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  • TITLE
  • DEDICATION
  • DECLARATION
  • ACKNOWLEDGEMENT
  • CONTENTS
  • LIST OF ABBREVIATIONS USED
  • I. INTRODUCTION
  • Organisation of the thesis
  • II. FUNCTIONALIZED POLYMERS AND THEIR CHEMICAL APPLICATIONS: A REVIEW
  • Part A CHEMISTRY OF REACTIVE POLYMERS: PREPARATION AND PROPERTIES
  • II.1 Preparation of Functionalized polymers
  • II.1.1 Polymerization
  • II.1.2 Chemical functionalization of synthetic organic polymers
  • II.1.2.1 Functionalization of polystyrene
  • II.2 Properties and characterization of functionalized polymers
  • II.2.1 Physical form
  • II.2.1.i Linear polymers
  • II.2.1.ii Crosslinked polymers
  • a) Microporous or gel-type resins
  • b) Macroporous and macroreticular resins
  • c) Popcom polymers
  • d) Macronet polymers
  • II.2.2 Reactivity of functionalized polymers
  • II.2.3 Characterization of functionalized polymers
  • Part B CHEMICAL APPLICATIONS OF FUNCTIONALIZED POLYMERS
  • II.3 Advantages and limitations of functionalized polymers
  • II.4 Polymeric reagents
  • II.5 Polymeric catalysts
  • II.6 Application of functionalized polymers in mechanistic studies
  • II.6.1 Introduction: The three-phase test
  • II.6.2 Cyclobutadiene intermediates
  • II.6.3 Benzyne intermediate trapping
  • II.6.4 Fries rearrangement
  • II.6.5. Benzil-benzilic acid rearrangement
  • III. BECKMANN REARRANGEMENT IN POLYMER MATRICES RESULTS AND DISCUSSION
  • RESULTS AND DISCUSSION
  • III.1 Polymer Synthesis
  • III.1.1 Divinylbenzene (DVB) -crosslinked polystyrene
  • III.1.2 Tetraethyleneglycoldiacrylate (TTEGDA) -crosslinked po
  • III.2 Functionalization of polystyrene
  • III.3 Chloromethylation of polystyrene
  • III.4 Preparation of crosslinked polystyrene-bound oximes
  • III.4.1 Preparation of polymeric benzophenone oximes via Friedel-Crafts acylation reaction
  • III.4.2 Preparation of polymeric benzyl phenyl ketoximes via Grignard reaction
  • III.5 Beckmann rearrangement of the polystyrene-bound oximes
  • III.6 Characterisation of the functionalized polystyrene resins
  • III.7 Studies on reactivity
  • III.8 Reaction rate studies of the Beckmann rearrangement of polymeric oximes
  • III.9 Effect of the polymer backbone
  • III.9.1 Effect of the nature of crosslinking
  • III.9.2 Effect of the degree of crosslinking
  • III.10 Effect of solvent
  • III.11 Comparison of the reaction rates of polymeric oximes and their low-molecular weight analogues
  • IV. KINETIC CHARACTERISTICS OF FUNCTIONAL GROUPS ATTACHED TO A CROSSLINKED POLYMER: BECKMANN REARRANGEMENT IN DVB-CROSSLINKED-PS-BOUND OXIMES
  • RESULTS AND DISCUSSION
  • IV. 1 Preparation of crosslinked polystyrene-bound dibenzylketoxime
  • IV.2 Beckmann rearrangement of crosslinked polystyrene-bound dibenzylketoxime
  • IV.3 Spectral characterisation of the functionalized polystyrene resins
  • IV.4 Reaction kinetic studies
  • IV.5 Quantitative analysis using solid-state IR spectroscopy
  • IV.5.1 Quantitative analysis using Shimadzu IR-470A spectrophotometer
  • IV.5.2 Two-peak method
  • IV.6 Kinetic characteristics of the Beckmann rearrangement of the polystyrene-bound oximes
  • V. EXPERIMENTAL
  • V. 1. Source of chemicals
  • V.2. Physical measurements
  • V.3. Synthesis of styrene-divinylbenzene copolymer: General procedure
  • V.4.Synthesis of styrene-tetraethyleneglycoldiacrylate copolymer: General procedure
  • V.5. Preparation of chloromethylmethylether
  • V.6. Chloromethylation of styrene-based copolymers: General procedure
  • V.7. Estimation of chlorine in the chloromethyl polystyrene
  • V.8. Preparation of the polymeric benzophenone oximes
  • V.9. Preparation of the polymeric oximes
  • V.10. Estimation of the hydroxyl capacity of polymeric oximes: General procedure
  • V.11. Beckmann rearrangement of the polymeric oximes
  • V.12. Analysis of the rearrangement products
  • V.13. Determination of the amino capacity of the amino resin: General procedure
  • V.14. Rate measurements
  • V.15. Preparation of crosslinked polystyrene-bound dibenzylketoxime
  • V.16. Beckmann rearrangement of the polystyrene-bound dibenzylketoxime
  • V.17. Analysis of the product of rearrangement of dibenzylketoxime
  • V.18. Kinetic studies
  • V.19. Quantitative analysis using IR spectroscopy
  • VI. CONCLUSION AND OUTLOOK
  • VII. REFERENCES
  • APPENDICES