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TITLE
DEDICATION
ACKNOWLEDGEMENT
DECLARATION 1
DECLARATION 2
CONTENTS
List of Abbreviations
I. Introduction And Objectives
II. Polymer-Metal Complexes: Synthetic, Structural And Analytical Aspects
II.A. Formation Of Polymer-Metal Complexes
II.A.1. Complexation of Polymeric Ligand with Metal Ion
a. Pendant Complexes
(i) Monodentate Pendant Complexes
(ii) Polydentate Pendant Complexes
b. Inter- and/or Intra-Molecularly Bridged Complexes
II.A.2. Polymerization of Coordinated Monomers
a. Polymerization of Vinyl Compounds Containing MetalComplexes
b. Polycondensation of Metal Complexes containing FreeFunctional Groups
c. Ring-Opening Polymerization
II.A.3. Reaction of Peripheral Functional Groups inMetal Complexes with Polymers
II.A.4. Coordination Polymers
a. Linear Coordinated Polymers
(i) Bifunctional Ligands
(ii) Simple Compound or Ion as Ligands
b. Network-coordinated Polymers
II.B. Analysis and Characterization Of Polymer-Metal Complexes
II.B.1. Spectral Characterization of Polymer-~etalComplexes
a. Formation of Polymer-Metal Complexes
b. Coordination Structure of Polymer-Hetal Complexes
c. X-ray Analysis of Polymer-Metal Complexes
d. Microenvironment Around Metal Ions
II.B.2. Stability Constants of Polymer-Metal Complexes
II.C. Specific Applications Of Polymer-Metal Complexes.
II.C.1. Catalytic Activities of the Polymer-MetalComplexes
II.C.2. ~echanochemical Systems
II.C.3. Biologically Important Polymer-Metal Complexes
a. Complex Formation of Metal Ions with Biopolymers
(i) Metal complexes of Polypeptides
(ii) Metal Complexes of Nucleic Acids and RelatedCompounds
(iii) Mixed Ligand Complexes
II.C.4. Polymeric Ligands in Metal Ion Separations
II.D. Macromolecular Effects On Complexation
II.D.1. Matrix structure
II.D.2. Matrix Nature
II.D.3. Matrix Configuration
II.D.4. Effect of Spacer Grouping
II.D.5. Effect of the Extent of Crosslinking
II.D.6.Steric Effects
II.D.7. Intramolecular Chelation
II.D.8. Electrostatic Effect
III. Complexation Of Polyacrylamide-Supported Amines: Effects Of The Variables Of The Nature And Extent Of Crosslinking On Complexation
Results And Discussion
III.A. Preparation Of Crosslinked Polyacrylamides
III.A.1. Divinylbenzene-Crosslinked Polyacrylamide
III.A.2. N, N-Methylene-Bis-Acrylamide Crosslinked Polyacrylamide
III.A.3. Tetraethyleneglycol Diacrylate Crosslinked Polyacrylamide
III.B.Transamidation Of Crosslinked Poly-Acrylamides: Preparation Of Poly (N-2 aminoethylacrylamide) S
III.C.Complexation Of Amino. Functions Supported On Crosslinked Polyacrylamides
III.C.1 Effect Of The Nature And Extent Of Crosslinking
III.C.2.Time-Course Of Complexation
III.C.3. Recyclability Of Complexed Resin
III.C.4. Specificity Of Complexed Resin
III.C.5. Swelling Characteristics
III.C.6. Kinetics Of Complexation
a.Diffusion, Adsorption and Interaction of Metal Ions withCrosslinked Polyacrylamide-Supported Amines
i. Langmuir Type
ii. Frumkin Type
III.C.7. Infrared Spectra
III.C.8. ESR Spectra
III.C.9. Scanning Electron Microscopy
Fig. 111.21. SEPls of (a) DVB-Crosslinked Aminopolyacrylamideand (b) Cu (I1) Complex
Fig. 111.22. SEWS of (a) NNMBA-Crosslinked Aminopolyacrylamideand (b) Cu (I1) Complex
Fig. 111.23. SEMs of (a) TTEGDA-Crosslinked Aminopolyacrylamideand (b) cu (I1) Complex
Fig. 111.24- SEMs of Swollen (a) TTEGDA-CrosslinkedAminopolyacrylamide and (b) Cu (I1) Complex
IV. Complexation Of Polymer-Supported Dithiocarbamates
Results And Discussion
A. Complexation Of Polyacrylamide-Supported Dithiocarbamates
1. Preparation Of Polyacrylamide supported Dithiocarbamates
2. Complexation Of Polyacrylamide supported Dithiocarbamates
a. Effect Of The Molecular Character And Extent Of Crosslinking
b. Time-Course Of Complexation
c.Recyclability Of Complexed Resins
d. Swelling Characteristics
B. Complexation Of Polystyrene-Supported Dithiocarbamates
1. Synthesis Of Polystyrene-Supported Dithiocarbamates
2. Complexation Of Polystyrene supported Dithiocarbamates
a. Effect Of The Extent Of Crosslinking
C. Characterization Of Dithiocarbamate-Metal Complexes
1. Infrared Spectra
2. Esr Spectra
3. Scanning Electron Microscopy
Fig. IV.15. SEMs of (a) TTEGDA-Crosslinked Polyacrylamide-Supported Dithiocarbamate and (b) Cu (11) Complex
Fig - IV.16. SEMs of (a) Polystyrene-Supported Dithiocarbamateand (b) Cu (I1) Complex
V. Thermogravimetric Investigations Of Polymer-Metal Complexes
Evaluation of Kinetic Parameters
Results And Discussion
A. Thermogravimetric Studies Of The Metal Complexes Of Polyacrylamide Supported Amine
1. Metal Complexes Of DVB-Crosslinked Polyacrylamide-Supported Amines
a. Metal Complexes Of 4% DVB crosslinked Aminopolyacrylamide
b. Cu (II) Complexes Of Aminopoly acrylamides With Varying Extents Of DVB-Crosslinks
2.Cu (II) Complexes Of Aminopoly-Acrylamides With Varying Extents Of NNMBA-Crosslinks
3. Metal Complexes Of 2% TTEGDA crosslinked Aminopolyacrylamide
B. Thermogravimetric Studies Of The Metal Complexes Of Polymer supported Dithiocarbamates
1. Metal Complexes Of Polyacrylamide Supported Dithiocarbamates
a. Metal Complexes Of 4% DVB Crosslinked Polyacrylamide Supported Dithiocarbamate
b. Metal Complexes Of NNMBA Crosslinked Polyacrylamide Supported Dithiocarbamates
c. Metal Complexes Of 2% TTEGDA Crosslinked Polyacrylamide Supported Dithiocarbamate
2. Metal Complexes Of polystyrene supported Dithiocarbamates
a. Cu (II) Complexes
b. Ni (II) Complexes
c. Comparison Of The Thermal Decompositions Of Cu (II) And Ni (II) Complexes
VI. Experimental
1. General
a. Materials
b. Instrumental
2. Preparation of Crosslinked Polyacrylamides.
a. polyacrylamides Crosslinked with Divinylbenzene
b. Polyacrylamides Crosslinked with N, N-Methylene-bisacrylamide
c. Polyacrylamides Crosslinked with Tetraethyleneglycoldiacrylate
3. Transamidation of Polyacrylamides to Poly (N-2-aminoethylacrylamides)
4. Estimation of Amino Groups in ~oly (~-2-aminoethylacrylamide) ~: General Procedure
5. Preparation of Poly (N-2-dithiocarbamatoethylacrylamide) s from Poly (N-2-aminoethylacrylamide) ~: GeneralProcedure
6. Chloromethylation of Divinylbenzene-crosslinkedPolystyrenes
a. Preparation of Chloromethyl Methyl Ether
b. chloromethylation of Polystyrenes: General Procedure
c. Estimation of Chlorine in the ChloromethylPolystyrenes
7. preparation of Polystyrene-Supported Amines
a. Aminomethyl Polystyrene (2)
b. (N-Ethy1) aminomethyl Polystyrene (3)
c. Ethylenediaminomethyl Polystyrene (4)
d. Hexamethylenediaminomethyl Polystyrene (5)
e. Reaction of Chloromethyl Polystyrene with LimitedAmount of Diamines (5) and (6)
8. Sodium Dithiocarbamates of Amino Polystyrenes (2a-6a): General Procedure
9. Preparation of Polymer-Metal Complexes: GeneralProcedure
10. Estimation of Metal Ions
11. Swelling Measurements
12. Recycling of Complexed Resins.
13. Kinetics of Cu (1I) Complexation of Polyacrylamide-Supported Amines: General Procedure
14. Adsorption Studies
VII. Summary And Outlook
VIII. References