Sulfur-Containing Polymers From Synthesis to Functional Materials

A must-have resource to the booming field of sulfur-containing polymers

Sulfur-Containing Polymers is a state-of-the-art text that offers a synthesis of the various sulfur-containing polymers from low-cost sulfur resources such as elemental sulfur, carbon disulfide (CS2), carbonyl sulfide (COS) and mercaptan. With contributions from noted experts on the topic, the book presents an in-depth understanding of the mechanisms related to the synthesis of sulfur-containing polymers. The book also includes a review of the various types of sulfur-containing polymers, such as: poly(thioester)s, poly(thioether)s and poly(thiocarbonate)s and poly(thiourethane)s with linear or hyperbranched (dendrimer) architectures. The expert authors provide the fundamentals on the structure-property relationship and applications of sulfur-containing polymers.

Designed to be beneficial for both research and application-oriented chemists and engineers, the book contains the most recent research and developments of sulfur-containing polymers. This important book:

• Offers the first comprehensive handbook on the topic
• Contains state-of-the-art research on synthesis of sulfur containing polymers from low-cost sulfur-containing compounds
• Examines the synthesis, mechanism, structure properties, and applications of various types of sulful-containing polymers
• Includes contributions from well-known experts

Written for polymer chemists, materials scientists, chemists in industry, biochemists, and chemical engineers, Sulfur-Containing Polymers offers a groundbreaking text to the field with inforamtion on the most recent research.

Introduction xiii

1 Synthesis of Sulfur-Containing Polymers Through Multicomponent Polymerizations 1
Yuzhang Huang, Rongrong Hu, and Ben Zhong Tang

1.1 Introduction 1

1.2 Multicomponent Polymerizations of Elemental Sulfur 2

1.2.1 Multicomponent Polymerization of Sulfur, Dialdehydes, and Diamines 3

1.2.2 Multicomponent Polymerization of Sulfur, Diynes, and Aliphatic Amines 5

1.2.3 Multicomponent Polymerization of Sulfur, Benzyl Diamines, and Aliphatic Diamines 7

1.2.4 Multicomponent Polymerization of Sulfur, Diarylacetic Acids, and Aliphatic/Aromatic Diamines 9

1.2.5 Multicomponent Polymerization of Sulfur, Diisocyanides, and Aliphatic Diamines 11

1.3 Cu(I)-Catalyzed Multicomponent Polymerizations of Sulfonyl Azides/Hydrazides 13

1.3.1 Multicomponent Polymerization of Sulfonyl Azides, Alkynes, and Amines/Alcohols 14

1.3.2 Multicomponent Polymerization of Sulfonyl Azides, Alkynes, and Other Monomers 16

1.3.3 Multicomponent Polymerization of Sulfonyl Hydrazide, Alkynes, and Diphenyl Dichalcogen 20

1.3.4 Topological Polymers Prepared from Sulfonyl Azides and Alkyne-Based MCPs 20

1.4 Multicomponent Polymerizations with Thiol-Related Monomers 22

1.4.1 One-Pot Multicomponent Tandem Polymerization of Alkyne, Carbonyl Chloride, and Thiol 22

1.4.2 Multicomponent Polymerizations with Cyclic Dithiocarbonate 25

1.4.3 Multicomponent Polymerizations with Cyclic Thiolactone 26

1.5 The Applications of Sulfur-Containing Polymers Prepared from MCP 28

1.5.1 Chemosensors 28

1.5.2 Metal Ion Removal/Enrichment 29

1.5.3 Cell Imaging 30

1.6 Conclusion 31

Acknowledgments 34

References 34

2 Carbon Disulfide Derived Polymers 39
Gulzar A. Bhat and Donald J. Darensbourg

2.1 Introduction 39

2.2 Synthesis of Thiiranes (Episulfides) 41

2.3 Copolymerization Reactions 44

2.3.1 Copolymerization of Carbon Disulfide and Episulfides 44

2.3.2 Copolymerization of Carbon Disulfide and Epoxides 51

2.3.2.1 Scrambling Mechanism for Sulfur/Oxygen Atoms 58

2.3.2.2 NMR Scrambling Studies 60

2.3.2.3 Mixed Species Scrambling 60

2.4 Other Related CS₂-Based Polymers 63

2.5 Concluding Remarks 74

Acknowledgments 74

References 74

3 Carbonyl Sulfide Derived Polymers 81
Cheng-Jian Zhang, Jia-Liang Yang, Xiao-Han Cao, and Xing-Hong Zhang

3.1 Introduction 81

3.1.1 Overview of COS 81

3.1.2 Preparation of COS 82

3.1.2.1 Direct Reaction of CO and Sulfur 82

3.1.2.2 Using Carbon Disulfide (CS₂) 82

3.1.2.3 Laboratory Preparation of COS 83

3.1.3 Environmental and Safety Considerations 83

3.1.4 COS Chemistry 84

3.1.4.1 Dissociation 84

3.1.4.2 Hydrolysis 84

3.1.4.3 Oxidation 85

3.1.4.4 Reduction 85

3.1.4.5 Reaction with SO₂ 86

3.1.4.6 Reaction with Ammonia and Amines 86

3.1.4.7 Miscellaneous Reactions 86

3.1.4.8 The Claus Reaction 87

3.2 Metal Catalysts for COS Copolymerization 87

3.2.1 Zinc-Cobalt(III) Double-Metal Cyanide Complex 89

3.2.2 Catalysts Centered with Chromium (Cr) 93

3.2.3 Catalyst Centered with Iron (Fe) and Cobalt (Co) 95

3.2.4 Alkoxy Metal Salts 96

3.3 Organocatalysts for COS Copolymerization 96

3.3.1 TEB-Organic Base Pair 97

3.3.2 Dual-Site Lewis Pair 101

3.3.3 Thiourea-Organic Base Pairs 104

3.3.4 Supramolecular Anion 107

3.4 Oxygen-Sulfur Exchange Reaction 110

3.5 Utilization of O/S ER for Poly(thioether)s 113

3.5.1 COS-Epoxides Route to Poly(thioether)s 113

3.5.2 CS₂-Epoxides Route to Poly(thioether)s 115

3.5.3 Repurposing Poly(monothiocarbonate)s to Poly(thioether)s 120

3.6 Crystalline COS-Derived Polymers 121

3.7 COS-Derived Block Polymers 123

3.8 Properties of COS-Derived Polymers 124

3.8.1 Thermal Properties 124

3.8.2 Crystalline Properties 126

3.8.3 Optical Properties 129

3.8.4 Electronic Properties 132

3.9 Summary and Outlook 137

References 138

4 Thiol-Based Click Polymerizations for Sulfur-Containing Polymers 147
Die Huang, Anjun Qin, and Ben Zhong Tang

4.1 Introduction 147

4.2 Thiol-Ene Click Polymerization 148

4.2.1 Radical-Initiated Thiol-Ene Click Polymerization 148

4.2.2 Thiol-Ene Michael Addition Click Polymerization 151

4.3 Thiol-Yne Click Polymerization 154

4.3.1 Radical-Initiated Thiol-Yne Click Polymerization 154

4.3.2 Base-Mediated Thiol-Yne Click Polymerization 156

4.3.3 Metal-Catalyzed Thiol-Yne Click Polymerization 157

4.3.4 Spontaneous Thiol-Yne Click Polymerization 159

4.4 Other Thiol-Based Click Polymerizations 159

4.4.1 Thiol-Epoxy Click Polymerization 160

4.4.2 Thiol-Isocyanate Click Polymerization 163

4.4.3 Thiol-Halogen Click Polymerization 164

4.5 Conclusion 164

Acknowledgments 166

References 166

5 Synthesis of Polythioesters 171

Li-Yang Wang and Wei-Min Ren

5.1 Introduction 171

5.2 Synthesis of Aromatic Polythioesters 172

5.3 Synthesis of Semi-aromatic Polythioesters 174

5.4 Synthesis of Aliphatic Polythioesters 179

5.5 Summary and Concluding Remarks 185

Acknowledgments 186

References 186

6 Polymers with Sulfur-Nitrogen Bonds 191
Hatice Mutlu and Patrick Theato

6.1 Introduction 191

6.2 Synthesis of Sulfur-Nitrogen Containing Polymers 192

6.2.1 Poly(sulfenamide)s 192

6.2.2 Poly(diaminosulfide)s 196

6.2.3 Poly(aminodisulfide)s and Poly(diaminodisulfide)s 199

6.2.3.1 Poly(aminodisulfide)s 200

6.2.3.2 Poly(diaminodisulfide)s 201

6.2.4 Poly(oxothiazene)s 205

6.2.5 Poly(sulfonylimidate)s 207

6.2.6 Poly(sulfonylamidine)s 213

6.3 Applications of Polymers with Sulfur-Nitrogen Bond 221

6.3.1 Biomedical Applications 221

6.3.2 Metal-Ion Detection 225

6.3.3 Flame Retardant Chemicals Based on Polymers with Sulfur-Nitrogen Bonds 227

6.3.4 Energy Storage Applications 228

6.4 Conclusion and Outlook 229

References 229

7 Thioester Functional Polymers 235
Suzan Aksakal, Resat Aksakal, and C. Remzi Becer

7.1 Introduction 235

7.2 Thioesters: Structural Features, Reactivities, and Reactions 236

7.3 Preparation of Thioester Containing Structures 237

7.3.1 Access to Thioester Containing Polymers: Thioesters in the Side Chain 238

7.3.2 Access to Thioester Containing Polymers: Thioester in the Chain End 246

7.3.3 Access to Thioester Containing Polymers via Polymerization Process 247

7.3.4 Access to Thioester-Bearing Structures via Post-modification Approach 249

7.4 Post-Polymerization Modification of Thioesters 251

7.5 Conclusion and Outlook 254

References 256

8 Thiophene-Based Polymers: Synthesis and Applications 265
Haifeng Ji and Xiaojie Zhang

8.1 Introduction 265

8.2 Development of Synthetic Methods 266

8.2.1 Oxidative Polymerization and Electrochemical Polymerization 266

8.2.2 Transmetalation Polymerization 269

8.2.2.1 Polymerization with Ni Catalysis 269

8.2.2.2 Polymerization with Pd Catalysis 273

8.2.2.3 Suzuki Coupling Method 274

8.2.2.4 Stille Coupling Method 275

8.2.2.5 Direct Arylation Method 276

8.2.3 Other Polymerization Methods 278

8.2.3.1 Photoinitiated Polymerization 278

8.2.3.2 Solid-State Polymerization 280

8.2.3.3 Acid-Catalyzed Polymerization 283

8.3 Applications of Polythiophene and Its Derivatives 284

8.3.1 Organic Thin-Film Transistors 285

8.3.2 Organic Photovoltaics 286

8.3.3 Organic Light-Emitting Diodes 287

8.3.4 Biological Applications 288

8.4 Conclusions and Future Scope 290

References 290

9 High Refractive Index Sulfur-Containing Polymers (HRISPs) 305
Johannes M. Scheiger and Patrick Theato

9.1 Introduction 305

9.2 Basics of Optics 306

9.2.1 Absorption and Refraction 306

9.2.2 Refractive Index 307

9.2.2.1 Refractive Index Determination 308

9.2.3 Dispersion 311

9.2.4 Birefringence 312

9.3 High Refractive Index Polymers (HRIPs) 313

9.3.1 General Strategies and Applications 314

9.4 Sulfur-Containing HRIPs 315

9.4.1 Polyimides and Polyamides 315

9.4.2 Poly(meth)acrylates and Polythioacrylates 321

9.4.3 Polycarbonates and Polyesters 325

9.4.4 Thermosets 327

9.4.5 Inverse Vulcanization 328

9.5 Conclusion and Outlook 334

References 335

10 Selenium-Containing Dynamic Polymers: From Synthesis to Functions 339
Jiahao Xia and Huaping Xu

10.1 Introduction 339

10.2 Synthesis of Selenium-Containing Polymers 340

10.2.1 Step Growth Polymerization 340

10.2.2 Radical Polymerization 342

10.2.3 Ring-Opening Polymerization 345

10.2.4 Synthesis of Dendrimer and Hyperbranched Selenium-Containing Polymer 345

10.3 Selenium-Containing Dynamic Covalent Chemistry 348

10.3.1 Diselenide Bond 348

10.3.2 Se—S Bond 351

10.3.3 Se—Te Bond 351

10.3.4 Se—N Bond 353

10.4 Selenium-Containing Dynamic Materials 356

10.4.1 Selenium-Containing Elastomer 356

10.4.2 Selenium-Containing Surface/Interface Materials 360

10.4.3 Selenium-Containing Nanomaterials 360

10.5 Conclusion and Outlook 362

Acknowledgments 363

References 363

11 Poly(disulfide)s 367
Raju Bej and Suhrit Ghosh

11.1 Introduction 367

11.2 Synthesis of Poly(disulfide)s 369

11.2.1 Oxidative Polymerization of Dithiols 370

11.2.2 Ring-Opening Polymerization (ROP) of Cyclic Disulfide 374

11.2.3 Photo-Induced Disulfide Metathesis 375

11.2.4 Fragmentation Polymerization 375

11.2.5 Self-Organizing Surface-Initiated Polymerization (SOSIP) 377

11.2.6 Thiol-Disulfide Exchange Reaction 378

11.3 Amphiphilic PDS and Drug Delivery Application 381

11.4 Cell-Penetrating Poly(disulfide)s 388

11.5 Summary and Outlook 389

References 389

12 Reduction-Responsive Disulfide-Containing Polymers for Biomedical Applications 393
Xing Wang and Decheng Wu

12.1 Introduction 393

12.2 Disulfide-Containing Topological Polymers 395

12.2.1 Systems with the Disulfide Linkages 395

12.2.2 Disulfide-Containing Linear Polymers 395

12.2.2.1 Linear Polymers with Cleavable Backbones 396

12.2.2.2 Linear Polymers with Cleavable Side Chains 397

12.2.3 Disulfide-Containing Dendritic Polymers 398

12.2.3.1 Disulfide-Containing Hyperbranched Polymers 399

12.2.3.2 Disulfide-Containing Dendrimers 400

12.2.4 Disulfide-Containing Polypeptides and Proteins 401

12.2.5 Disulfide-Containing Polymeric Nanoparticles 403

12.2.5.1 Disulfide Linker for Amphiphilic Polymers 403

12.2.5.2 Disulfide Linker for Nano-Assemblies 404

12.2.5.3 Controlled Fabrication of Solution Nano-Assemblies 406

12.2.6 Disulfide-Containing Crosslinking Hydrogels 407

12.2.6.1 Disulfide-Crosslinked Micro-/Nanogels 407

12.2.6.2 Disulfide-Crosslinked Macroscopic Hydrogels 407

12.2.6.3 Disulfide-Crosslinked Natural Hydrogels 410

12.3 Disulfide-Containing Polymers for Biomedical Applications 412

12.3.1 Targeted Drug Delivery 412

12.3.1.1 Disulfide-Containing Nano-Assemblies for Targeted Drug Delivery 413

12.3.1.2 Disulfide-Containing Nanogels for Drug Delivery 414

12.3.1.3 Disulfide-Containing Hydrogels for Drug Delivery 415

12.3.2 Gene Delivery 416

12.3.3 Biomedical Imaging 418

12.3.4 Drug Conjugates 419

12.3.5 Self-healing/Self-repairing 420

12.4 Summary and Perspectives 422

References 424

Index 429

Xing-Hong Zhang, PhD, is Full Professor at Department of Polymer Science and Engineering, Zhejiang University, China. His current research interest focuses on the synthesis and catalysis of sulfur-containing polymers and polycarbonates.

Patrick Theato, PhD, is Full Professor at Karlsruhe Institute of Technology, Germany. His current research interests mainly focus on the synthesis of precisely tailored polymers.