Silicon Containing Hybrid Copolymers

1 Introduction of Organosilicon Materials 1
Huihui Shi, Jing Yang, Zibiao Li, and Chaobin He

1.1 Introduction 1

1.2 Synthesis of Polymeric Organosilicon Materials 2

1.2.1 Polysiloxanes 3

1.2.2 Polysilsesquioxanes 5

1.2.3 Other Polymeric Organosilicon Materials 7

1.3 Applications 10

1.3.1 Biomaterials 10

1.3.2 Optical and Electronic Materials 13

1.3.3 Surface Modification 15

1.4 Conclusion and Outlook 18

References 18

2 Reactive Functionally Terminated Polyorganosiloxanes 23
Yuanyuan Pang, Junqiang Justin Koh, Zibiao Li, and Chaobin He

2.1 Types of Functionalized Polysiloxane and Their Synthesis 23

2.1.1 Types of Functional Polysiloxanes 23

2.1.2 Polysiloxane with Monofunctional Terminals 25

2.1.3 Polysiloxane with Difunctional Terminals 25

2.1.4 Polysiloxane with Functional Side Groups 27

2.2 Functionalized Polysiloxane as Macromers 30

2.2.1 Modifying Degree of Polymerization of Functionalized Polysiloxanes 30

2.2.2 Cross‐Linking of Functionalized Polysiloxanes 30

2.2.3 Polysiloxane‐Containing Block and Graft Copolymers 35

2.2.3.1 Polysiloxane‐Containing Segmented and Multiblock Copolymers by Step‐Growth Polymerization 35

2.2.3.2 Polysiloxane‐Containing Graft Copolymers 41

2.2.3.3 Polysiloxane‐Containing Copolymers by Hydrosilylation and Click Chemistry 42

2.3 Functionalized Polysiloxane as Macroinitiators and Macrochain Transfer Agents 43

2.3.1 Conventional Radical Polymerization 43

2.3.2 Controlled Radical Polymerization 45

2.3.2.1 Atom Transfer Radical Polymerization (ATRP) 45

2.3.2.2 Reversible Addition Fragmentation Chain Transfer (RAFT) Polymerization 47

2.3.2.3 Other Controlled Radical Polymerization Methods 50

2.3.3 Ring‐Opening Polymerization (ROP) 50

References 54

3 Functionalized Polyhedral Oligomeric Silsesquioxanes (POSS) and Copolymers: Methods and Advances 63
Huihui Shi, Jing Yang, Zibiao Li, and Chaobin He

3.1 Introduction 63

3.2 Synthetic Strategies for Functionalized POSS 64

3.2.1 Octafunctional POSS 65

3.2.1.1 Hydrolysis and Condensation from RSiX₃ Monomer 65

3.2.1.2 Modification of Substituents 66

3.2.2 Monofunctional POSS 71

3.2.2.1 Corner Capping of T₇R₇(OH)₃ 71

3.2.2.2 Modification of Substituents 73

3.2.3 Bifunctional POSS 73

3.2.3.1 Some Special Cases 73

3.2.3.2 Some Developing New Strategies 74

3.3 Synthetic Protocols for Hybrid POSS‐containing Polymers 76

3.3.1 Preparation from Monomers 78

3.3.1.1 Radical Polymerization 79

3.3.1.2 Ring‐Opening Polymerization 81

3.3.1.3 Step‐Growth Polymerization 83

3.3.1.4 Other Polymerization Methods 86

3.3.2 Preparation from Polymers 87

3.3.2.1 By Conventional Organic Reactions 87

3.3.2.2 Some Advanced Methods 91

3.4 Conclusion 91

References 91

4 Nanostructured Self‐assemblies from Silicon‐containing Hybrid Copolymers 97
Hong Chi, Beng Hoon Tan, Fuke Wang, Chaobin He, and Zibiao Li

4.1 Introduction 97

4.2 Mechanism in Self‐assembly of POSS and PDMS‐Based Copolymers 99

4.2.1 Stimuli‐Responsive Micelles 100

4.2.1.1 pH‐Sensitive Micelles 100

4.2.1.2 Thermosensitive Micelles 103

4.2.1.3 Photoactive Micelles 104

4.2.2 Other Mechanisms in Different Assemblies 104

4.2.2.1 Micelles 104

4.2.2.2 Spheres 105

4.2.2.3 Sheets 106

4.3 Application 107

4.3.1 Biomedical Applications 107

4.3.2 Photodynamic Therapy 109

4.3.3 Coating 111

4.3.4 Optical Sensors 112

4.4 Conclusions and Perspectives 113

References 113

5 Superhydrophobic Materials Derived from Hybrid Silicon Copolymers 119
Lu Jiang, Xian Jun Loh, Chaobin He, and Zibiao Li

5.1 Introduction 119

5.2 Hybrid Silicon Copolymer Materials with Superhydrophobic Property 120

5.2.1 PDMS‐Incorporated Hybrid Copolymer Materials 120

5.2.2 POSS‐Incorporated Hybrid Copolymer Materials 122

5.3 Application of Superhydrophobic Silicon Copolymer Materials 128

5.3.1 Oil–Water Separation 128

5.3.1.1 PDMS‐Based Superhydrophobic Materials 131

5.3.1.2 POSS‐Based Superhydrophobic Materials 135

5.3.2 Self‐cleaning and Antifouling 136

5.3.3 Anticorrosion 137

5.3.4 Other Applications 138

5.4 Conclusion 140

References 140

6 Silicone Copolymers for Healthcare and Personal Care Applications 145
Weiren Cheng, Dan Kai, Xian Jun Loh, Chaobin He, and Zibiao Li

6.1 Silicone Copolymers for Biomedical and Healthcare Applications 145

6.1.1 Adsorption and Cell Interaction on Silicone Copolymer Surface 145

6.1.1.1 Antifouling Effect of Silicone Copolymer Surfaces 148

6.1.1.2 Antibacterial Effect of Silicone Copolymer Surfaces 148

6.1.1.3 Silicone Copolymers in Tissue Engineering and Regenerative Medicine 150

6.1.1.4 Silicone Copolymers Based Bio‐coating 150

6.1.2 Self‐assembly with Silicone Copolymers 152

6.1.2.1 Silicone Copolymers for Drug Delivery and Bioimaging 153

6.1.2.2 Silicone Copolymers in the Construction of Artificial Cells 154

6.2 Silicone for Personal Care Applications 157

6.2.1 Silicone Oil Emulsions 157

6.2.2 Silicone Copolymers as Surfactants 158

6.2.3 Silicone for Hair Care 159

6.2.4 Strategies for Depositing Silicone on Hair 160

6.2.5 Silicone for Skin Care Applications 161

6.3 Conclusions 162

References 163

7 Construction of Organic Optoelectronic Materials by Using Polyhedral Oligomeric Silsesquioxanes (POSS) 167
Fuke Wang, Xuehong Lu, Zibiao Li, and Chaobin He

7.1 Unique Properties of POSS for Building Organic Optoelectronic Materials 167

7.2 POSS‐Based Organic Electroluminescence Materials 171

7.3 POSS as a Building Block for Electrochromic Materials 181

7.4 Other Applications of POSS in Organic Optoelectronic Materials 189

7.5 Conclusions 195

References 196

8 Hybrid POSS Nanocomposites: An Overview of Material Toughening and Fire Retardancy 201
Junhua Kong, Beng H. Tan, Xuehong Lu, Zibiao Li, and Chaobin He

8.1 Introduction 201

8.2 Polypropylene/POSS Composites 202

8.3 Polycarbonate/POSS Composites 206

8.4 Polystyrene/POSS Composites 211

8.5 Polyester/POSS Composites 216

8.6 Polyepoxides/POSS Composites 220

8.7 Summary 233

References 233

9 3D Printing Silicone Materials and Devices 239
Jayven Yeo, Junqiang Justin Koh, Fuke Wang, Zibiao Li, and Chaobin He

9.1 Introduction 239

9.2 Extrusion‐Based Printing 240

9.2.1 Fused Deposition Modeling (FDM) 240

9.2.2 Direct Ink Writing (DIW) 242

9.2.2.1 Rheology‐Controlled Shape Retention 242

9.2.2.2 Coaxial Printing 245

9.2.2.3 Embedded 3D Printing 245

9.3 Jetting‐Based Printing 247

9.3.1 Inkjet 3D Printing (IJP) 247

9.3.2 Aerosol Jet Printing (AJP) 249

9.4 Vat Photopolymerization/Light‐Based/Photocurable 3D Printing 251

9.4.1 Stereolithography (SLA) 252

9.4.2 Digital Light Processing (DLP) 252

9.4.3 Photopolymerization Process 252

9.4.3.1 Photoinitiator 253

9.4.3.2 Photocurable Polymers 254

9.5 Potential Applications 260

References 261

Index 265

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