the co-ordinating site or by a chemical reaction between a polymer and a low
molecular weight compound having co-ordinating ability. The synthesis
results in an organic polymer with inorganic functions. The metal atoms
attached to polymer backbone are bound to exhibit characteristic catalytic
behaviour, which are distinctly different from their low molecular weight
analog.'Indeed, many synthetic polymer-metal complexes have been found to
possess high catalytic efficiency, in addition to semi conductivity, heat
resistance and biomedical potentials.
1.1 CLASSIFICATION OF POLYMER-METAL COMPLEXES
The pdlymer-metal complexes may be classified into different
groups according to the position occupied by the metal, which is decided by
the method of preparation. The methods include complexation between a

ligand function anchored on a polymer matrix and metal ion, reaction of a
multifunctional ligand with metal ion and polymerization of metal containing
monomers.
1.1.1 Complexation of polymeric ligand with metal ion
The analytical applications of chelating polymer depend on many
factors. Normally a metal ion exists in water as a hydrated ion or as a complex
species in association with various anions, with little or no tendency to
transfer to a chelating polymer. To convert a metal ion into an extractable
species its charge must be neutralized and some or all of its water of hydration
must be replaced. The nature of the metal species is therefore of fundamental
importance in extraction systems. Most significant is the nature of the
functional group and/or donor atom capable of forming complexes with metal
ions in solution and it is logical to classify chelating polymers on that basis.
This method of classification is not meant to imply that these systems are
mutually exclusive. Indeed, some polymers can belong to more than one
class, depending on experimental conditions. Among the many ligands
introduced 8-acryloyloxyquinoline is one of recent origin (Kaliyappan et al
1999).
This kind of polymer-metal complex is prepared by the chemical
reaction of a polymer, containing ligands with metal ions. Typical examples
are listed in Table 1.1 Generally, the reaction of a polymeric ligand with a
metal ion or a stable metal complex, in which one co-ordination site remains
vacant, results in different structures that can be grouped into pendant and
interlintra molecular bridged polymer-metal complexes(Tsuchi& and Nishide
1977).

1.1.1.1 Pendant metal complexes
A pendant metal complex is one in which the metal ion is attached
to the polymer ligand function, which is appended on the polymer chain.
Based on the chelating abilities of the ligands, pendant complexes are
classified as monodentate or polydentate polymer-metal complexes.
The monodentate pendant polymer-metal complexes are formed
from a metal ion or stable metal complex in which the central metal ion is
already masked with low molecular weight ligands except for one
co-ordinating site that remains vacant. In these complexes, the effects of
polymer chains are exhibited clearly and the polymer-metal complexes rue
often soluble in water or in organic solvents, since it contains few bridged
structures which reduce the solubility.
Even if the metal ion or the metal complex has more than two labile
ligands, it is often possible to form a monodentate complex by selecting an
appropriate reaction condition. When the reaction between the metal ion or
metal complex, the probability of the substitution of the second labile ligand
of the metal ion would be very less, resulting in a predominantly monodentate
type (Kurimura et al 1971).
When the polymer backbone contains multidentate ligands the
co-ordination structure of polymer-metal complex can be represented in
Scheme-1 .
L : Coordinale otom (or ) grarp, M = MIW ion

Polydentate ligands often results in the formation of stable metal
complexes with bridged structure (I) (Pittman et a1 1971).
Most of the chelating resins come under this category. These are
characterized by their relatively well defined co-ordination structure. Here the
effect of the polymer chain is more predominant (Pittman et al 1971).
1.1.1.2 Interlintra-molecular bridged polymer-metal complexes
When a polymer ligand is mixed directly with metal ion, which
generally has four or six co-ordinate bonding sites, the polymer-metal
complex formed may be of the intra-polymer chelate type or inter-polymer
chelate type as shown in Scheme-2.

The co-ordination structure in this type of polymer-metal complex is
not clear and it is often difficult to distinguish between intertintra-molecular
bridging. Thus it is not easy to elucidate the polymer effect in studying the
characteristics of the polymer-metal complexes. Intra-polymer metal complex
is sometimes soluble, while inter-polymer metal eomplex results precipitation
of the linear polymer-metal complexes as exemplified by poly(acrylic acid)-
Cu(I1) complexes (Tsuchida et al 1974).
1.12 Complexation of multifunctional ligands with a metal ion
Co-ordination polymers have been used since before restored
history, though not recognized as such until recently. For instance, the tanning
of leather depends on the co-ordination of metal ions with the proteins which
make up the hide. These protein-metal ion complexes resist bacterial attack
for weathering which befall non-tanned animal skins. Metals bound to other
natural polymers including proteins, affect numerous enzymatic and
membrane interactions (Vallee et al 1978).
A low molecular weight compound with multifunctional ligands on
both ends of the molecules grows into a linear network polymer. The polymer
chain is composed of co-ordinate bonds and the ligand is the bridging unit as
per the following representation (Scheme-3).
Multifunctional ligands capable of forming this type of coordination
polymers are classified into linear co-ordinated polymers and
network co-ordinated polymers (Parquet).

Linear co-ordinated polymers can be of two types. In one case the
polymer chain is composed of bifictional ligand and metal ions as
exemplified by copper complex of poly(thiosemicarbazide)(II) (Tomic and
Campbell 1962 and Donaruma et al 1979).
In the other case a simple compound or ion can function as a
bridging ion giving rise to a polymeric structure, as in the case of copper
complex of poly(wamino acid)s(III and IV) (Palumbo et al 1978).
N-CH
1'9
Parquet polymers are flat, netlike organic macromolecules in which
a metal is completely enmeshed. This type of polymer-metal complex is
formed by 'template reaction' between two functional groups of the ligand
induced by their' co-ordination to metal ions, resulting in the following
chelated type metal complexes (Scheme -4).

L= Co-ordinating atom or group M=Metal ion
Polyphthalocyanato copper(I1) (V) and polyporphyrinatocopper(II)
(VI) complexes are the most common examples.
Polyphthalocyanato copper(I1) complex is formed by the reaction of
pyromellitic dianhydride, cupric chloride and urea in the presence of a
catalyst at 180°C.The complex varies from green to black in colour and has
molecular weights up to 4000. Polyporphyrinato copper(I1) complex is
formed by the reaction of copper(I1) acetylacetonate with tetracyanoethylene
at 200°C under vaccum(Sharpe 1976).These polymers are of interest because
of their thennal stability, potential electrical properties and similarities to
haemoproteins. .

1.13 Polymerisation of metal containing monomer
These types of polymer-metal complexes are known for their clear
co-ohnation structure. Polymerisation occurs by radical or ionic initiation to
form a polymer of high molecular weight as depicted below (Scheme-5).
Cu-complex with Schiff base ligand containing vinyl group (VII)
has bsen mported (Tsuchida et al 1974).

VII
Methacrylate monomers can co-ordinate with amines
Co(I1I)complexes to form cis-dimethacrylato-tetramineCo(II1) perchlorate
(VIII) and methacrylato-pentamineCo(I1) perchlorate(1X). Homo and
co-polymerization of these polymer-metal complexes with methacrylic acid
have been carried out using redox initiators (Osada1975).

1.2 STRUCTURE AND REACTIVITY
Although various extensive investigations on polymer-metal
complexes have been reported, most of the complexes are too complicated to
be discussed quantitatively due to the non-uniformity of their structure. These
compounds include not only 'complexes of mammolecules' but also the
structurally labile 'metal complex'. Before detailed information can be
obtained about the properties of polymer-metal complexes, especially about
the reactivity and catalytic activity, their structure must be elucidated. A
polymer-metal complex having a uniform structure may be defined as
follows:
1. The structure within the co-ordination sphere is uniform i.e. the
species and the composition of the ligand and its configuration
are identical in any complex unit existing in the polymer-metal
complex.
2. The primary structure of the polymer ligand is known.
If the structure within the co-ordination sphere is identical in a
polymer-metal complex and a monomeric complex, their reactivity ought to

e the same even though the complex is bound to a polymer chain. However,
it is clear that the reactivity is sometimes strongly affected by the polymer
ligand that exists outside the co-ordination sphere and surrounds the metal
complex. The effects of polymer ligands can be explained in terms of two
factors:
1. The steric effect, which is determined by the conformation and
density of the polymer ligand chain,
2. The special environment constituted by a polymer ligand
domain.
Hence it is possible to prepare polymer-metal complexa having
different end use applications by varying the polymer chain, nature of the
ligand and the metal ion (Tsuchida et al 1977).
13 POLYMER-METAL COMPLEXESA SURVEY
Polymers containing the metal as part of a pendant or substituent
group may be formed when a complex possessing functionalized ligands
undergoes polymerization. The most widely studied complexes are vinyl
metallocene and their derivatives, formed through radical polymerization of
vinyl monomer containing the transition metal ions (X and XI)
(Pitbnm1977).

When a 'naked' metal ion is added to a solution of a polymer ligand
such as poly(acry1ic acid),poly(vinyl alcohol),poly(ethyleneimine) or
poly(vinylpyridine), a polymer chelate is rapidly formed (Tsuchida and
Nishide 1977).
The radical polymerization of copper complex with Schiff base
ligand containing the vinyl group has been reported (Tomono and Tsuchida
1974). Nishikawa and Yanada (1964) have synthesized the organocobalt
compounds containing vinyl groups (XI1 and XIII), which could not be
homopolymerised. However, they were copolymerized with styrene. The
reaction and photodecomposition of these polymers were also studied and
compared with those of monomeric organocobalt complexes and Vitamin BIZ.

One of the advantages of incorporating metal ions into polymer
supports is exemplified by a set of titanocene complexes. Soluble titanocene
complexes have poor hydrogenation catalytic activity because of the
formation of dimers. Attachment of titanocene to 2% cross-linked resin
produced a resin complex that showed only 15% catalytic activity in
comparison with homogeneous complex. In contrast to this, attachment of the
same complex to a 20% cross-linked polymeric ligand produced a catalyst 60
times more active than homogeneous catalyst (Grubbs and Kroll 1971). The
equilibrium situation of complex formation between a polymer and a labile
metal ion viz. Cu(ll), Ni(ll), Zn(ll), or Co(II), gave information about the
characteristics of the polymeric ligands(Greger et al 1955).
Davankov and Rogozhin (1974) prepared the polymer containing
L-proline units by the reaction of a chloromethylated
st~mcdivinylbcnzme copolymer with amino group of L-Roline. The
L-Proline rain in the presence of Cu(I1) ions displayed a much higher affinity
to the D-amino aci& 'than to L-enantiomers i.e, the L-isomers of alanin, valin,
leucine and mline resins than did their D-enantiomers, thus affording their
sfwation.

HO- C =O
Sevendir and Mirzaoglu(l994) synthesized new metal complexes,
bis-(amino-R-glyoxime)~ and poly(amidoxime)s with Cu(II),Ni(II) and
Co(II).Cu(lI) complex was shown to be square planar while Co(I1) and Ni(I1)
complexes octahedral with water molecules as axial ligands.
Bajpai et a1 (1993) prepared a poly(ethy1ene aspartate)(PEA) by
melt condensation of D,L-aspartic acid and ethylene glycol. PEA containing
pendant amino and carbonyl groups in its repeating cham was used as the
polymeric ligand for complexation with metal ions viz. Cu(II), Ni(II), Co(II),
Mn(II), Zn(II), Cd(II), Mg(II), Pb(I1) and Hg(II).Complexation was found to
be effective in DMSO. The resulting complexes were coloured solids,
possessing high thermal stability.
The modification of polystyrene-2% divinylbenzene with
2,2'-dipyridylamim afforded an immobilized chelating system. A number of
transition metal complexes of the polymer were prepared and competitive
binding studies conducted to demonstrate the versatility of the system. A
unique selectivity for Fe(II1) in organic media was observed in metal ion
mjxture(Kratz and Hcndricker 1986).
Mohapatra (2003) synthesized I-bisbidentate and 1-bistridentate
adye ligands and their metal complexes.

Cone shaped poly(az0methine) crystals by polycondensation of
4-aminobmzaldehyde and studied on the morphology control of intractable
polymers during solution polymerization, and succeeded in preparing the
whiskers of poly(poxybenzoyl) and other aromatic polyesters by
polymerization in liquid parafin. These whiskers tin formed by the reaction
induced crystallization of oligomers duiing solution polymerization. The
polymer chains are along the linear axis of the whiskers and they show single
crystal nature. This morphology and chain alignment is desirable to endow the
essential properties for industrial materials such as organic reinforcements
(Kimura et al2003).
Gigy Abraham et a1 (2003) studied the photo induced conductivity
of polyvinyl esters and polyesters with azochromophores in the polymer
backbone. The photoinduced changes in conductivity of polyvinyl esters
having pendant azobenzene groups and polyesters with azo groups in the
polymer backbone are described. Reversible photoeffect increase in
conductivity was observed in all cases. A reasonable explanation has been
offd for the photoeffect on conductivity.
8-hydroxyquinoline terephthalate Ni(I1) and Cu(I1) complexes were
synthesized by Mishra et al (2002). These terephthalates are known in
industry f a their polymeric heat and chemical resistant and tolerant nature.
Besides industrial and biological significance mixed ligand chelates have their
theoretical and chemical importance.
Rakcsh K.Sha (2001) developed a green analytical method for
&paration and precncentration of trace amounts of copper from
aqueous sampl~cs using aurin tricarboxylic acid-immobilized silica
gel(ATA-SG).Considering the selectivity and strong interaction of ATA
towards ooppa, the conditions were optimized for the uptake of copper from

the aqueous solutions. Molecular modeling of ATA also performed on ATA
immobilized silica gel.
Panish et al (1975) synthesized chelating resins from 8-
hydroxyquinoline and formaldehyde and resorcinol,-pnd stuked its swelling
properties. A study of the rate controlling factors has led to the synthesis of
modified resins with high exchange rates, suitable for rapid separation of
individual metal ions from mixture on columns.
Michael et al (2007) synthesized 8-hydroxyquinoline-guanidine-
formaldehyde terpolymer by using the monomers of 8-hydroxyquinoline,
guanidine and formaldehyde and elucidated the structure on the basis of IR,
'H-NMR, and calculated the activation energies and thermal stabilities.
The metal ion uptake behaviour of formaldehyde condensed resins
of phenolic schiffs bases 4,4'-diaminodiphenyl and 4,4'-diamino
diphenylmethane with o-hydroxy benzaldehyde were utilized for the removal
of metal ions like Cu(II), Ni(II), and UO(I1) from dilute aqueous solutions.
The pnsence of spacer group like -CH2 unit in the schiff s base adds an
advantage sites towards metal ion recovery and consequently attributed to the
higher metal ion uptake percentage (Dey et a1 2004).
Roy et al (2004) synthesized a new chelating polymer through the
co-polymerization of styrene and maleic anhydride in the presence of divinyl
benzene as the cross-linking agent (XV). This chelating matrix has a high
resin capacity for metal ions such as Cr, Fe, Ni, Cu and Pb.

The chelation properties of 4hydroxyacetophenone and its
substituted derivatives have been extensively studied. A copolymer prepared
by condensation of 4-hydroxyacetophenone and oxamide with formaldehyde
in the presence of an acid catalyst proved to be a selective chelating ion-
exchange copolyme~ for certain metals. Chelating ion exchange properties of
this copolymer were studied for ~e)', cu2+, ~ i~*, co2+, zn2+, cd2', pb2+ and
Hg2' ions. A batch equilibrium method was employed in the study of the
selectivity of metal-ion uptake involving the measurements of the distribution
of a given metal ion between the copolymer sample and a solution containing
the metal ion. The study was carried out over a wide pH range and in media
of various ionic stxmgths. The copolymer showed a higher selectivity for ~ e"
ions than for co2', zn2', CU", ~i", cd2+, pb2+ and Hg2' ions (Gurnule et a1
2003).
The chelation behaviour of Mannich-type polymers, poly[8-
hydroxyquin@ipcrazineN,N-diyl-bis methylene and poly[8-hydroxyquin
(piperazinc N,N -dimethyl ethylene diamine-N,N- diyl-bis methylene)] to
trivalent lanthanide metal ions were studied and the metal ion uptake of these
polymm was achieved at pH W and perchlorate as the counter ion
(Ismail et al2003).
(2~xylatophcnyl~)~ldoximato triphenyl phosphine
platinum (11) wns prsparrd by Sangib Ganguly (2004). The enhanced intuust
of the platinum carboxylatm due to their anti-blastoma activity led us to

synthesise square planar platinum(I1) complexes using a tridentate ligand
containing carboxyl group in conjuction with azo and oxime function.
Metal ion uptake properties of polystyrene supported chelating
polymer resins functionalized with glycine, hydrox-+nzoic acid, Schiff base
and diethanolamine has been studied. The effects of pH, time and initial
concentration on the uptake of metal ions have been studied. The uptake of
metal ion depends on pH. The resins are more selective at pH 10 for Pb(I1)
and Hg(II),whereas at pH 6 they are found to be Cd(I1) and Cr(V1) selective.
The resins are recyclable and are therefore employed for the removal of heavy
metal pollutants from industrial waste water (Ravikumar reddy et al2003).
Samal et a1 (2002) reported the synthesis of two phenol
formaldehyde type resins by condensing phenolic Schiff base of o-hydroxy
acetophenone and 4,4'-diamino diphenyl ether with formaldehyde and
fuhldehyde respectively. The resins were used for the preconcentration
and separation of Cu(l1) and Ni(I1) ions from aqueous solutions. These resins
are used in column operation study for Cu(I1) ions (XVI).
The polystyrene anchored Schiff base was obtained fm 4-amino-5-
m~~3-methyl-l,2,4~amlc,3-formylsalicylic acid and chloromethylated

polystyrene and complexed with metal ions like CU", z?, MO", cd2+and
studied their geometry (XVII) (Kumar et al2003).
XVII
A series of monomers were prepared by reacting (meth)acryloyl
chloride with 2,4-dihydoxy benzophenone, 2,4-dihydroxy benzaldehyde and
2,4-Qhydroxy acetophenone. The monomers were polymerized and
complexed with Cu(II)/Ni(II) metal ions and characterized (XVIII). These
polymer-metal complexes initiated the polymerization of N-vinyl pyrrolidone.
Cu(l1) complexes were found to catalyse the oxidation of cyclohexanol to
cyclohexanone in the presence of H202 (Kaliyappan et a1 2003, and Sankar
et al 2008).
xwn
X= H20 for Ni(I1)

Poly(2-hydroxy-4-methacryloyloxy acetophenone semicarbazone),
poly(2-hydroxy-4-acryloyloxyacetophenonte) and poly(2-hydroxy4
methacryloyloxy acetophenoneoxime) were synthesized and complexed with
various metal ions. The polymer metal complexes were synthesized by the
reaction of the metal acetates with the polyker and characterised
(Thamizharasi et al 1999).
Rivas (2001) synthesized polychelates of poly(maleic acid) with
Cu(II), Ni(II), Co(II), and Zn(II).Elemental analysis, as well as magnetic,
spectral and thermal properbes in addition to electrical conductivities of the
chelates wen investigated and possible structures have been assigned to the
polychelates.
The complexes of Cu(II),Co(II), and Zn(I1) with ligosalicylaldehyde
were synthesized. Due to the groups of -OH and -CHO in its structure
oligosalicylaldehyde has the capability of co-ordination with different metal
ions (Mart et a1 2004) (XIX).
XIX
nYce new &ordination polymers have been p@ by
hydrothermal reaction of squaric acid pyrazine and the metal halides by
Nathcr et a] (2003). In their crystal structwes the metal atoms are
co-ordinatd by four watm molecules and two pyrazine ligands within slightly

distorted octahedral structure. The pyrazine ligands connect the metal atoms
via N,N' coordination to linear chains which are connected via hydrogen
bonding.
Poly(thiofurfural) was prepared from &I aqueous solution of
furfuraldehyde, saturated by bubbling hydrogen sulfide for 2 hours. The use
of this resin is to uptake specific metal ions from aqueous solution. In metal
industry refining of some metals takes place in strong acidic solution and the
presence of other metals as impurities provokes remarkable disadvantages and
introduces a negative ecologic impact from residual industrial water
(Damascen0 et al2002).
Chloromethylated polystyrene with divinylbenzene (3%) has
been functionalized through-NH-CH2- bond with bis(2-aminophenyl)
disulphide(XX). The resulting chelating resin has been characterized by
elemental analyses, infrared spectra and metal ion uptake capacity. Using
batch equilibrium technique, the sorption capacities of both As(II1) and A m
were determined and they show strong adsorption at pH 4.5. The effect of the
presence of coexisting ions have also been examined. The sorption and
desorption cycles have been examined using a column packed with the resin
without any loss of column performance which indicate the possibility for its
reuse. The developed column technique has been used for the removal of
arsenic species from natural water (Mondal et al2002).

Rirradiation grafhng technique was employed for graft
polymerization of the polyglycidyl methacrylate chains onto the
polypropylene backbone. The incorporation of the sulfonate groups via ring
opening of the epoxy groups of poly(GMA) graft chains was fulfilled by
reacting the GMA grafted sample with ~a~~~,.~or~tion
properties of the
synthesized adsorbent towards cuZtions in aqueous solution (pH 3.8) were
investigated (Bondar ct al2004).
2,1-dihydroxyacetophenone was treated with acryloyl chloride and
polymerid to get poly(2-awtyl-6hydroxyphenyl acrylate). The polymer
metal complexes were obtained with the aqueous solution of Cu(II)Mi(II)
with the polymer. The polymer metal complexes were characterized by FT-IR
and the results revealed that the ligands are co-ordinated through the oxygen
of the keto group and oxygen of the phenolic -OH group with the metal ions.
The electronic spectra and magnetic moment of polymer-metal complexes
showed an distorted octahedral and square planar structure for Ni(I1) and
Cu(I1) complexes respectively. The X-Ray diffraction studies revealed that
the polymers are amorphous and polymer-metal complexes were crystalline.
The thermal stability and glass transition temperature of the polymer-metal
complexes w m found to be higher than that of polymer (Nanjundan et a1
2005).
Polycondensation method is based on the capacity of some
monomeric wganic ligands to react with aldehydes forming polymeric
sorbents. Some times cross- linking agents (phenol or resorcinol) are used
(Schemed). In the same way chelating resins based on 8-hydroxyquinoline,
irninodiadc wid, ad derivatives of hydroxy acetophenones have been
synthesized The propetty of chelating sorbent to react with metallic ions
certain fivorablc conditions is determined by the nature of the

functional groups andlor donor atom (O,N,S) capable of forming chelate
rings(Bilba et al 1998).
Scheme - 6
The sorption of water vapor into the polyelectrolyte complex of
poly(acry1ic acid)ipoly(4-vinyl pyridine) has been investigated. The
interaction of water with specific polymer site plays an important role in the
sorption. The large amounts of water incorporated by the expansion can not
be dispersed homogeneously in the network, and indicate clustering tendency
(Hirai et al 1989).
Poly@iperazinylphosphorimine) was prepared and complexed with
Cu(II), Ni(II), Cd(II), Mg(I1) and Ca(I1) metals in neutral aqueous medium.
The polymer was treated with model emuent and the efficiency of the
polymer was tested using AAS quantitatively (Kumaresan et a1 2003).
N,N-bis(acety1 acetone)-o-phenylene diamine cobalt@) Schiff base
complex of polymer bound analogue have been prepared and characterized
for their structure and catalytic activity. The spectral and magnetic
measuremetits have suggested a square planar structure for cobalt(I1) complex
both in homogeneous and heterogeneous state (Gupta et a1 2003).
PoIy[N,N' bis(dimethy1 silyl) ethylene diamine] was pnpared from
ethylene diamine and (CH,)fiiCl2 and treated with metal ions and the
conductivity measurements have been canied out (Arafa Isam 2003)
(Sch-7).
5

(Et3)N
n(CH3)2 Sic12 + n NH2CH,CH,NH2-- [(CH,)2S~CH2NH]n
Toluene
I
Poly(1-vinylimidazole-co-methyl methacrylate) copolymers were
obtained from copolymerization of 1-vinylimidazole, and methylmethacrylate
and complexed with Cu(I1) and characterized by various physical and
chemical methods (Wu et a1 2003).
A new water soluble polyethyleneimine-N-methyl hydroxamic acid
was synthesized and complexed with various metal ions and its selectivity of
Fe(lI1) have been investigated over Th(IV).The binding properties of these
polymers have been evaluated using both potentiometric and spectrophoto-
metric methods (Bisset et al2003).
Cross-linked polystyrene-6-glycines were carried out and correlated
with the nature of cross-linking agent with polymer support. The metal uptake
properties were with the following order. Cu(I1) > Cr(II1) > Mn(II1) > Co(I1)
> Fe(1II) > Ni(I1) > Zn(II).The extent of metal uptake by various cross linked
systems varied with the nature of cross linking agent. The catalytic activities
of these complexes w m investigated towards the decomposition of H202.
With increasing rigidity of the cross-linking agent, the catalytic activities
d@xead (Jw et a1 2003).
Poly(2-hyd10~y4~loylox~hewne fddehyde) was
Prrparsd froRn a mixture of 2-hydroxy4methacryloyloxy~~etophenoneoxime

and 37% formdin solution and then polymerized using benzoylperoxide as
free radical initiator.An aqueous solution of Cu(II)/Ni(II) acetate was added
drop wise, to get polymer-metal complexes. These complexes found to
catalyse the ester hydrolysis and oxidation of phenol and also initiate the
polymerization of N-vinylpyrrolidone (XXI) (Kaliyappan et al 1994).
Membrane permeation combined with complexation was
tested for radioactive processing purpose. Complexing agents such as
poly(ethyl&e), poly(acrylic acid), poly(acty1ic acid amide) were tested.
The variation of the decontamination factor with different pH of the feed
solution, & c4mccntrations of alkali metals were determined. All p l p m

show the highest ability of binding cobalt ions in the vicinity
of pH 7 (Zakrewska et al2002).
Water insoluble resin poly(2-aqlamide-2-methyl-1-p~opane
sulfonic acid-c&vinyl pyndine) through a radical polymerization was
synthesized by Rivas et al (2003). The metal ion retention properties were
studied by batch and column equilibrium procedures for Hg(II),Cu
(II),Cd(II),Zn(II) etc. The retention of Hg(I1) from a mixture of ions was
greater than 90%, and also studied the interactions between the metal ions
and water soluble polymers and their applications through their liquid phase
polymer based retention technique, which combines the use of water soluble
polymer and membrane ultrafiltration.
Graft copolymers and networks of gelatin were synthesized with
three acrylamides(acrylamides,2-acrylamido-2-methyl-l-propane sulfonic
acid and N-isopmpyl acrylamide) by using a redox initiator. Sorption of ~ e~',
CT*, and CU" ions from their aqueous solutions was studied on selective
hydrogels. Structural aspects of hydrogels also determine the quantum of
metal ion uptake (Chauhan et al2003).
Balasubrarnaniam et al (2005) synthesized the polymeric ligands by
condensation of thiosemicarbazide with the appropriate substituted
acetoacetanilide. These ligands react with RuCI3(PPh3, to give hexa
co-ordinated Ru(1ll) complexes. The ligands and their complexes have been
tested for invitro growth inhibitory activity against E.Coli by using the disc
difiion method. From the results it is concluded that all the complexes
exhibit moderate activity against all species of bacteria. The complexes are
more toxic than their parent ligand.
Atstphi Sugh et al (1979) synthesized macro reticular polystyrene
basad chelating rmin with oxime and diethylamino hctional groups. The

esin is stable in acid and alkaline solutions, no decrease in nitrogen content
or capacity for sorption of Cu(I1) is observed when it is exposed to 3M HCI
and 1M NaOH for 7 days. The resin has higher capacity for Cu(I1) than for
other metal ions tested and the time required for 50% uptake of Cu(I1) is
2.OmmoYg at pH 6. In a column operation, quantitative recovery of Cu(I1) is
achieved by elution with 1M HCI and the resin can used repeatedly.
Samal et al (1999) synthesized the chelating resin by condensing
phenolic Schiff bases derived from 4,4'-diamino diphenyl sulfone and
o-hydroxy acetophenone with formaldehydeIfurfUraldehyde. The polymeric
Schiff bases were found to form complexes readily with transition metal ions
[Cu(II) and Ni(II)]. The resins and complexes were characterized by usual
analytical method. The effect of contact time, pH, temperature, the size of the
adsorbent and the concentration of the metal ion solution on the metal uptake
behaviour of the resins were studied.
Aganval et al (2004) synthesized a PVC-based sensor for Nd(II1)
ions based on chelating inorganic ion-exchange resin [tetracycline-sorbed
zirconium(1V) tungstiphosphate TCZWP] as an electm active material. The
sensor exhibits a nemstian response for Nd(II1) ion over a wide concentration
range. The detection limit has been found to be IX~O-~M. The proposed
membrane sensor reveals good selectivity for Nd(II1) with regard to other
trivalent lanthanide metal ions and could be used in the pH range 3-7 as well
as in the partially non-aqueous media. The sensor has also been successfully
used as an indicator.
Pardcshi a al (2002) prepared the Schiff bases [N-2-hydroxy-I-
naphthaldehyde]-3-~ub&tuted aniline. The solubility constant of their
complexes with l&thanide(n) ions have been determined and 3&0.1°C
potentiometrically in 600/ov/v dioxandwater mixtwe and 0.1M NaC104 ionic

strength. The lanthanidc h m 1:l andl:2 complexes with all the Schiff bases
and the trend in logk values show a break at Gadolinium.
Marcu et al(2003) prepared some novel transition metal complexes
with azomethine containing siloxanes and their polyesters and characterized
by spectroscopic methods.
The ion exchange study of poly[(2,4-dihydroxy benzophenone)
butylene] was checked by batch equilibration method with selected metal ions
Cu(II),Ni(II),Fe(III), and UOz (VI) at varying electrolyte concentration, pH,
and time It is found that, resin can be used as an ion-exchanger
(Joshi et a1 2006).
Salih (2002) synthesized a polymer containing 1,4,8,11 -tetraaza-
cyclotetradecane with acryloyl chloride. The affinity of the polymeric
material for transition metal ions was used to characterize the polymeric
structure, and to test the adsorption-desorption of the selected ions
[Cu(II),Ni(II),Cd(II),Pb(lI)] from aqueous media containing different amounts
of these metal ions (5-800 ppm) at different pH values(2-8). It was found that
the adsorption rates were high and the adsorption equilibrium was reached in
about 3Omin.
Salem et al (2004) synthesized two new chelating polymers
poly[8-hydroxyquinoline-5,7-diyl(piperazine-N,N'-bis methylene)] and
poly[8-hydroxyquinoline-5,7-diyl (N,N1-dimethylethylenediamine
N,Nf- bismethylene)]. The chelation properties of these polymers towards the
divalent metat ions M~~',C~~',CU~' were studied as a function of contact time
and pH; the use of pipcrazine as a spacer group was found to considerably
innease the capacity-and selectivity towards divalent metal ions.

A wide range of Cu(I1)-polyamine complexes have been
investigated by EPR and electronic spectroscopy. The polyamims involved as
ligands range from diarnines to tetraamines so that a wide range of complexes
having very different equitorial ligand field strengths have been investigated
(Barbucci et al 1976).
Gurnule et al (2002) synthesized terpolymer resins by the
condensation of salicylic acid and melamine with formaldehyde, 4-hydroxy
acetophenone and biwet with formaldehyde in the presence of acid catalyst
The chelating properties of this polymer were studied for CU~',N~~',CO~~,Z~~+
ions. A batch equilibrium method was employed in the study of the selectivity
of metal ion uptake involving the measurements of the distribution of the
given metal ions between the polymer sample and a solution containing the
metal ion. Chelating properties of this resin have also been studied for metal
ion uptake over a wide pH range and in media of various ionic strength.
Patel et al (2004) synthesized acrylic copolymers with different feed
ratios of 8-quinoloyl methacrylate with methyl methacrylate by free radical
polymerization, and studied the metal ion uptake capacity using different
metal ion solutions under different experimental conditions. Due to the
presence of pendant ester bound quinolyl group, the copolymers are capable
of adsorbing the tested cations from their aqueous solutions.
A chelating phenol-formaldehyde polymer, poly(salicylaldoxime
3,s-diylmethylene) was synthesized and characterized by Ebraheem et a1
(1997). The sorption properties of the resin towards various divalent metal
ions wm studied as a function of pH and contact time. The resin has high
selectivity towards cu2+ ions and showed fast rates of metal ion uptake.

Nakajima et a1 (2006) studied the mechanism of copper adsorption
by polyvinyl polyanylate (PVPA) using ESR and magnetic mearmrements.
The ESR spectrum of Cu(I1) ion in PVPA are axial type with tetragonally
distorted octahedral symmetry. The absorption peaks originated from
Cu(l1)-Cu(l1) dimer was also observed.
Gitzel et al (1986) studied the electron transfer reaction between a
polymer- bound Fe(II1) porphyrin and polymer bound Mn(1I) porphyrin
(XXII) and reported that polymer chains play a role on the same
Trimellitic anhydride and pyromellitic dianhydride have been
polywndmsad with Cu(I1) phenonthline complex as a comonomer in the
Presence of anhydrous zinc chloride under selective conditions (Biswas and
Mukhcrjee 1995). -The% polycondensates failed to initiate the cationic
~ol~msrizati~n of N-vinyl carbazole(NVC), which was explained as due to

steric mtriction faced by the bulky NVC moiety inhibiting access to the
metal centres which remain co-ordinated and surrounded by phenonthroline
groups.
Polymeric benzene tricarbonyl chromium complexes were
synthesized by radical copolymerization of benzyl acrylate tricarbonyl
chromium with styme and by a reaction of dimethylaminotricarbonyl
chromium with poly(styrene-co-acrylic acid). The polymeric chromium
complexes gave transparent films and on UV irradiation under nitrogen led to
dinitrochromium. A predominant feature of the polymeric dinitrogen
complexes was their extraordinarily high stability in air compared with the
corresponding low molecular analogs (Pittman and Martin 1973).
Europium and terbium salts of methacrylic acids (MA) and octanoic
acid (OCA), were prepared and fluorescence spectroscopy of these polymer
under Wlvisible excitation was investigated. The fluorescence intensity of
the rare-earth metal ion increased with increasing rare-earth metal ion
contents. Further ionic aggregates existed in terbium octanic polymeric
systems (Bank et a1 1980).
Patel et al (1994) synthesized a series of new cation exchangers
based on the monomer, N-(3-hydroxy4acetyIphenyl-maliemide) by addition
polymerization. Ion exchange studies showed the possibilities of the use of
these polymers in the selective separation of several important metal ions.
Rm-wh metal [Dy(lIl), Er(III), Eu(II1) and Sm(III)] salts of
copolymers of methylmethacrylate-methacrylic acid, stymeacrylic acid,
I-vinyl naphthalene-acrylic acid and 1-vinylanthracene-styrene acrylic acid
were prepad and their fluorescence intensity were studied. The Er(II1)
polymer complex system displayed typical concentration quenching
behaviow d n g maximum at 4-5 wt% of Eu(II1) and decreasing with

further increase in Eu(II1) contents, suggesting that the ionomer contains ionic
aggregates (Busev a al 1981).
Porous poly(hydroxamic acid) chelating resin was prepared by the
reaction with poly(ethylacry1ate) cross-linked with divinyl benzene and
hydrophilic cross-linking agent and hydroxylamine. 'This resin showed better
metal extraction properties and faster adsorption rate than those cross-linked
with divinyl benzene alone. Alkali treatment enhanced the binding rate for
metal ions because of the formation of other chelating ligands or micropores
(Lee and Hong 1995).
Complexation of palladium(I1) with poly(N-methacryloyl-L-
asparagine) (PNMAB~) and N-isobutyloyl-I-asparagineO\nBABN) was
reported by Lekchiri et a1 (1987). Both formed 1N complexes involving one
carboxylate and one secondary amide nitrogen at low pH. On the other hand,
at higher pH NIBANBN gave a 2N complex involving the primary and
secondary amide groups, while PAMACN gave a 2N complex involving two
carboxylate and two secondary amide groups of two different side chains of
the polymers.
A solid phase technique for thin film preparation of polynuclear
transition metal complexes such as Russian blue and magnus green salt on a
solid matrix of Nafion membrane was reported by Honda et al (1989). This
paved a new way for the production of solid state electrochemical devices.
Water soluble acrylamide polymers were prepared by gamma
radiation. These polymers were tested on copper and magnesium sulphate
solution for uptake of Cu(I1) and Mg(I1) ions. It was found that the ion uptake
depends on the pH value and the polymer concentration (Siyam and Hanna
1994).

Okamato ct al(1981) investigated the binding properties of trivalent
metal ions to polyelectrolyte through Tb(II1) luminescence studies. Tb(II1)
was condensed with poly(acrylic acid) and poly(methacry1ic acid). It was
found that the metal ion binding site was equivalent over a wide range of
Tb(II1) polymer ratios. Further, the number of solvent molecules co-ordinated
by Tb(II1) in the various polymer complexes ranged between 3.5 and 4
molecules of water of hydration.
Thamizharasi and Venkata Rami Reddy (1992) prepared poly(2-
hydroxy-4-methacryloyloxyacetophenone) and its Cu(I1) and Ni(I1)
complexes. Elemental analysis of polychelates suggested a metal-ligand ratio
of 1:2 and all the polychelates were poor electrical conductors.
Anchoring the imidazole ligand bis-(imidazole-2-yl)methylamino
methane onto poly(glycidylmethacrylate-cc-trimethylpropane trimethacrylate)
by a ring opening reaction of pendant group with the secondary mine group
of the ligand, resulted in a highly Cu(I1) selective hydrophilic resin. The batch
extraction experiments showed a very high selectivity in the pH range 1.1-6.0
for Cu(1l) over Ni(II), Co(II), Zn(I1) and Cd(I1) as chloride salts in buffered
solutions (Van Berkel et a1 1995).
Catalysis of the solvolysis of organophosphorous esters by polymers
of aliphatic amines, imidazole, pyridine, 2,2'-bipyridine and their
Cu(I1)-complexes was using diisopropyl flourophosphate as a mcdel
substrates. The greatest catalytic activity was exhibited by Cu(I1) complexes
of polymers containing the 2,2'-bipyridine group (Bao and Pitt 1990).
Ganeshpure et al(1989) reported the epoxidation of alkene with
iodosylkmzcne cata)y$cd by polymeric Schiff base chelatts, in which metal
ions, Mn(lI), Cr(1II) and Fe(III), were anchored on polymeric Schiff s base

chelates (XXIII) for the epoxidation of alkenes were compared using styrene
and norboranes as substrates. Mn(I1) complex was superior to Cr(II1) and
Fe(II1).
HoaH.c
- - +
OHC CHO
X
Teranishi et al (1994) found that the surface area of polflstyrene)
based chelate resin functionalized by tridentate ligand can increase by four
orders of magnitude by complexing with multivalent cations such as Fe(III).It
was reported further that the change in specific surface area, which is an
important factor to apply the chelate resin-metal complex to surface
dependent functions, such as catalyst support and gas absorbent, greatly
depends on the co-ordination structure of metal ions in the chelate resin.
A new homopolymer derived from ci~arnaldehyde and
2-substituted aniline and its Cu(II), Ni(II), Co(II), Zn(II), Cd(1I) and Hg(II)
complexes were synthesized, characterized and their antimicrobial activity
demonstrated (Adelz et a1 1993).
Huang Chuch-Jung et al (1991) synthesized a series of polyamideirnide
metal chelate films by transition metal ions [Ag(I), Cu(II), Ni(I1) and
CO(II)] mixed with tlic polyamide-imide metal chelate films were reduced by
various reducing agents and the reduced films exhibited low surface
resistivity mmd 10~-10' n/cm2.1'he surfaces of these conductive fib

proved to be metallised by means of X-ray analysis. The metal adhered on the
film was believed to be responsible for the improvement of electrical
conductivity.
Basita et a1 (1994) reported the synthesis of resins by reacting
p-hydroxy acetophenone semicarbazone with substituted benzoic acid and
formaldehyde in the presence of acid and base catalysts(XX1V) and
investigated their ion exchange property, influence of electrolytes on the
metal uptake of Cu(II), Ni(II), Zn(II), Mg(II), Mn(I1) and Co(II),as also
distribution of metal ions at different pH.
Chelating ligand in polymeric network is based on -CH2- linkage. In
this case polymer like styrene-divinyl benzene co-polymer was first
chloromethylated and then allowed to react with the mine or thiol group of
the chelating ligand resulting immobilized solid support which may cany
various donor atoms (Scheme-8).

-
[R= Chelahng lipd]
I
Scheme - 8
CH2Cl CH2 NH-R
The chloromethyl group not only reacts with primary or secondary
mine but also with thiol group as evident by the linkage of thiomethyl,
dithizone or dehydrodithizone into the matrix. X-ray photo electron
spectroscopy (XPS) was conducted to identify the chemical state of sulphur
and oxygen in the resin matrix and physical state was measured by scanning
electron microscope (SEM) by Saha et al(2000).
lminodiacetic acid was the first example to introduce nitrogen-atom
into the polymer. Other ligands like thiourea, nitrosonsrcinol, thiazole and
thiozoline, phenyl alanine, anthranilic acid azide, triazoethiol, piprerazin,
were also incqmmted. Liu et al (1987) described the synthesis of chelating
resin through histidine moiety with four functional pups viz carboxylic
group, u11-ad ainine p up and two nitrogens in the imidazole ring which
are mtid sites of co-ordination to metal ions. Other workns have also
been h~&&ad aminopyrazolone, lysine-Na,Nediaceticacid, 8-hydroxy

quinoline,l-(2-aminoethyl piperazine,N-5-formy1 salicylidine)ethane, methyl
urea into the polymeric matrix.
Although amide linkage is acid sensitive, there are reports in which
polymeric matrix was functionalized through this bond.
Philips and Fritz (1980) incorporated N-phenyl hydroxamic acid
into the styrene divinylbenzene co-polymer. The method was popular by the
successful introduction of various ligands like tertiary aliphatic amide,
acyloxime, cystein, 8-amino quinoline, thiosalicylarnide into the polymer
matrix (Scheme-9).
%&-=& -
ii" %""
[R- Acove bgmd]
Dev and Rao (1995), (199Sa), (1996) incorporated bicine,
bis-~,Nfsalicylidine)1,3 propane diamine,N-hydroxyethylethylenediamine
moieties through esterification reaction. Several workers introduced
hexylthioglygoiatc, thioglycolate, 1-hydrazinophthalazine into the solid
moiety. M m cyclic ligands like crown ethers sometimes give interesting
results because this'type of ligand is specific for a particular element. The
incorporatiDn of 7-aza-1,4,10,13-tetrathio cyclohexadecane into ply

(glycidylmethacrylate) leads to such type of matrix which is very selective for
noble metals (Scheme-lo).
Q.rOzo
COOH
'\,I /'fOF 0
Chelating resins can also be obtained by the polycondensation of
monomeric active chelating ligand. In this way resins containing
ethylenediarnine, dithiocarbamate, 8-hydroxyquinoline-5-sulphonic acid has
been synthesized. A ring opening metathesis polymerization technique was
described by Sinner et al (1998). For preparation of dipyridylamide-
functionalized polymer which may be used as a solid phase metal ion
collector.
1.4 APPLICATIONS OF POLYMER-METAL COMPLEXES
1.4.1 Catalytic activity of polymer-metal complexes
A catalyst by definition increases the rate of a chemical reaction
without being consumed in the reaction. In homogeneous catalysis, catalysts
are used in solution. However, heterogeneous catalysis offers the advantages
of ease of squation from products and lack of corrosiveness.
Organic nactions are extensively catalysed by polymer-metal
complexes (Tsuchida and Nishidc 1977). A polymer suppod group often
has catalytic propcrties analogous to that of the same group used in

homogeneous catalysis. The catalytic cycle of a polymer-metal complex-
catalysed reaction is illustrated by the following equations (Scheme-1 1).
Where M= metal ion, L=ligand, S=substrate
In the first step the substrate co-ordinates to a metal catalyst
forming an intermediate mixed complex (LMS). The substrate is then
activated by metal ions and dissociates fiom the catalyst. The complex
catalyst, having accomplished its purpose, is regenerated to the original
complex. The catalytic action of a metal ion depends substantially on the
nature of the ligands in the intermediate mixed complex.
The catalytic activity of the polymer-supported metal complexes
possesses the following features:
b Homogeneous catalytic activity is retained by transition metal
.complexes on binding to the resin.
> The economy and convenience of heterogeneous catalysis is
attained.
> The steric environment of the catalyst is altered and substrate
selectivity is incnased.
b The catalytic sites(sing1e metal atom) can be separated by
binding to the rigid region of the support. By avoiding the

formation of ligand bridged complexes greater catalytic activity
is gained.
% Polymer bound catalyst can be employed under conditions
comparable to those of conventional homogeneous catalyst (i.e)
at temperatures below lOO0C and at ambient pressures.
Samudranil Pal (2002) synthesized copper(1I)complexes with aroyl
hydrazones which are receiving continuous attention due to their
structural,magnetic,electron transfer and catalytic properties and as models for
metalloenzymes containing dicopper active sites.
Iolinda Aiello et a1 (1997) synthesized monomeric and polymeric
oxovanadium(N) complexes containing 5-(4'-alkyl-pheny1azo)-8-hydroxy
quinoline ligands. These azo compounds experience the photochemical
isomerisation and are therefore of interest for applicative purposes.
Oxovanedium(1V) complexes containing the 5-phenylazo-8-hydroxy
quinolinato moiety combine features which could be useful in molecular
materials (XXV).
1.4.1.1 Oxidative reactions
Oxidative d o n s of organic compounds with molecular oxygen
take place with high efficiency and selectivity in the presence of Werner-type
metalcumphe3rrsedascatalysts.

Metal complexes catalyze oxidation of compounds having mobile
hydmgms such as ascorbic acid, hydroquinone, phenols and mines, in the
presence of molecular oxygen. In this reaction a substrate co-ordinates to the
metal catalyst, and then the substrate is one-electron oxidized by the metal ion
with higher valency (Scheme-12).
The first example of catalysis by a polymer-metal complex was
reported by Lautsch et al (1955). Metalloporphyrin was linked to a poly
(phenylalanine) chain by peptide bond. The catalytic properties of this
polymer-Fe(II1) porphyrin complex were compared with Fe(II1) porphyrin in
the oxidative reaction of phenylenediamine. The catalytic activity of the
polymer complex was twice as large as that for the corresponding analog.
During the study of Cu(I1) catalysed oxidation by molecular oxygen
of ascorbate, hydroquinone as well as tetramethyl-p-phenylenediammonium
salt and I-(2,5-dihydmxyphenyl) isopropylarnmonium cations in the presence
poly(L-histidine) (PLH). Pecht et a1 (1967) noticed addition of PLH enhances
the catalytic efficiency of Cu(1I) towards negatively charged and neutral
substrates, but inhibits it towards positively charged substrates PLH-&(IT)
complex catalysed reaction became zero order in substrate concentration at
relatively low concentration of substrate exhibiting Michaelis-Menten
kinetics.
Hatano et a1 (1971) and Nozawa and Hatano (1971) studied the
catalytic efficiency of poly(~/L-lysine)-~u(~~) complex towards oxidation of
3,4-dihybxy-phylalanine.The oxidation was asymmetricdly catalysed:
the Dimmer of the subsmte co-ordinated to complex more strongly and its

oxidation rate was greater than that of L-enantiomer. This was ascribed to the
helical structure of the complex in aqueous solution (pH 10.5).
Polymer-metal complexes often exhibit high catalytic efficiency in
the decomposition of Hz02 as per the reports: Poly(&diketone)-Cu(I1)
(Nozawa ct a1 1968) various poly(amino acid)Cu(II) (&gel and Bauker 1968)
and poly(4-vinylpyridine)Co(II) (Sasaki 1968). Hojo et a1 (1978) employed
Cu(I1) poly(vinyla1cohol) as catalyst for decomposition of H202 and reported
that the relation between the initial rate and initial concentration of Hz02
varied in accordance with the rate expression of Michaelis-Menten type.
The oxidation of various alcohols by the poly(t-carbobenzoxy-L-
1ysine)-Cu(I1) complex was studied by Welch and Rase(l969).The polymer
catalyst showed selectively in oxidation by virtually excluding alcohols of
bulky structure such as diisopropyl and diisobutyl carbinol with admitting
simple alcohols such as n-butyl,iso butyl and sec-butyl. It was suggested from
st~uctural studies that the selectivity of the polymer catalyst resulted from
highly complex geometry of molecular cage formed by helix and the amino
acid side chain mund the co-odnation Cu(I1).
Oxidation of axorbate and hydroquinone by molecular oxygen was
found to be enhanced by poly(amino-organosilaxane)~ (PA0S)-Cu(1I)
complex. In contrast to Cu(I1) catalyzed reaction become zero order in the
substrate concentration at relatively low concentration of the substrate
exhibiting Michaeiis-menten kinetics (Noburu et a1 1986).
Lti and Wang (1993) reported the selective oxidation of
ethylbenzene, n-propylbmzene, and n-butyl benzene catalysed by organic
polymer supported RuIII) complexes under oxygen or air in the absence of
solvent in hsterogeneous phase. The reaction afforded the comsponding

ketone and alcohol in good yield. The catalytic selectivity of total ketone and
alcohol ranged from 98% to 100% with the different mthenium polymer
bound 22'-bipyridine complexes.
Valodkar et al(2004) studied the swelling and catalytic activities of
chloromethylated styrene divinylbenzene and .-its Mn(1I)complexes.
Manganese (11) anchored L-valine bound poly(styrene-divinylbenzene) has
been shown to catalyse the epoxidation of alkenes in the presence of alkyl
hydro peroxide under mild conditions. The catalysts can be recycled without
any loss in selectivity. Slow deactivation of the catalysts was observed over
extended reuse. Apart from the reaction conditions, the nature of aminoacid
and the stability of its metal complex on the surface of polymer support will
determine the formation of active species responsible for product selectivity
in oxidation reactions.
Kaliyappan et a1 (2003) synthesized and characterized poly(2-
hydroxy4acryloyloxy acetophenone-formaldehyde) (XXVI), metal
complexes from 2,4-dihydroxy acetophenone, acryloyl chloride and
formaldehyde and the polymer formed was complexed with metal
acetates[Cu(ll)Mi(II)]. Polymer metal complexes of Cu(I1) was found to
catalyse the ester hydrolysis and oxidation of phenol.

Reddy et al(2004) prepared complexes of Cu(II), Ni(II), Co(II), and
Fe(Il) with 1-phcnyl-1,2-propanedione-2-oxime thiosernicarbazone. These
complexes show much enhanced nuclease activity in the presence of oxidant
(XxvrI).
X=Watcr molecule m FgI) and Co(Q complexes
1.4.1.2 Hydrogenation reactions
XXVII
A very high catalytic activity was observed for the hydrogenation of
olefins catalyzed by poly(acrylic acid)-Rh(1I) complexes in homogeneous
solution. The catalyst effected preferential reduction of the olefinic bond in
case of substrates having additional functional groups such as diallylether,
allyaldehyde and cyclohexene-I-one. In addition greater substrate selectivity
and sensitivity to the size of the alkane was also observed in the above
reduction (Hirai and Nakarnura 1974).
Grubbs and Kroll (1971) reported the rate of hydrogenation of
olefins with a polymeric supported Rh(1) catalyst. The rate was 6.25 times
greater for cyclohexene than that for cyclooctene. The substrate selectivity
was attributed to the restriction of the substrate entering the pons of the
ligand beads and indicated that the raction mainly takes place inside the resin
pamcles.

Card et a1 (1979) reported poly(styry1)bipyidine Pd(I1) acetate to be
usell catalyst for the hydrogenation of alkenes and alkynes. More
substituted or sterically bulky group got reduced rapidly than the less
hindered olefins. In the case of alkynes, preferential reduction to alkenes in
good yield without isomerisation was achieved by stopping the reaction after
consumption of one equivalent of hydrogen.
Nayak et a1 (1985) prepared a polymer supported Pd(I1) species by
means of an oxidative addition reaction between Pd(PPh,) and
chloromethylated cross-linked polystyrene and employed it for the reduction
of alkenes and alkanes under mild conditions. The high recycling efficiency
of the catalyst and solvent effects on the reaction rates were also investigated.
Bis-benzonitrile dichloropalladium(I1) was supported on two
copolymers containing carboxyl and bipyidyl groups and employed as
catalyst for hydrogenation of olefins under mild conditions. The co-ordination
environment and the nature of the metal species on the polymer were studied.
Based on environmental evidence it was proposed that polymer-palladium
complexes initially contain palladium atoms with chloride atom bridges,
which are cleaved in activation. The catalysts were found to be active towards
the hydrogenation of olefins under ambient conditions. The kinetic and
mechanistic wpts of the hydrogenation of styrene and acrylonitrile and
recycling capacity data have been reported (Mani et al 1990).
Palladium acetate anchored on to a copolymer support containing
chxyl and pyridyl groups was found to be highly selective for the
hydrogenation of dime and alkynes. In the case of disubstituted alkynes, cis-
alkyncs were formed predominantly. The loss of metal due to leaching was
very small under the conditions employed (Mani et al 1993).

1.4.13 Hydrolysis
The catalytic hydrolysis of oligophosphates by poly(L-1ysine)-
Cu(I1) complexes has been reported. The PLL-Cu(I1) complex showed strong
catalytic activity and attacked pentaphosphate exclusively, thus producing
orthophosphate as the main product. This result was ,e)cplained by the chelate
structure of PLL-Cu(I1) (Moriguchi 1966).
Nozawa et a1 (1972)(1968) found that poly(L-1ysine)-Cu(I1)
complex exerted a symmetrically selective catalysis on the hydrolysis of
phenyl alanine ester, whereas Cu(I1) ions and bis(bipyndyl)Cu(II) had no
catalytic activity. The improved stability of the intermediate PLL-Cu(I1)
complex with the D-ester was considered responsible for the catalytic activity.
Brcslow and Overman (1970) attached the Ni(I1) complex to
cyclohexamylose, which formed a hydrophobic cavity, as drawn in XXVIII,
and studied the hydrolysis of pnitrophenyl acetate. The reaction was
accelerated by a factor of 10' over the uncatalysed system, the increased
reactivity being the result of binding of the substrate in hydrophobic cavity.
The hydrolysis of p-nitmphenyl acetate over catalysts such as
~oly(vin~limi~~~) was studied. The activation parameters indicated a

second order reaction with high catalytic activity attributed to the synergetic
action of the polymer groups. An acetylation deacetylation mechanism on
the reactive site was proposed (Huang and Ho 1981).
Kaliyappan et al (1996) synthesized Poly (2-hydroxy Cmethacryl
oyloxybenzophenone) was prepared from 2,4 dihyQoxybenzophenone and
methacryloyl chloride using benzoyl peroxide as free radical initiator and the
p~lychclates were prepared with Cu(I1) and Ni(I1) ions. The polychelates are
having very low electrical conductivity. The ester hydrolysis of ethyl acetate
to ethanol yields around 15% using Cu(I1) and Ni(I1) polychelates.
Gomez et al (1982) studied the hydrolysis of pnitrophenylacetate
spectrophotometrically in ethanol-water at 26OC and pH 8 in the absence and
presence of poly(4-vinylimidazole) and Cu(II).First order kinetics in
p-nitrophenyl acetate was observed. The rate was increased by addition of
4 o6 M Cu(I1).
1.4.1.4 Hydroformylation
Polymer supported catalysts have been used for hydroformylation
reactions, (Scheme-13), the reaction sequence ~nvolving addition of an
aldehyde group to the terminal or the internal carbon atom of an alkene. The
ratio of the two aldehydes formed was dependent on catalyst used. For
example in ihe case of the two homogeneous catalysts,Rh(acac)(CO)z and
Rh(acac)(CO)PPh,, the ratios of normal to branched chain aldehydes were
found to be 1.2: 1 and 29 : 1 respectively.
R -CH=CHz + co + HI -+ R -CH2 -CH,-CHO
or
R-CHrCH,
I
CHO

Whcn these catalysts were bound to the polymer, the ratio further
changed. Thus, when Rh(acac)(COz) was equilibrated with a phosphonated
poIyrner(C02) polfistyrene), poly(vinylchloride) or silica normal and
branched aldehydes were formed in the ratio 2-2.5 : 1. The increase in the
ratio was an indication of displacement of C=O by a polymeaic phosphine
ligand. Changing the amount of cis-trans-bound catalyst also influenced the
qtio of nonnal to branched product (Pittman and Hiro 1978).
Van Dyke et a1 (1979) reported Rh(1) phosphine complexes attached
to polyfmethylsiloxanes) catalyst which were active in the hydroformylation
of 1-hexene to heptaldehyde or isoheptaldehyde. Extensive degradation of
the catalyst occurred during the reaction.
Polymer-supported chiral phosphine-containing catalysts for the
preparation of chiral products, especially by hydroformylation was reported
(Stille 1983). By exchanging a transition metal onto the cross-linked polymer
support, a catalyst was obtained giving chiral products in high enantiomeric
excess.
Pan et al (1985) synthesized polystyrene and polystyrene-divnyl
benzene containing up to 32% divinyl benzene. Polystyrene peroxide was
exchanged on to the polymer supports. Hydmformylation reactions of a-
olefins wera investigated in the presence of SnCI2. This polymeric catalyst
displayed high selectivity to the linear aldehyde (95%) and high activity.
Polyaluuminazanes, polytitanozenes and polystanazanes and their
complmcs with Rh or with Co-Ru were prepared and used for the
hydmformyIstion of 1-heptene. All of the Ru-complexes could not tolerate
higher reaction btm, when higher selectivity is wanted, except for the
P~lyal-Rh ~~llplex. But the Co and Ru bimetallic complex of

polyaluminazane could catalyse the hydroformylation of I-heptene at higher
temperatun without any decrease in catalytic activity and with a selectivity of
- 70% for branched aldehyde (Cao et al 1989).
Capaka et al (1971) reported that the polymer-supported pH and Pt
complexes catalyse the hydrosilylation reaction. The rate of hydrosilylation
reaction decreased as electron withdrawing substituent groups were
substituted in the alkene molecule. Although hydrosilylation with
biethoxysilane proceeded uniformly with all supported catalysts, complexes
that were good catalysts for hydrosilylation with Et3SiH were poor catalysts
for the reaction with CI3SiH and vice versa. The reaction conditions for
hydrosilylation using a polymeric catalyst were mild and comparable to those
with homogeneous catalysts such as chloroplatinic acid.
Kinetic and catalytic studies were carried out to evaluate the role of
polymeric organosilicon support of rhodium phosphine catalysts for
hydrosilylation of C=C bonds. All kinetic data showed that modification of
Wilkinson's complex by polysiloxyalkylphosphine(insoluble) and silalkyl
phosphone(soluble) ligand essentially had no effect on the kinetics parameters
and mechanism of the hydrosilylation of 1-hexene (Marciniec et al 1982).
Heterogeneous poly(9-10-anthraleneviny1ene)-Pt complex was
prepand. Hydrosilylation of CH2=CHCH2-OPh with (EtO),SiH in the
presence of the catalyst gave 81% Ph(CH2)3Si(OEt)3 (Pomerantseva et al
1984).
Michalska -and Ostazewski (1986) synthesized a series of
~olyamides kving different rnunbers of methylene groups in their repeating
units by inurfdal polycondensation of terephthalyl chloride with piperazine

and aliphatic diamines, H;N(CH*),,NH2 (n = 2, 6, 10). The materials, with
high t h d stability, were used for immobilization of Rh and Pt complexes.
The bound catalysts exhibited high activity in hydrosilylation of 1-hexene.
The activities of the Rh complexes were dependent on the structure of the
polyamide support, decreasing with increasing distance between the amide
groups and closely paralleled the changes in the degree of crystallinity of the
polymers. Repeated use of the polymers bearing Rh complexes showed the
bond between the metal and polyamide to be fairly stable.
Xiao et al(1989) prepared a silica supported poly(w diphenylphos
phinoundecylsiloxane) platinum complex. The addition of trimethoxysilane
to 1-hexane in the presence of the complex catalyst yielded 80-90% of
hexyltrimethoxysilane. Measurement of the rates of the reaction with various
substrates indicated the order; hexene > styrene > dodecene > allylglycidyl
ether. Platinum complex could be easily recovered by filtration after the
reaction and repeatedly used with same activity.
1.4.1.6 Polymerization initiation
Tsuchida and Nishide (1980) used Cu(II)/Mn(II) poly(4-
vinylpyridine) complexes as initiator for the preparation of phenolic
polymers. The rate of the reaction, yield and molecular weight of the polymer
were high.
Tetrahydrofuran was polymerized in the presence of sebacoyl
chloride and AgClO,, terminated with primaryamine, treated with sodium
naphthalene and used to initiate the copolymerization of methyl methacrylate,
styrene, and arrylonitrile. A thermoplastic elastomeric methyl metharrylate-
tebnhydroh block copolymer was prepared which had tensile strength
157 Wcm2 (Xhcn et al 1983).

Anionic polymerization of acrylamide was initiated with
poly(ethyleneoxi&)-di-sodium salt in several solvents at various
trmperstures. The Michael type. addition of alkoxide anion of the ply
(ethylmeoxide)-di-sodium salt to acrylamide proceeded exclusively via a H-
transfer mechanism. The polymerization at relatively low temperature in
plar solvent resulted in the formation of long and shod chain branchings at
nitrogen atmosphere in the amide group. In the polymerization at higher
temperature in a non-polar solvent, the branching structure was greatly
reduced and almost linear poly(8alanine) was obtained (Murakami et al
19851.
Water soluble poly(viny1phosphate)-Cu(I1) complex was active as a
free radical initiator for the polymerization of styrene in the presence of
carbon tetrachloride. The maximum conversion was observed at neutral pH
(Maeng et a1 1985).
Acrylic acid-styrene copolymer-supported Nd showed high catalytic
activity and stereospecificity for butadiene polymerization. The cis-1,4
content of polfibutadiene) was 98.7%. The system was also used for isoprene
polymerization to give poly(isoprene) with 95% cis-1,Ccontent (Li et a1
1988).
1.4.2 Ion selectivity
The main applications for the chelating polymers are based on the
high selectivity of the materials for particular ions. There are many mining or
pollution situations in which the precious or toxic ion is a small part of a
mixture of many other ions, and if this ion can be recovered specifically, the
energy and material fiuirements of the process can be reduced dramatically.
However, largescale commercial use of chelating resins as is common with
simple ionzxchaage resins has not really arrived, except, in some water-

softening areas whm undesirable multivalent ions such as Ca(I1) and Mg(I1)
replace monovalent ions. One potentially important example of this
technology is in the use of the new membrane cells for the electrolysis of
brine.
These cells used are Perfluorosulfonic (Nation R) and perfluoro
carboxylic acid ion-selective membranes to select the two halves of the
electrolysis cell. Chelation effect in these membranes strongly holds
multivalent ions in the membrane and blocks the passage of commercially
important monovalent ions. Irninodiacetic-acid chelate resins are often used to
purify brine before electrolysis to overcome this problem.
A series of new copper-selective aminopyridine Dowex resins were
designed for large-scale hydrometallurgical separation of copper from its ores
(Ford et al 198 1).
In situ acid leaching of copper-ore dumps results in dilute copper
solutions of pH=I-3; many other metal ions; such as Fe(I1) and Ni(I1) are
present as well. The Dowex resins can be used for the selective recovery of
the copper in this case. Another copper-chelating resin of even faster
selectivity, Sinorex-Cu(I1) has been designed for higher pH (3-6) copper
solutions such as, those found in copper-ore dumps treated by microbial
leaching in high rainfall areas. Considerations of resin cost and metal price as
well as the methods of handling resins on the large scales involved have so far
prevented have full commercialization of these polymers. Monomeric
chelating materials either in solvents or adsorbed on polymers is used
commercially for the solvent extraction of copper mining solutions, but this
technique is not 8s potentially advantageous as chelating resins at low
concentmia of copper.Anoth possible large scale application of chelating
resins is tbe Aective -oval of precious metals from sea water(Mauria et al
1980). Rm-h p j ~ in s a number of uranium-deficient co~ntrits, e.g.

Germany, Japan, Russia and UK are investigating the recovery of uranium
from sea water using chelating resins (Pan et al 1982). These include
materials such as amidoximes, poly(hydroxamic acid)s and various other
experimental resins. Selective removal of gold from seawater, although the
subject of a number of patents, is equally far from reality. However, the use of
chelating resins to remove gold from mining solutions of cyanide or chloride
salts, and also waste solutions from precious metal manufacturing is more
important. Activated carbon or various commercial anion exchange resins are
now used to recover gold from such solutions, but they are very unselective
and recover a mixture of metals (Hodgkin et a1 1985). Very selective
chelating resins with isothiouronium structures are available and can be used
to separate the anionic gold complex ions from other non-precious metal ions.
These resins are the Srafion (Jones et al 1977) and Monivex (Mauritz et al
1980) resins.
Commercial chelating resins have mainly been used in analytical
applications, especially in the preconcentration of trace elements from
solutions. For eg; the retention of traces (0.5-4ppm) of Zn, Cd, Pb, and Cu
extracted from sea water on a ChelexlOO resin has been studied (Vernon et al
1983). The same resin and method were used for the preconcentration of
Cu(II), Zn(I1) and Pb(I1) from urine. Comprehensive lists of recent analytical
reports on chelating resins used in interesting and important ways of
concentrate selection and analysis of metal ions in practical situations are
available (Asthemier et al 1983).
Another promising new application for chelating resin is in
mokcular medicine, where very short-lived isotopes must be removed quickly
and ~cltctively fromanother and daughter ions. A recent example is the use of
Pyrogallol-fimna]&hy& polymer made for the sepaxation of "Ga and "Ge
ions (Naming et al 1981).

Chelating polymers have many potential applications for the
selective removal and recovery of metal ions from industrial waste solutions
(Koster et al 1967). The selective removal of mercury, using resins
(Warshawsky et a1 1980) with thiol groups, is one a& application. However,
in general the commercially available resins are not quite selective enough
and the few extremely selective chelating polymers discovered have not been
made into the physical forms-beads, fibres, membranes, etc. that will give the
required kinetic, physical, and most important, the economic properties for
large scale commercial isolation of individual ions. Many chelating polymers
have been fabricated on a small scale into different forms, membranes and
hollow fibres, othm than ion exchange resins in attempts to get more
convenient materials for the selective separation of ions in special
applications(Aganval et al 1975).
1.43 Biological activity
Aswar et al (2004) synthesized Schiffs base derived from
4,4'-bis[salicylaldehyde]-5-azodiphenylmethane and aniline and its metal
chelates. The ligand and its polychelates have also been screened for their
antimicrobial activities using various microorganisms and they have been
found to be moderately active against the organisms.
Ssdhan Ramanik (2004) prepared a chelating resin (2-
benzirnidazoylrnethyl) amine with chloromethylated polystyrene. Trace
quantities of Ag(1) present in photographic washings and medical samples
viz.silvn sulphadiazine ointment and chawan prash were preconcentrated by
column chtomatogrep;hy using this chelating resin.

Complexes of Cu(II),Ni(II) and Co(I1) with Schiff base ligands by
condensation of thioacetami&,4-aminowetanilide with 2-furfuraldehyde or
4-chlmbenzaldehyde have been synthesized. Some of the complexes have
been screened for their antimicrobial activity (Mishra 2002).
Albion metallosates has the foliar version of albion metal aminoacid
chelates are made to allow for increased absorption from leaf surfaces. They
are formed according to sound chemical properties of reacting ingredients in
proper proportions and under proper conditions to achieve chelation. Their
formation as aminoacid chelates can be demonstrated through standard
chemical properties and chemical instrumentation widely acknowledged
being capable of measuring chelation. The metal metallosates contain inherent
charge characteristics which are capable of traversing the various layers of
cuticle and cell walls without being bound by them. They also possess
characteristics which make them compatible for passing through the
plasmalemma by active transport when split apart at the sites of usage of the
metal atoms can assume for their niches in the metabolic hierarchy of the
plant and the resulting free aminoacid are left to be nutritive benefit whenever
they may be needed in the metabolic processes. There are no xenbiotic
ligands to metabolise, detoxify or sequester as with synthetic ligands such as
EDTA, foliar application of albion metallosates metal aminoacid chelates are
thus compatible with the inherent anatomy and physiology of plants and
constitute a highly bioavailable means for improving crop nutrition and
productivity (Robert B.Jeppson 1999).
1.5 PLIYSICOCHEMICAL PROPERTIES
1.5.1 Exchange capacity
The exchange capacity of chelating resin towards metal ions
%xnds on the mount of the chelating ligand incorporated into the polymeric

matrix as well as the nature of the donor atoms present in the active site. It
was observed that a conventional ion exchange resin has lower exchange
capacity than that of a chelating resin.
1.5.2 Kinetics
Kinetic property of a chelating resin mainly depends on the nature
and degree of cross-linking. The sorbents with the best kinetic characteristics
are those which have low degree of cross-linking. The sorption of metal ion
on the resin is by particle diffusion mechanism or by second order kinetics.
1.5.3 Analytical applications
The selective sorption of certain elements in the presence of others
based on the different stabilities of the complexes formed by functional
groups of the sorbents has led to the use of these materials for selective
pmncentration and separation of metal ions present in environmental,
biological or industrial matrices.
The choice of an effective chelating resin depends on polarisability,
selectivity, exchange capacity, kinetics, and stability characteristics of the
polymer. Akaiwa and Kawamoto (1982) discussed the advantages of having
synergistic agent on a chelating resin to enhance sensitivity and separation of
trace metals. The concept of hard and soft acid and base provides an
important guideline for the selection of the method. Usually 0, N, S
(sometimes P) are present in the chelating resin which determine the ability to
interact with the metal ions forming chelated ring. Functional groups of the
chelating rain usually act as bases: Oxygen containing functional groups are
hard and sulfirr containing groups are soft. Functional group with basic
nitrogen bas an intermediate character.

Table 1.2 transpires that separation of metals can be carried out (i)
by azo functionalized resins having phenolic -OH group, heterocyclic
N-donor atoms, (ii) resins anchored by -CH2 groups, (iii) resins having amide
linkage, (iv)esterified resins or (v) polycondensed resins. After separation
metals are usually analysed by WNis spectrophotometry or atomic
absorption spectrometry techniques. It is evident from Table 1.2 that major
work has been carried out on separation of transition metals present in
environmental samples.
1.53.1 Applications of functionalized resins having phenolic -OH
group
The resin having I-nitroso-2-naphthol as an active group was used
by Ghosh and Das (1981) for the selective separation of ~d" and U" with
exchange capacities of 0.67 and 0.43mmol g-' respectively. Separation of pdn
was based on the observation that at pH 1.0 appreciable amount of pdn was
sorbed on the resin column, where other metals are not sorbed at all. At
pH 5.9 most of the metal ions are sorbed along with U" which might be
eluted with 0.5M Na2C0,. The resin is useful particularly for the estimation
of uN in sea water. They also described the use of 2-nitroso-I-naphthol and
the exchange capacities of the metal ions like ~ g", ~i", znU, cdn, ~n', v",
cfl', Feu', CO", ~ u b pd%ere d examined. It was found that the values are
high for pdU, cuU, Hgn and U" with a capacity of 0.93mmol g-] for pdn at pH
1 .O, 0.87, 0.98 and 1.2mmol g.' for CU", H~~ and U" respectively in the pH
range 5.5-6.0. Separation of ~ d" was achieved by taking the advantage that at
pH 4.5 no pdN was so.M and hence complete separation of these two metals
is possible.

Sdid Matrix Active group Metal studied instrumental Technique A~pUcfitions
Nihbsomsorcinol CU", Z~"CO" ~d",
Hg",Nil',~n",~e"'
Tracer synthetic mixture
Thiazole and thiazoline Hg" Tracer
Sea water
Phenyl planinc CU", H$ AAS
Sea water
Anthranilicacid hydrazide ~d",h' ,R~",RU",OS~'
AU"',A~'
Spectrophotometry Synthetic mixture
Poly(ethytacrYtate) Triazoethiol CU", Z~"CO" c~",H~",A~' AAS, tracer
Sea water
Phenol- ' PiprraZine CU" AAS
fddehyde resin
Amklite IRC-50
Chlmethyl PS
Histidine
Aminopyrazolone
CU", z~",H ",Ag' AU"', ~e"' Spectrometry, AAS
A~'Au"', Pd 51, .~n" AAS
Natural water
Chlommethyl PS Lysine-Na Na -diacetic
acid
Trivalent hard metals Spectrometry
IF Phenol formaldehyde
Lysine-NO NO -diacetic
acid
8-hydroxyquinoline
1 -(a-Aminomethyl)
piperazine
Pr1'',Nd"'
CU" Online AAS
Spectrophotometry
AU~~~,RU'",OS~,P~'~,I~~V
Synthetic mixture
Synthetic mixture
(N-5-Fonnyl
salicy1idine)ethane
~e"' CU", Pb" cd" AAS
Methyl thiourea,guanyl
thiourea, dithiocarbarnate
CU", zn"NiU Cd" AAS
Chloromethyl Cyclohexene CU",C~",Z~",N~" AAS
Synthetic
PS-DVB
Oxide and sulfide
Mixture
Chloromethyl PS Bis-(2-aminophenyl)
Disulfide
As"',AsV HG-AAS
Polluted water

Salicylic acid anchored Amberlite XAD-2 was used by Saxena et a1
(1994, 1995) for znn and Pb" recovery. The resulting chelating resin is very
selective for those metals having the maximum capacities of 0.018 and
0.002mmol g-' respectively. They applied the proposed method by taking the
chelating resin in a column and passing well water through it at pH 5.0 at a
flow rate of 2-5 ml mid'. The metals thus sorbed were eluted by 1-2 M HCl
with a recovery of 98% and 100% for ~n%d ~b"res~ectivel~
Lce et al(1995) used the resin containing 4-(2-thiazolylazo)resorcinol
(TAR) for the trace preconcentration of CU",N~",P~",CO",C~ "and ~n~ with
exchange capacities of 0.81,0.36,0.32,0.27 and 0.05 mmol g-' respectively, at
pH5.4. Except CU" and CO", most of the metal ions were recovered
quantitatively (96%) by elution with 10mll-2M HNO,, at a flow rate 0.08ml
mid1. Desorption of CU" was completed by using 2M HN03 with 98.8%
recovery at a flow rate 0.08ml min".~ut 100% recovery of con was not
possible due to oxidation of CO" to CO"' and subsequent formation of con'-
TAR complex.The same group of workers also used TAR containing resin for
the separation of uV' The resin was packed in a mini-column and the solution
of different geological standards were allowed to pass through it after
maintaining the pH at 5.4 along with complexing agents such as 1,2
diaminocyclohexane.~,~,~,~'- tetaraacetic acid (CDTA) and NH4F.b this
condition ody uV1 was sorbed and the other ions were not. The retained u"'
was completely eluted by 0.2M HN03 with a standard deviation

preconcmtration of the above metals from tap, river and natural water and
human urine, milk from ores with a recovery of 95.99%
Pyrocatechol immobilized Amberlite XAD-2 was used by Tewari
and Singh (2000), and the exchange capacities are 0.040,0,023,0.092,0.073,
0.053, 0.028rnmolg"for Cd, Co, Cu, Fe, Ni and Zn fespectively. The average
recovery was found to be 97 to100% with a deviation of 1.4 to 2.1 %. The
method has been found to be useful for the separation of these metals from
river, tap water and from vitamin tablets.
o-Arniniphenol anchored amberlite XAD-2 was used by Kumar et a1
(2000) for the separation of CU", Cd", CO", ~ i", ~ n and " ~ b" with exchange
capacity values of 0.053, 0.030, 0.056, 0.055, 0.045 and 0.016 mmolg"
respectively. These metals are desorbed with 4M HNO, with 91-98%
recovery.
Quinalizarin anchored Amberlite XAD-2 was used for trace
recovery of Cur', ~d", CO", ~b", ~ n and " ~ n with " the capacity of 0.05,
0.015, 0.027, 0.025, 0.02, 0.017mmol g"respectively in the pH range 5.7-7.0.
The river water was passed through the column containing the modified resin
at the desired pH and desorbed simultaneously all the metals by 2-4M HNOs.
Pyrogallol immobilised Amberlite XAD-2 can also serve as a trace
metal pnconcentrator. The loading capacities 0.041, 0.020, 0.046, 0.051,
0.016, 0.032, 0.046, 0.036, and 0.012mmolg" were obtained for CU', cdn,
con, ~i', pb" MM~", ~e'' and uN respectively at the pH range
5.5-7.O.The rctaintd metal ions can be simultaneously desorbed by 2-4M
HNOl or HCI with an average recovery of 90-99% h m river water.
M d
et a1 (2001, 2002), used polystyrene-divinylbmzene
fUnctionaii& with 2-naphthol -3,6-disulphonic acid (NDSA) for the

speciation of chromium. The important feature of this method is that it can
selectively sorb crV' at pH 1.5 while cfll at pH 6.0 leading to the complete
separation of the above species. The maximum exchange capacity for the
resin was found to be 1.18 and 0.40mmolg*l for cr"' and cr" respectively.
The method has been used for the speciation chromium in natural water by
column separation with a recovery of 98.5%.
Davies et al (1959) first introduced o-hydroxyarsonic acid by N=N
linkage (Scheme 14). Ghosh et al (1981) synthesized the resin containing
I-nitroso-2-Naphthol and 2-nitroso-1-naphthol. StyraBrajter et a1 (1987)
prepared pyridylazoresorcinol containing chelating resin. Kumar et al (2003)
described the functionalisation of Amberlite XAD-2, o-aminophenol, trion,
quinalizarin and pyrogallol. The amount of ligand incorporated during the
course of the reaction was calculated by elemental analysis. As the chelating
resin contains a weak base functional group like phenolic-OH, it is expected
that the sorption of the metal will depend on the pH of the medium.
Scbeme-14
[R- chclnhng I~gand]

The a20 groups supply N- chelator and phenolic -OH supplies 0
donor which make the resin (N,O) donors and should be selective for
transition metal ions. It can be found from the above discussions that most of
the resins were selective for transition metal ions and thus it can be thought
that the active group containg phenolic -OH pup if anchored by am
function should be selective for transition metals.
1.5.3.2 Applications of au, functionalid resins containing heterocyclic
N donor sites
Chattopadhyay et a1 (1997) applied a resin containing imidazole
moiety for the separation of Hg" and ~d form waste water. They found that
the exchange capacities are 0.62 and 0.75 mrnol glrespectively for the two
metals at pH 6.0. Recovery was quantitative and satisfactory.
Das et al (2006) reported, the use of resin containing imidazole
moiety and used it for the separation of ~d" and ~g' from geological and
medicinal samples. The maximum exchange capacities for ~ d" at pH 5.5 - 6.5
is 0.67 mmol g-' and for ~g'1.49 mmol g" at pH 4.0-5.0. The sorbed pdn was
desorbed by 12M HCI and ~g' by 5% thiourea in 0.5M HC104 with an
average recovery of 100% and 95% respectively.
Sequential separation of CU" and ~n" from each other and from
biological samples by the use of imidazolylazo resin was claimed by Mondal
et al (2001). They found the exchange capacities to be 0.94 and 0.60mmolg1
at pH 5 for CU" and zn" respectively. Taking the resin in a short column
solutions containing cuU and ~ n" were allowed to sorb and then 01" was first
eluted by 1M sulpho salicylic acid followed by 1M HCI with a recovery of
100%.

Polystyrcn~DVB modified with 6-mercaptopurine is selective for
Cu(I1) and Zn(I1) and Cd(I1) with exchange capacities of 1.48, 0.52 and
0.33 mmol g-l, respectively in the pH range 5.5-6.0 .The metals are
sequentially separated from biological samples by using 1M neutral
suphosalicylic acid (SSA) for Cu(II), 5% thiourea in 1M HC1O4 for Cd(I1) and
1M HCl for Zn(II) with a maximum error of 8.4%.
Banejee et al (2003) separated V(IV) and V(V) from natural water
by using a chelating resin containing imidazole 4,s-dicarboxylic acid. The
exchange capacities V(N) and V(V) were found to be 0.45 and
1.57 mmol g",respectively at pH 3.0. Speciation studies have been canied out
by sorbing both the species by column method followed by sequential elution
with 0.1M malonic acid for V(IV) and 0.1 5M NaOH for V(V).
If the active group contains a heterocyclic N-donor atom, it should
be selective for class b metals, azo functionalised resins containing
heterocyclic N-donor atom may be used. Separation of precious metals like
Pd(ll), Pt(II), Ru(l1) and Rh(I1) by the use a chelating resin containing
anthranilic acid azide moiety was described by Siddhanta and Das(1984). The
exchange capacities were found to be 0.85, 0.60, 0.20 and 0.60mmol g-' for
Pd(II), Pt(lI), Ru(Ir) and Rh(I1) respectively at pH 6.0. The metals are
separated by sorbing all the ions in a short column at a flow rate of
1.3 ml min'l followed by s sequential elution .At first Pd(I1) was eluted by
130 ml of 4M HCI and then Rh(II1) and Ru(II1) by I50 ml of 6M HCI. At last
Pt(I1) was eluted by 150 ml of 11M HCI with recoveries of 99.5-100%.
Phdnol formaldehyde resin anchored with 8-hydroxyquinoline was
found to chelate Cu(Q selectively at ng level with a capacity of 1.74 mmol g-'
at pH 3. In the column operation Cu(I1) can be separated from various
synthetic mi- by sorbing the metal ions in that column at pH 3.0 under a
flow IT& of 1 ml~'. The ntained Cu(I1) was separated by elution with 3M

HCI under flow injection manifold, where preconcentration was performed
on-line prior to detection.
The resin containing thiol and alcoholic -OH group are highly
selective for Cu(I1) over Cd(II),Ni(II) and Zn(I1) at pH 5.6. At higher pH, the
sorption of Cu(I1) gets higher with a maximum distribution coefficient
(log & ) of 4.91 as a result of the deprotonation of amino groups which are
involved in chelation.
Mondal et al (2002) used bis-(o-aminophenyl)disulphide anchored
chelating resin which is more selective for different species of arsenic due to
the presence of S and N donor sites. Both the forms of arsenic viz., As(I1I)
and As(V) were strongly sorbed by the column packed with the above resin at
pH 5.5 with exchange capacities of 0.016 and 0.013mmol g-' respectively.
Complete &sorption of both As(II1) and As(V) took place by 1M HCI with a
recovery of 98%.
Singh and Gupta (2002) used diethylenetriaminepentaacetic acid
anchored resin for Th(1V) recovery from sea water. The resin is very selective
for Th(N) and In(I1) with an exchange capacity of 1.86 and 1.75mmolg-I
respectively at pH 6.0 for both. The two ions were separated from tap water in
the column method under the flow rate of 4-5 ml min-I. The metals were
eluted by IM HNO, and subsequently measured by EDTA titration.
Sugi et a1 (1978, 1980) used acyloxime hnctionalized resin which is
highly selective for Cu(I1). The loading capacity for Cu(I1) was found to be
2.0mmolg" at pH 6.0 in batch experiment. Sorbed Cu(I1) was quantitatively
recovered by the use of IM HN03 or HCI.
Das end Das (1999) used the chelating resin containing quinaldenic
acid amide, which is very selective for Hg(I1) due to the presence of

heterocyclic N donor atom. The exchange capacity of the resin was found to
be 1.98 mmol g" at pH 5.5 in which other elements like Zn(II), Cd(II), Cu(II),
Ni(II), and Ft(II1) are negligibly sorbed. Thus Hg(I1) could be separated from
waste water by taking the resin in a column at pH 6.0 and desorbiig the
metals by 10% thiourea in 1M HC104.
The chelating resin containing quinaldenic acid amide group falls
into the border line of soft bases region and is expected to complex with soft
cations like Pt(IV) and Pd(I1) .The maximum sorption capacities for Pt(1V)
and Pd(l1) were found to be 0.19 and 0.36 mmol g" respectively at pH 1.0.
Both the species was sorbed in a short column at a flow rate of 0.5 ml min".
Pd(I1) was eluted by 1% DMG-CHCI3 mixture. After its quantitative recovery,
Pt(IV) was eluted by 4M HCI with a recovery of 99%.
The polycondensed resin containing pyridine moiety is selective for
Hg(II), Cd(I1) and Zn(I1) at pH 1.O.The maximum sorption capacity for Hg(I1)
was found to be 6.0 mmol g" in the pH range 1-5. They explained the
sorption behavior of the metal ions by forming the anionic species at lower
pH. Similar pattern was observed for Cd(II) and Zn(I1). However, the resin
also bind Cu(I1) at pH 4.0 with a maximum value of 10.2 mmol g-' which is
very encouraging to preconcentrate this metals from sea water with a recovery
of 98.7%.
1.6 CHARACTERISATION OF FUNCTIONALISED
POLYMERS AND THEIR METAL COMPLEXES
Spectroscopic methods commonly employed by organic chemists in
Stntcaual determination, have proved useful in the case of hctionalized
~ol~mers and their metal complexes. This technique includes infrared, nuclear
magnetic moomfce and difies reflectance spectroscopy.

In addition elemental analysis, viscosity, gel permeation
chromatography, magnetic moments, thermogravimetry, differential scanning
calorimetry and X-ray diffraction studies come handy, in characterization.
1.6.1 Infrared spectroscopy
The formation of polymer-metal complexes can be followed from
their characteristic absorption bands in infrared spectrum. The i.r, absorptions
by a ligand are shifted after complex formation with metal ions.
The absorption peak at 1600 cm-' due to vw or voN of polyvinyl
pyridine (PVP) shifted to a higher wave n umb by about 20 cm-' in the case
of cis(Co(m)2 PVPCI)Cl2. When compared to pyridine, the peaks due to
vc

Although carbon and hydrogen analysis are often canied out
routinely, this technique is most usehl when an element such as nitrogen,
halogen, sulphur, phosphorous and metal ions is gained or lost in the reaction.
It is noteworthy that some metal ions can be readily quantified by titiimetiic
methods (Jaffery et a1 1994).
1.6.4 Viscometry
Viscometry is a useful technique for determining the polymer
molecular weight. The viscosity of the polymer solution is considerably high
compared to that of the pure solvent.
1.6.5 Gel permeation chromatography
Gel permeation chromatography (GPC) has been used as a
technique in the evaluation of molecular weight of the polymers. It is a special
type of liquid-solid elution chromatography which is based on the effective
permeation of solute molecules into rigid gel particles. The large molecules
are unable to penetrate deep into the void spaces in the gel and hence get
eluted them first. Therefore, elution volumes are proportional to the molecular
weights of-the polymer. This technique is rapid, convenient and provides
more reliable and reproducible results.
1.6.6 Thermogravimetric analysis
Themogravimetry (TGA) is a technique which follows the weight
changes of a materia! as a function of temperature. Alternatively weight loss
can be meas4 as a function of time at constant temperature. Application of
~~mn~~ppvtmetry in polymer-metal complexes include comparisons of the
nlative tfrePmal .stability, the percentage of absorbed or crystal water, metal

oxides content, studies of degradation kinetics, direct quantitative analysis of
various copolymer metal complexes and oxidation stability.
1.6.7 Differential scanning calorimetry
Differential scanning calorimetry (DSC) is a technique of
nonequilibrium calorimetry in which the heat flow by maintaining a thermal
balance between the reference and sample by changing the current passing
through the heaters under two chambers. For instance the heating of the
sample and reference proceed at predetermined rate until the heat is emitted or
consumed by the sample. If an endothermic occurrence takes place the
temperature of the sample will be less than that of the reference. The DSC
measurements provide heat of transmission, heat of reaction, percentage
incorporation of substance and rate of crystallization or melting.
1.6.8 Magnetic moment studies
The paramagnetism or diamagnetism of polymer-metal complexes is
determined by magnetic studies. Paliwal and Kharat (1989) observed Zn(I1)
complex of &9'-(2-hydroxy-5-methyl benzoy1)-p-divinylbenzene to be
diamagnetic in nature, whereas Cu(II), Ni(II),Fe(II) and Co(II) complexes
paramagnetic. Cu(II), Ni(II), Co(II), and oxovanadium(1V) complexes of
2,4-dihydroxybmzaldehyde oxime-formaldehyde copolymer were found to be
paramagnetic in nature (Patel and Patel 1990).
1.6.9 MfPuw rellcctance spectroscopy
Difh reflectance spectroscopy (DRS) covers the infnued, visible
and ultraviolet region of the spectrum. In principle bulk and surface properties
of cataly$ts can be studied using DRS. Kortum (1969) reported that a
compnha29ive theory for the interaction of light with a medium that absorbs

and emits the radiation is necessary for quantitative work. The application of
DRS is essential to find out the framework siting of elements in metal
complexes (Kellerman 1979)
1.6.10 X-ray diffraction
X-ray powder diffraction is an important technique used in the study
of polymer-metal complexes. It is used to identify the phase, check the purity,
find out crystallinity and calculate unit cell parameters (Rudolf et al 1986)
1.7 SCOPE AND OBJECTIVES
Polymer science, over the years has stimulated interest all over the
globe because of polymers making an impact as commodity, engineering and
speciality materials. As a consequence of exploitation of newer domains,
many diversifications have been accomplished. Among them, polymer-metal
complexes studies have emerged as noteworthy. This field is interdisciplinary,
finding applications in diversified fields viz, organic synthesis, waste water
treatment, hydrometallurgy, polymer drug grafts, recovery of trace metals,
nuclear chemistry and models for metalloenzymes. Since it is a heterogeneous
system it has among others, the advantages of easy separation of products and
lack of corrosiveness.
EV& though it is of relatively recent origin, the literature survey
indicates voluminous work turned out by researchers all over the globe.
Taking into consideration, the pre-eminent importance assumed and
potentiality as futuristic material, the present investigation was taken up,
which deals with synthesis, characterization and application studies on
poly(acry1ate)s containing pendent ligand with heterocyclic nitrogen and
hydroxyl functions and their divalent metal complexes. The objectives are:

1. Synthesis of new functionalized monomers:
8-hydroxy-5-azoquinoline phenylacrylate
8-hydroxy-5-azoquinoline phenylmethacrylate
2. Synthesis of macromonomers
8-hydroxy-5-azoquinoline phenylacrylate-formaldehyde
8-hydroxy-5-azoquinoline phenylmethacrylate-formaldehyde
3. Synthesis of polymers
poly(8-hydroxy-5-azoquinoline phenol-formaldehyde)
poly(8-hydroxy-5-azoquinoline pheny1acrylate)-formaldehyde
poly(8-hydroxy-5-azoquinoline phenylmethacry1ate)-
formaldehyde
4. Characterisation of monomers and macromonomers by
elemental analysis, IR and 'H-NMR spectroscopy
5. Polymerisation of hnctionalized monomers and
macromonomers by free radical polymerization.
6. Complexeation of polymers with Cu(II)Mi(II) ions in DMF
medium.
7. Characterisation of polymers by solubility, viscosity, GPC,
elemental analysis, FT- IR, 'H-NMSTGA and DSC.
8. . Characterisation of polymer-metal complexes by elemental
analysis, FT-IR, TGA and DSC, DRS, XRD, magnetic moment
and conductivity measurements.
9. Application oriented studies viz oxidation, hydrolysis,
polymerization initiation and recyclability and metal uptake
studies W g poly(8HSAQPA) Cu(II)Mi(II) complex as model.

2.1 MATERIALS
CHAPTER 2
EXPERIMENTAL
Acrylic acid(Merck), methacrylic acid(Merck), hydroquinone
(BDH), 8-hydroxy quinoline (Fluka), benzoyl chloride(BDH), copper(I1)
acetate (Fluka), nickel(I1) acetate (Fluka) were used as received.
2.2 PURIFICATION OF CHEMICALS
2.2.1 Acetone
Acetone was dried with anhydrous calcium sulphate, filtered and
distilled. The fraction boiling at 57'C was collected (b.p 57'C) (Furniss et al
1994).
2.2.2 Chloroform
Chloroform (1000ml) was shaken several times with half of its
volume of water, dried over anhydrous calcium chloride for 24 hrs and
distilled. The portion boiling at 61°C was collected @.p. 61°C) (Furniss et a1
1 994).
2.23 N,N-Dimethyl formamide
N,N-Dimethyl formamide (DMF) was purified by azeotrapic
distillation with ~ ~.1000ml of DMF with lOOml of benzene B Z ~ O ~

which distilled between 70-75OC was collected. The residual DMF was
shaken with powdered barium oxi&, filtered, distilled under nitrogen
atmosphere at reduced pressure and the fraction boiling at 76°C/39mm Hg
was collected @.p76°C/39mm Hg) (Fumiss et al 1994).
2.2.4 Ethanol
Rectified spirit (1000rnl) was refluxed with calcium oxide for 6hrs,
allowed to stand over-night and distilled. The fraction boiling at 80°C was
collected @.p.80°C) (Furniss et al 1994).
2.2.5 Methanol
Methanol (1000ml) was treated with magnesium metal and distilled.
The fraction boiling at 65°C was collected @.p. 65OC) (Furniss et a1 1994).
2.2.6 Ethyl methyl ketone
Ethyl methyl ketone (EMK) (1000ml) was dried with anhydrous
calcium sulphate, filtered and distilled. The fraction boiling at 80°C was
collected @.p. 80°C) (Furniss et a1 1994).
2.2.7 Tetrahydrofuran
~etrah~drofuran (THF) (1000mi) was dried with calcium sulphate
and filtered. It was fiuther treated with lithium aluminium hydride. The
mixture was refluxed for 6hrs over a steam bath and distilled. The fraction
boiling at 65°C was collected and stored over metallic sodium (b.p.65-660C)
(Fumiss et a1 1994).

Triethylamine was distilled and the fraction boiling at 89OC was
collected (b.p.89OC) (Furniss et al 1994).
2.2.9 Purikation of paminopbenol
paminophenol was recrystallised from distilled ethanol.
2.2.10 Purification of &bydroxy quinoline
Recrystallised from rectified spirit then with water.
2.2.11 Purification of initiator
Benzoyl peroxide (5g) was dissolved in 50ml chloroform and
precipitated by adding 50ml methanol (Pemn and Arnarigol988).
23 PREPARATION OF 8-HYDROXY-5-AZQQUINOLINE HYDROXY
BENZENE
8-hydroxyquinoline (4.35g 0.03M) was dissolved in conc.HC1
(20ml) and kept below 5OC in a ice bath. paminophenol (3.27g, 0.03M) was
dissolved in conc.HCI (20ml) by heating and the solution formed was cooled
down quickly to a temperature below 5OC with vigorous stirring to obtain a
suspension. To this suspension was addtd sodium nitrite (2.550, 0.03M) in
20ml of water. After stirring at 0-5OC for 30 minutes a yellow solution was
obtained To this 8-hydmxyquinoline solution was added slowly while
stirring. The mixtun was then stirred for half an hour and then neutralized
with saturated Na2CQ3 solution. The product precipitated out
the solutioll and WBS collected by filtering (7g, yield 80%) of 8-hydroxy-5-

azoquinoline hydrox~c was obtained after recrystallising the crude
product from ethanol (Mang et a1 1996).
2.4 PREPARATION OF ACRYLOYL CHLORIDE
Acryloyl chloride was prepared according @.the method of Stempel
et a1 (1950). A mixture of acrylic acid (46g, 0.64mol), benzoyl chloride
(178.8g, 1.28mol) and hydroquinone (0.5g) were taken in a 2L round bottom
flask and distilled at a fairly rapid rate. The hction boiling between 91-100°C
was collected which is then redistilled and the fraction boiling between 73-
75OC at 740mm Hg was collected, Yield 24 g (70%).
2.5 PREPARATION OF METHACRYLOYL CHLORIDE
Methacryloyl chloride was prepared from methacrylic acid (43 g,
0.5 mol) and bwoyl chloride (140.5g, lmol) adopting the method for the
preparation of acryloyl chloride. At first the fraction boiling between
95-140'C was collected which is then redistilled and collected, the hction
boiling between 95-97% at 740 mm Hg. Yield 19g, (66%).

2.6 MONOMER SYNTHESIS
The monomer 8-hydroxy-5-azoquinoline phenylacrylate (i) was
~reparcd by reacting 8-hydroxy-5-azoquinoline .hydroxybenzene (5.3g,
0.02M), hiethyl amine (2.78m1, 0.02M), EMK (251111) were taken in a three
necked flask quipped with stirrer, thermometer and stoppered funnel and the
contents were cooled to -S°C.Acryloyl chloride (Smmol) in EMK (2SmI) was
added drop wise with constant stining at that temperature. The reaction
mixture was gradually allowed to attain ambient temperature and stirring
continued for another 2hrs.The quaternary ammonium salt formed was
filtered. The filtrate was thoroughly washed with distilled water, dried over
anhydrous sodium sulphate and the solvent evaporated in vacuo. Yield: 75%.
By adopting similar procedure, the other monomer 8-hydroxy-5-azoquinohe
phenyl methacrylate(ii) was prepared (yield 82%).
2.6.2 Shydrory-5-~zoquinoline phenol-formaldehyde (8H5AQP-F)
A mixture of 8-hydmxy-5-azoquinoline hydroxy benzene (Smmol),
37% formalin solution (5mmol) and oxalic acid (0.2g, 3 ~O@en in a
reaction tube, sealed and placed in an oil bath at 100°C for 24 hrs. The tube
was then cooled, desealed and the water decanted. The solid remaining in the
tube was dissolved in DMF. The resulting solution was added drop wise to
10% aqueous sodium chloride solution (S00mI) with constant stining. The
product (iii) that wtcd was filtered, washed several times with distilled
water and dried in vacuo (yield 81%).

8-Hydroxy-5-azoquinolinephenol-formaldehyde (8HSAQPF) (2.6g,
0.02M) in DMF, triethylamine (2.78ml, 0.02M), hydquinone (0.5g) and
DMF (25ml) were taken in a three necked flask -equipped with a stirrer,
thermometer and separating funnel and the contents were cooled to 0 to -S0C.
Acryloyl chloride (1.8rnl,O.O2M) was added drop wise with constant stirring
at that temperature. The reaction mixture was then stirred for another two hrs
at room temperature and the quaternary ammonium salt was filtered off. The
filtrate was thoroughly washed with distilled water, dried over anhydrous
sodium sulphate and the solvent was removed to get a solid (iv)(yield 82%).
The IR and 'H-NMR spectra were consistent with the assigned
structure. By adopting similar procedure, the other macro monomer 8-
hydroxy-5-azoquinoline phenylmethacrylate-formaldehyde (v) was prepared
(yield 70%).
2.7 POLYMERISATION
The monomers i-v (except iii) were polymerised by free radical
polymerization using benzoyl peroxide as initiator. A typical procedure for
the polymc~ization of 8HSAQPA is described: 8-hydroxy-5-azoquinoline
phenyl acrylatc (3mmol) DMF (50rnl) and benzoyl peroxide 0.5g were taken
in a lOOml standard naction tube and purged with nitrogen gas for 3Omin,
closed and kept in a thennostat at 70°C for 8hrs and cooled. Excess of
methanol was added to the content, the precipitated poly(8HSAQPAXI) was
fikred, w W
with methanol and purified by dissolving in DMF and
mipitating with methanol. The purified polymer was dried in vacuo at
50°C fm conslant weight. By adopting similar p d w , the other polymm
Poly(8-hydmxy5-amquinoline phenyl mthacrylate(II), PO~Y@-~Y~XY-~-

azoquinoline phenol fddehy&)(III), poly(8-hydroxy-5-azoquinoline
phenyl acrylate formal&hyde(IV) and poly(8-hydroxy-5-azoquinolint
phenyl methacrylatc(V) were prepared.
2.8 PREPATION OF POLYMER-METAL COMPLEXES IN DMF
MEDIUM
Polymer-metal complexes were prepared at mom temperature by
solution technique. A typical procedure for the preparation of
poly(8H5AQPA>Cu(II) complex (Ia) is as follows. The polymer (6mmol of
repeat unit) was dissolved in 301111 of DMF. An aqueous solution of
Cu(II)/(Ni(II) acetate (0.62g) was added drop wise with constant stirring and
the pH of the solution was adjusted to 7 with dilute ammonium hydroxide
solution. The resulting mixture was digested on a water bath for 2hrs and kept
overnight at morn temperature. The precipitated polymer-metal complex of
Cu(I1) (Ia) was filtered, washed with hot distilled water followed by ethanol
and dried at 60°C in vacuo. By adopting similar procedure, the other metal
complexes (Ib, 11% Ilb, 111% IIIb, IVa, IVb, Va, Vb) were prepared.
2.9 CHARACTERISATION
2.9.1 Chemical Method
2.9.1.1 Eatlmrtion of metal content
lg of polymer-Cu(I1) metal complex was decomposed in muffle
furnace at 250°C for 2hrs.The decomposed product was washed with distilled
water, the residue dissolved in concentrated sulphuric acid(l0ml) and ma&
up to lOOml in a standard measuring flask. 20ml of the made up solution was
titrated against standard sodium thiosulfate iodometridly.
lg of polymer-Ni(I1) metal complex was decomposed in muffle
at 250°C for Zhrs. The decomposed product was washed with

distilled water, the midue dissolved in concentrated sulphuric acid(l0ml) and
made up to lOOml in a standard measuring flask. 20 ml of the made up
solution was complexed with standard DMG and estimated gravimetrically.
2.9.1.2 SolubUity test
Solubility of the polymers was determined in various solvents viz.
DMSO, DMF, THF, DMAc, methanol, acetone and chloroform. 2-3mg of
substance was treated with 5ml of solvent and kept aside for 6hr with
occasional shaking. If the polymer is insoluble in cold condition, the mixture
was heated and cooled.
2.9.1.3 Viscosity
1% solutions of the polymer in dimethylformarnide were prepared
and filtered through glass filter to remove any dust particles. The dust free
polymer solutions were taken in an Ubbelohde suspended level viscometer
with a flow time of 160 seconds for dimethylfomamide at room temperature.
Flow times for the polymer solutions and solvent were recorded at the same
temperature. Intrinsic viscosities [q] for the polymer solutions were
determined using the following set of expressions.
Relative viscosity q, = tl/ttl
where ti and t2 arc time of flow for solvent and polymer solution
respectively.
Specific viscosityrl, = qr =I
The intrinsic viscosity [q] was calculated by plotting, qrp versus C
and wrtrspalatine straight line to zero concentration. The intercept
0btahe-d gives tbe value of [q] for polymer.

2.9.2 Analytical metbod
2.9.2.1 Elemental analysis
Elemental analysis was canied out on a HERAEUS-CHNO-RAPID
ANALYSER with sample weight of 3-5mg.
2.9.2.2 Gel permeation chromatography
The weight and number-average molecular weights ((Mw) and
(G.)) of the polymers were determined on a gel permeation chromatography
(Waters 501) equipped with a ultra gel column and refractive index (RI)
detector. Tetrahydrofuran was used as a mobile phase in the column. The
column was calibrated with standard polystyrene samples of molecular weight
ranging from 1,00,000 to 5,000.
2.9.23 Infrared spectroscopy
IR spectra (KBr pellet) of the polymer and their respective metal
complexes were recorded on a Bomem MB 104 FT-IR spectrophotometer.
2.9.2.4 'H-NMR spectroscopy
'H-NMR spectra of the polymers were recorded on a 400 MHz
'H-NMR spectrometer at room temperature in DMSO-d6 using TMS as
internal standard.
2.9.25 Differential Scanning Calorimetry
The glass transition temperature (Tp) of the polymers and their metal
complexes wen dacrmined on a Mettler-TA3000 differential scanning
calorimeter at a hating rate of 1 S°C/min with a sample weight of Smg in air.

2.9.2.6 Tbemogrrvfmetric analysis
The thermogravimetxic analysis of the polymers and polymer-metal
complexes were wried out on a Mettler TA3000 thermogravimetric analyzer.
5mg of sample was charged in the thermobalance of the analyzer and heated
from ambient temperahue to 800°C at a uniform rate of 1O0C/min in nitrogen
atrnosph~rc.
2.9.2.7 Mapetlc moment measurement
Magnetic moment studies of the plymer-metal complexes were
conducted using Guoy method with sample weight of 2mg and corrected for
the diamagnetism of the component atom using Pascal's constant.
2.9.2.8 Diffuse reflectance spectroscopy
Diffuse nflectmce spectra of the polymer-metal complexes were
recorded on a karl-zeiss VCU-28 spectrophotometer using MgO pellets.
2.9.29 X-ray diffraction
Thc X-ray difhction experiments were performed on Phillips PW
1820 diktometcr with staton camera, using CuKa radiation of wavelenth
1.542 A'.
2.9.2.10 Ektrkd conductivity measurements
Thc electrical conductivity measurements for polymer-metal
COItIplexss wort && out on a Keithley 640 electrometer, in the form of a
pella (thiclrm&-3mm, diameter IOmm, length 2mm). Silver paint Was

applied on either side of the pellet to act as a supporting electrode and provide
good conducting contact between sample and electrode. The temperature of
the sample was measured using Chromel-Alumal thermocouple. The whole
assembly was kept inside a metal jacket and evacuated. The sample
temperatun was controlled using a heating coil on the metal jacket. The
instrument was calibrated with a low conductivity standard sample to ensure
no tracking in the instrument.
2.10 APPLICATION STUDIES
2.10.1 Catalytic aetMty of polymer-metal complexes
2.10.1.1 Polymerisation initiation
Polymerisation initiation reaction was canied out in a 100 ml
standard polymerisation tube taking N-vinylpyrrolidone (3.5mmol), polymer-
metal complex (0.05mmol) (based on the metal) and EMK(lOm1) and
deaerating the mixture, by passing nitrogen gas for half an hour. The
polymerization tube was sealed and kept in a thermostat for 8hr at 75°C.
Then the reaction mixture was poured into a beaker containing excess of
methanol. The precipitated polymer was filtered and washed with benzene.
The purified polymer was dried in vacuo at 60°C (Tsuchida and Nishide
1980).
Polyma metal-complex (0.05mmol based on the metal),
ethylacetate (lDml), distilled watefl25ml) and methanol(l5ml) wcre taken in a
1hd round bottomed flask and mixed well. The reaction mixhrre was kept
in a thamoatat at 60°C and nitrogen was bubbled through the solution for
Sh. The d o n &me was filtered. Aliquot(lpl) was withdrawn and
BnalYsed by prs chromntography (Angelici and Hopgood 1968).

2.10.2 Metal uptake mdies of polymer In the preaence of electrolytes
The polymer sample(25mg in 25ml of DMF) was added in an
electrolytic solution (25ml) of sodium chloride of known concentrations. The
pH of the solution was adjusted by using O.lMHC1 or O.lMNHo .The solution
was stirred for 24h at room tempemture. To this mlution lOml of 0.1M
solution of metal ion Cu(II)/Ni(II) was added and the pH was adjusted to the
required value. The mixture was again stirred at 25OC for 24hrs and filtered.
The solid was washed and the Cu(I1) ion content was detennined
iodimetricallly and Ni(I1) ion by gravimetrically. The amount of the metal ion
uptake of the polymer was calculated from the difference between a blank
experiment without the polymer and the reading in the actual experiments.
The experiments were performed in the presence of sodium sulphate with
Cu(I1) and Ni(II) ions.
2.103 Effect of pH on metal-ion uptake
The optimum pH of the metal ion uptake was determined with a
batch equilibration technique. Excess of metal ions Cu(II)/'Ni(II)(lOml, 0.1M)
were shaken with 25mg of the resin for 24hrs. The pH of the solution was
adjusted before equilibration over a range of 1-10 with weak acidlbase. The
complex was filtered off, and the concentration of the Cu(I1) ion remaining in
the filtrate was detennined by iodometrically and Ni(I1) by gravimetrically.
2.10.4 Effect of contact time on metal-ion uptake
The saturation time was obtained by plotting pentage of metal
uptake against conmct time by keeping initial metal ion concentration fixed
(2000kg per lorn]). The metal ions Cu(II)/Ni(II) were shaken with 25mg of
the min. The complexes were filtered off, and the concentration of the Cu(I1)

ion remaining in the filtrate was determined by iodomehically and Ni(I1) by
gravimetrically.
2.10.5 Regenerative ability
The regenerative ability of polymer-metalpmplex was carried out
as follows. Polymer-metal complex(Ia)(l.Og) was taken in a boiling tube. To
this hydrochloric acid (10m1, 7M) was added and set aside for lhr. The blue
colour solution thus formed was filtered and the polymer was washed with
dilute HCI, distilled water and dried in vacuo at 50°C. The dried polymer was
used again for complex formation. This revealed the good recyclability and
stability of the polymer under acidic condition. This cycle was repeated
several times to detmine the reusability of the functiondised polymer (Kratz
and Hendricker 1986).

CHAPTER 3
RESULTS AND DISCUSSION
The investigation comprises synthesis of new functionalised
monomers and mammonomers, their respective polymers in DMF medium,
complexation of polymers with divalent metal ions, characterization of the
monomers, polymers and polymer-metal complexes. The research work deals
with the studies on application of the polymer-metal complexes and
conductivity studies. It also includes the model studies on the application of
the polymer-metal complex Ia and Ib towards polymerization initiation as also
suitability of the complexes towards regeneration / recyclability in aqueous
solution.
3.1 SYNTHESIS OF MONOMERS
Monomers containing a free radical polymerisable
acryloyVmethacryloy1 group with functionalised co-ordinating site were
synthesized. The acryloyVmethacryloyl chloride was treated with 8-hydroxy-
5-azoquinoline hydroxy benzene (Figure 3.1) in the presence of hiethyl mine
in DMF. The preparation of monomers is shown in Figure 3.2.
3.2 SYNTHESIS OF MACROMONOMERS
M~~r~rnonomm containing the polymerisable vinyl group were
s~nthesizcd by condensing 8HSAQPAl8HSAQPM.4 with fonnaldehydc in the
Presence of oxalic acid. The synthesis of formaldehyde resin was shown in
Fim 3.3 and the synthesis of mammonomers, polymers are shown in
Fim 3.4 and Figun 3.5.

Figure 3.1 Synthesis of ghydrory-5-nzoquinolinehydroqbellzene
Figure 3.2 Preparation of (meth)acrylate monomers

" + HCHO -
N=
\ / OH
Oxalic acid
100 'C
(iii) or (III)
Figure 33 Preparation of formaldehyde resin

R-C=CH2
I
y=o
BPO
_.c
R- CH, F=
c=o
N=N N=N
when R = H Poly(8HSAQPA-F)
R = CH3 Poly(8H5AQPMA-F)
Figure 3.4 Synthesis of macromonomers and polymers
R

DMF
When R = H Poly(8HSAQPA) -I
R = CH, Poly(8HSAQPMA) -11
Figure 3.5 Synthesis of polymers

33 CHARACTERISATION OF MONOMERS AND
MACROMONOMERS
Table 3.1 summarizes the physico-chemical characteristics of
monomm and macromonomers. The elemental analysis data are in good
agreement with the calculated values.
3.4 SYNTHESIS OF POLYMERS
The monomers and macromonomers (i,ii,iv,v) were polymerized by
free radical polymerization using benzoyl peroxide as initiator in an inert
atmosphere at 70°C for 8hrs in a standard polymerization tube (Figure 3.4,
3.5). The yield of the polymers (Table 3.2) are in the order II>III>N>I>V.
3.5 PREPARATION OF POLYMER-METAL COMPLEXES
The polymers were dissolved in DMF medium and treated with
aqueous solution of Cu(II)Mi(II) metal ions in the presence of a few drops of
ammonia at ambient temperature(Figure 3.6). The yield of the polymer-metal
complexes is given in Table 3.3.Ni(II) complexes are formed in a lower yield
than Cu(I1) complexes in some cases. This is in line with the report by
Gustafson(l968) that the formation constant of poly(methacIy1ic acid)-metal
complex decreased in the order Cu(1I) > Ni(II) and also the deprotonation
capacity of Cu(I1) is more than that of Ni(I1) (Rivas 2003 and Mendez et al
1990).

L
No
I
I1
111
IV
V
Table 3.2 Yield of the polymers I-V
Polymer
Poly(SH5AQPA)
Poly(8HSAQPMA)
Pol y(8H5AQPF)
Poly(8HSAQPA-F)
Poly(8HSAQPMA-F)
Yield (%)
69
75
72
70
68
-

M = Cu2'1 Ni2'
(For Ni, X = H,O)
Figure 3.6 Synthesis of polymer-metal complexes

3.6 CHARACTERIZATION OF POLYMERS AND POLYMER-
METAL COMPLEXES
3.6.1 Solubility
The solubility of the polymers in various solvents was tested and
results are summarised in Table 3.4. At ambient temperature all the polymers
are soluble in chloroform, THF, DMF, DMAc, and DMSO while they arc
insoluble in common organic solvents viz,. benzene, toluene, methanol, CC4,
acetone. All the polymer-metal complexes are insoluble in non-polar and
hydroxyl solvents whereas swell in DMF, DMAc and DMSO.
3.6.2 Viscosity
The viscometric results are shown in Figure.3.7 and Table 3.5. The
intrinsic viscosity q was obtained by extrapolating qwc to zero concentration.
The results reveal that the molecular weights of these polymers are
moderately high.
3.6.3 Molecular weights
The weight (Mw) and number (En) average molecular weight and
polydispersity index (Mw / k ) of the polymers were determined by gel
permeation chromatography and the data are presented in Table 3.5. The
polydispersity indexes of the polymers are around 2.1-2.2. This is suggestive
- -
of chain termination by radical recombination. The MW and M. values are in
accordance with intrinsic viscosity data.

Table 33 Yield of polymer-metal complexes Ia-Vb
No
1
2
3
4
5
6
7
8
9
10
Polymer metal complexes
Poly(8HSAQPA)-Cu(I1)
Poly(8HSAQPA)-Ni(I1)
Poly(8H5AQPMA)-Cu(I1)
Poly(8HSAQPMA)-Ni(I1)
Poly(8HSAQPF)-Cu(I1)
Poly(8HSAQPF)-Ni(I1)
Poly(8HSAQPAF)-Cu(I1)
Poly(8H5AQPAF)-Ni(I1)
Poly(8HSAQPMA)-Cu(I1)
Poly(8H5AQPMA)-Ni(I1)
Yield(%)
80
79
85
84
75
73
85
83
68
65

DMF
DMAc
DMSO
+ = Soluble, - = Insoluble
Table 3.4 Solubility parameters of I-V
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t

(12 a4 a6 a8 1.0
Concentration
Figure 3.7 Viscometric results of polymers

Table 3.5 Intrinsic viscosity and molecular weights of polymers I-V

3.6.4 Elemental analysis
The C, H, N, and 0 of the polymers and polymer-metal complexes
were analysed by elemental analysis. The metal ion content was analysed by
titrimetric and gravimetric method respectively. The data are presented in
Tables 3.6 and 3.7. It may be noticed that the metal to ligand ratio in all the
polymer-metal complexes is 1:2.
3.6.5 Infrared spectroscopy
The infrared spectra of polymers and polymer-metal complexes are
shown in Figure 3.8-3.12 and the corresponding spectral data presented in
Table 3.8.The polymers exhibit strong bands around 1700-1750cm'l due to
C=O group of ester. Strong bands around 1540- 1590cm" may be due to N=N
group. The medium intense band around 11 70 cm-' due to the ester C-0 and
one around 1350cm-' due to phenolic C-0 in the polymer undergo shift
towards higher frequency in the polymer-metal complex suggestive of the
pendant ligand involved in co-ordination. The broad absorption in the region
3400-3000 cm" is due to intramolecular hydrogenbonded-OH stretching
(Freedman 1961) presumably formed between phenolic -OH and heterocyclic
nitrogen. This band completely disappears in the spectra of copper-metal
complex (except in IIIa) establishing the involvement of the phenolic-OH in
co-ordination (Garg et a1 1971). However, in the case of nickel complex there
is a strong absorption around 3500 cm-I, which does not disappears even on
the sample being heated uptol5O0C. This band, therefore has to be due to
water molecules taking part along with Ni(I1) ions during co-ordination
(Kaliyappan et a1 1994). The band around 725 cm-' and 550cm" conesponds
to metal-oxygen vibration and metal-nitrogen vibrations. (Veno and Martell
1953 and Zundtl 1969).

Figure 3.8 IR spectra of poly(SHSAQPA)(a), poly((8HSAQPA)-
Cu(II)@) and poly(8HSAQPA)-Ni(II)(c)

Figure3.9 IR spectra of poly(8HSAQPMA)(a), poly((8HSAQPMA)-
Cu(II)(b) and poly(8HSAQPMA)-Ni(II)(c)

Figure 3.10 IR spectra of poly(EHSAQPF)(a), poly((8HSAQPF)
Cu(II)@) and poly(8HSAQPF)-Ni(II)(c)

Figure 3.11 IR spectra of poly(8HSAQPAF) (a), poly((8HSAQPAF)-
Cu(l1) (b) and poly(8HSAQPAF)-Ni(I1) (c)

Figure 3.12 IR spectra of poly(lHSAQPMAF)(a), poly((BH5AQPMAF)-
Cu(II)(b) and poly((lH5AQPMAF)-Ni(II)(c)

3.6.6 'H-NMR Spectroscopy
'H-NMR spectra of the polymers (I-V) are shown in
Figure 3.13-3.17. The chemical shift values are presented in Table 3.9. All
the spectra shows signals at 9.53 - 8.66 are a result of aromatic-OH. In all the
polymers, the signals due to aromatic protons appear as a broad multiplet in
the region 8.1-6.26. The resonance signals ar&nd 2.9- 2.28, 1.9-1.28 and
1.4-1.256 are due to backbone methine, methylene and &methyl proton
respectively (Kaliyappan et al 1996a and Vijayalakshmi et al2006).
3.6.7 Differential Scanning Calorimetry
DSC thermograms of polymers and polymer-metal complexes are
presented in Figure 3.18-3.22 and the T, values are indicated in Table 3.10.
The data reveals a minimum value of 140°C for polymer and the maximum of
390°C for polymer metal-complexes. The comparatively higher T, values for
methacrylate polymers and their metal complexes may be ascribed to the
bulky nature of the substituent group and the excessive cross-linking due to
the methylene bridges (Bondi 1955). The T,values of methacrylate polymers
and their metal complexes are 20-50" C higher than those of the corresponding
acrylate polymers and their acrylate polymer metal complexes since the glass
transition temperature for polymer-metal complexes are controlled by fiee
volume. A similar observation of higher T, values for polymer-metal complex
over polymer was reported by Eisenberg and King (1977), ascribing the same
to strong ion dipole interaction and decreased average segmental mobility.
The DSC thermograms indicate sharp T, for polymer-metal
complexes as against broad T, for the respective polymers indicating that the
polymer-metal complexes are crystalline while the polymers are amorphous.

(O 9 6 i e s - 7
6 PPM
2
Figure 3.13 'H-NMR spectrum of poly(8HSAQPA)

Figure 3.14 'H-NMR spectrum of poly(SH5AQPMA)

- lb L 0
SPP~
Figure 3.15 'H-NMR spectrum of poly(8HSAQPF)

Figure 3.16 'H-NMR spectrum of poly(8HSAQPAF)

Figure 3.17 'H-NMR spectrum of poly(8HSAQPMAF)

Table 3.9 'H NMR spectral data of polymers I-V

Figure3.18 DSC curves of poly(SHSAQPA)(a), poly((8HSAQPA)-
Cu(II)(b) and poly(8HSAQPA)-Ni(II)(c)

Figure3.19 DSC curves of poly(8HSAQPMA)(a), poly(8HSAQPMA)
Cu(II)@) and poly(8HSAQPMA)-Ni@I)(c)

Figure 3.20 DSC curves of poly(8HSAQPF)(a),poly(8HSAQPF)-
Cu(II)(b) and poly(8HSAQPF)-Ni(II)(c)

Figure 3.21 DSC curves of poly(8HSAQPAF)(a), poly((8HSAQPAF)-
Cu(II)@) and poly(8HSAQPAQ-Ni(II)(c)

& tio t i tto tie 310
I
3m 410 40 510
Tcmpcratun ('c)
Figure 3.22 DSC curves of poly(SHSAQPMAF)(a), poly((SH5AQPMAF)
-Cu(II)(b) and poly(SH5AQPAMF)-Ni(II)(c)
I
//
/ I

3.6.8 Thermogravimetric Analysis
The thermal stability and decomposition temperature of polymer
and polymer-metal complexes were studied by thermogravimetric analysis in
nitrogen atmosphere. The TGA traces are given in Figure 3.23-3.27. The
thennoanalytical data are presented in Table3.10 and Table 3.11. All the
polymers and polymer-metal complexes start to decompose around
100-275OC and around 300-39% respectively. Around 700°C the polymers
lose 99%, while the polymer-metal complexes 60-91% weight. The residue
left behind in the complexes corresponds to the formation of respective metal
oxides. The Cu(I1) complexes are comparatively more stable than Ni(I1)
complexes. (Kaliyappan et al 1996 and Vijayalakshmi et al2006a)
From the TGA traces of polymers it is observed that the stability
follows the order: Cu(I1) complex > Ni(I1) complex > polymer. Similar trend
was observed in the case of both Ni(I1) and Cu(I1) complexes. In all the cases
polymer and respective Cu(I1) complex show two step degradation, where as
Ni(I1) complexes show three steps degradation. This may be ascribed to
elimination of water molecule followed by chain scission and carbonization,
in the case of Ni(I1) complexes.
3.6.9 Magnetic Moment Measurements
The magnetic moments of all the complexes were measured and the
data furnished in Table3.12. The magnetic moment values of all the Cu(I1)
polymer- metal complexes (Ia-Va) are in the range of 1.45 - 1.78 Bohr
magnetons (BM), which is in close agreement for square planar structure.
The values of Ni(I1) polymer-metal complexes(1b-Vb) range around
3.13 - 3.85 Bohr magnetons (BM), which is in accordance with octahedral
configuration(Pate1 and Patel 1990; Kaliyappan and Kannan1996).

Figure 3.23 TGA curves of poIy(8HSAQPA)(a),poly(8H5AQPA)-
Cu(II)(b) and poly(8HSAQPA)-Ni(II)(c)

Figure 3.24 TGA curves of poly(8HSAQPMA)(a), poly(8HSAQPMA)-
Cu(II)(b) and poly(8HSAQPMA)-Ni(II)(c)

Temp" C
Figure 3.25 TGA curves of poly(8H5AQPF)(a),poly(8H5AQPF)-
Cu(II)@) and poly(8H5AQPF)-Ni(II)(e)

Figure 3.26 TGA curves of poly(8H5AQPAQ(a),poly(8HSAQPAQ-
Cu(II)(b) and poly(8HSAQPAQ-Ni(II)(c)

Figure 3.27 TGA curves of poly(8HSAQPMAF)(a), poly((8HSAQPMAF)
-Cu(II) @) and poly(8HSAQPMAF)-Ni(Il)(c)

Table 3.12 Magnetic Moment of the Polymer-metal Complexes Ia-Vb
Polymer-metal
complex
IV a
IVb
Va
Vb
Magnetic moment
(BM)
1.75
3.81
1.82
3.95

3.6.10 Diffuse reflectance spectroscopy
The diffuse reflectance spectra of the polymer-metal complexes are
shown in Figure 3.28 - 3.32. The diffise reflectance spectra of all the Cu(I1)
polymer-metal complexes contain two bands, one around 15,150cm'~ and
another around 23,900cm" which may be to assigned d-d transition
corresponding to a symmetry forbidden ligand-metal charge transfer band of
square planar configuration. Similar observations for Cu(I1) complexes were
reported by several workers (Pate1 and Pate1 1990; Patel et al 1994 and
Kaliyappan et al 1996b).The diffuse reflectance spectra of all Ni(I1)-polymer
metal complexes show three bands around,12,525,14350, 16,500cm" which
may be due to 3~zs(~)+3~2,(~), 3~2g(~)+3~lg(~), and 'A~~(F)-+~TI,(P),
transitions respectively. The results are in accordance with octahedral spin-
free nickel complexes exhibiting three bands in their electronic spectra
(Jorgenson 1962: Figgis 1962; Vijayalakshmi, et a1 2006b)
3.6.11 X-ray diffraction studies
The X-ray diffractograms are shown in Figure3.33-3.37. The x-ray
diffraction studies shows that all the polymers are amorphous whereas their
polymer-metal complexes possess good crystalline nature. The crystallinity in
polymer-metal complexes may not due to any ordering in polymers induced
during metal chelates anchoring, more so, since anchoring of metals to
polymers would, imply interchain cross-linking between polymeric chain,
which should fuaha reduce rather than enhance any such ordering. The
appearance of crystallinity in polymer-metal complexes may be due to the
inherent crystalline nature of the metallic compounds (Eisenberg and King
1977).

Wave number em.'
Figure3.28 DRS spectra of poly((SH5AQPA)-Cu(II)(a) and
poly(8H5AQPA)-Ni(II)(b)

Wave number cm.'
Figure 3.29 DRS spectra of poly(8HSAQPMA)-Cu(II)(a) nod
poly(8H5AQPMA)-Ni(II)(b)

Wave number cm.'
Figure 330 DRS spectra of poly(8H5AQPF)-Cu(II)(a) and
poly(8HSAQPF)-Ni(II)(b)

Wave number cm-'
Figure 331 DRS spectra of poly((SH5AQPAF)-Cu(II)(a)
and poly(8H5AQPAF)-Ni(II)(b)

Wave number cm"
Figure 332 DRS spectra of poly((8HSAQPMAF)-Cu(II)(a) and
poly(8HSAQPMAF)-Ni(II)(b)

Figure 333 X-ray diffractogram of poly(8H5AQPA)(a),poly(8H5AQPA)-
Cu(II)@) and poly(8HSAQPA)-NiOI)(c)

Figure 3.34 X-ray diffractogram of poly(8HSAQPMA)(a),
poly(8HSAQPMA)-Cu(II)(b) and poly(8HSAQPMA)-
Ni(II)(c)

Figure 3.35 X-ray diffractogram of poly(llHSAQPF)(a),
poly(8HSAQPF)- Cu(II)(b) and poly(8HSAQPF)-Ni(II)(c)

Figure 3.36 X-ray diffractogram of poly(8HSAQPAF) (a),
poly(8HSAQPAF)-Cu(II)(b) and poly(8HSAQPAF)-
NiCII)(c)

Figure 3.37 X-ray diffractogram of poly(SHSAQPMAF)(a),
poly(8HSAQPMAF)-Cu(II)(b) and poly(8HSAQPM.
Ni(II)(c)

3.7 STRUCTURE OF POLYMER METAL COMPLEXES
From IR, 'H-NMR, diffuse reflectance spectra, elemental analysis,
magnetic moments and the structure of polymers it appears that the
complexation of metal ions may possibly be occumng between two groups
from different polymeric chains as shown iqFigure 3.38.
Figure 3.38 Structure of Polymer-metal Complexes
3.8 ELECTRICAL CONDUCTIVITY MEASUREMENTS
The electrical conductivity of the polymer metal complexes was
obtained by taking the reciprocal values of the specific resistivity of the
polymer metal complexes, measured by Keithley electrometer. The
conductivity values are listed in Table3.13. The electrical conductivity data
reveals that all the polymer-metal complexes are poor electrical conductor, the
values for Cu(I1) complexes being higher than that of Ni(I1) complexes
(Dewar and Talati 1964, Patel et a1 1994). This is in close agreement with
reported values for poly(2-hydroxy-4-methacryloyloxyacetophenone)
Cu(II)/Ni(II) complexes (Thamizharasi and Reddy 1992).

3.9 APPLICATION STUDIES
Poly(8H5AQPA)-Cu(II)Mi(lI) complexes were taken as model for
studies viz oxidation, hydrolysis, polymerization initiation and recyclability.
The oxidation of cyclohexanol to cyclohexanone in the presence of H202
proceed only with Cu(I1) complex. Yield (15%).
Table 3.13 Conductivity of the polymer-metal complexes Is-M
Polymer No.
Ia
IVa
Conductivity (ohm-' em")
2.7 xlw9
2.11 x1w9

Hydrolysis of ethylacetate with distilled water and methanol is
catalysed both by Ni(I1) and Cu(I1) complexes, the latter resulting in
comparatively more yield (21%) than the former(l5%).
Ni(I1) as well as Cu(I1) complexes initiate polymerization of
N-vinylpyrrolidone in DMF at 75°C giving yield of 28% and 35%
respectively.
Treatment of both Cu(I1) and Ni(I1) complexes with dil.HCl(7M)
result in quantitative regeneration of the polymer. The dechelated polymer
undergoes complexation with original efficiency. The reproducibility of the
above result was established by repeating the sequence several times,
revealing thereby the good recyclability as well as stability of the polymers
under acidic conditions.
3.9.1 Effect of pH on metal ion uptake properties
The effect of pH on the metal uptake of the chelating agents on solid
polymeric materials is a very important parameter. Ionization of the chelating
ligand and the stability of the metal-ligand complexes vary when changing
the pH shows a trpical behaviour of pH-sensitive polymer. In general, the
metal uptake was seen to significantly increase with increasing pH .This result
could be explained by metal-ion competition with protons at varying pH;
when the pH increased, the electron pair of the nitrogen of quinoline ligand
from polymers were more available to interact with the metal ions
(Table 3.14). Similarly, at higher pH, the aromatic -OH indicated a higher
metal-ion affinity to form polymer-metal complexes. Complex stability
depends strongly on the pH, at low pH, where the majority of the quinoline
goups are prbtonated, the metal-ion affinity is poor and the complex stability
is low. As the pH increases, the affinity and stability of the polymer-metal
complexes increases. The magnitude of increase, however, was different for

different metal cations. Cu(I1) was absorbed selectively to the higher extent
over the pH range (Figure 3.39-3.41). In general, the retention of polymer-
metal complexes increased as pH increased(Mende2 et a1 1990;
vijayalakshmi et a1 2007).
90 -
85 -
0,
Y -
d
5 80-
2 -
E 75-
0,
D
+
m -
70-
60
2 3 4 5 6 7 8 9 1 0 1 1
PH
Figure 3.39 Percentage metal uptake of poly(8HSAQPA) at different pH

Figure 3.40 Percentage metal uptake of poly(BH5AQPMA) at different
pH

Figure 3.41 Percentage metal uptake of poly(8HSAQP-F) at different pH

Figure 3.42 Percentage metal uptake of poly(8HSAQPA-F) at different
PH

Figure3.43 Percentage metal uptake of poly(8HSAQPMA-F) at
different pH

Table.3.14 Percentage metal uptake of polymem at different pH
Polymer pH Percentage Copper
Uptake
Percentage Nickel
Uptake
I

3.9.2 Influence of electrolytes on metal ion uptake properties
Table 3.15 -3.19 reveals that the amount of metal ions taken up from
a given amount of a polymer depends on the nature and concentration of the
electrolyte present in the solution. In the presence of chloride and sulfate ions
the uptake of Cu(I1) and Ni(I1) ions increases with an increasing concentration
of the electrolytes. This observation can be explained on the basis of the
stability constant with these metal ions (Gurnule 2003a).
3.93 Effect of contact time on metal-ion uptake
The rate of Cu(I1) adsorption was more than that of Ni(I1). Several
authors (Mendez et a1 1990) have noted higher adsorption of Cu(I1) over other
metal ions. It is known that the insoluble chelating resins take up transition
metal ions in high yields from aqueous media, but they often adsorb metal
ions very slowly due to the lower activity of the ligands placed inside the
resin. The metal complexing nature of the polymer depends not only on the
nature of the ligand groups, but also their accessibility towards metal ions.
Thus steric hindrance by the polymeric matrix and the hydrophobic nature of
the polymer ligands can limit the chelating reaction (Sankar et a1 2007).
The presence of quinoline ring nitrogen atom was responsible for
higher uptake percentage of the metal ion (Figure 3.44). However, in case of
formaldehyde resin, the reason could be due to the connection of various
structural units through -CH2 groups leading to a rigid network structure.

Table 3.15 Percentage metal uptake of poly(8HSAQPA) with different
electrolytes
/ Metal I pH / Electrolyte / Percentage of the metal ion taken
(mol L") up in the presence of
0.05
0.1 90

Table3.16 Percentage metal uptake of poly(8HSAQPMA) with
different electrolytes

Table 3.17 Percentage metal uptake of poly(8HSAQP-F) with different
electrolytes

Table3.18 Percentage metal uptake of poly(8HSAQPA-F) with
Metal
Ion
different electrolytes
pH
3
Electrolyte
(mol L")
0.01
0.05
0.1
Percentage of the metal Ion taken
up in the presence of
NaCl
Nn2S04
73
55
75
51
90
3 5

Table3.19 Percentage metal uptake of poly(8HSAQPMA-F) with
different electrolytes

Figure3.44 Metal uptake in different contact time for the polymer

3.10 MODEL STUDY OF POLYMER METAL COMPLEXES IN
AQUEOUS MEDIUM
A model study was carried out for the preparation of
Poly(8HSAQPA) complex with Cu(II), Ni(I1) in aqueous medium at room
temperature. The polymer metal complexes were characterized by elemental
analysis, magnetic moment, and diffuse refletance spectroscopy studies.
The elemental analyses are presented in Table3.20. The magnetic
moment, diffuse reflectance spectral data are presented in Table 3.21. The
results reveal that the structure of Cu(I1) complex is square planar, whereas
Ni(I1) complex is octahedral. These complexes were also tested for
regeneration/recyclability, indicating good recovery, which will be of
immense value in water-treatment, hydrometallurgy and trace metal ions
removal. The structure of polymer metal complexes is shown in Figure 3.45.
Figure 3.45 Structure of polymer-metal complexes

CHAPTER 4
SUMMARY AND CONCLUSION
The investigation comprises synthesis and characterization studies
of polyacrylates containing pendant ligand with heterocyclic nitrogen and
hydroxyl functions and their Cu(II)/Ni(II ) complexes in DMF medium, along
with application oriented studies for the complex, poly(8HSAQPA)
Cu(II)/Ni(II) as a model. The following salient results emerged out of this
investigation:
Acrylates containing pendent ligand with heterocyclic
nitrogen and hydroxyl functions undergo free radical
polymerization under inert atmosphere with moderate
conditions giving the polymers in good yield.
$ The polymers in DMF are converted to polychelates in good
yields, by treatment with aqueous solution of Cu(II)Mi(II)
ions.
*:+ The polymers are freely soluble in THF, DMF, DMAc, and
DMSO and insoluble in benzene, toluene, acetone and
methanol, while the polychelates are insoluble in all these
solvents.

9 The molecular weights of the polymers (Mw) arc modmtely
high of the order 3.72~10'- 3.96~10' as evidenced by
viscosity and GPC.
Q TGA and DSC studies reveal that the polychelates arc more
heat resistant than the respective polymer counterparts, the
initial decomposition (10%) being around 300°C for the latter
as against around 400°C for the former.
Q The amorphous nature of the polymers in contrast to
crystallinity of the respective polymer-metal complex is
indicated by DSC and XRD analysis.
*:* Elemental analysis reveals that the metal to polymer ligand
ratio is 1:2 in all the cases. Further, metal ion uptake by the
polymers follows the order: poly(8HSAQPA-F) >
poly(8HSAQP-F) > poly(8HSAQPA) > poly(8HSAQPMA)
>poly(8HSAQPMA-F) at different pH, and all the polymers
shows higher metal ion uptake at higher pH at different
concentration of electrolytes.
9 As evidenced by Infra-red, DRS and magnetic moment data,
in the case of Ni(I1) polychelates co-ordination with the metal
involves quinoline nitrogen and -OH groups along with
two water molecules leading to octahedral structure. On the
other hand, the structure of Cu(I1) complex is squre planar
where co-ordination with metal is only through - N and -
OH fhnctions.

9 All the polychelates possess poor electrical conductivity as
shown by electrical conductivity measurements, thus
behaving as insulators.
*:* Application oriented study on poly(8HSAQPA)-Cu(II)/
Ni(I1) complexes reveal the following:
Both complexes catalyse hydrolysis of ester and initiate
polymerization of N-vinyl pyrrolidone.
Recoverylrecyclability of the polymers from the
complexes in acid medium (7M) HCI is good and
reproducible. Further, the polymers are stable in the said
acidic conditions.
Cu(I1) complex catalyse the oxidation of cyclohexanol
to cyclohexanone in the presence of H202, while Ni(I1)
chelates do not.
The model study of synthesis and characterization of
poly(8HSAQPA) complexes with Cu(I1) and Ni(I1)
ions indicate that:
Cu(I1) complex is square planar
Ni(I1) complex is octahedral
Recovery of the polymers from the polychelates in acid
medium is good, the polymers being stable under those
acidic conditions. This will be of immense value in
water treatment and recovery of trace metal ions.

REFERENCES
Adelz.E.S, Ashraf.A.E.B, Mostafa.A.D, Mohamad.A.E.E, and
Sami.A.M., Polym Degradn. and Stability., (1993), 42, 1-1 1.
Agarwal.H, and Chandra.S., Indian Joumal of Chemistry., (2004),
43A, 2361-2364.
Aganval.M, Bennett.R.B, Stump.I.G, and D'Auria.J.M.,Anal Chem.,
(1975), 47,924.
Akaiwa.H and Kawamoto.H., Rev.Anak.Chem., (1982), 6,65.
Ange1ici.R.J and Hopgood.D., J.Am.Chem. Soc., (1968), 90, 25 14-
25 17.
Arafa.1, El-Ghanem.H and Al-Shalapi.R., J.Inorg and Organometallic
Polymer.,(2003), 13,69.
Astheimer.L, Schenk.H.J, Whi1te.E.G and Schwochan. K., Sep. Sci
Technol., (1983), 18,307.
Aswar.A.S, Bansod.A.D, Aswa1e.S.R and Mandik.P.R., Indian
Journal of Chemistry., (2004), 43A, 1892- 1896.
Atsushi Sugh, 0gawa.N and Hashizurne.H., Talanta., (1979), 26,189-
192.
Bajpai.U.D.N, Rai.S, and Bajpai.A., Polym Int., (1993), 32,215-20.
Balasubramaniam.K.P, Karvembu.R, Chinnasamy.V and Natarajan
K., Indian Journal of Chemistry., (2005), 44A, 2450-2454.
Bmazak.J.L, Wats0n.H.C and Kendrew.J.C., J.Mol.Biol., (1 965),
2,130-7.
Banerjee.D, Mondal.B.C, Das.D and Das.A.K.,Microchim.Acta.,
(2003), 141,107.
Bmk.E, 0kamato.Y and Veha.Y., J.Polym. Sci., (1980), 25,35948,

Bao.Y.T, and Pitt.C.G., J Polym Sci A: Polyrn Chem Ed., (1990), 28,
741-58.
Barbucci.R and Campbell.M.J.M., Inorganica Chemica Acta., (1976),
16,113-120.
Basita.T.K, Lenka.S and Nayak.P.L., Macromol.Rep A., (1994),
31,5361.
Bilba.D, Bejan.D and Tofan.l., Croatica Chimica Acta., (1998), 71(1),
155-178.
Bisset.W, Jacobs.H, Koshti.N, Stark. P and Gopalan.A., Reactive and
Functional Polymers., (2003), 55, 109-1 19.
Biswas.M, and Mukherjee. A., J. Appl. Polyrn. Sci., (1995), 56,501-
8.
Bolto.B.A., J.Macromol.Sci. Chem A,, (1980), 14,107-12.
Bondar.Y, Kim.H.J, Y0on.S.H and Lim.Y.J, Reactive and Functional
Polymers., (2004), 58,2313-2321.
Breslow.R, and Overman. L.E., J.Am.Chem.Soc., (1970), 92,1075-7.
Busev.A.1, Tiptsova.V.G, and 1vanov.V.M. Moscow Mir.,
(1981),105. (Translated from Russian by Alexander Rosikin).
Cao. S.K, Huang. M.Y, and Jiang Y.X. J Macmmol.Sci. Chem A.,
(1989), 26,381-9.
Capaka.M, Svoboda.P, and Heltlej's., Tetrahedron Len., (1971),
4787.
Card.R.J, Liesner.C.E, and Nekers.D.C., J.Org Chm., (1979), 44,
729-34.
Chattopadhyay.P, Sinha.C, and Pal Fresenius.D.K, J.Anal.Chm.,
(1997), 357,368.
Chauhan.G.S, Kumar.S, Kurnari.A and Sharma.R., J. Applied
Polymer Science, (2003), 90,3856-3871.

Coleman.A.K., New concepts in the handling of industrial wastes.
Chem Ind., (1975), 5,5344.
C0lman.P M, Freeman.H.C, Guss.J.M, Murata.M, Nonis.V.A,
Ramshaw JAM, and Venkatappa.M.P., Nature., (1978). 275319%
324.
Damasceno.J, Gomes. C.A.T, Reiurnont. J, Sanchez.R., Materials
Research., (2002), 5,2201-204.
Das.D, Das. A.K, and Sinha.C., Talanta., (1999), 48, 1013.
Das.D, Dinda.J, Mondal T.K, Sarcat.K.K and Sinha.C., J.Indian
Chem.Soc., (2006), 83,861.
Davankov.V.A, and Rogozhin.S.V., J Chromatogr., (1974), 60, 280-
3.
Davies .R.V, Kennedy.J, Lane.E.S. and Willirams.J.L., Appl.Chem.,
(1959), 9,368.
Dev.K and Rao G.N., Talanta.,(1996), 43,45 1.
Dev.K and Rao G.N.,Analyst.,(l995), 120,2509.
Dev.K and Rao.G.N., Talanta.,(l995a), 42, 591
Dewar.M.J.S, and Talati.A.M., J.Arn.Chern. Soc., (1964), 86,1592-
1595.
Dey .R.K, Acharya.S, Sama1.S. and Ray.A.R., Indian J.of Chemical
Technology (2004). 11,695-703.
Donaruma.L.G, Kitoh.S, Walswork.G, Depinto.J.V, and
Edzwald.J.K., Macromolecules., (1979), 12,435-8.
Ebraheem. K.A.K and Hamdi.S.T., Reactive and Functional
Polymers., (1997), 34, 5-10.
Eisenberg. A, and King.M., Academic Press, Inc., New York, (1977),
2,45.
Figgis. B.N., Introduction to ligand fields,Wiley Interscience,
Newyork., (1962), 25.
Flcming.C.A, and Nicol.M.J., Proc Hydrometallurgy., (1981), 81, 1.

F0rd.W.C and Balakrishnan.T., Macmmolecules., (1981), 14,284.
Freedman.H.H., J.Am.Chem. Soc.,(1961), 83,2900-2905.
Fumiss.B.R, Hannaf0rd.A.J. Smith P.W and Tatchell.A.R.,(1994),
'Vogel's textbook of practical organic chemistry' ,Fifth edition,
ELBS, London.
Ganeshpure P.A, Satish.S, and Sivaram.S., J Mol Catal., (1989),
5O:Ll-L5.
Garg.C.L,Narasimhan.K.V and Tripathi B.N., J.Inorg.Nucl.Chem.,
(1971), 33,387-392.
Gh0sh.J.P andDas.H.R., Talnanta., (1981), 28, 274.
Gigy Abraham and Purushothaman.E., Indian J.of Chemical
Technology., (2003), 10,175-1 79.
Gitzel.J, Ohno.H, and Tsuchida.E., Polymer., (1986), 27,1781-7.
Gomez.E, Freer.J and Bae2a.J. Bol. Soc. Chil. Quim., (1982), 27,
188-90.
Greger.H.P, Luttinger.L.B, and Leol.E.M., J.Phys Chem.,(1955), 59,
34.
Gmbbs.R.H, and Kroll.L.C., J Am Chem Soc., (1971), 93,3062.
Gupta.K.C, Abdul Kadir.H.K and Chand.S., J.of Macromolecular
Science Pure and Applied Chemistry., (2003), 40,475-500.
Gurnule.W.B, Juneja H.D and Paliwal.L.J.,Reactive and Functional
Polymers., (2002), 50, 95-100.
Gumule.W.B, Rahangdale.P.K, Paliwal L.J, and Kharat R.B.,
Reactive and Functional Polymers., (2003), 55,255-265.
Gumule.W.B, Rahangdale P.K, Paliwal L.J, and Kharat R.B,
J.Applied Polymer Science., (2003a), 89,787-790.
~ustafson.~.~ and Lirio.J.A., J.of Physical Chemistry., (1968),72, 5.
Hirai.H, and Nakamura.Y., Chem Lett., (1974),4,809-14.

Hi1ai.Y and Nakajima.T., J. Applied Polymer Science., (1989), 37,
2275-228 1.
Hodgkin.J, and Eibl. R., React.Polym. Ion Exchange sorbents ,
(1985), 3,78-93..
Hojo.N, Shirai.H, Chijo.Y, and Hayashi S., J.Polym.Sci. Polym.Chem
Ed., (1978), 16,447-55.
Honda. K, Chiba.K, and Hayashi.H., J Macromol Sci Chcm
A.,(1989), 26,609-20
Huang Chuch-Jung, Yen Chiah-Chao, and Chang Teh-Chou., J.Appl.
Polym.Sci., (1991), 42,2267-77.
Huang.W, Ho.P, and Huaxue Tangbao., (1981), 32,783-843.(CA. 97:
22951r)
Iolinda Aielo, Ghendini.M and Zanchini.C., Inorganica Chimica
Acta., (1997), 255,133-137.
Ismail.A.J, Ebraheem.K.A.K, Mubarak.M.S, and Khalili.F.I., Solvent
extraction and ion exchange.,( 2003),21,issuel.
Jaffery.G.H, Basselt.J, Mendham.J, and Dennery.R.C.,1994,Vogel"s
Text book of quantitative Chemical analysis, Fifth edition, ELBS,
London.
Jones. K.C and Grinstead.R.R., Chem Ind., (1977), 637.
Jorgensen. C., Absorption spectra and chemical bonding in
complexes, Pergamon press, Oxford, (1962), 15.
Jose.J, J0hn.M and Mathew.B., J.of Macromolecular Science Pure
and Applied chemistry., (2003), 40, 863-879.
Joshi.J.D, Patel N.B. and Patel. S.D., Iranian Polymer Journal, (2006),
15(3), 219-226.
Kaliyappan .T and Kannan.P.,Prog. Polym. Sci., (2000), 25,343-370.
Kaliyappan .T, Swaminathan C.S and Kannan.P., Eur.Polym.
J.,(1996a), 33, 59-65
Kaliyappan.T, and Kannan.P., J Polym. Sci part A., (1996), 60,947-
53.

Ka1i~wan.T~ Anupriya.R, and Kannan.P., Makromol Chem Pun
Appl Sci., (19991, A36(4), 517-30.
G1iya~pan.T~ bnnan.P, and Reddy.A.V.R., Polym.Mater., (1994),
11,121-128.
Kaliyappan.T, Rajagopan.&
Science., (2003), 90,2083.
and Applied Polymer
Gliyappan.T, Swarninathan C.S, and Kannan.P., Polymer., (1996b),
37,2865-9.
Kellerman.R., Spectroscopy in heterogeneous catalysis, Academic
press., (1979), 86.
Kimura.K, Zhuag. J.H, Kida.M, Yamashina. Y, and Sakaguchi. Y.,
Polymer ., (2003), 35,(5), 455-459.
Kortum.S., 1969,"Reflectance spectroscopy" Springer-verlag,Berlin.
Koster.G, and Schmuckler.G., Anal.Chem. Acta., (1967), 38, 179.
Kratz.M.R, and Hendricker.A., Polymer.,(1986), 27,1641-3.
Kumar.D, Syamal.A, and Gupta.P.K., J.of Indian Chem.Soc., (2003),
89. 3-6.
Kumar.M, Rathore.D.P.S, and Singh.A.K., Analyst,(2000), 125,1221.
Kumaresan.S and Kannan.P., Indian J.of Chern,Tech.,(2003), 10,180-
185.
Kurirnara.Y, Tsuchida.E, and Kaneko.M.J., J.Polym. Sci.Polym.
Chem Ed A., (1971),19,3511-9
Kunmura.Y,Yarnada.K, Kanek0.M and Tsuchida.E J.of Polymer
SciencepartA-l., (1971), 9,3521-3527.
Lautsch.W, Broswer.W, Biedemann.W, and Gnichtel.H.,
J.Polym.Sci.,(l955),17,479-510.
Lee.T.S, and Hong.S.I., J Polym Sci Polym Chern Ed.,(1995), 33,
203-10.
Lei.Z, and Wang.Y., Macromol. Rep A.,(1993), 30,233-9.

LekM.A, Morecellet.J, and MorecelletM., J.Polym Sci.
Polym.Chem Ed., (1987),25,223 1-40.
Li Y. Gaofenzi Xuebao. C.A., (1988), 109,7023.
Maeng. K.S, S0ng.H.Y and Back.J.K. NonmunjipChungham
Taehekkyo Kongop Kyuk Yonsguso.C.A.(1985), 106,19137d
Mang .X, Natansolin. A and Rochon.P., Supra Molecular
Science.,(l996), 3 (4),207- 213.
Mani.R, Mahadevan.V, and Srinivasan.M., British Polm.J.,(1990),
22,177-184.
Mani.R, Mahadevan.V, and Srinivasan.M., J.Macromol. Sci, Pure
Appl Chem A,, (1993), 30,55769.
Marciniec.B, Urbaniak.W and Pawlak., J Mol Cata1.,(1982),14,323-
31.
Marcu.M, Cazacu.M, Viad.A., Racels.C., Applied Organomctallic
Chemistry., (2003),17,693-700.
Mart.H, and Vilayetoglu. A.R., Polymer Degradation and Stability.,
(2004), 83,255-258.
Mathur.N.K, Narang.C.K, and Williams.R.E., Polymers as Aids in
Organic Chemistry. New York: Academic Press., 1980.
Mauritz.K.A, Hora.C.J, and Hopfinger.A.J.,Adv Chem Ser.,
(1980),187,123.
Mendez .R, and Pillai.V.N.S, Analyst., (1990),11,213.
Michalska.Z.M, and Ostazewski.B., J.Organomet Chem., (1986), 299,
259-69.
Mishra.A.P, Tiwari.V.K and Singhai.R., Indian J. of Chemistry,
(2002), 41A, 2092-2095.
M0hapatra.B.B and Saraf.S.K., J.Indian chem.Soc., ( 2003), 80, 696-
699.

[115] Mondal .B.C, Das.D, and Das.A.K., Anal.Chim.Acta.,(2001),
450,223.
Mondal.R.C, Das.A.K., Indian Journal of Chemistry.,(2002),
41A,1821-1825.
Mondal.B.C, Das.D, and Das.A.K., Talanta., (2002), 56,145.
Moriguchi.Y., Bull. Chem. Soc. Jpn.,(l966),39,2656-65.
Murakami.Y, Suzuki.T, Takegami.Y., Polym J (Tokyo)., (1985),
17,855-61.
Nakajima.A.N, Sakai.J, and Yamauchi., J. Applied Polymer Science.,
(2006), 102,5372-77..
Nanjundan.S, Unnithan.C.S, Selvakumar.C.S.J, and Penlidis.A.,
Reactive and Functional Polymers.,(2005), 62, 11-24.
Nather.C, Greve.J, and Jeb.1. Z.,Naturoforch., (2003), 58b, 1-7.
Nayak.S.D, Mahadevan.V and Srinivasan.M., J., Cata1.,(1985)
92,327-39.
Nishikawa.H and Yanada.S.,Bull. Chem. Soc. Japan., (1964), 37, 8-
12.
Noboru.K, Yukihiko.U, Koji.Y.1, and Yoshiro.S., Polymer, (1986),
27,293-8.
Nose.Y, Hatano.M, and Kambara.S., Makromol Chem., (1966), 98,
136-47.
Nozawa.T, Akimoto.Y, and Hatano.M., Makromol Chem., (19721,
158,214.
Nozawa.T, and Hatano.M., Makromol Chem., (1971), 141,31-41.
Nozawa.T, Hatano.M, Yansamot0.T and Kambura.S., Makromol
Chem.,(1968),115,10-6.
Okamato.Y, Veba.Y, Dzanibekov.N, and Banks.E., Macromolecules.,
(1981), 14, 17-22.
Osada., Makromol Chem., (1975), 176, 1893-6.

Palumbo.M, Cosani.A, Terbojerich.M., Peggion. Macromolecules.,
(1978), 11,1271-5.
Palumbo.M, Cosani.A, Terbojevich.M, and Peggion.,
Macromolecules., (1978), 10,813-20.
Pan.C, Zhao.Y, Chen.Y. Zhongguo Kexue Jishu Daxuve Xuebao.,
(1985), 15(4), 439-46 (CA. 105: 208287t).
Pan.H.K, Yarusso.D.J, Knapp.G.S, and Copper.S.L.,J.Pol ym.Sci.
Polym. Phys. Ed., (1982) 21,1389.
Pardeshi.P.K, Pa1askar.N.G and Choudhekar.T.K., J. of Indian
Chemical Society (2002), 79,958-959.
Pa1rish.J.R and Stevenson.R., Analytica Chimica Acts., (1975),
70,189-198.
Patel S.A, Shah.B.S, Patel.R.M, and Patel. P.M., Iranian Polymer
Journal., (2004), 13(6), 445-453.
Patel.B.K, and Patel.M.M., Indian J. Chem., (1990), 29A, 90-92.
Patel.D.K, Patel.C.G, and Parmer.J.S., Macromol Rep A., (1994),
31.297-301.
Pecht.1, Levitzk.A and Anbar.M., J. Am. Chem. Soc., (1967), 39,
1587.
Penin.D.D and Armarigo W.L.F, (1988)'Purification of laboratory
chemicals' Pergamon press, New York.
Phi1ips.J and Fritz.J.S., Anal.Chim.Acta., (1980),121,225.
Pittman Jr. C.V and Hiro.R., J Org Chem., ( 1978), 43,640-3.
Pittman Jr. C.V and Martin.G.V., J. Polym Sci A, Polym Chcm Ed.,
(1973), 11,2753-65.
Piitman Jr. C.V, Veges.R.L, and Jones.W., Macromolecules., (1971)
4,291-7.

[I631
Pittman Jr. C.V, Veges.R.L, Jones.W, and Elder.J., Macromolecules.,
(1971) 4,302-8.
Pittman. C., Organometallic reactions,Plmum press,Newyork., (1977)
6,36.
Pomerantseva.M.G, Belyakova. Z.V, Shchepinov.S.A, Efimova.L.A,
Chemyshev., Zh Obshch Khim., 1984,54(2), 3546 (CA.IO1,7258c).
Pratik.E.P.Michae1, Barbe.J.M, Juneja.H.D, and Paliwa1.L.J. Eur.
Polym.J.,(2007), 43,4995-5000.
Rakesh K.Sharma., Pure.Appl.Chern., (2001), 73,(1), 181-186.
Ramirez.R.S, and Andrade.J.D.,Polym Prcpr Am Chem Soc, Div
Polym Chem.,(1974), 15,391-4.
Ravikumar Reddy.A and Hussain Reddy.K., Proc.Indian
Acad.Sci.Chem.Sci.,(2003), 115, (3), 155-160.
Reddy.K.H, Babu.M.S, Babu.P.S. and Dayanand.%, Indian Journal of
Chemistry., (2004), 43A, 1233-1238.
Rivas.B.L, and Segue]. G.V., Polymer Bulletin., (2001), 46,271-276.
Rivas.B.L, and Villegas.S., J.Applied Polymer Science., (2003), 90,
3556-3562.
Rivas.B.L, Periera.E.D, and Villoslada.I.M.,Prog.Polym.Sci., (2003),
28,173-208.
Rivas.B.L, Seguel.G.V, and Ancatripai.C., Polymer Bulletin.,(2000),
44,445-452.
Robert B.Jeppsen , Ph.D Thesis.(1999).
Roy P.K, Rawat.A.S, Choudhary.V, and Rai.P.K., J. Applied Polymer
Science., (2004), 94,1771-1 779.
Rudolf.P.R, Saldaniaga.C.H, and Clearfield.A., J.Phys.Chem.,(l986),
90,6122-25
Sadhan Pramanik.P, Dhara.K, and Chattopadhyay.P., Talanta.,
(2004), 63, 485-490

Saha.B, Iglesias. M, and Strent. M., Solvent Extr.1on Exch., (2000),
18.133.
Salem.N.M, Ebraheem. K.A.K, and Mubarak.M.S.,Reactive and
Functional Polymers., (2004), 59,63-69.
Salih.B., J. Applied Polymer Science., (2002), 83, 1406-1414.
Samal.S, Acharya.S, Dey.R.K, and Ray.A.R., Talanta., (2002), 57,
1075-1083. -
Samal.S, Mohapatra.N.K, Achariya.S, and Dey.R.K., Reactive and
Functional Polymers., (1999), 42,37-52.
Samudranilpal, Proc.Indian Acad.Sci.Chem.Sci.,(2002), 114, (4),
417-430.
Samuelson.O., Ion exchange separations in analytical chernistq. New
York: Wiley., 1963.
Sangb ganguly., J.of Indian Chem.Soc., (2004), 81,327-329.
Sankar.R, Vijaya1akshmi.S Subramanian.S, Rajagopan.S and
Kaliyappan. T., Eur.Polym. J., (2007), 43,4639-4646.
Sankar.R, Vijaya1akshmi.S Subramanian.S, Rajag0pan.S and
Kaliyappan. T., I. Appl Polym Sci., (2008), (in press).
Sasaki.T.,Bull Chem Soc Japan., (1968), 14,24406.
Saxena.R, Singh A.K and Sambi.S.S., Anal.Chim.Acta.,(l994), 295,
199.
Saxena.R, Singh.A.K, and Rathore.D.P.S., Analyst., (1995), 120,
2509.
Schmuckler.G., Talanta., (1965), 12,281-90.
Sevindir.H.C, and Mirzaoglu.R., Macromol Rep A., (1994), 31, 399-
410.
Sharpe A.G. The chemistry of cyano complexes of the transition
metals. New York: Academic Press., (1976) (275pp.).
Siddhanta.S, and Das.H.R., Indian J. Chem, Sect A.,(1984), 23,937.

[I811 Sigel.H, and Baukcr.S., Helv Chim Acta., (1968), 51(6), 1246-56.
Singh.D.K and Gupta.K., J.Indian Chem.Soc.,(2002), 79,447.
Sinner.F, Buchmieser.M.R, Tessadri.R, Mupa.M,Wurst.K and Bonn.,
J.Am.Chem.Soc., (1998), 120,2790.
Siyam.T and Hanna.E., Macromol Rep A.,(1994), 31,349-56.
Stempel .G.H, Gross R.P. and Mariella., J.Am.Chem.Soc., (1950), 72,
2299.
Styra-Brajte1.K and Zeotorzynska.E., Fresenius Z., haLChem.,
(1987), 112,315
Sugii.A, Ogawa. N and Hashizume.M., Chem.Pharm.Bull., (1978),
26,798.
Sugii.A, 0gawa.N and Hashizume. H., Talanta., (1980), 27,627.
Teranishi.T, Harada.M, Asakura.K, Asanuma.H, Saito.Y, and
Toshima.N., J Phys Chem., (1994), 98,7967-75
Tewari.P.K and Singh A.K Talanta.,(2000), 53,823.
Tewari.P.K and.Singh.A.K , Fresenius., J.hal.Chim.,(2000), 367,
562.
Tham~zharasi. S, and Venkata Rami Reddy. A, Balasubramanian. S,
Reactive & Functional Polymers, (1999), 40,143-153.
Thamizharasi.S, and Venkata Rami Reddy. A., Polymer., (1992), 33,
2421-3.
T0mic.E.A and Carnpbell.A., J.Polym. Sci., (1962), 62,379-386.
Tsuchida.E, and Nishide.H., ACS Symp.Ser., (1980), 121,147-163.
Tsuchida.E, Tomono.T, and Honda.K., J Polym Sci A Polyrn Chem
Ed., (1974), 12,1243-55.
T8uchida.E. and Nishide.H., Advances in Polymer science., (1977),
24,59-73.

Vadolkar.V.B, Tembe.G.L, Ravindranathan.M, Rarn.R.N and
Rama.H.S., J.of Macromolecular Science Pure and Applied
Chemistry partA,(2004), Vol-A, 7839-858.
Vallcc.B.L, and Ri0ndan.J.F. In: Li CH, Editor. Proceedings of the
International Symposium on Proteins. New York:Academic Press.,
(1978), p. 23-7.
Van Berkel.P.M, Driessen.W.L, Kodhaas.GJAK, Reedijik.J, and
Shcrington.D.C., J Chem Soc, Chem.Commun., (1995), 2,147-8.
C
Van Dyke C.K, and Farrell.M.0, Baucher.L.L., Fundam.Res
Homogenous Cata1.,(1979), 3,659-69.
Veno.K, and Martell.A.E., J.Phys.Chem.,(l953), 60, 1270-1275.
Vernon.F, and Shah.T., React Polym.,(1983), 1,301.
Vernon.F., Anal Chem Acta., (1976), 87,491-3.
Vemon.L.P, and Seely.G.R., The Chlorophylls., New York:
Academic Press, 1966.
Vijayalakshmi.S, Sankar.R, Subramanian.S, Rajagopan .S and
Kaliyappan. T., Designed Monomers and Polymers.,(2006), 9,
(5),425-437.
Vijayalakshmi.S, Sankar.R, Subramanian.S, Rajag0pan.S and
Kaliyappan. T., J. Appl. Polym.Sci., (2007), 104,797-802.
Vijayalakshmi.S, Subramanian.S, Rajagopan3 and Kaliyappan.T., J.
Appl Polym Sci., (2006a),101,1506-1510.
Vijayalakshmi.S, SubrarnanianS, Rajag0pan.S. and Kaliyappan.T.,
J.Appl. Polym.Sci, (2006), 99, 1516-1522 .
Washawsky.A, Firberg.M.B, and Ras.Y.B., Purif Meth., (1980), 9,
209.
Welch.R.C.W, and Rase.H.F., Ind Eng Chem Fundam., (1969), 8,
389-97.
Wu.K.H, Chang.T.C, Wang.Y.T, H0ng.Y.S and Wu.T.S., Eur.
Polym.J., (2003), 39,239-245.

[214] Xiansen. Z, Hongzhi. Z, Xinde.F., Gaofenzi Tongxum.,
(1983),5,375-80 (CA. 100: 176217~).
[215] Xiao.C, Lin.Y, Luo.C,Tian.Z., Wuhan Daxue Xuebao Ziran
Kexueban., (1989), 1,81-86 (CA. 110: 231731~).
[216] Zakrzewska-Trmade1.G and Harasimoviez.M., Desalination., (2002),
144,207-212.
[217] Zundel.G, Hydration and intermolecular interaction ipfiared investigations
i
with polyelectrolyte membranes Academic Press, Inc., New York. (1969).

LIST OF PUBLICATIONS
1. Studies on Poly(8-hydroxy-4azoquinolinephenyImethacqhte) and its
metal complexes, S. Vijayalakshmi, S. Subrarnanian, 3. Rajagopan, and
T. Kaliyappan, Journal of Applied Polymer Science, Vol. 99, 15 16-1 522
(2006)
2. Studies of Poly(8-hydroxy-4-azoquinolinephenol-formaldehyde) and its
metal complexes, S. Vijayalakshmi, S. Subrarnanian, S. Rajagopan,
and T. Kaliyappan Journal of AppliedPolymerScience,Vol. 10 1,1506-
15 1 O(2006)
3. Studies on Poly(8-hydroxy-4azoquinolinephenylacryle) and its metal
complexes, S. Vijayalakshmi, R. Sankar, S. Subramanian, S.
Rajagopan, and T. Kaliyappan, Designed monomers and polymers Vol.
9 No.5, 425-437,(2006).
4. Synthesis and metal uptake studies poly(8-hydroxy-5-azoquinoline
phenylacrylate- formaldehyde) resin and its metal complexes.,
S. Vijayalakshmi, R. Sankar, S. Subramanian, S. Rajagopan, and T.
Kaliyappan Journal of Applied Polymer Science, Vol. 104, 797-802
(2007).
5. Synthesis and chelation properties of new polymeric ligand derived from
ply( 8-hydroxy-5-azoquinoline hydroxy benzene), S. Vijayalakshmi,
R. Sankar, S. Subramanian, S. Rajagopan, and T. Kaliyappan,
European polymer journal 43,2007,4639-4646.

Studies on Pol (8-h droxy-4-
azoquinolinep K eny l methacrylate) and its Metal Complexes
5 Vijayalakshmi, S. Subramanian, S. Rajagopan, T. Kaliyappan
@tportmmt of Chmrsty, Pond~chmy Enpneenng College, Podlchery -605014, lndu
~rirlved IY July 2U03, accepted 4 Februaty 2Kl5
lhll 10 lW2/appZWI
puhl~shed odme m Why IntAence (www mtersnence wdey cam)
po.vc\e.arrs suggss ha1 he mlal.hgand raho ~r. abou~ 1
? fie pltcnr.ate xtrr hrIncr chraclaud 3) uhared
speara. X-ray dlfhacbm, spearal studies, andmagnetlc
lrre rad~cal uubtor Poly(8hydroxy-4-azoq~~1loI1nephenyl~ moments Thermal anaiy~es of the polymer and plychelates
methacrylate) poly(BH4AQPMA) was charadenred by m were camed out m au 0 ZWs Wdey Perlod~olr hc 1 Appl
hared and nuclear magnehc rmnance techquen The rnrr Polp B 59 1516-1522,ZW
lvrdar waght of the polymer was detmnmed by gel per
mrahon chromatography Cu(I1) and Nl(n) mrnplexes of
?dy(8H4AQPMA) were prepared Elementnl analy~ir of
ABSTRACT &Hydroxy-4-azoquulohephenyLmetha"yl
ate (RHIAQPMA) was prepared and polym~nzed m ethyl
melhyl ketone (EMK) at 65'C usmg bmzoyl peroude as
Key words Ion exchangers, metal-polymer mmplexer, rad-
leal polymenzahon
INTRODUCTION
leagues1213 Oune groups bound to polymers via car-
In recent years, polymer metal complexes gamed con-
,~derable mterest owmg to the11 amachve appllcahons
In dlvers~hed helds, such as catalys~, extrachon of
metals mcludmg rad~oachve elements, and blrrmor
yanic chemistry water and waste water treatmentst-*
The complexahon of metal Ions w~th polymer matnces
tin taming funcho~l l~gands results In supenor prop
rrhes compared w~th the sunple compound counterparts
Orgmc polymers when complexed w~th morxamc
metals unpart 5ex1brhty due to the orgaruc mop
rw and stab~ltty due to morgaruc funcbons The
chelate forrnlng polymeric I~gands, charactenzed by
reactwe funchonal groups contammg 0, N, and S
donor atoms and capable of morhhng to different
mehl luns, have been extensively studled "" AW
later, methacrylates, and thetr >orrespondmg and
bon-carbon bonds prepared by FnedelXrafk alkylahon
of Amberl~te XE-305 wlth Echloromethyl-8
hydroxyqlunolme have led to hydrophob~c resm of
low capaclty Thne materials a h eexh~b~t amazmg
shudural vanahons A hydrophlltc oune resm with
enhdnced copper Ion exchange capacity has teen synthesued
from alkylated poly(benzylarmne) and
Moromethyl-&hydroxyqwnohe " The elech.omc
and EPR stud~es on Spheron-1WO shows a 2 1 mol
raho for NI(U) and Co(I1) complexes In continuanon
of our research m polymer-metal complexe~,'~'~ the
present mveshgahon deals wth the synthesis, charactenzahon
and thermal property of new poly(&hydroxy4azoqumohnephenylmethacryhte)
and ~ts
Cu(ll) and NI(II) complexes
:hlor~des are vmyl monomers that are read~ly con-
EXPERIMENTAL
rerted to lunchonal monomers, and rad~cal polymerizahon
m suitable salvenb was found to be effechve
Materials
for a metal- on scavenger Oxme w extens~vely w d m &hydroxy4-azoqumoLnehydroxyUe was preanalyhcal
chemwhy as a photometric agent and/or pad accordmg to Mang and coworkers " Benzoyl perextrachon
agent h e ~s a selechve and has conse- onde was reay5t.d~d from a chlomform-&ol
quently attracted great mterest as a potenhal chelator mixture Methacrylay1 chlonde was prepared by a re
for h e metelitc ~ons Separahon of translhon metal ported procedwle
Ions on vanous ome chelabng mm, mcludmg commeroal
oune, was reported by Pamsh and col-
Monomer synthea~s
Conrspnhu to T Kahyappan (tkaByappan2MlB Gf L~20'~roq,",
yahw mm)
and 2-butanone 25 mL were placed m a tluee necked
4 d ~pplid polymn -. vol 9. ,516-I= (m, fllpk httd w~th a snrrer, thermometer, and vrahng P ~ W ~ ~ o m c r l k ~ h e l 7he contents m the flask were cooled tu -?C

hlethactyloylchlondc (1 8 mL. O OW) In 20 mL of
: butanone was added dropwlse w~th constant stir-
8-hydroxy-4-aroqumolmephenyhethac'ylate [poly-
(8H4AQPMA)I was hltered, washed wlth methanol,
r~ng and cmhg The reachon muture was gradually
~llowed to reach room temperature, and shrnng was
and dned (Yleld 85% )
~ontlnued for 2h The quaternary ammonium salt
formed was then hltered off The hltnte was washed
P"puahon Of
i~th d~shlled water and dnd overanhydroussodlum
wiiatt. and the solvent was evaporated In wcuo (veld
Yioe) The LR and 'H NMR spectra were conskent
The polymer (6 Gmmol of repeat un~t) was hlved m 30 mL of DMF An aqueous solubon of Cu(ll)/
Nl(11) 0 62g acetate was added dropwlse wlth constant
w~th the ass~gned shucture (Scheme 1)
shmng, and the pH of the mtuhon was adjusted to 7
wlth d~lute ammonium hydroude soluhon The resulhng
muture was d~gested m a water bath for 2h
and kept overn~ght at room temperature The pmp ltated ~~I~(BH~AQPMA)CU(U)INI(U) complex was
fdtered, washed with hot &hiled water, and dnd shydruxy-4-azoqumohephenyImethacrylate (3 5M)
In DMF (10 mL) and benzoyl perowde (05g) were
placed m a standard reamon tube and deaerated by
passmg oxygen free iuhogen gas for 30 mm The
reacten tube was closed and kept ma thermostat at
65" for 8h 'he contents were then cooled and
pouted over methanol (100 mL) Thepreap~tated poly
The IR spectra of the polymer and polymer metal
complexes were recorded usmg KBr pellets The IH
TABLE l
UemrnW Analyois far Poly 18HhAQPMAI and 16 Metal Complcxca
Elemental analyr~s lwaght pemnt)
Carbun -----
Hydrop Oxy~en Nlhugen Metal
Abbmrhon hpud fmula Cal' Fd Cal' Fd W a Fd Cal' Fd W a Fd
- - ,
"~alcukted pemntlp of C, H, N, 0, and metal lorn for polymer-metal mmplexer bad on the value of x = y = 2 W
a - 2 a, y I 2 01.

Figure 1 IR specha of poly(~H4AQPMAl (a), poly(SH4AQPMA)-Cu (U) (b), and poly(BH4AQPMAt NI(II) (r).
NMR s p of the polymers were recorded on a
IFOL GSX 400 MHz spectrometer in DMSO d, uslng
!etramethyKie as the internal standard Molecular
n'e~ghts (M., and M,) of the polymers were kkrmlned
by GFC (Water's model 410) using THF as
eluent Elemental analyses were performed on a
Coleman CHN analyzer. The metal content of polymer
metal complexes was determined usmg the titrmetnc
procedure after dwpmposing the polychelates
hvl concentrated HCI, perchloric, HNO, and H,SO,.
The vrscosity measurements were made in THF at
O"C with an Ubbelohde suspended level viscometer.
The magnetic moments were measured using the
hay method. The diffuse reflectance spcha (500-
2WOnm) were measured on a Varian Car). 5E W-vis
- b pk
NU( spphotometer. X-ray &adon experimentr
were performed with a Phillp PWlBZO diffractom-
eter. Therrnogravirnetnc analysis (TGA) was carried
out in a Seiko thermal m1yser. A hng sample was
used at a heatng rate of 15'C min-' in air.
RESULTS AND DISCUSSION
The monomer (I) was prepared and polperked in
DMF using benroyl peroxide as initiator with a good
yleld Polymer metal complexes were obtained in a
DMF containing polymer in an aqueous solution of
metal ions Cu(II) and NiO in the presence of a few
drops of ammonia. The polymers were soluble in
DMF, THF, and DMSO, and insoluble in common
TABLE I1
1R Specin1 Dala of PoIy(BH4AQPMAI md Ik Metal Cornplexn
OH, C-hnr., N-N, Phenok C -0 Esferic C-0, &N,

L 1 0
6 ppm
Fiyn 2 'H NMR spchum of poly(KH4AQPMA)
urganic solvents like benzene, toluene, methanol, and mer metal complex was heated up to 150aC suggesk
uter All the plychelates are sparingly soluble in the coardinahon of H,O molecules to N1(11) polyche-
THF and DMF The elemental analysis data for ply- lates. The strong bands at 1750 on-' and 1570 GI-'
mers and polymer-metal complexes are presented m may be ascribed to C-0 ester and ketomc groups,
lahle I The elemental analyse data suggest that the respechvely. The medum intensity band at 1190 cm-'
metal to polymer ratio is 1 : 2. The intrinsic \,iscosity m the speckurn of the polymer is due to the hydrogen
bonded mg system of the ligand. The band around
725 cm-' corresponds to metal-oxygen vibration. The
detemed to be O.SldL/g.
other absorptions observed are presented m Table U.
The number average molecular weight (M,,) atld The 'H NMR spedrum of ply(8H4AQPMA) is shown
wght average moleqlar weight (M,,.) of the m F~gure 2. SignaL due to aromatic protons appear as
wly(BH4AQPMA) were determined by gel perme broad multiples in the region 8.11-6.236. The s~gnals
JhOn chromatography using tetrahydrofuran (M, 1 76
at 9 126 are due to aromatic -OH. The signals around
y 10' M,, = 3.94 x 10'). The plydispers~ty urdex
3.9-2.016 are due to methylene and methyl protons.
M,,,/M,, for poly(BH4AQPMA) is 2.16. The theoreti-
The relationship between the elechonic properties
cal !,slue of M,/M, for poly(BH4AQPMA) suggests a
strong tendency for chain terminahon by radical reof
the metal ion in the complex and the sterwchemscombmation.
try of the hgand in the environment present was ar-
The IR s p a of poly(BH4AQPMA) and its plyrived
at tentatively on the basisof the data availablein
chelates are shown in Flgure 1. The absorption band the I~terature."-~ The electronic spectrum of Cu (0
War 333W cm-' wrresponds to phenolic -OH stretch- polychelates contaq a broad band at 15L50cm1 and
log. Ths band disappears in the spectra of the metal a weak band at 23,750an '.The pition of the band
complex, estabkhing the involvement of phenolic at 15,250m ' is in good agreement with those gener-
-OH in the coordination polymer. Ni(U) polychelaks ally obse~ved for square planar CuN) mmplexes and
a slmng band at a higher frequency region (3400 may be assigned to the kansition hg - 2~11( The
"'I) than that assigned for the phenolic -OH group. weak band at 23,750 on-' may be assigned to the
fie fad that hnd rwnah even when the poly- symmetry forbidden ligand -+ metal charge transfer
I

Figure 3 X-ray d~firachon of poly(BH4AQPMA) (a) poiy(BH1AQPMA)Cu (0) (b), and poly(BH4AQPM.4)- Nl(II) Q1
PI* l TGA

TABLE 111
~nnogravimetnc Data of Poly(SH4.4QPM.4) and Ib Metal chelate#
Tempratwe ('Ci cornponds to
Sample T, (T) 10 30 50 70 90 Char % at 7WC
polr,(BH4AQPMA) 19 275 333 ?45 475 625 0
~OI~,(~H~AQPMA)CU(~) 325 365 4% !dO 620 685 8
pOiv(8H4AQPMAi-N~(n) 265 585 425 585 625 635 6
transthon 2.~'~ A square planar mnhgurahon may be are = 244 and g = 2 14 The g values are
lentahvely ass~gned for the Cu(U) polychelates very consistent with NI(LI) m an octahedral envtmn-
The electrontc spectrum of NIOI) polychelates ment
,bows two broad bands at 16,500 cm" and 14,150 Cum) polychelates have a magnetic moment of
m-' and a weak band at 12,250 cn-I The first two I BBM, md~cahng the square planar conhgurat~on
hands may be ass~gned to the translhon )T,(R -r
S,(P) and the latter to a spm forb~dden transihon to
an upper state ansmg from the 'D state of the free ton
The magnehc moment of 3 35BM and the paramagnehc
behavlor of Nt(II)complexes suggest d~torted
octahedral geometry for NI(~ polychelates The X-ray
Manch and Femol~as have made slnular obsewahms
and ass1 ed an octahedral geometry for N I com- ~
ylrxn" F ' Based on the companson of the present
data wlth that 01 the l~terature, an octahedral conhguiatton
may be assigned for the Nl(IIi complex
dlffractogram of poly(BH4AQPMA) and tb CuO and
Nt(1l) complexes are shown ur Flgure 3 The X-ray
dlffrachon studas lndlcate that paIy(BH4AQPMA) IS
amorphous, whereas I@ polychelates possess good
crystalhity The nystallin~ty m polychelates may not
The e p r spectrum of the cupnc complex shows a be due to any ordermg m poly(BH4AQPM.4) lnduced
strong slgnal charactenshc to that of blvalent copper, dumg metal chelate anchonng, more so since the
kh~h IS attnbuted to the square planar cupnc ton m
the center w~th the oxygen of the phenohc -OH and
heterocycl~c nitrogen groups on the x and y axu Low
sptn NIOI) In an octahedral held wtth tetragonal dlsikrtton
LI expected to have a spm orb~t couplmg
parameter of g > 0 and, as a consequence, & > g-
Thee p r parameters calculated for the N10n complex
anchonng of metals to the polymer would ~mply mter
cham aosshkng between poly(BH4AQPMA) inter
chams, whlch should further reduce rather than enhance
any such ordenng The appearance of crystallin~ty
m poIy(BH4AQPMA)-metal complexes may be
because of the tnherent crystalline nature of the metall~c
compounds

mplass-+m -hue ~pdy(%QPMA), 6 Bollo. B A Im Erch Pdlut Conhol 1979.2.213
plly(8H4AQPMA>Cu0. and ~~~IBH~~QPMA)-NI@! 7 ?pdemn,C J , FIEnsdroH. H K Angew Chm In1 Ed Engl1962,
11 .., h .
chebtE3 a found to be 1%. 325, and 265T. respechvely,
8 Rolhn. L D 1 Am Chem Sa 1975.97.2132
The d~fference m tahslbon may be ambd to the crys- 9 hag", R S, Gaul, 1, Zohk. A, Slamb, D K ]Am Chm Sa
lalllnlt)' of the pdymer-md comph and a m acmr- 1980.102.1033
dance wlth X-ray diffradm study 'he TGA tans of 10 Rnas. B L Soqual. G V . Geckelrr, K E J Appl Poiym Sa 2m1,
FOly(BH4AQPMA), ply(BH4AQmvL4)Eum), and ply- 81.1310
,~HUQPMA~NIO chelate are shown m Flgure 4 The 11 Kunnura, Y. Tauch!dr, E. Mko, M 1 Polym So 1971, A19,
3511
ddlcrenhal thed analfical data are presented m ~ a -
12 Pmh I R Am Chm 1982. Y, 1BW
ble 1u the p0lychekkS be loseabut SO% werght nte 13 Pam& J R W Prad 1975.24,W
iu(m plychelate are found to be more stable than 14 Wanhawky, A Deshc, A, R w , G, Pahhm~x, A Read
VI@) poly chekles 'he IR IH NMQ ep r, eiedrmuc Polym 19M. 2.301
~~edra, and ma+ momenb studla mnfvmed that 15 %l~yappm, T, Rapgopah S ,bum P 1 AppI PoIymSa ZOg)
~hc chelahon of metal ions may pmsibly be occumng
khveen two groups from dBemt plymem chams, as
(horn ur Scheme 2
2M1.w
I6 Phyappan T, Rapgopan, S, Kmm P J Awl Palym So ZmP,
91,494
17 Manti. X. Natlnsoljn. A, Won, P Suprnmol50 1996,3,207
The authors are grateful to RSlC Ill (Madras) Chenna~ for
?mv~dmg whumentai faahha One of the authors, TK, w
18 S1mpi.C H,Gm,R P,Mane&,R PIAmChcmSal9M.
n, zm
I9 Lwta I. Managek. 2. Palova& R J Mawmol h Chem
Rrataiul to DST, Government of India for the award of
)oung SoenMt
1975, A9, 1413
20 Mabv~ya. I, Shukla, I' R, Snvastlva. L N 1 horg Nud olcm
1973, 35 1706
21 Mamn,, R I. Mma, S POC Chem Sa. London, W970, A32,
Reference
1 Kaliyappan T m, P Frog Polym 50 2W. 25 343
173
22 hynmal A ble, K S Ind J Chm 1978, A16 45
23 Dub>&.) L Mam, R L horg Chem 1966.7.2203
I Hum& W 6 , Hu, Q .S Pu, L 1 Org Chem 1999.64.794U 21 lorgauen C K Ahrphm Sp&a and Chemtcal Bondsng m
i lrr C H Krm J S.5uh.M Y,Le W AnalChimANIW7
119 Wl
I Vernon. L P, SrPly, C R The Chlorophglls Acadmtc Prmr
Uew YarL 1%6
r Bollo B A I Mmmol 50 Chem 1980 A14 107
Compl~xer Pergamm Pres Word, 1%2 15
25 F'w B N Inhodurnon to hgand ReIda. Wdqhtmmw
New York, 1%2, 25
16 Mnnch, W , Fwohrr, W I 1 Chem Sa 1%1,38,192
27 Bortop, 0.lorgmwn.C K AN Chw Sund 1957 11. 1223

Studies of Poly(8-hydroxy-4-azoquinolinephenol-
formaldehyde) and Its Metal Complexes
S. Vijaydaknhmi, S. Subrammian, S. Rajagopan, T. Miyappan
Deplrlmoil of Chcmlslry, Pondlchmy Engineering Collcge, Pondlchemj 605014, lndvl
R~elved 24 Srptember 2W4, accepted 12 May 2M5
DO1 10 lWZIapp22943
Published onhe m Wlley InterSoence (www mtemence wlley con)
ABSTRACP Poly(&hydmxy+quurolnephenol.form
aldehyde) restn (BH4AQPF) was prepared by mndens~ng
8 hydroxv Cazqumoltne phenol wlth formaldehyde (1 1
mol mho) m the pmence of oxalic acld Polychelates were
obtamed when the DMF mlubon of poiy(BH4AQPF) mn
alnlng a kw drop of ammonla was treated w~th the aqueous
dut~on of CuU) and NI~) ions The polymeric ram
and polymer-metal complexes were charactenzed mth ek mental analvrlr and specnal rtu&es lhe elemental analvss
the polvmer-meal compleha 9uggeted that the metal.
i - gand ran" was 1 ? Thr U1 rpnra, data ,,I tne pdj.
hrtates ~ld~rated that tr mds werr cwtJnatcd wu~gh
1NTRODUCnON
Polymer-metal complexes have been of interest to
many reearchers durmg the past three decades m
lhght of then ppoteal applicabons m dtvenlhed field.$
such as organlc synthesis, wastewater treatment, hydrometallurgy,
polymer drug grafb, recwvery of trace
metal ~ons mcludmg radloachve elements, catalybc
reamow, and models for enzymes' A number of
polymer-contammg chelahng hgands, mcludmg polydentate
ammes, mwn ethers, and prphynn, have
been reported2 Selechve chelahon of spenhc metal
IOIU from a metal ion nuxhrre by usmg a number of
tetradentate hgands attached to polystyrene &vmyl-
the Ntrogen and oxygen of the phenolr --OH group Lhffuse
reflectance spectra, electron paramagnehc resonance,
and magnetlc moment shd~es revcaled that the polymermetal
complexes of the Cu(n) mmplexer were square planar
and those of the Ntm) complexen were odahedral X-ray
diffract~on studies revealed that the plyrna metal mmplexes
were nystabne The thermal propemen of the plyme
and polymer-metal complexes were aim emed BZmb Wtlq Pendxalo Lu J Appl Polym b. 101 1%-1510,ZM
Key words metal-polymer complexes, radical polymew-
hon, Ion exchangers, macromonomen, vlscmity
reachon of phenol fonnaldehyde and pprazme was
reported by Hodgkm et al" conhnuahon of our
reearch9Io m this area, the present amcle deals w~th
the synthes~s and charactenahon of poly(&hydmxy-
4azoqumohphenol-formaldehyde) and ~ts Cum)
and NIUI) metal complexes
EXPERIMENTAL
B-Hydroxyqrunolmc and 4armnophenol (Fluka,
h e was demonstrated by Melby et a1 'Chelahng
France) were punhed accordmg to standard procedures,
the solvents were punhed usmg standard plt~ cedures and then used, and B~hydmxy4aqumolmeh
droxybenzene was prepared accordmg to Mang
et a1 '
resm prepared by mplycondensahon of 8-hydromaumolme
or phenol denvahves lrke 2.armno Synthesis of mammonomer
phenbi, prewrcyhc hid, or mranol with fonnalde
hyde were re rted b Pennmgton and Wdhams'and
Anstov et alcYkorblet a1 prepared a selechve Ionexchange
resm by reachng a condensahon product of
24dhydroxyacetophenone and anthrdlc ac~d wlth
fomldehyde Parmer et a17 synthesized 2,4-dhydroxy
acetophenone fonnaldehyde ram m an andic
medium and stud14 16 chelahon propemes Prepanhon
of a copper-selechve polymeric Iigand by the
RHydmxy4azoqwolmehyhxybenzene (5 3 g,
0 OM), formaldehyde (Loba, Ind~a) (1 2 g, 0 04M), and
oxahc acid [(Merck, Ind~a) 0 18 g, 3 % (wiw)] were
added to a round.bottomed flask, sealed, and kept at
IWC for 24 h m an 011 bath The formaldehyde resm
formed m the flask was washed w~th bhlled water
and then dissolved m DMF, and NaCl (10%) soluhon
was added to preclpltate the resm Then the resm was
hltered and dned The IR and 'H-NMR spectra were
consistent w~th the assigned strumre (Scheme 1)
iounu] o f ~ p p~ w ~ ~ nvol o 101,1506-1510 e
(2006)
~dey~aiodnls,~nc
ow
Synthesis of polymer meld complexes
Polymer metal complexes of CU(U)/NINI were pre
pared m an alkalme medtum at mm temperature

Scheme 1
The polymer (1.37 g, 0.W5M) was dissolved m 30 mL
01 DMF An aqueous solution of Cu(lI)/Ni(n) acetate
(0 62 g) was added dropwise with constant stirring,
and the pH of the soluhon was adjusted to 7 w~th
d~lute ammonium hydrox~de soluhon The rnulhng
m~xture was digested on a water bath for 2 h and kept
avernight at room temperature The precip~tated
~~I~(BH~AQPF)CUO~INI(U) complex was filtered,
washed w~th hot dlshlled water, and dried.
The 1R spcira of the polymer and polymer metal
complexes were recorded on a Bomem MB 104 FllR
spectrometer from M0 m ~LWI anrmi uslng KBr pellets
The 'H-NMR spectra of the polymer were recorded on
a JEOL CSX rMO MHz spfftrometer usmg DWd, as
the solvent and tetramethylhe as the lntemal standard
The molecular weighs (&,and M,,) of the polymers
were determ~ned by CPC (Water's model 410)
usmg THF as the eluent Elemental analyses were
performed on a Colemdn CHN andpr The metal
Figure 1 LR sWra of (a) poly(BH4AQPA. (b) ply-
(8H4AQFF)-Cum), and (c) ply(BH4AQPF)-Ni@).
content of the polymer metal complexes was deter-
mined uslng a titrimetric procedure after decompos-
ing the polychelates with concentrated HCI, perchlc-
nc, HN03, and HISO,, The visrosity measurements
were made in TW at WC with an Ubbelohde s w
pended level viscometer. The glasrtrmition temper-
atures of the polymers and metal complexes were
detemuned by differential scanning colorimehy
(DSC) with a hpnt 9W theml analyzer at a heat-
mg rate of 15'C/min in air.
The magnetic moments were measured using the
Guoy method. The diffuse reflectance spstra (5C-
2WO run) were measured on a Varian Cary 5E W-
vis-NIR spettrophotometer. X-ray diffraction experi-
ments were performed in a Philips PW1820 diffrac-
tometer Thennogravimetric analysis (TCA) was
carried out in a S eh Insbents Inc. A 5-mg sample
was used at a heahng rate of 15'C/min in air.
RESULTS AND DISCUSSION
The novel poly(BH4AQPR was synthesized from
Bhydmxy4az~qumolurehydmxybenzene and form-
TABLE l
ElammW Analpi1 of Poly(BHIAQPF1 and Its Metal Compltxcs
Elemental analyru (wetght percent)
-----
Csrbon Hydrcgen Oxygen Nitmgen Metal
AWmr*Um Empvidlormula Cal.' Fd Cal.' Fd Cal.' Fd Cal' M. W: Fd
f P o l ~ ( @ f ~ ~ C18tI~I 69.31 69.33 4W 401 11.54 1152 15.15 15.14 - -
PoI~(~I~~AQF'F)€u(~I) (C,,H,&N,),

TABLE I1
IR Spectral Data of Wy(8HUQPR and Ib
Metal Complexes
Sample OH.,. C-N, N-N., M-N.,,
Poly(SH4AQPFl 31CQ,, IW,, IW,,, -
Polv(SHAQPWu(ll) - 'mu, l%s,,, n.5
roly(BH4AQPP)-N~(U) i3CQg, 1M15*, 1540,, 735
b-brmd, +-strong
aldehyde m the pmenm of ode acld Polymer metal
complexes were obtamed fmm a DMF soluhon of
polymer and an aqueous soluhon of the metal ions
Cu(ll) and NiO m the prfsence of a few drop of
ammonu The polymers were soluble m DMF, THF,
and DMSO and mluble m common organic solvents
hke benzene, toluene, methanol, and water The ele
mental analysw data for the polymer and polymermetal
complexes are presented In Table I The elemenial
analysrs data suggested that the metal to polymer
ratio was 1 2 The mhu~~lc vmity [TI! was obtaned
by extrapolahng q, /C to a zero concenbahon The
ntnnslc v-lty ~~~~I~(BH~AQPF)
was detemuned
to be 0 59 dL/g
The number-average molecular welghtJM,) and the
weight-average molecular weight (M,,,) of the
polg(BH4AQPF) were d e t e d by gel prmeahon
chromatography usmg tetrahydrofuran (M. = I81
and M, = 3 99 x 10') The polydepers~ty Index (M,,l
M., for poly(BH4AQPF) was 2204 The theorehcal
value of &/(;I. for poly(BH4AQPF) suggested a
strong tendency for cham terminahon by radical re
combinahon
The LR spectra of poly(BH4AQPF) and its polyche.
late6 are shown m Flgure 1 The IR spectra show a
Figure 3 X-ra diffraction of (a) pdy(SH4AQPF)-Cum),
(bl poly(8~1AdpC-Nlm)
medium broad band extendmg from 28W to 3MX)
an'' that IS assigned to the overlappmg peaks be-
cause of aliphahc C-H stretch [< 3000 an-'), are
mahc C-H stretch (> 3010 an-'), and ~ntramolecular
and intermolecular hydrogen-bonded phenolic 0-H
stretch (31W-36W mi-') In the spectra of the ply-
chektes th band deappeared, leanng behutd s ha~
peaks for aliphahc and aromahc C-H stretdung vibrahons
So there was a loss of phenol~c -OH hydrogen
in coordlnahon with the metal ~ms The Nifll)
polychelates showed a strong band m a hgher-fre
quency regon (3300 mi-'), suggeshng the coordmhon
of H,O molecules wlth N I The ~ frequency at
lh00-1605 an-' suggests C-N absorphon and a fre
quency of 9M) cm-I represents a 12,4,6-tetrasubsh-
Figure 4 TGA tram of (a) poly(8H4AQPF). (b)
poly(8H4AQPF)-Cuill). and (c) poly(8H4AQPFkNilUl

POLY(IH4AQPF) AND ITS METAL COMPLEXES
TABLE 111
Thermal Analpa Data of Poly(BH4AQPFl and 1s Metal Complnes
Temperahue ('C) corresponds lo
%mple T, (TI 10 30 M m Above m
tuted phenyl nng I' The other absorphons observed
are presented m Table 11 The 'H-NMR spectrum of
poly(BH4AQPF) 1s shown In F~gure 2 Signals from
aromahc protons appear as broad mulhpiets m the
regon 8 11-6 23 B Thesslgnals at 9 53-8 6 Gare a result
of ammahc --OH The signal around 2 55 8 resulted
plychelates contamed a broad band at 15,430 cm-'
and a weak band at 23,900 an ' The posihon of the
hand at 15,430 an ' was m god agreement wtth
those generally observed for square phnar Cu(ln
curnplexej and could be assigned to the transition BIg
- 'A,, The weak band at 23,903 an ' could be as-
s~gned to the symmetry forb~dden l~gand - metal
charge transfer translhon ''-I9 The Cu(Il) polychelates
could be mlgned a square planar conhguratlon
'Ihe eledzonlc spectrum of Nl(I1) plychelates
showed two broad bands, at 16,300 cm and 14.350
n ', and a weak band at 12,525 cm ' The hrst two
bands could be asslgned to the transrhon fl,(F) -
'T,(P) and the latter to a spmforbidden transition to
an upper state ansmg from the 'D state of the free Ion
Manch and Fernoh have made smlar observat~ons
and ass1 ed an octahedral geometry for Nl(lI) com-
plexeszlTBased on a cornpansan of the present data
with that m the Ilterature, the NI(II) complex could be
assigned an octahedralcanfigurahon
The EPR spectnun of the mpnc complex showed a
hedral geometry of the NI@) plychelates The X-ray
diffractogram of poly(BH4AQPF) and 16 Cu(lI)/N~(ll)
complexes are shown m Rgure 3 The X-ray diffra~
tlon stumes mdicated that ply(BH4AQPF) was amor
phous, whereas 16 polychelates possessed good cry*
tahty The crystallmity of the polychelates may not
have been a result of any ordemg m poly(BH4AQPFJ
Induced dunng metal chelate anchomg, more m be
from methylme protons
The relahonshp between the electro~c properhes
of the metal ion m the complex and the sterwcherms- cause anchoring of metals to polymer would lmply
*n ul Ihr l~gand m L+r en, lronment prmni war ar- mrerchaln nosrhkmg 01 plylb~4A~~F) mtrrchak.
.:\ rc at rentanvelv on the bash ol lht datd asallable n whch should hare further reduced r a h than enthe
l~terature '>" The electmnrc spectrum of Cu(Il) hanced any such ordenng The appearance of crystalllruty
m the poly(BH4AQPF)-metal complexes may
have occurred because of the inherently crystalhe
nature of the metallic compounds
The glasshanslhon temperaturn 01 ply(BH4AQPF).
poly(8H4AQPFKu0, and poly(8H4AQWN1iT
&late were found to be 135C, 305"C, and 245f.
mpechvely The difference m hamlhorr may be asolbed
to the c~~~talluuty of the polymer-metal mmplexes and
was In accordance with the results of the X-ray dlflracbon
study The TGA tram of the ply(BH4AQPF),
poly(8H4AQpFIcu0, and ply(8H4AQpPN10 che
late are shown m Figure 4 and Table U1 All the plychelate
lost about 90% of thm welght 'Ihe Cum) ply chelate were found to be more stable than the N I ~
ply &elates The nt 'H-NMQ @K e b ~ spxtra, c
and magnetu moments studm confumed that chehhon
of the metal ions may possibly have been occumng
between two pups from different polymeric chams,
shown ln Scheme 2
rhong agnal charactenshc of that of blvalmt copper,
which was attr~buted to the square planar cupnc Ion
m the center wlth the oxygen of phenohc --OH and
The authors are giateld to RSlC liT (Madras) Cbm~ for
provldmg msmmenld faallhes One 01 he aulors (T K ) IS
the heterocycl~c rutfogen pups on the x and y axes
Low-spur NI~) m an octahedral field with tetragonal
dlstomon was expected to have a spm orbit couplmg
Parameter of g > 0 and la a consequence, g > g' The I
M" -
EPRparameterscakmlPted for the NI(~ complex were
DMF
fi = 2 601 and g' = 2 10 The g values were very
conslatent mth NI@) m an octahedral envlmnment
Ihe Cu(m polychelates had a magnetlc moment of
1 48 BM, inhhng a square p h r mnfigurat~on The
magnetic moment of 3 35 EM and the paramagnehc
behav~or of Ni(ll)mmplexa suggest a distorted &a-
X
M = Curl NP
(For NI X = t$O)
Scheme 2

Rra"ful to DST, Government of India, for the award of
young Soentlot
References
1 Kahyappan. T. IDnrun, P hog Polym Sn 2W. 25.343
? Pdswn, C I. Fdmfl, H K Angw Chm. Int Ed End
1%2, 11,6
3 Meby. L ! I Am Chem bc l9W. 57.W
4 Pmmm. L D, WJlum, M B Ind Ens: Chm 1959.9.759
1961. W. I1
x Hcdgh, 1 H , ElbL R Rend Polym Ion EichSarbslb985,3, K3
u bl~yappm.T.Rapg0pm.S .Kuvun.P I AppiPolymSoZM1,
W, 2 w
12 NhB, K Mrud Abrorphm Spcawopy 2nd d.
N a p Japan, 1964. p 20
13 Lustoh 1, Mnnagek, Z. Palovock, R 1 Mammol 50, Chem
1975, A9.1413
14 Waviyr, I, ShuW., P R. Snvartava. L N 1 Inorg Nud Chem
19n. 35.1706
15 Mnrtiru, R L , Mlaa. S FCC CT,m 5a. Lcmdon,5r 1970, A32.
m
16 Syamal, A , Kale, K S Ind J Chem 1978. Al6, (6
17 Dublrkl, L. Madlnl, R L lnarg Chpm 1%. 7, LM3
18 Img- C K Abbolptlon Sprctra and C h d hdmg m
Complexes, Pngma Rrar Oxiord, UK. 1% p 15
19 Fgp, 8 N Infrducuon to Ltgand Reldr. Wdq Inlevlace
New Yark. 1W. p 25
20 Man&. W, Femolns W I 1 Chcm Soc 1%1,3R,192
21 Bortop. 0, lorgman, C K Acta Chem Sund 1957, 11.l223

Drsr ncd Mmomers and Polymrrs Vol 9 No 5 pp 425-437 (2006)
0 "$2006
Also avulablc onl~ne www bnU nUdmp
Studies on poly(8-hydroxy-4-azoquinolinephenylacrylate)
and its metal complexes
S VUAYALAKSHMI, R SANKAR, S SUBRAMANIAN,
S RAJAGOPAN and T KALIYAPPAN
Dcpamtvnr of Chemurry. Pondtchew Englneenng College, Pondreherry 605 014, lndu
Abshoet-Poly(8-hydroxy4-4~~oq~1noI~nephenyIa~rylate prepared fmm acryloyl chlonde wrth condenmuon
products of 8 hydroxyquinolrne and Cammophenol, was polymerized m DMF at 70°C
using bcnwyl pcmxlde as milrator Polychelatcs wen obmned In alhlrne solution of polymenc Irg.
and with the aqueous rolut~on of Cum) and NI(II) Polymer was charactenzed by IR and 'H-NMR
techn~ques The molecular weight of the polymer was deumuned by GPC The polychelates were
chamcmmd by elemental anplys~s, X ray d~ffracnon, IR and elcctronrc spectral shlmes The thermal
pmpcrtles of polymer and polychelaus were studred The metal ron uptake pmpmes of the polymer
at Lffmnl pH are also srudld
Krywordr Poly(8-hydroxy-4-~~oqu1nol~nephenylacrylate polychelates, oxlne polymers. crystal
lmlty, polyma-m~al wmplexes
1. INTRODUCTION
The polychelatu, prepared by chelatron of metal Ions w~th functtonal groups In
the polymer rnatnces, have supenor propernes, whrch are mfficult to achleve from
comspondlng monomenc metal complexes [l] The chelate resln, functtonallzed
by rnuln dmtate I~gand, rs often used for these purposes Polychelates have a
w~de rangeaf applsuons, such as sem~conductors [2], catalysts [3], or controlled
nlease agents for drugs, b~oc~des (41, recovery of mce metal Ions [5] and nuclear
chemistry [6] A number of polymer bound chelattng l~gands Including ply
dentate ammes, crown ethers, porphynns and polyaclylam~de ~m~ndacetate are
also repow. Chelanng polymenc reslns are found to be more selectwe by nature
~n the removal of metal ions [7-91
The polpar of vrnyl benzoylacetone was prepared from vlnyl benzaldehyde and
co-polpenzed to polymer, whch readily forms complexes wlth Nr(U), Cu(II),
'To tvhan campondmsc should bc addressed E m l lkal1yappan2001@yahoo wm

Co(I1) and Au(II) [lo]. The free radical polymerization of Cu(I1) complex with
Schiff's base ligand containing vinyl group and radical polymerization of methacrylate
monomers coordinated to Co(Il) have been reported [I I]. Polymeric Schiff's
base chelates based on various functional polymers have been investigated [12- 151.
8-hydroxyquinoline (oxine) is extensively used in analytical chemistry as a photometric
agent and or extraction agent. Oxine is selective ~IEI has consequently
attracted gnat interest as a potential chelator for these metallic ions. Among the
earliest chelating resins to be studied were analogues of EDTA, viz., Dowex A-1,
chelex-100 and chelex-20 [16, 171. These resins continue to be useful in a wide
variety of systems. Some of the metals extracted from seawater and other systems
with chelex-100 and Dowex A-1 are Sc, V, Fe, Co, Ni, Cu, etc. Separation of transition
metal ions on various oxine-chelating resins, including commercial oxine, was
reported by Panish et al. [18]. In this investigation new azo polymeric ligands and
its chelate-forming ability with various divalent metal ions have been studied.
2. EXPERIMENTAL
2.1. Materials
8-Hydroxy-4-azoquinolinehydroxybenzene was prepared according to Mang et al.
[19]. Benzoyl peroxide was recrystallised from chloroform-methanol mixture.
Acryloyl chloridk was prepared by a reported procedure [20].
2.2. Monomer synthesis
8-Hydroxy-4-azoquinolinehydroxybenzene (5.3 g, 0.02 M), triethylamine (2.78 ml,
0.02 M), hydroquinone (0.5 g) and 2-butanone (25 ml) were taken in a three-necked
flask equipped with a stirrer, thermometer and separating funnel. The contents
were cooled to -5°C. Acryloylchloride (1.8 ml, 0.02 M) in 20 ml 2-butanone
was added drop-wise with constant sliming and cooling. The reaction mixture
was gradually allowed to reach room temperature and stining was continued for
2 h. The quaternary ammonium salt formed was then filtered off. The filtrate was
washed with distilled water, dried over anhydrous sodium sulfate and the solvent
was evaporated in vacuo (yield 85%). The IR and NMR spectra were consistent
with the assigned structure (Scheme I).
2.3. Polymerisation
8-Hydroxy-4-azoquinoline phenylacrylate (8H4AQPA, 3.5 M) in 10 ml DMF and
benzoyl peroxide (0.5 g) were taken in a standard reaction tube and deaerated by
passing oxygen-free nitrogen for 30 min. The reaction tube was closed and kept
in a thermostat at 70 f 1°C for 8 h. Then the contents wwe then cooled and
poured over methanol (100 ml). The precipitated poly(8-hydroxy 4-azoquinoline
phenylanylate) (poly(8H4AQPA)) was filtered washed with methanol and dried
(yield 86%).

PoIy(8~hydmxy4-awquvloli~phcnylacryhtc) and 10 metal complurs 427
2.4. Prepamtion of polychelates
HNO,
O'C
The polymer (6 mmol of repeat umt) was dissolved in 30 ml DME An aqueous
soluhon of Cu(II)Mi(II) acetate (0.62 g) was added dropwise with constant stining
and the pH of the solution was adjusted to 7 with dilute ammonium hydroxide
solution. The resulting mixture was digested on a water bath for 2 h and kept
overnight at room temperature. The precipitated poly(8H4AQPA)Cu(II)/Ni(II)
complex was filtered, washed with hot distilled water and dried. Yield: 80% for
Cu(I1) polychelates and 83% Ni(II) polychelates.

Pdy(8~h>.dwd-nzoquinoli~p~nylaeryht~) and its me& complucs 429
2.5. Determination of metal uptake at different pH
The polymer sample (25 mg) was dissolved in DMF and the pH of the solution was
adjusted to the required value by using either 0.1 M HCI or 0.1 M NH3. The solution
was stirred and 5 ml of a 0.1 M solution of metal ions (Cu(JQ/Ni(II)) was added
and the pH was adjusted to the required value. The mixture was stirred at room
temperature for 24 hand filtered. The solid was washed, the filtrate and the washings
were combined, and quantitative determination of metal ion concentration was done
by following the titration method for Cu(II) and dimethyl glyoxime method for
Ni(I1).
2.6. Measurements
The IR spectra of the polymer and polymer metal complexes were recorded using
KBr pellets. The 'H-NMR spectrum of the polymer was recorded on a Jeol
GSX 400 MHz spectrometer in DMSOG using tebamethylsilane as the internal
standard. Molecular weights (M, and M,) of the polymer were determined by GPC
(Waters model 410) using tetrahydrofuran (THF) as eluent. Elemental analyses
were performed on a Coleman C, H, N analyzer. The metal content of a polymer
metal complexes were determined using titrimetric procedure after decomposing
the polychelates with conc. HCI, perchloric acid, HNOJ and HzS04. Viscosity
measurements were done in THF at 30°C with an Ubbelohde suspended level
viscometer.
The magnetic moments were measured using the Guoy method. The diffuse
reflectance spectra (500-2000 nm) were measured on a Varian Cary 5E W-Vis-NIR
spectruphot~meter. X-ray diffraction experiments were performed with a Philips
PW 1820 diffractometer. Thermogravimetric analysis (TGA) was carried out using
a Seiko analyzer. A 5 mg samplewas used at a heating rate of 15O"Ctmin in air.
3. RESULTS AM) DISCUSSION
The monomer (I) is prepared and polymerized in DMF using benzoyl peroxide as
initiator with a good yield. Polymer metal complexes were obtained in a DMF
containing polymer in an aqueous solution of metal ions Cu(II) and Ni(II) in the
presence of few drops of ammonia. The polymers were soluble in DMF, THF and
DMSO and insoluble in common organic solvents like benzene, toluene, methanol
and water. All the polychelates an sparingly soluble in THF and DME The
elemental analysis data (Table 1) suggest that the metal to polymer ratio is 1 :2. The
intrinsic viscosity [q] was obtained by extrapolating qsw to zero concentration. The
intrinsic viscosity of poly(BH4AQPA) obgned was 0.47 Ng.
The number-average molecular weight (Mu) and weight-average mo@lar weight
(aw)
of the poly(BH4AQPA) were determined by GE ugng THF (Mu = 1.76 x
I@, z, = 3.72 x 10'). The polydispersity index (M,/M.) for poly(lH4AQPA)

n m 1. IR spectra of poly(BH4AQPA) (8). poly(8H4AQPA)-Cu(I1) 0) and poly(8H4AQPA).
NiO (c).
- -
is 2.1 1. The theoretical value of M,/M, for poly(lH4AQPA) suggests a strong
tendency for chain termination by radical combination.
The IR spectra of poly(BH4AQPA) and its polychelates are shown in Fig. 1. The
absorption band near 3300 cm-' corresponds to phenolic -OH stretching. This
band disappears in the spectra of metal complex establishing the involvement of
phenolic -OH in the co-ordination polymer. Ni(I1) polychelates show a strong band
at a higher frequency region (3400 cm-') than that assigned for the phenolic -OH
group. The fPct than this band remains even when the polymer metal complex was
heated up to 150°C suggests the coordination of Hz0 molecules to Ni(I1). The smng
bands at 1736 cm-I and 1600 cm-' may be ascribed to C-0 ester and ketonic
groups, respectively. The medium intensity band at 1190 cm-' in the spectrum of
polymer is due to the hydrogen-bonded ring system of the ligand. The band around
720 cm-I cornsponds m metal oxygen vibration. The other absorptions observed
arc presented in Table 2. The 'H-NMR sptrum of poly(8H4AQPA) is shown in
Fig. 2. Signals due to aromatic protons appear as a broad multiplet in the region
7.016.136. The resonance signals around 2.9-2.286 are due to the methylene and
methine protons.

'hblt 2
IR spectral data of poly(BH4AQPA) and ~ts metal complexes
Sample OHsu C=O cstnur N=N,u Phmohc C-0 Estenc C-Om M-0*
Poly(8H4AQPA) 30%3400(b) 1736(.) 1575(,) 1381 1180 -
Poly(8HAQPA)- - 1738(,) IS@)(,) 1378 LIW 720
ctlml

Rlgm 3. X-ray Lffr8ctlon of poly(BH4AQPA) (a), poly(BH4AQPA)-Cu(U) (b) and poly(BH4AQPA)-
Nl(U) (c).
broad bands at 16 500 cm-I and 14 250 cm-' and a weak band at 12 350 crn-I. The
first two bands may be assigned to the transition 'TI@) -+ 3TI(~) and the latter
to a spin forbidden transition to an upper state arising from the ID state of the free
ion. Similar observations have been made and assigned an octahedral geomey to
Ni(II) complexes (28.291. Based on the comparison of the present data with that of
the literature, an octahW configuration may be assigned to the Ni(II) complex.
The EPR spectrum of cupric complex shows a strong signal characteristics to
that of bivalent copper which is attributed to the square planar cupric ion in the
center with the oxygen of phenolic -OH and heterocyclic nitrogen groups on the
x and y axis. Low-spin Ni(I1) in an octahedral field with tetragonal distortion is
expected to have spin orbit coupling parameter of g z 0 and as a consequence
gb gg. The EPR parameters calculated for the Ni(I1) complex are gll = 2.425
and gi = 2.12. The g values are very consistent with Ni(LI) in an octahedral
environment. Cu(II) polychelates have a magnetic moment of 1.56 BM, indicating
the square planar configuration. The magnetic moment of 3.23 BM and the
paramagnetic bchaviour of Ni(I1) complexes suggest distorted octahedral geomey
for Ni(II) polychelates. The X-ray diffractograms of poly(8H4AQPA) and its Cu(II),
Ni(U) complexes are shown in Fig. 3. The X-ray diffraction studies indicate that
poly(BH4AQPA) is amorphous, whereas iu polychelates possess good crystallinity.

Poly(8-hydmxy-4-arogui~11wphcnyhc~late) and 18 metal complucs 433
EYgurr 4, fGA wes of poly(BH4AQPA) (a), poly(BH4AQPA) Cu(U) (b) and poly(BH4AQPA)
Nlm) fc)
The crystalllnlty In plychelates may not be due to any ordenng In poly(SH4AQPA)
Induced dunng metal chelates anchonng, more so slnce anchonng of metals to
polymer would imply ~nterchun cross-l~nlang between ply(SH4AQPA) mterchuns
whch should further nduce rather than enhance any such ordenng The appearance
of crystallln~ty In ply(BH4AQPA) metal complexes may be because of lnherent
crystalhne nature of the metallic compounds
The glass-trans~tlon temperatures for poly(SH4AQPA). poly(lH4AQPA)-Cu(II)
and poly(lH4AQPA)-N1(n) chelates are found to be 140, 305 and 275°C respectlvely
The mfference In translhon may be ascnbed to the crystalll~uty of the
polymer-metal complexes and 1s In accordance wlth X-ray bffrachon study The
TGA traces of ply(SH4AQPA), poly(SH4AQPA)-Cu(I1) and ply(BH4AQPA)-
Nl(11) chelates are shown In Rg 4 The d~fferentlal thermal analytical data are
presented In Table 3 All the polychelates lose about 90% we~ght The Cu(I1) polychelates
arc found to be more stable than Nl(II) polychelates The IR, 'H-NMR,
EPR, electronrc spectra and the magnetlc moment studres confirmed that the chelaoon
of metal Ion mght poss~bly be occurring between two groups h m mfferent
polymenc chiuns are shown m Scheme 2
3 I Applrcahon studres
The relahve amounts of the metal Ions taken up by the polymenc resln Increases
wlth an rncreaslng pH of the m&um The results reveal opnmum pH of 7 and

nbk 3.
Thcnnogmvimctnc data of ply(BH4AQPA) and 1t.s metal chelares
Sample Tg PC) Temperature ('C) correspnd~ng to 6 welght loss Char at 7WC (6)
~n %n 5n 7n 'XI
P'
E

Poly(8-hydmxy4-azogu1noliwphcnyhcryInuJ and its metal complucs 435
BPO
II - 70°C
Cu2'1Ni2' - DMF
M = Cu2*INiZ+
(For NI, X = H20)
above for the maximum uptake of copper and nickel using poly(8H4AQPA) as the
ion exchanger.
The high selectivity of resin towards Cu(1I) and Ni(lI) is shown in Fig. 5,
which shows the sorption behavior of metal ions at different pH. Generally resins
containing sulphur and nitrogen atoms as ligands have high affinity for Cu(II)/Ni(II)
130-321. Chelation was assumed to occur on basis of increase in pH, when the resin
was shaken with the metal ion solution.
Polymer recovemi with HCI (7 M) from the complexes is good and reproducible.
Further, the polymer is stable in the acidic conditions.

Figure 5. Pmentage metal uptake of poly(BH4AQPA) at mffennt pH
Acknowledgements
The authors are grateful to RSIC IIT (Madras) Chennai for providing instrumental
facilities. T. K. is grateful to DST, Government of India for the Young Scientist
award.
REFERENCES
I. T. Kaliyappan and P. Kannan. Pmg. Polym. Sci. 25,343 (2000).
2. Y. Saegusa. T. Takasluma and S. Nakamura. I. PoIym Sci. Polym Chem Edn. 30.1375 (1992).
3. G. Cdman. I. Am Water Ass. 73.652 (1981).
4. M. Wlumbo. A. Cosaru, M. Terbojench and E. Peggion. J. Am. Chem. Soc. 99,939 (1977).
5. L. Bamaszal, I. C. Weston and J. C. Kendnw. J. Mol. Biol. 12, 130 (1965).
6. S. S. lseid, C G. Kuehn, J. M. Lyon and A. Mernfield, I. Am. Chem Soc. 104,2632 (1982).
7. C. I. Pedcrson and H. K. Fnnsdroff.Angnu. Chem IN. Edn. Engl. 11.6 (1%2).
8. L. D. Rollman. I. Am Chm. Soc. 97,2132 (1975).
9. R. S. hsgo, I. Gaul, A. Zombcck and D. K. Stamb, I. Am Chem Soc. 102,1033 (1980).
10. B. L. km, H. A. MaNrana X. Ocampo and I. M. Peric. I. Appl. Polym. Sci. 88.1995 (2001).
11. Y. K u r w E. Tsuchida and M. Kaneko, I. hlym Sci. A19.3511 (1971).
12. M. Y. Khuhawarand A. H. Channar. Mncromol. Rep. A32.523 (1995).
13. D. Wohrie. H. Bohlcn and G. Mcycr, Polym Bull. 11.143 (1984).
14. T. Kdiyappm, S. Rajagopan and P. Kannan, 1. &PI. Polp Sci. 90,2083 (2003).
15. T. Kdiyappn. S. Rpjagopnn and P. Kannan. Appl. hlym. Sci. 91.494 (2004).
16. C. Kantipuly, S. Kauagsdda, A. Chow and H. D. Gesser, TahIa 37.813 (1978).

Poly(8-hydm~y4-aroguinolinephenyl1~rylate and its tnctal complexes 437
17. 7. Kaliyappan, R. Anupriya and P. Kannan, Makmmol. Chem Pun Appl. Sci. 36.517 (1999).
18. J. R. Panish. Ann Chem 54.1890 (1982).
19. X. Mang, A. Namsolin and P. Rochon, Supramol. Sci. 3,207 (1996).
20. G. H. Stempel, R. P. Gross and B. Mariella, I. Am, Chem. Soc. 72,2299 (1950).
21. I. Luston, 2. Managck and R. Palovcick, I. Macmmol. Sci. Chem. A9, 1415/1975).
22. Malaviya, P. R. Shukla and L. N. Srivastava I. Inorg. Nucl. Chcm. 35,1706 (1973).
23. R. L. M d n and ~ S. Mioa, Pmc. Chcm Soc. London ,432,473 (1970).
24. A. Syamal and K. S. Kala, Ind. I. Chem. A16.46 (1978).
25. L. Dubicki and R. L. Mamni, Iwrg. Chem. 7.2203 (1966).
26. C. K. lorgensen, in: Absorption Spectra d Chemical Bonding in Complexes, p. 15. Pergamon,
Oxford (1%2).
27. B. N. Figgts. In: introduction to Ligd Fields, p. 25. Wilcy-Interscience. New York, NY (1x2).
28. W. Manch and W. I. Pernolias, J. Chem Soc. 38, 192 (1961).
29. 0. Bostop and C. K. Jorgcnson. Acfa Chrm. Scd. 11.1233 (1957).
30. A. Sugi and N. Ogawa, Chem Pharm. Bull. (Tokyo) 24.1349 (1976).
31. A. Sugi. N. Ogawa and M. Hisamitsu. Chem Pharm. Bull. (Tokyo) 26.798 (1978).
32. J. E Dingman Jr., K. M. Gloss, E. A. Milano and S. Slggia, Ad. Chem. 46,774 (1974).

Synthesis and Metal Uptake Studies on Pol (hhydroxybazoquinoline
hen lacrylate- formaldehyde^ Resin
and its Metal e amp r exes
S. Vijayalabhmi, R. Sanku, S. Subnmanian, S. Rajagopan, T, Wyappan
Deprrtmmt of Chmtlslrq, Pondlchmy Englnemng College, Pad~chmy 605014, lndi
ABSTRACT 8-hydroxy5~azoqu1noI1nephenylacrylah- the metal to Lgand raho u about 12 The palymer meial
lormaldehydr (BHSAQPA-F) macmmonomer was pw complexes were a h charactenzed by LK XRD, mp&c
pared from acryloylchbnde, wlth cundewhon products moments, and thermal analyms The eff& of pH and
of Bhy~fraqalwoIwphenol~brmaldehyde, and ply- elRbolyte on the metal uptake behavlor of Be ream were
merued m DMF at 7PC uslng benzoyl perox~de as free also studled %I \rl>ley Penodtrah inc I ~ppl Polyn h
rad~cal mbator Poly(BH5AQPA-F) was characterued by 101 797-802. ZW
~ntrared and nuclear magnet resonance spearoscop~c
trchques Polychelates were obtamd m ahhe soluhon Key woh Bhydroxydazoquolure. diffuse reflectance
01 plynenc llgand wlth the aqueous soluhon of CuOll spemm, thermal analyua, metal uptake, apedrmoplc
and NI~) Elemental analysis of polychelales suggests that sNdles
INTRODUCTION
Chelabng polymen can play an unportant role tn solvmg
envuonmental probh Qlelabng resm a bask
caUy an o p polymer conmg donor atoms that
can succensfully mteract wlth the metal lorn through
coordmte bond and polymer backbone makes them
more &ent by offemg large surface area
Polymer metal complexes have been of mterest to
many researchen dunng the past three decades tn
the l~ght of the11 pomhal a llcdhons m dlvenlfied
held.! hke orgatuc synthesis,
PP
waste water keahnent,'
hydrometallurgy,' polymer drug grafts.' recovery of
trace metal ~OIIS,~ and nuclear chermstry"h add17
bon, they are F& used as mdek for enzymes ''
The determwhon of trace toxic metal ions and
the11 removal w~th chelatvlg polymers have gamed
great Importance m envuonmental appllcahom
buse of theu hqh degree of selectivity, hgh loading
capacity, vnsahhty, dunbhty, and enhanced
hydmphihaty9 Olelahng ion-exchange resins wth
s@c chelabng gmups attached to polymers have
found extensive use m the separahon and preconmkahon
of metrl im lCIZ
In recat ycars, the development of su~table funchonalued
chektmg resm for trace meal preconcen-
'*! InterScience'
tratlon and separahon prov~des a new unpehls to
extrachon approach El-Sonbah and coworkers have
studied the new sohd polymer metal complexes of
several stencally hmdered heterocychc hgand~'~'~
Most of the workers charactenzed N=N-Inkage by
the presence of a band m the regon 1570-1579 an?
m LR spectrum As the chelabng resm contams a
weak baslc functional group hke phenohc -OH, it
s expected that the sorphon of the metal depend on
the pH of the m&um In conhnuahon of our
research work m polychelates,'617 m hs arhcle, we
report synthess, charactemahon, and apphcahon
study on poly(&hydroxy-5azoq~1l1ohephenylany-
late-formaldehyde) [poly(BHSAQPA-F)] resm and I@
metal complexes
MPERIMENTAL
Benzoyl pernude (BDH, In&) was ~~ from
chloroform/methanol nuxture 8-hydroxy qurnolme
(BDH, In&) was rec@alhzed fmm meboL Aayl-
oyl chlonde and 8-hydmxy-5-aquuqhe hydro7
b e were prepared by the procedure reported la'
-
A nuxture of 1 11, Bhydroxy-Saqrunohe hydmxybenzene
and 3Wo formah dubon, and 3°W/WJ of
lo& of A@ed Polymm SdsKe, Vd 1M, 797-SCn (m7) oxahc and were placed m a mund-bottom tlaak
02W W~ky Pend~d. Inc
sealed and put m an 011 bath at 100°C for 24 h The
c;

I 4 HCHO -
OXALIC ACID
100 .c
Scheme l Synthesrr of macromonomer B-hydroxy 4azoquohephenylaqluttfo~de
flask was then cooled to room temperature and
desealed and wata was decanted The sohd ranammg
m the tlask a dlssohred m NJJ-dlmethyl fonnam-
~de, and the resulhng soluhon was added dropww
to large ex- of 10% aqueous sodturn chlonde soluhon
with cmutant s m g 'Ihen, the red compound
was hltered and washed weral tunes with dishlled
water unhl free of chlonde Lon and dned at 60°C
m
deaerated by passmg oxygen fm Nihogen for
30 mm 'he reachon tube was closed and kept m a
thermostat at 70°C for 8 h A large excess of metha-
nol was added to the contenb and the precipitated
poly(BH5AQPA-F) was bltered, washed wtth metha-
nol, and punhed by N,N-d~methyl formamidefmeth-
aml mixture Polymer was dried under reduced
pnssure at 64°C for constant we~ght
Synthma of poly(8HSAQPA-Fl metal chelates
8HSAQPA-F (26 & O W , Inethykmme (278 mL,
Po'Y"'er were p'Tared at room tan-
0 OW, hydqwone (0 5 g), and DMF (25 mL) were
peTature by soluhon *que A Wlal procedw
am a thmeck flask equpped a smr fOr the preparamn of ~ l Y " ' ~ cht?late ~ m ) a as hithermometer,
and separpm be,, and the
lows Po~~~~H~AQPA-R (5 m ~ of l repeat m
mL) and the pH
were cmled to 0 to -5°C Acryloyl chlonde (1 8 mL,
thesolubm was adpted
OO?M) was added dropwlre wlth constant shmng at to mth amurn hyhx'de aquears
tRnperatuR ne muture was then
mhhon of Cum) acetate (2 moi) was added drop
wise
~hrred for another 2 h at nam temperature and the
to the plymer with mnstant sw
quaternary ammoruurn salt was h~tered off he ~II- mublre was Qeted On a for
hate was thomugNy washed with dst~IIed water and
and kept Over at room temperature The predried
over anhydrous and the clpitated Poly(RH5AQPA-&metaI cmpler was fda
remwed to get a mbd IR 1~ IH.NMR spect
d , washed with hot bidled water, followed by
methanol, and dned at WC m wuo A slmllar pmawm
cavusmt with the awped structure
dure was adopted for the pprahon of NI(II) chelate
(Scheme 1)
Y~eld 83% for Cum) and 85% for NO 8H5AQPA-F (3 5M) m DMF and benzoyl perox~de IR specha were warded on a Bomem MB 104 mR
(05 g) wm t~h n a standard reachon tube and spectmphotometu usmg KBr pellets The 'H-NMR

SYNTHESIS AND METAL UFTAKE STUDIES ON POLY(8HSAQPA.F)
TABLE l
Elmental Analvsls for Polv(8H5AOPA.F) , - and Itl Metal Comolnls
Elemental malvas (wnght prm4
Carbon Hvdrwm Orvsm Nahmm Meal
~ ,
- - - , - . -----
. - . 0-
Abbrwuuon Empzncal formula Cal a Fd 01' Fd Cd' Fd Cal' Fd 61' Fd
PoIy(BH5AQPA.R CI*H,X)&~ 6887 6886 395 3% 145 1452 1268 12.66 - -
PoIyI8HSAQPA~F)CuIll) lC~rH,iOJrl~).€u(Il) 5794 5793 3 07 308 12 19 12 17 1067 1068 16 13 16 14
Poly(8HSAQPA FtN10ll (CIPH~~O~~I)~-N~I~I
lH10)~ 5876 5873 3 11 312 1237:1239 1UB2 1084 1494 1492
'Calculated percentage of C. H. N, 0 md metal Ions for polymer-metal complexes based on the value of r = y = 2 W,
Found x=202,y=201
spectra were recorded on a JEOL-GSX 400 MH: Effect of pH on metal ion uptake
spedromPter m deuterated DMSO as solvent using
TMS as lntemal standard The molecular we~ghts
The ophmum pH of the metal Ion uptake was determmed
wlth a bakh eqdlbrahon (eduuque Excess
[M, and M,) were determined by gel permeahon
of metal Ions Cu(n)/N~(ll) (10 mL, 01M) were
chromatograph (Waters model 401) The dhse reshaken
with 25 mg of the resrn for 24 h The pH of
flectance specha of the polychelates were recorded
the mluhon was adlusted before equlllbrahon over a
on a Carl-Zews VSU-ZP spectrophotometer The
range of 1-10, wlth weak ac~d/base The complex
mgnetlc moments were detemuned by Guoy methwas
hltered off, and the concentrahon of the Cu(II)
od and corrected for the dlamagnehsm of the comton
remamlng m the filtrate was detemuned by
ponents uslng Pascal's constant The thermogravi-
~odometncally and Ni(Il) by gravunetncally
memc analys~s of the polymer was performed on a
Mettier 20W TA thermal analvzer The C. H, and N
contents were determmed wlth an Elemental analyzer
(Elementar, van0 EL, Hanau. Germany)
RESULTS AND DISCUSSION
Metal uptake studlm of polymer
m the pmence of elcctmlytea
The polychelates were mluble m common organlc
solvents but moderately soluble m DMF The elemental
analysw data for poly(BH5AQPA-F) and
metal complexes are presented m Table I The ele-
The wlvmer sam~le (25 ma m 25 mL of DMFl was mental amlvsw data suaested a metal to volvmer
addid an e1elect;olyhc soluhon (25 mL) of a known raho of I 2, and ~t e ;good agreement ;I& the
concenhahon The pH of the soluhon was adlusted calculated values
by usmg 0 1M HC1 or 0 1M NHJ The soluhon was Vwcos~ty measurements were done by usmg
shrred for 24 h at mom temperature To h soluhon, Ubbelohde suspended level vlscometer The mtnnsic
10 mL of 0 1M solution of metal ~cn CU(Q/NI(II] was
added and the pH was adpted b the requued
v~scosity [q] was obtalned by extrapolatlng q.p/C to
zero concenhahon and it was found to be 0 61 dL/
value The mutun was agam shned at 25°C for 24 h g The resulk reveal that the molecular welght of
and hltered The mhd was washed and the Cum) ion the polymer w moderately high The number avercontent
was detRrmned ~adunetncallly and NI by age molecular we~ght (M,) and the welght average
gravunetncdy The amount of the metal Ion uptake
of the polymer was calculated from the difference
behvem a blank expemmt w~thout the polymer and
the readmg m the achtal expnmenb The expenmolecular
we~ght (M,) of the macromonomer
(BHSAQPA-F) were determmed by gel permeahon
chromatography usmg tetrahydrofuran as solvent,
and found M, = 143 x ld, M, = 279 x ld and
nenb were pe*ormed m the presence of several elec- for the polymer[poly(8H5AQPA-F)] (M.) = 163
tmlytes wlth Cu(U) and Nl(4 low x lo', (M,) = 3% x 10' and the polydrspers~ty
TABLE I1
IR Sphal Data of PolylBHSAQPA-F) and Its Metal Complexer
bple OH, C+ster.,. N=N, Phmohc C-0 M-N, M-0.
Poly (8HSAQPA.P) rmrWnr 17@ 1% 1375
PolyCSHSAQPA.F'&u(ll) 1735~ 1555' 1380 720 5%
Paly (SH5AQPA.P) -NIN) 3100. 1735~ l55P 1385 735 525
' Blold
:Medium
%

~ndex (M,)I(M,) = 2 16 for ply(BH5AQPA-F) sug-
gests for cham temahon by rad~cal combmahon
Chuactmuhon
hym 1 'H-NMR spedrum of polg(BH5AQPA F)
The 1R spffhum of ply (BHSAQPA-FJ shows a medurn
bmd band m the regon NX-3200 an-lwhch
may be aw'gned to phenobc -OH strethg The
phenohc -OH band IS not present m the sp&a of
N I ply(BH5AQPA-FJ ~
shows strong bands at 1730
an-', wluch may be assigned to C=O of ester "-a
The other absorphm are presented m Table Il
The 'H-NMR spgtnun of ply(BIi5AQPA-FJ (F% 1)
charactenzed by a mulhplet around 6 576 ppm
was due to aromahc protons, and the s ~ pat l 795
ppm my be ass~gned to protons of Ar-OH The res-
Cu(m polychelater T~IS lnd~cates the loss of phenol~c
onance s~gnals at 185 and 2 2 ppm may be assigned
to methylene and rnethme protons, mpechvely As
the polychelatn were not soluble In common or-
-OH and parhupahon of oxygen of the -OH pup ganlc solvents, the 'H-NMR spectra of the polych~
m metal mordmahon The absorpbon band around latn were not reported
IMW17W on-' due to C=N of qumohe alro
undergo a shlft, wluch IS due to N of quohe cmr
hhng wlth the metal
NI(Q polychelates show a strong band around
34W an-', and tfur band remam even when the
polymer metal complexes were heated up to 19°C
T~IS suggests coordmahon of water moleculn to
The fuse reflectance spectrum of Cu(ll) ply
chelate5 contam two bands, one at 14,800 an-' and
another at 22.W an", wluch may be ass~gned to d-
d hansihon correspondurg to E,-Tzg translhon
In the electronic specha, the N I chelate ~ plymels
arehc@&bytimebardsat99jOan ',157~an I,
and 24,625 cm-I, whlch may be ass~gned to ' A ~ ~
TABLE PI
ThumcpwKtrir DaU of Poly(8HSAQPA-Fl md Ih Metd Chelate
Tempramre (Ci mrrrsponds to
hP't T, ('C) 10 30 M 70 90 Char % at XXI C
Pdy(SH5AQf'A-Fl 165 98 2RO 420 490 MXI 0
P~~~MSAQPA-F)-~~(U) IBO 3% 1180 fm - 10
P~~(UHSAWA.~NI(U) % za as 570 - 37

SYNTHESIS AND METAL WAKE STUDLES ON WLY(8HSAQPA-F) 801
would lmply mtercham awhkmg hem ply
(8H5AQPA-FJ mterchams, wh~ch 6hdd turther re
duce rather hn enhance any such o~denng The ap warance of crvstaUmtW m WIVIBH~AQPA-F~ metal
complexes may be beck df Aerent c&alhe nature
of the metalhc compounds
The TGA data for ply (8H5AQPA-F) and plychelaks
are present@ m Table Ill The thermal analyhcal
data mhcate dist m poly(BH5AQPA-F) loss of
welght b e p at 120°C and degradahon of the plymer
OCM at W C whereas the polychelates were
very stable up to 7WC, and th~s md~cate hgher
thermal stablhty of the plychelatm compared wlth
the parent polymer (Scheme 2)
The results of the batch eqrul~bnum study, carned
out with the polymer sample of ply(8HSAQPA-F),
are shown m the Flgure 2 From h study certam
generahhons may be made about the behavlor of
the polymer sample By keeping the concentrahon of
Cum) and NI(U) hxed, when the pH of the soluhon
Scheme 2 Spthes~s oi poly(8-hydroxy-Sazquolme was vaned, the resm showed lgher uptake percentphenylaaylate-fddehyde)
rean and its CuINl com- age of Cum and Nl(11) at pH 7 The amount of
plexes
metal 10% taken up by the poly(8HSAQPA-F) Increases
w~th the mcreasmg pH of the medium The
- qW and Vwn - vlm ~ I ~e~pechvely ~ maptude , of the mcmse, however, s different for
GmeraUy, oadhedrd spm hee NIO mmplexes ahht d~fferent metal cahons
three bands m ther ele3mruc sp&a ""
Cum) polychelates have a mapehc moment of
175 BM, md~cahng square pianar conhgurahon The Inlluence of elecbolytes on metal upuke
magnehc moment of 3 81 BM and the paramagnehc
behanor of Nl(1I) complexes suggest distorted octa-
Table 1V reveals that the amount of metal Ions taken
hedral geometry for Nt(U) polycheiates '"" up from a gven amount of a polymer depends on
The X-ray d~ffrachon studies mdlcate that ply(&
the nature and concentrahon of the electrolyte pres-
HSAQPA-F) s amorphous whereas lb polychelates
possess good crystalhne nature The ctystalim~ly m
TABLE N
prlychelates may not be due to any ordenng m ply Ptreenbg Mttll Uptake of Poly(8HSAQPA-PI
(BHSAQPA-F) tnduced dumg metal chelates anchor- w~lh D~ffennt Elatrolvtw at Dtffmnt pH
"& more so smce anchomg of metab to polymer
;/;. ; , ; , ; , , ,I
a I I
I
N?+
~ehl ton
cu2+
pH
3
5
(mol L")
001
005
01
001
NsCi
n
15
90
V9
NaS04
3a
52
56
710
7
005
01
001
852
W
95
80
i9
%
005 96 %5
3
01
001
005
97
e4
81
96
40
42
5
0 1
001
005
82
83
86
46
71
79
01 88 82
W 7 001 853 90
Offi 35 92
Pigwe 2 McW ~rm uptake behav~or of poly(BH5AQPA-R 01 90 95
mn at dlterent pH

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--H EUROPEAN
.;J' ScienceDirect POLYMER
€w3'ER Eumpcln Polymer Journal43 (2W7) 463944 JOURNAL
Synthesis and chelation properties of new polymeric ligand
derived from 8-hydroxy-5-azoquinoline hydroxy benzene
R Sankar, S. Vijayalakshmi, S Subramaman, S. Rajagopan, T. Kaliyappan '
8-Hydroxy-hzoqonohne phcnyl mcthacrylatbfonnaldehyde (BHSAQPMA-F) macromonomer was prepared from
mcthaayloyl chlondc wth wndc~atlon products of 8-h)drox).S.w.cqumoltnc phenol-fonnaldchyde. and ~ l y m e d
in DMF at 70 T using bcntoyl wrou& as free rad~cal ~nltlalor P~I~I~HSAQPMA.FI uas characvrucd br lnfrared
and nuclear mapchc Anan6 s&troscop~c cechnlqucs Polychelata & c ob&cd when the DMF sohaon oithc rcsln
wnmlnc fnu droos of ammoma was trcaled mth the aaueous solut~on of CullIl/N~(Ill Elemental anahs~s of thc mivchelatea
&at the metal to hgand taho was abouil 2 The 1R spsVa of ~olychclater sumt the& metals'wck
cwrdrnatcd through (he oxygen of the phenoltc-OH group and n~tro* of the qu~nolme hgand-The DRS and mapew
moment data lndleate a souare olanar for Cullll wmolcx whereas anahedral for NU) mmolcr The TGA data re&
the t h l ttab~hty of th; rend and the polych~latts'~-ray d~ffractlon study revealcd ;be lnkrporatlon of the metal lorn
s~@l~fieantly enhanced the dep of crystallln~ty The sorpuon propma of the chelare-fomg m~n towards vanous
dlvalent mnal ions [Cull) and NI(II)] wm studled as a funn~on of pH and electrolyte
O 2007 Elvvln Ltd All nghtr rescrvcd
In m t years there have ban a growing lnterest
tn design and synthnts of polymer-metal wmplexes
due to thnr spa1 properttes and potentla1 applicatlons
m mrpbon, waste water treatment, organlc
synthesa, hydromctallurgy, catalysa and raovery
of ma metal elements [I41 Polymer-metal wm-
Wl&M576. ar fma mnm 0 lW7 Blrmn Ltd All nghU nscr
dog I0 lOlf4~nu~~kWlM015
plexes are m general word~nattng polymers contain.
mg one or more electron donor atoms such as N, S,
0 and P that can form coordinate bonds \nth most
of the toxlc heavy metals A polymeric Ilggand e usually
used to selecttvely b~nd a spx16c metal ion tn
mtxtwe to isolate unporlant metal 1011s from wastewater
and aqueous media One type that has been
cxtens~vely used ln the separatron and pmnanlraclon
of metal ~ons 1s chelatmg Ion exchange mtn
wth s@c chelattng group attackd to polymer
[S-71 Among polymers tho% contmq nltrogcn
as donor atoms have been synthesmd and used m
complexatlon of wansibon metal cations Various

Author's personal copy
nitrogen containing ligands such as salicylaldiminate
derivatives (83, oligoethylcneimine 193, vinylmine
1101 imidazok derivative [Ill quinoline [I21
have been uscd in preparation of rains.
8-Hydroxy quinoline (o~ne) is a ligand whose
reactivity towards metal ions is well known from
the literature [13,14] and it is widely uscd as wmpkxing
agents. Sighai et al. described the kinetic
parameters of Ni(I1) and Cu(I1) chelate with 8-
hydroxyquinoline 1151. The intcrsction of heavy
metal ions and 8-hydroxy quinoline wuld be used
to enrich the heavy metals in water and their analysii
[Ib]. Mannich polymers containing 8-hydroxy
quinoline as the pendant chelating agent with dierent
spam groups possessed good chelating properties
at pH vdw gnater than 6 1171. The SchiR basc
transition metal complexes are a family of attractive
oxidation catalysts; Sivagamasundari and Rameh
synthesii Ru(I1) complexes containing bidentate
schiffs bases and studied their catalytic activity
towards oxidation of organic substrates in the presence
of N-methylmolphol'ie.N-oxidc [IB]. In wntiuation
of our interest in synthesis of new
quinol'ie m d s 119-223, we describe herein the
synthesis of new azo based quinoline ligand and
its chelate forming ability with various divalmt
metal ions at different pH and electrolyte.
h y l pero~de (Ruka) was nerystalliscd from
chlorofonn/mnhanol mixture. 8-Hydroxy quinol'ie
(Fluka) was rsrystall'i from methanol. Methacryloyl
chloride was prepared by the reported procedun
1231.
2.2, Synrhuir of 8-hydroxy-krroguinoline hydroxy
benzene
8-Hydroxyquinol'ie (4.35 & 0.03 M) was dissolved
in wnc. HCI (20 ml) and kept below 5 'C
in an ice both. pAmiiophenol (3.27 g. 0.03 M)
was dimlvcd in wnc. HCI (201111) by heating and
the solution formed was woled down quicldy to a
tempentun blow 5OC with vigorous stirring to
obtain a loiutiw. To hii solution was added
sodium nitrite (2.55 & 0.03 M) in 20ml of water.
A h airfins at 0-5 'C for 30 min a yellow solution
was obtained. To hii 8-hydroxyquinolie solution
Was added slowly whik 8tining. Thc mixture was
then stid for half an hour and then neutralized
with saturated Nag01 aqueous solution. Thc prod
uct pwipitaud out from the solution and was
collected by filtering (7 & yield 80%) of 8-hydroxy-
5.azoquinoline hydroxy bnuene was obtained after
rcnystdlising the crude product from ethanol [24].
2.3. Synfhesu of 8-h)Woxy.S-a:oquinoline phenol.
formaldehyde
A mixtun of 1:2, 8-hydroxy-5-azoquinolinc
hydroxy bnuene and 37% formalin solution, and
3°/4W/W) of oxalic acid were placed in a round-bot-
tomd Bask, scaled and kept in an oil bath at I00 'C
for 24 h. The flask was then woled to room temper-
ature, desealed and water was decanted. The solid
remaining in the Rask was dissolved in NJ-
dmethyl formamide and the resulting solution was
added drop wise to large e xw of 1!Yh aqueous
sodium chloride solution with constant siig
and the red compound was filtered washed several
ties with distilled water until free of chloride ion
and dried at 60 'C in Vacuo. Yield: 83%.
2.4. Synthesir of 8-hydroxy-5-a:oguinoline phmyl
mefhacrylale-formaldehyde (BHSAQPMA-F)
8-Hydroxy-5-azoquinolinephenol-formaldehyde
(8HSAQPF) (2.6 g, 0.02 M), triethylamine (2.78 ml,
0.02 M), hydroquinone (0.5 g) and DMF (25 ml)
were taka in a three necked flask equipped with a
stirrer, thermometer and separating funnel and the
wntents were cooled to 0 to -5 TC. Mcthacryloyl
chloride (1.8 ml, 0.02 M) was added drop wise with
constant stirring at that temperature. The reaction
mixture was then s i i for another 2 h at room
temperature and the quaternary ammonium salt
was hltnrd off. The Gltrate was thomugbJy washed
with distilled water, did over anhydrous sodium
sulphate and the solvent was movcd to get a solid.
The IR and 'H NMR spxtra were consistent with
the assigned structure. Yield: 7%
8-Hydroxy-5-azoguinolim phmyl methacrylate-
formaldehyde (3.5 M) in DMF and bmoyl pmx-
ide (0.5 g) wm taken in a standard rraction tube
and deaerated by passing oxygen fm nitrogen for
30 min. The reaction tube was closed and kept in
a thermostat at 70 T for 8 h. A large cxcarr of
methanol wss added to the contents and the pmip

itated poly(8HSAQPMA-F) was filtered, washed
with methanol and purified by N.Ndiiethy1 form-
amide/methanol mixture. Polymer was dried under
nduced pressure at 60'C for constant weight.
Yild: 77%.
2.6. Synthesis of poly(8HSAQPMA-F)-merol
chelntes
Polymer metal chelatcs were prepand at room
temperature by solution technique. A typical proa-
dure for the preparation of polymer-Cu(I1) chelate
was as follows. Poly(8HSAQPMA-F) (5mmol of
repeat unit) in DMF (75 ml) and the pH of the solu-
tion was adjusted to 7 with dilute ammonium
hydroxide. An aqueous solution of Cu(I1) acetate
(2.5mmol) was added drop wise to the polymer
solution with conslant stirring. The mixture was
then digested on a water bath for 2 h and kept over
night at room temperature. The precipitated ply-
(BHSAQPMA-F)-metal complex was filtered,
washed with hot distilled water, followed by metha-
no1 and dried at 60 T in vacuo. A similar procedure
was adopted for the preparation of Ni(1I) chelate.
Yield: 83% for Cu(1I) and 81% for N(I1).
2.7. Trms~tion metal ion selecriuity of
poly(BH5AQPMA-F) of dperent pH
The optimum pH of the metal ion uptake was
determined with a hatch equilibration technique.
Excess of metal ions Cu(lI)/Ni(II) (IOml, 0.1 M)
were shaken with 25 mg of the resin for 24 h. The
pH of the solution was adjusted before equilibration
ovcr a range of 1-10 with weak acidbase. The pre-
apitetcd complex was Gltned OK, and the wnccn-
tration of the Cu(I1) ion remaining in the filtrate
was determined by iodomevically and Ni(I1) by
gravimetrically.
2.8. Trmirion metal ion seleclivity of
poly(8HSAQPMA-F) in the presence of elecfrolyfes
Author's personal copy
The polymer sample (25 mg in 25 ml of DMF)
was added in an elmlytic solution (25 ml) of a
known wnanuation. The pH of the solution was
adjusted by using 0.1 M HCI or 0.1 M NH,. The
soluti~ was stirrcd for 24 h st room trmperature.
To this solution lOml of 0.1 M solution of metal
ion Cu(IIm(ll) was added and the pH was
adjusted to the rcquircd value. The mixture was
again atid at 25 T for 24 h and filtered. The solid
was washed and the Cu(I1) ion content was deter.
mined iodimctricallly and Ni by gravimevically.
The amount of the metal ion uptake of the polymcr
was calculated from the diBmna between a blank
experiment without the polymer and the mdmg
in the actual exphents. The experiments wae
domed in the prseoce of several ekctrolyts
with Cu(I1) and Ni(I1) ions.
IR spectra were recorded on a Bomm MB 104
R-IR spcctrophotometer using KBr pllets. The
'H NMR spcrra were nmrded on a JEOL-GSX
400 MHZ spectrometer in dmterated DMSO as sol-
vent us'ing TMS as internal standard. The molecular
weights (M, and M.) were determined by gel per.
meation chromatograph (Waters model 401). The
C, H and N wntents were determined with an Ele-
mental analyzer (Elementar, vario EL, Hanau, Ger-
many). The viscosity measurements were made in
THF at 30 'C with an Ubbelohde suspended level
vixometer. The magnetic moments were deter-
mined by Guoy method and corrected for the dia.
magnetism of the components using Pascal's
constant. The diffuse retlectance spectra (500-
2000nm) were measured on a Varian Caly 5E
UV-vis-NIR spcctrophotometer. X-ray di&action
experiments were performed in Phiiips PW1820 dif-
fractometer. The thermo gravimetric analysiis of the
polymer was performed on a Mettler 2OOO TA ther-
ma1 analyzer.
3. ResultP and discussion
The macromonomer (11) containing polymeriz-
able vinyl goup was synthesized from S-hydroxy-
5-azoquinoline hydroxy benzene (I) and formaldehyde
in the presence of oxalic acid. The macromonomcr
(111) was polymerized in DMF medium using bm.
zoyl peroxide as fre radical initiator with a good
yield (Scheme I). Polymer-metal complexes wcre
obtained in DMF containing polymer in an aqueous
solution of metal ions Cu(I1) and Ni(I1) in the pres.
en= of a few drops of ammonia The polymers were
soluble in DMF, THF, aMJ DMSO, and insolubk
in common organic solvents like benzene, toluene,
methanol, and water. AU the polychelatcs were
sparingly soluble in THF and DMF. The elemental
analysii data for polymers and polymer-mtal com-
plexes w m presented in Table I. Theelemental data

Author's personal copy
suggest that the metal to polymer ratio wasl:2 and it
was in good agrerment with the calculated values.
The intrinsic viscosity [IT] was obtained by extrapolating
q,JC to pro concentration. The intrinsic
v~scosity of ply(8HSAQPMA-F) was found to be
0.64d~g-I. The results reveal that the polymer
was moderately high molecular weight. The number
average molsular weight (M,) and weight average
molecular weight (M,) of the poly(BH5AQPMA-
F) were determined by gel permeation chromatography
uing tetrahydrofuran and were M. = 1.85~
10'; M, = 3.96~ 10'. The polydispersity index
(M,/M.) for polfi8HSAQPMA.F) is 2.1. The result
was in aocordanet with the viscosity value. The the-
oretical value of MJM. for polfi8HSAQPMA.F)
suggests a strong tendency for chain termination
by radical recombination.
The IR spenra of pdfi8HSAQPMA-F) and its
polychclates were shown in Fig. 1. The medium
absorption band in the region 3400-3000 an-] mrresponds
to phenolic-OH stretching. The phenolic-
OH stretching disappears in the spectra of polyche
latcs, indicating aordination. NiII) polychclate
show a strong absorption band in 3250 cm-I owing
to coordination of water mol& to metal ions
[25,26]. This band remains even when the polyche
lates were heated upto 1% "C, poly(BH5AQPMA-
F) shows strong bands at 1745cm-I and 1163
an-', which may be assigned to CEO ester and
C-0 esteric groups, respectively. The band around
725 an-' and 525 cu~'corresponds to metal-nitrogen
and metal+xygcn vibration.
nc IH-NMR spect~m
of p ~ i y ( 8 ~ ~ ~ ~ ~
(Fig. 2) characterized by a multiplet around M.M
was due to aromatic protons, and the signals at
Fig. I IR rpstra of (a) ply poly(8HJAQPMA.F). (b) poly-
(8HSAQPMA-F)CU(II) md lc) ~~~(SHSAQPMA.F)-NI(II).
Tlbk l
h m u l d y l L 81. of poly(8HJAQPMA.F) and iU mctnl cornpluea
Abbnnbo. Empirical fornula Elerncntnl pnslysk (weight prcml)
m a Hydrogen Olym Natmm Mr~l
01.' Fd. ~d.' Fd. c.I.' Fd. &I.' Fd. w.' Fd.
POlfi8HSAQPMAF) (CBHIPINJ~ 69.51 6955 4.35 4.39 13.91 13.88 12.11 12.18 - -
PoM8HSAQPMA~lI) (Cdo4@N4N$.CU(Il) 58.9 58.55 3.43 3.51 11.78 12.05 10.31 10.22 15.58 15.68
Poly(8HSAQPMAP).Nin) C~I@,NI),~Niill)(H@), 5704 56.99 3.80 3.W 15.22 15.18 9.98 9.94 13.96 13.99
pup of C. H, N, 0 md motnl iw, for polymer-mcul mmp*rm buad on the nh. of r = y - 2 found: x r 2.02,
Y-2.01.

9.256 may be asrigned to protons of AI-OH. The
rmwce signals at 4.2 and 2.96 may be assigned
to methykne and methine protons, respxtively.
As the polychelatcs were not soluble in common
organic solvents, the 'H-NMR spectra of the ply-
chelatu wore not rrportcd.
The di5uae reflectance spectra of Cu(1I) and
Ni(I1) polychelatcs wcrc shown in Fig. 3. The elw
tronic spectrum of Cu(I1) polychelates contains
two hands, one at 15,050~11-' and another at
22.150cm-', which may be assigned to 6d transi.
tion wmsponding to E, - T2, transition. A square
planar conhguration may bc tentatively assigned for
Cu(I1) plychelate in the present casc [27]. In the
electronic spectra, the Ni(l1) polychelate shows
three bands at 23.500 an-', 15,150 cm-I, and
Author's personal copy
Fag 2 'H NMR ipDtrvm of ply(8HJAQPMA-F)
ifyq
i '
9,950m", which may be assigned to 3~2ap,
3T2d.9 and 'Tzdn - 'Tla,, transitions, respectively.
Genemlly, octahedral spin free Ni(I1) com.
plexes exhibit three bands in their electronic
spectra [28,29].
Magnetic susceptibility measurements of transition
metal complexes give an indication of the
geometry of the li&ds around the central metal
ion. The Cu(I1) polychelate had a magnetic moment
of 1.82 BM which fall in the normal range (1.75-
2.20 BM) expected for magnetically dilute Cu(I1)
complexes, indicating a square planar configuration
[30]. The magnetic moment of 3.92 BM and the
paramagnetic behaviour of Ni(I1) complexes suggest
a distorted octahedral geometry of the Ni(I1)
polychelate [3 1,321.
The X-ray diiiractogram of pob(8HSAQPMA.
F) and its c~(II)/N~(~I) com~lex~s were shown
in Fig. 4. The X-ray diffraction indicated that
poly(SH5AQPMA.F) was amorphous, whereas
their polychelates possessed good crystallinity. The
crystallinity of polychelates may not be due to
ordering in polymer induced during metal chelates
anchoring, more so, since anchoring of metals to
the polymer would imply inter chain cross-linking
between polymeric chains, which should further
reduce rather than enhance any such ordering.
The appearance of crystallinity in polychelatcs
may be due to the inherent crystallime nature of
the metallic compounds.
The TGA traces of poly(SH5AQPMA-F) and its
Cu(1I) and Ni(I1) complexes were shown in Fig. 5.
lam urn, *,m yrrm zrm
I
w
W.n-lm.I)
Fis 3. DRS lp~m of (n) poly(SH5AQPMA.F~~ll) md (b)
Fi. 4 X-my diktopm af (a) pMSHSAQPMA.F), (b)
ply(SHSAQPMA.n.Ni(l1) and (c) ~OI~(SHSAQPMA-P>
pdHlH5AQPMA.F)- N111). CNll).
-

The transition tcmpcratw (Td for ply(8-
HSAQPMA-F), ply(8HSAQPMA-F)-Ni(I1) and
poly(8HSAQPMA.F)-Cu(11) w8s found to be 175,
355 and 390 "C, respectively (Fig. 6). The diaemcc
in transition may be ascribed to the crystallinity of
the polymer-metal complexes and is in aocordancc
with the X-ray diffraction study. Loss of weight
begins at 140 *C and the degradation ofthe polymer
occurs at 700 OC whereas the polychelates were very
stable up to 7W°C and this indicate higher thermal
stability of the polychelatcs compared with the par-
ent polymer. Cu(I1) polychelares are found to be
more stable than Ni(I1) polychelatcs. The 1R.
NMR, magnetic moments, elemental analysis of
Ftp. 5 TGA miva of (I) poly(8HSAQPMA.F). (b) ply.
(IIHSAQPMA-FkNi(11) sad (s) poly(8HSAQPMA.F)Cu(11)
Fig. 6. DSC am of (I) poiy(SHJAQPMA.F), (b) ply.
(IIHSAQPMA.F)-CqI) md (e) polfi8HJAQPMA-FkN(lI).
Author's personal copy
Scheme 2. Synrheals oi polfi8-hydrory.5-uaqwnohe phmyl
mnh.crylau-formddchyds) mlo and its Cu(ll)iN~(lI)
wmplnct
the polychelatcs and the structure of the polymeric
ligand, it appears that the chelation of metal ions
may occur between two groups from d117ercnt poly-
meric chains as shown in Scheme 2.
3.1. Effect of pH on metal ion uptake properties
The effect of pH on the metal uptake of the chc.
luting agents on sold polymeric materials is a very
important parameter. Ionization of the chelating
ligand and the stability of the metal-ligand complexes
vary when changing the pH. Fig. 7 shows a
typical bebaviour of pH-sensitive polymer. In general,
the metal uptake was seen to aignifimtly
increase with incnasing pH [33]. Thii refull auld
be explained by metal-ion competition with protons
at varying pH; when the pH increased, the elmon
pair of the nitrogen of quinoline ligand from ply-
(8HSAQPMA.F) was more available to interact
with the metal ions. Similarly; at higher pH, thearomatic
-OH prmntcd a higher metal-ion atfinity to
form polymer-metal complexes. Complex stability
depends strongly on the pH, at low pH, where the
majority of the quino'nc groups arc protonated,
the metal-ion abity is poor and the complex sobilily
is low. As the pH increases, the &ly and
stability of the polymer-metal complexes incrwcs.
The magnitude of bre~sc, however, was different
for different metal cations. Thc results indicate

Author's personal copy
on the natw and conccn~ation of the elcctrolytc
prmnt in the solution. In the presence of chloride
and sulfate ions the uptake of Cu(I1) and Ni(11) ions
increases with an increasing concentration of the
electrolytes. This ohtion can be explained on
the bask of the stability constant with these metal
ions [34,35].
3.3. Resin regenenpion
:k
To be viable material for chelation system, the
resin must be chemically stable The poly(8
, , , , , , , HSAQPMA-F)
7 M HCI. Polychelates could easily were placed be regenerated in a desorption with
sa
medium and stirred for 2 h at room temperature.
The defheiated polymcr undeKWmt complexation
Fil. 7. Mstl ioo uptake bshavlow of poly(8HSAQPMA-F)
mm at diamnt DH.
with the original efficimcy. To obtain resin reusability,
the sorption-dcsorption cycle war repeated four
times with the same adsorbent. More than 95% of
2;:
Cu(1I) was absorbed selectively to the higher extent ~ l p " ~ f ~
over the pH range.
ity of the polymer under acidic conditions.
3.2. Inpucnce ofelectrolytes on rneral ion uptoke
properties
g, c m c l h
Table 2 reveals thdt the
Iden UP froma Pen Ofa pol'mcr
Ions
A resln ,gHSAQPMA.Fj based on condensat~on
reaction of 8-h~drox)-5-azoqumohnc phenyl methacrylav
\nth formaldcb)de m rhc presence of oxaitc
PaernUsc MrU Upuks dpoly(8HSAQPMA-Fl wth d~Lreal
alarol)m at diliermt pH
McUl ion pH Ehtrolpe (mol L ') Pemntapc of the
mMI tan tnkcn up m
acid catalyst has been synthesized and metal com-
plexes were prepared. These complexes have been
characterized and were assigned a metal to ligand
ratio of 1:2. The prepared ligand possessed high
thermal stability which shows good chemical stabil.
ity that facilitates thcchelation at neuml pH values.
The thermal stability ofpolymcr and itspolychelates
follows the order poly(BH5AQPMA.F)-Cu(lI) >
poly(8HSAQPMA.F)-N$n) 2 poM8HS-AQPMA-F).
The above mentioned results strongly recommend
the use of the prepared polymeric ligand in metal
ion removal of study of Cu(1I). Finally, it may be
concluded that the ion-exchange ability of this poly-
mer with various divalent metal ions in an aqueous
medium at pH 6 and above could be effectively used
for the removal of heavy metals from water and
wastewater.
The authors thank SAIF, IIT, Chennai (Ma-
dras), India for providing instrumental facilitia.
One of the authors (T.K) is grateful to DST, Gov-
ernment of India for the award of young scientist.

Ref-
Author's personal copy
[I] KILylpprn T, Kmnm P Rog Polym Sn 2W0,25 343
I21 Flm RC. Zukeu 1 laorg Chnn 2MI.U) 2466
[31 bnupvly C. KItraiadh S, Chaw A. Owcr HD Tnlanta
1990.37 491
141 Akchh A. Shemagon DC Chsm Rcv 1981.81 557
[51 Rlvw 81, Muoz C J Appl Polym Sn 2037,104 1769
I61 Ebnhm MK. Hamdl ST Rcrcc Funa Palym 1997.34 5
[7] LLyrpprn 1. Swm~mthm CS. Kwan P Bur Polym J
1997.33 59
[8J Alcllo I, Ohdm M, Zenchmn C lnorg a m Acta
19992% 133
(91 Troch~md A. Kolvr EN, Wa~aqaska M Rcsst Polym
1988.7 197
(101 JMW L, Momllet J, Dclporv M, Momlk M Eur Polym J
I'R218 - . IIR5 . . [I 11 Van kkcl PM. DnPvn WL. Kodhw GJAA, Rcldllk J,
Shrmnoon DC J Chcm Soc Chcm Commun 1995 147
[I21 Kahyapp~ 1, Anupnya R, Kpmn P J M m Sa Purr
Appl Chm 1999,A36517
(131 Phdllp. IR Chrm Rev 1956,552721
1141 Parnah JR Ann Chcm 1982.54 18%
1151 Mlahrs. AK. T1w.n VK, Sm&i R lndkan 1 Chrm
2M2,41A 2W2
1161 Llu X, Zhun D. Chsng D Chm Abtr 2W0.133 3474h
1171 Sslm NM, Ebnhan KAK. Mutarak MS Reset Funcl
Polm 2W.59 63
[I91 V ~yWhrm S. Suk- S, IUjapw S, Ka11yapp.n
T J Appl Polym Sn 2W6,99 1516
Dl Vl~nyahkahm~ S, Subrunvllan S, IU~agow S, Wlysppsn
T J Appl Polm Sn 2W6.101 1546
I211 V~~aynlJrshmt S. &nku R. Subnmsm S. Rqa~opn S.
Kal!yrppm T Dm Monomer8 Polp UYM.9 425
I221 Vl)lys!&hl S, &nh R, Svbramuuan S, R~).(opln S,
Ksllyappm T J Appl Polym SCI 2007,104 797
P31 Stempel GH, Cras RP, Mnnclla RP 1 Am Chcm Sa
1950.72 2299
[24] Mang X. Ntiaa~olm A. Rochon P Supnmol sa
1996.3 4207
1251 Nakmalu K lafnnd Ahrpi~on Spxrompy 2 cd
Nakdo, Japan, 1964
[261 Fmdmnn HN J Am Chcm Sa 1%1.93 29M
I271 Paul Mshcndrs R, Paul MR, Paul MN J Mmomal Sa
Chcm 1986,23 1503
1281 Flgg. BN Introdunlon lo Ltgmd Flclds, Vol 2 New
yark Wlley Intcrsamce. lW2
I291 Man& W, Femollas WJ J Chm Soe 1961.38 192
001 SsrLsr AR, Bandyopsday RK Synth Ran loor Ma Org
Chcm 1990,20 167
[31] Hahswsy BJ J Chm Soe A 1972 11%
I321 El-Sonbss AZ. Hcfnl MA Polym Dcg Stab IW4,43 33
1331 DN K, Rm GN Tslanta 1996,43 451
1341 Pakl BS. Paul SR Makromol Chcm 1979,180 1159
1351 Pakl HS. Paul SR J M~kmmol Scl Chnn 1982.106 1383