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IIT Kharagpur
CONTENTS
Title Page i
Certificate by the Supervisors
ii
Declaration iii
Acknowledgements v
Abbreviations and Symbols
vi
Abstract x
Contributions xi
Contents xiii
Chapter 1 Introduction 1
1.1 Free radical polymerization : General considerations 1 1.2 Controlled Radical Polymerization (CRP) 2 1.2.1 Classification of Controlled Radical Polymerization Methods
3
1.2.2 Persistent Radical Effect 3
1.2.3 Nitroxide Mediated Stable Free Radical Polymerization (SFRP)
5
1.2.4 Reversible Addition Fragmentation Chain Transfer Polymerization (RAFT)
5
1.2.5 Degenerative Chain Transfer (DT) 7 1.2.6 Metal Mediated Controlled Radical Polymerization or Atom transfer Radical Polymerization (ATRP)
8
1.2.7 Hybrid organic/inorganic nanocomposites: recent advances in ATRP
1.2.8 Polymer protected metal nanoparticles
24
30
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1.3 Material applications 32
1.4 Scope and objectives of the thesis 34
1.5 References 36
Chapter 2 Experimental 41
2.1 Materials 41
2.2 Sample preparation 42
2.2.1 Preparation of monofunctional poly (ethyl acrylate) (PEA) via ATRP in bulk
42
2.2.2 Preparation of monofunctional PEA via ATRP in solution
43
2.2.3 In situ preparation of PEA/clay nanocomposite via ATRP
43
2.2.4 Preparation of PEA-clay nanocomposite by solution blending
2.2.5In situ preparation of PEA/clay nanocomposite via conventional radical polymerization
44
44
2.2.6 Synthesis of 2-bromopropionate-functionalized nanoclay platelets
44
2.2.7 Surface initiated ATRP of EA (SI-ATRP) from initiator-functionalized nanoclay platelets
45
2.2.8 Cleavage of grafted polymer chains 46 2.2.9 Preparation of monofunctional poly (hexyl acrylate)
(PHA) via ATRP in bulk
46
2.2.10 Preparation of monofunctional PHA via ATRP in solution
47
2.2.11 Preparation of ABA block copolymers 47
2.3 Characterization 49
2.4 References 55
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Chapter 3 Atom Transfer Radical Polymerization of Ethyl Acrylate
57
3.1 Introduction 57
3.2 Results and Discussion 58
3.2.1 Kinetics of the polymerization 58
3.2.2 Effect of initiator 60
3.2.3 Effect of solvent 62
3.2.4 Effect of temperature 64
3.2.5 End group analysis 66
3.3 Conclusions 69
3.4 References 70
Chapter 4 Effect of Nanoclay as Additive in ATRP of Ethyl Acrylate: a One Pot Preparation of Tailor-Made Polymer Nanocomposite
73
4.1 Introduction 73
4.2 Results and Discussion 74
4.2.1 Effects of nanoclay as additive in ATRP of EA 74 4.2.2 Morphological study of in-situ prepared nano
composites by WAXD and TEM
83
4.2.3 End group analysis 84
4.3 Conclusions 86
4.4 References 87
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Chapter 5 Structure and Properties of Tailor Made Poly (ethyl acrylate)/Clay Nanocomposites prepared by in situ ATRP
89
5.1 Introduction 89
5.2 Results and Discussion 90
5.2.1 Molecular weights of virgin poly (ethyl acrylate) and its nanocomposites
91
5.2.2 WAXD studies 92
5.2.3 Microscopic observations 93
5.2.4 Dynamic mechanical properties 95
5.2.5 Rheological behavior 98
5.2.6 Thermogravimetric analysis (TGA) 101
5.3 Conclusions 103
5.4 References 104
Chapter 6
Hybrid Nanostructure of Poly (ethyl acrylate)/ Clay by Surface Initiated Atom Transfer Radical Polymerization (SI-ATRP)
105
6.1 Introduction 105
6.2 Results and Discussion 108
6.2.1 Synthesis of ATRP initiator-functionalized nanoclay platelets
108
6.2.2 Surface-Initiated ATRP of EA from 2-bromo propionate-functionalized nanoclay platelets
114
6.2.3 Morphological characterizations of the nanocomposites
118
6.2.4 End group analysis 119
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6.3 Conclusions 121
6.4 References 122
Chapter 7 Atom Transfer Radical Polymerization of Hexyl Acrylate
123
7.1 Introduction 123
7.2 Results and discussion 124
7.2.1 Optimization of the catalytic system 124
7.2.2 Effect of initiator 126
7.2.3 Effect of solvent 128
7.2.4 Effect of temperature 132
7.2.5 End group analysis 134
7.2.6 A comparative analysis of the kinetics of ATRP of acrylates with varying chain length
136
7.2.7 Effect of nanoclay as additive in ATRP of HA 137
7.3 Conclusions 138
7.4 References 139
Chapter 8A Synthesis and Bulk Properties of Poly (methyl methacrylate)-b-poly (hexyl acrylate)-b-poly (methyl methacrylate) (MHM) Triblock Copolymers
141
8A.1 Introduction 141
8A.2 Results and Discussion 142
8A.2.1 Polymer Synthesis 142
8A.2.2 Dynamic Mechanical Properties 144
8A.2.3 Tensile Properties 147
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8A.2.4 Morphology (AFM) 149
8A.3 Conclusions 151
8A.4 References 152
Chapter 8B
Application of Poly (methyl methacrylate)-b-poly (hexyl acrylate)-b-poly (methyl methacrylate) Triblocks as the Mediator for Preparing Organically Dispersible Gold Nanoparticle Aggregates
153
8B.1 Introduction 153
8B.2 Results and Discussion 154
8B.2.1 Stabilization of Gold nanoparticles by the MHM triblocks
8B.3 Conclusions
154
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8B.4 References 161
Conclusions and Future Scope of Study 163 Chapter 9
9.1 Conclusions 163
9.2 Future scope of study 167
