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  • TITLE
  • DEDICATION
  • CERTIFICATE
  • DECLARATION
  • ACKNOWLEDGEMENT
  • GLOSSARY OF TERMS
  • CONTENTS
  • PREFACE
  • 1. Introduction
  • 1.1 Physical blends
  • 1.1. 1 Miscible blends
  • 1.1.2 Compatible blends
  • 1.1.3 Incompatible blends
  • 1.1.4 Polymer alloys
  • 1.2 Interpenetrating network polymers
  • 1.3 Copolymers
  • 1.3.1 Alternating copolymers
  • 1.3.2 Random copolymers
  • 1.3.3 Graft copolymers
  • 1.3.4 Block copolymers
  • 1.4 A review on block copolymers
  • 1.4.1 Architectural variation
  • Fig.1.1 Representation of various block copolymer architectures.
  • Fig.1.2 Radial block copolymer architecture.
  • 1. 4.2 Synthetic methods
  • 1.4.2.1 Living polymerisation (sequential addition process)
  • 1.4.2.2 Step-growth polymerisation (Interactions of functionally terminated oligomers)
  • 1.4.2.3 Polymer growth from oligomer end groups
  • 1.4.3 Morphology of block copolymers
  • 1.4.4 Commercial importance of block copolymers
  • 1.5 Thermoplastic elastomers
  • 1.5.1 Commercial grade thermoplastic elastomers
  • 1.5.1.1 Styrene-based block copolymers
  • 1.5.1.2 Polyether-ester
  • 1.5.1.3 Polyurethane block copolymers
  • (i) Cast elastomers
  • (ii) Millable elastomers
  • (iii) Polyurethane thermoplastic elastomers
  • a. Synthesis of polyurethane elastomers
  • b. Properties
  • c. Morphological features of block copolyurethanes
  • Fig.1.4 Shematic rnorrphology of polyurethane thermoplastic elastomer.
  • d. Effect of hard segment on the properties of polyurethane elastomers
  • e. Effect of chain extenderr
  • f. Effect of diisocyanate.
  • g. Effect of hydrogen bonding
  • h. Effect of soft segment on the properties of the polyurethane elastomers
  • 1.6 Scope of the present work
  • 1.6.1 Objectives of the work
  • 1.7 References
  • 2. Experimental
  • 2.1 Materials
  • 2.2 Experimental
  • 2.2.1 Preparation of hydroxyl terminated liquid natural rubber
  • 2.2.2 Block copolymer synthesis
  • 2.2.2.1 One-shot process
  • 2.2.2.2 Two-shot process
  • Table 2.1 Overall compositions of the block copolymers of NR/EG (one-shot and two-shot)
  • Table 2.2 Overall compositions of the block copolymers of NR/PG (one-shot and two-shot)
  • 2.2.3 Polymer designation
  • Table 2.3 Overall compositions of the block copolymers of NR/1, 3-BDO NR/1, 4-BDO (one-shot and two-shot)
  • Table 2.4 Overall compositions of the block copolymers of NR/BPA (one- shot and two-shot)
  • Table 2.5 Optimum amount of catalyst in synthesis with various chain extenders (One-shot and Two-shot)
  • 2.2.4 Chemical methods of analysis
  • 2.2.4.1 Estimation of hydroxyl groups
  • 2.2.4.2 Determination of epoxy value
  • 2.2.4.3 Determination of iodine value
  • (i) Wijs method for the determination of iodine value
  • 2.2.4.4 Determination of carbonyl value
  • 2.2.5 Instrumental methods of analysis
  • 2.2.5.1 Determination of molecular weight
  • 2.2.5.2 Infrared spectral analysis
  • 2.2.5.3 Differential scanning calorimetric analysis
  • 2.2.5.4 Thermogravimetric analysis
  • 2.2.5.5 Scanning electron microscopy analysis
  • 2.2.5.6 Stress-strain behaviour
  • 2.2.5.7 Tear strength
  • 2.2.5.8 Hardness
  • 2.3 References
  • 3. Results and Discussion
  • 3.1 Preliminary studies
  • 3.1.1 Hydroxyl terminated liquid natural rubber
  • Fig.3.1 IR spectrum of liquid NR
  • Table 3.1 IR peak assignment of the liquid NR
  • Table 3.2 Data obtained from the chemical analysis of the liquid NR.
  • 3.1.2 Standardisation of the method of block copolymer synthesis
  • 3.2 IR studies
  • 3.2.1 Course of reaction
  • 3.3 Thermogravimetric analysis
  • Table 3.8 Data from TGA of NR/EG block copolymers (one-shot and two-shot)
  • Table 3.9 Data from TGA of NR/PG block copolymers (one-shot and two-shot)
  • Table 3.10 Data from TGA of NR/1, 3-BDO block copolymers (one-shot and two-shot)
  • Table 3.11 Data from TGA of NR/1, 4-BDO block copolymers (one-shot and two-shot)
  • Table 3.12 Data from TGA of NR/BPA block copolymers (one-shot and two-shot)
  • Fig.3.13 Onset of mass loss (first stage) versus hard segment content of thetwo- shot block of polymers.
  • Fig.3.14 Plot of first stage peak temperature versus hard segment content of thetwo-shot block col) olymers.
  • Fig.3.15 Plot of second stage onset temperature versus soft segment content of thetwo-shot block copolymers.
  • Fig.3.16 Plots of second stage peak temperature versus soft segment content of the two-shot block copolymers.
  • 3.4 Differential scanning calorimetric analysis
  • 3.4.1 DSC analysis of NR/EG block copolymer
  • 3.4.1.1 Two-shot products
  • Table 3.13 DSC results of NR/EG block copolymers (two-shot and one shot)
  • Fig.3.18 Plot of Tg values versus hard segment content of the two-shot block copolymers.
  • 3.4.1.2 One-shot products
  • 3.4.2 DSC analysis of NR / PG block copolymers
  • 3.4.2.1 Two-shot products
  • Table 3.14 DSC results of NRIPG block copolymers (two-shot and one-shot)
  • 3.4.2.2 One-shot products
  • 3.4.3 DSC analysis of the NR / 1, 3-BDO block copolymers
  • 3.4.3.1 Two-shot products
  • Table 3.15 DSC results of NR/1, 3-BDO block copolymers (two-shot and one-shotproducts)
  • 3.4.3.2 One-shot product
  • 3.4.4 DSC analysis of the NR 1, 4-BDO block copolymers
  • 3.4.4.1 Two-shot products
  • Table 3.16 DSC results of NR/1, 4 BDO block copolymers (two-shot and one-shotproducts)
  • 3.4.4.2 One-shot product
  • 3 4.5 DSC analysis of the NR / BPA block copolymers
  • 3.4.5.1 Two-shot products
  • Table 3.17 DSC results of NR/BPA block copolymers (two-shot and one-shot)
  • 3.4.5.2 One-shot product
  • 3.4.6 A comparative account of the DSC analysis
  • 3.5 Implication of DSC and TGA results
  • Table 3.18 Comparison of peak temperature (OC) of the final endotherm in DSC thermogram (I) with the peak temperature of the hard segment degradation in TGA thermogram (II) (two-shot products)
  • 3.6 Stress-strain behaviour
  • 3.6.1 Tensile measurements of NR / EG block copolymers
  • 3.6.1.1 Two-shot products
  • Fig.3.23 Stress-strnin curves of two-shot products of NR/EG
  • Table 3.19 Tensile properties of the NR/EG block copolymers (two-shot)
  • 3.6.1.2 One-shot products
  • Fig. 3.24 Stress-strain curves of one-shot products of NR/EG.
  • Table 3.20 Tensile properties of the NR/EG block copolymers (one- shot)
  • 3.6.2 Tensile measurements of NR / PG block copolymers
  • 3.6.2.1 Two-shot products
  • Fig. 3.25 Stress-strain curves of two-shot products of NR/PG.
  • Table 3.21 Tensile properties of the NR/PG block copolymers (two-shot)
  • 3.6.2.2 One-shot product
  • Fig.3.26 stress-strain curves of one-shot products of NR/PG.
  • Table 3.22 Tensile properties of the NR/PG block copolymers (one-shot)
  • 3.6.3 Tensile measurements of NR / 1, 3-BDO block copolymers
  • 3.6.3.1 Two-shot products
  • Fig.3.27 Stress-strain curves of two-shot products of NR/1, 3-BDO.
  • Table 3.23 Tensile properties of NR/1, 3-BDO block copolymers (two-shot)
  • 3.6.3.2 One-shot products
  • Fig.3.28 Stress-strain curves of one-shot products of NR/1, 3-BDO.
  • Table 3.24 Tensile propertic! of 1, 3-BDO block copolymers (one-shot)
  • 3.6.4 Tensile measurements of NR / 1, 4-BDO block copolymers
  • 3.6.4.1 Two-shot products
  • Fig.3.29 Stress-strain curves of two-shot products of NR/1, 4-BDO.
  • Table 3.25 Tensile properties of NR/1, 4-BDO block copolymers (two-shot)
  • 3.6.4.2 One-shot products
  • Fig.3.30 Stress-strain curves of one-shot products of NR/l, 4-BDO.
  • Table 3.26 Tensile properties of NR/l, 4-BDO block copolymers (one-shot)
  • 3.6.5 Tensile measurements of NR / BPA block copolymers
  • 3.6.5.1 Two-shot products
  • Fig.3.31 Stress-strain curves of one-shot products of NR/BPA block of polymers.
  • Table 3.27 Tensile properties of NR/BPA block copolymers (two-shot)
  • 3.6.5.2 One-shot products
  • Fig.3.32 Stress-strain curves of one-shot products of NR/BPA.
  • Table 3.28 Tensile properties of NIR/BPA block copolymers (one-shot)
  • 3.6.6 A comparative-account of the tensile properties
  • Fig.3.34 Hard segment content versus tensile strength (two-shot)
  • Fig.3.35 Hard segment content versus modulus of elasticity
  • Fig.3.36 Hard segment content versus elongation at break.
  • Fig.3.37 soft segment content versus elongation at break.
  • 3.6.7 Comparison of the tensile properties of one-shot and two-shot products
  • Table 3.29 Comparison of tensile strength of the one-shot and two-shot block copolymers of all series.
  • Table 3.30 Comparison of modulus of elasticity of the one-shot and two-shot block copolymers of all series.
  • Table 3.31 Comparison of elongation at break of the one-shot and two-shot block copolymers of all series.
  • 3.7 Fractographic studies using SEM
  • 3.7.1 Fractography of NR / EG block copolymers
  • 3.7.1.1 Two-shot products
  • Fig. 3.38 Tensile fractograph of NR/EG (70/30) -2
  • Fig.3.39 Tensile fractograph of NR/EG (50/50) -2
  • Fig.3.40 Tensile fractograph of NR/EG (30/70) -2
  • Fig.3.60 Tensile fractograph of NR/EG (30/70) -2
  • Fig.3.41 Tensile fractograph of NR/PG (70/30) -2
  • Fig.3.42 Tensile fractograph of NR/PG (60/40) -2
  • Fig.3.44 Tensile fractograph of NR/PG (40/60) -2
  • Fig.3.45 Tensile fractograph of NR/PG (30/70) -2
  • Fig.3.46 Tensile fractograph of NR/1, 3-BDO (70/30) -2
  • Fig.3.47 Tensile fractograph of NR/1, 3-BDO (60/40) -2
  • Fig.3.48 Tensile fractograph of NR/1, 3-BDO (50/50) -2
  • Fig.3.50 Tensile fractograph of NR/1, 3-BDO (30/70) -2
  • Fig.3.51 Tensile fractograph of NR/1, 4-BDO (70/30) -2
  • Fig.3.52 Tensile fractograph of NR/1, 4 -BDO (50/50) -2
  • Fig. 3.53 Tensile fractograph of NR/l, 4-BDO) (30/70) -2
  • Fig.3.54 Tensile fractograph of NR/l, 4-BDO (70/30) -1
  • Fig.3.55 Tensile fractograph of SR/BPA (70/30) -2
  • Fig.3.56 Tensile fractograph of NR/BPA (60/40) -2
  • Fig.3.57 Tensile fractograph of NR/BPA (50/50) -2
  • Fig.3.58 Tensile fractograph of INR/BPA (40/60) -2
  • Fig. 3.59 Tensile fractograph of NR/BPA (50/50) -1
  • Fig.3.61Tensile fractograph of NR/BPA (50/50) -2
  • 3.7.2 Fractography of NR / PG block copolymers
  • 3.7.2.1 Two-shot products
  • 3.7.3 Fractography of NR/1, 3-BDO block copolymers
  • 3.7.3.1 Two-shot products
  • 3.7.4 Fractography of NR / 1, 4-BDO block copolymers
  • 3.7.4.1 Two-shot products
  • 3.7.4.2 One-shot products
  • 3.7.5 Fractography of NR / BPA block copolymers
  • 3.7.5.1 Two-shot products
  • 3.7.5.2 One- shot products
  • 3.8 Morphology of the block copolymers
  • 3.8.1 NR / EG block copolymers
  • 3.8.1.1 Two-shot products
  • 3.8.2 NR / PG block copolymers
  • 3.8.2.1 Two-shot products
  • 3.8.3 NR / 1, 3-BDO block copolymers
  • 3.8.3.1 Two-shot products
  • 3.8.4 NR / 1, 4-BDO block copolymers
  • 3.8.4.1 Two-shot products
  • 3.8.4.2 One-shot products
  • 3.8.5 NR / BPA block copolymers
  • 3.8.5.1 Two-shot products
  • 3.8.5.2 One-shot products
  • 3.8.6 General observations regarding morphology
  • 3.9 Tear strength
  • 3.9.1 Two-shot products
  • Fig.3.62 Hard segment content versus tear strength (two-shot)
  • Table 3.32 Tear strength of various block copolymers by two-shot process.
  • Fig.3.63 Tear fractograph of NR/BPA (70/30) -2
  • FIg.3.64 Tear fractograph of NR/EG (70/30) -2
  • Fig.3.65 Tear fractograph of NR/PG (70/30) -2
  • Fig.3.66 Tear fractograph of NR/1, 4-BDO (70/30) -2
  • Fig.3.67 Tear fractograph of NR/BPA (50/50) -2.
  • Fig.3.68 Tear fractograp of NR/1, 3-BD0 (50/50) -2.
  • 3.9.2 One-shot products
  • Fig.3.69 Hard segment content versus tear strength (one-shot)
  • Table 3.33 Tear strength of variou block copolymers by one-shot process.
  • 3.10 Hardness
  • 3.10.1 Two-shot products
  • Fig.3.70 Hardness versus hard segment content of the block copolymers (two-shot)
  • Table 3.34 Shore A hardness of various block copolymers prepared by two-shotprocess.
  • 3.10.2 One-shot products
  • Fig.3.71 Hardness versus hard segment content of the block copolymers (one-shot)
  • Table 3.35 Shore A hardness of various block copolymers prepared by one-shot process.
  • 3.11 Effect of diisocyanate structure on the block copolymer properties
  • 3.12 References
  • 4. Summary and Conclusion
  • Scope for further studies
  • APPENDIX
  • List of Publications