Sulfur-Containing Polymers

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.

• Introduction xiii1 Synthesis of Sulfur-Containing Polymers Through Multicomponent Polymerizations 1Yuzhang Huang, Rongrong Hu, and Ben Zhong Tang1.1 Introduction 11.2 Multicomponent Polymerizations of Elemental Sulfur 21.2.1 Multicomponent Polymerization of Sulfur, Dialdehydes, and Diamines 31.2.2 Multicomponent Polymerization of Sulfur, Diynes, and Aliphatic Amines 51.2.3 Multicomponent Polymerization of Sulfur, Benzyl Diamines, and Aliphatic Diamines 71.2.4 Multicomponent Polymerization of Sulfur, Diarylacetic Acids, and Aliphatic/Aromatic Diamines 91.2.5 Multicomponent Polymerization of Sulfur, Diisocyanides, and Aliphatic Diamines 111.3 Cu(I)-Catalyzed Multicomponent Polymerizations of Sulfonyl Azides/Hydrazides 131.3.1 Multicomponent Polymerization of Sulfonyl Azides, Alkynes, and Amines/Alcohols 141.3.2 Multicomponent Polymerization of Sulfonyl Azides, Alkynes, and Other Monomers 161.3.3 Multicomponent Polymerization of Sulfonyl Hydrazide, Alkynes, and Diphenyl Dichalcogen 201.3.4 Topological Polymers Prepared from Sulfonyl Azides and Alkyne-Based MCPs 201.4 Multicomponent Polymerizations with Thiol-Related Monomers 221.4.1 One-Pot Multicomponent Tandem Polymerization of Alkyne, Carbonyl Chloride, and Thiol 221.4.2 Multicomponent Polymerizations with Cyclic Dithiocarbonate 251.4.3 Multicomponent Polymerizations with Cyclic Thiolactone 261.5 The Applications of Sulfur-Containing Polymers Prepared from MCP 281.5.1 Chemosensors 281.5.2 Metal Ion Removal/Enrichment 291.5.3 Cell Imaging 301.6 Conclusion 31Acknowledgments 34References 342 Carbon Disulfide Derived Polymers 39Gulzar A. Bhat and Donald J. Darensbourg2.1 Introduction 392.2 Synthesis of Thiiranes (Episulfides) 412.3 Copolymerization Reactions 442.3.1 Copolymerization of Carbon Disulfide and Episulfides 442.3.2 Copolymerization of Carbon Disulfide and Epoxides 512.3.2.1 Scrambling Mechanism for Sulfur/Oxygen Atoms 582.3.2.2 NMR Scrambling Studies 602.3.2.3 Mixed Species Scrambling 602.4 Other Related CS2-Based Polymers 632.5 Concluding Remarks 74Acknowledgments 74References 743 Carbonyl Sulfide Derived Polymers 81Cheng-Jian Zhang, Jia-Liang Yang, Xiao-Han Cao, and Xing-Hong Zhang3.1 Introduction 813.1.1 Overview of COS 813.1.2 Preparation of COS 823.1.2.1 Direct Reaction of CO and Sulfur 823.1.2.2 Using Carbon Disulfide (CS2) 823.1.2.3 Laboratory Preparation of COS 833.1.3 Environmental and Safety Considerations 833.1.4 COS Chemistry 843.1.4.1 Dissociation 843.1.4.2 Hydrolysis 843.1.4.3 Oxidation 853.1.4.4 Reduction 853.1.4.5 Reaction with SO2 863.1.4.6 Reaction with Ammonia and Amines 863.1.4.7 Miscellaneous Reactions 863.1.4.8 The Claus Reaction 873.2 Metal Catalysts for COS Copolymerization 873.2.1 Zinc-Cobalt(III) Double-Metal Cyanide Complex 893.2.2 Catalysts Centered with Chromium (Cr) 933.2.3 Catalyst Centered with Iron (Fe) and Cobalt (Co) 953.2.4 Alkoxy Metal Salts 963.3 Organocatalysts for COS Copolymerization 963.3.1 TEB-Organic Base Pair 973.3.2 Dual-Site Lewis Pair 1013.3.3 Thiourea-Organic Base Pairs 1043.3.4 Supramolecular Anion 1073.4 Oxygen-Sulfur Exchange Reaction 1103.5 Utilization of O/S ER for Poly(thioether)s 1133.5.1 COS-Epoxides Route to Poly(thioether)s 1133.5.2 CS2-Epoxides Route to Poly(thioether)s 1153.5.3 Repurposing Poly(monothiocarbonate)s to Poly(thioether)s 1203.6 Crystalline COS-Derived Polymers 1213.7 COS-Derived Block Polymers 1233.8 Properties of COS-Derived Polymers 1243.8.1 Thermal Properties 1243.8.2 Crystalline Properties 1263.8.3 Optical Properties 1293.8.4 Electronic Properties 1323.9 Summary and Outlook 137References 1384 Thiol-Based Click Polymerizations for Sulfur-Containing Polymers 147Die Huang, Anjun Qin, and Ben Zhong Tang4.1 Introduction 1474.2 Thiol-Ene Click Polymerization 1484.2.1 Radical-Initiated Thiol-Ene Click Polymerization 1484.2.2 Thiol-Ene Michael Addition Click Polymerization 1514.3 Thiol-Yne Click Polymerization 1544.3.1 Radical-Initiated Thiol-Yne Click Polymerization 1544.3.2 Base-Mediated Thiol-Yne Click Polymerization 1564.3.3 Metal-Catalyzed Thiol-Yne Click Polymerization 1574.3.4 Spontaneous Thiol-Yne Click Polymerization 1594.4 Other Thiol-Based Click Polymerizations 1594.4.1 Thiol-Epoxy Click Polymerization 1604.4.2 Thiol-Isocyanate Click Polymerization 1634.4.3 Thiol-Halogen Click Polymerization 1644.5 Conclusion 164Acknowledgments 166References 1665 Synthesis of Polythioesters 171Li-Yang Wang and Wei-Min Ren5.1 Introduction 1715.2 Synthesis of Aromatic Polythioesters 1725.3 Synthesis of Semi-aromatic Polythioesters 1745.4 Synthesis of Aliphatic Polythioesters 1795.5 Summary and Concluding Remarks 185Acknowledgments 186References 1866 Polymers with Sulfur-Nitrogen Bonds 191Hatice Mutlu and Patrick Theato6.1 Introduction 1916.2 Synthesis of Sulfur-Nitrogen Containing Polymers 1926.2.1 Poly(sulfenamide)s 1926.2.2 Poly(diaminosulfide)s 1966.2.3 Poly(aminodisulfide)s and Poly(diaminodisulfide)s 1996.2.3.1 Poly(aminodisulfide)s 2006.2.3.2 Poly(diaminodisulfide)s 2016.2.4 Poly(oxothiazene)s 2056.2.5 Poly(sulfonylimidate)s 2076.2.6 Poly(sulfonylamidine)s 2136.3 Applications of Polymers with Sulfur-Nitrogen Bond 2216.3.1 Biomedical Applications 2216.3.2 Metal-Ion Detection 2256.3.3 Flame Retardant Chemicals Based on Polymers with Sulfur-Nitrogen Bonds 2276.3.4 Energy Storage Applications 2286.4 Conclusion and Outlook 229References 2297 Thioester Functional Polymers 235Suzan Aksakal, Resat Aksakal, and C. Remzi Becer7.1 Introduction 2357.2 Thioesters: Structural Features, Reactivities, and Reactions 2367.3 Preparation of Thioester Containing Structures 2377.3.1 Access to Thioester Containing Polymers: Thioesters in the Side Chain 2387.3.2 Access to Thioester Containing Polymers: Thioester in the Chain End 2467.3.3 Access to Thioester Containing Polymers via Polymerization Process 2477.3.4 Access to Thioester-Bearing Structures via Post-modification Approach 2497.4 Post-Polymerization Modification of Thioesters 2517.5 Conclusion and Outlook 254References 2568 Thiophene-Based Polymers: Synthesis and Applications 265Haifeng Ji and Xiaojie Zhang8.1 Introduction 2658.2 Development of Synthetic Methods 2668.2.1 Oxidative Polymerization and Electrochemical Polymerization 2668.2.2 Transmetalation Polymerization 2698.2.2.1 Polymerization with Ni Catalysis 2698.2.2.2 Polymerization with Pd Catalysis 2738.2.2.3 Suzuki Coupling Method 2748.2.2.4 Stille Coupling Method 2758.2.2.5 Direct Arylation Method 2768.2.3 Other Polymerization Methods 2788.2.3.1 Photoinitiated Polymerization 2788.2.3.2 Solid-State Polymerization 2808.2.3.3 Acid-Catalyzed Polymerization 2838.3 Applications of Polythiophene and Its Derivatives 2848.3.1 Organic Thin-Film Transistors 2858.3.2 Organic Photovoltaics 2868.3.3 Organic Light-Emitting Diodes 2878.3.4 Biological Applications 2888.4 Conclusions and Future Scope 290References 2909 High Refractive Index Sulfur-Containing Polymers (HRISPs) 305Johannes M. Scheiger and Patrick Theato9.1 Introduction 3059.2 Basics of Optics 3069.2.1 Absorption and Refraction 3069.2.2 Refractive Index 3079.2.2.1 Refractive Index Determination 3089.2.3 Dispersion 3119.2.4 Birefringence 3129.3 High Refractive Index Polymers (HRIPs) 3139.3.1 General Strategies and Applications 3149.4 Sulfur-Containing HRIPs 3159.4.1 Polyimides and Polyamides 3159.4.2 Poly(meth)acrylates and Polythioacrylates 3219.4.3 Polycarbonates and Polyesters 3259.4.4 Thermosets 3279.4.5 Inverse Vulcanization 3289.5 Conclusion and Outlook 334References 33510 Selenium-Containing Dynamic Polymers: From Synthesis to Functions 339Jiahao Xia and Huaping Xu10.1 Introduction 33910.2 Synthesis of Selenium-Containing Polymers 34010.2.1 Step Growth Polymerization 34010.2.2 Radical Polymerization 34210.2.3 Ring-Opening Polymerization 34510.2.4 Synthesis of Dendrimer and Hyperbranched Selenium-Containing Polymer 34510.3 Selenium-Containing Dynamic Covalent Chemistry 34810.3.1 Diselenide Bond 34810.3.2 Se—S Bond 35110.3.3 Se—Te Bond 35110.3.4 Se—N Bond 35310.4 Selenium-Containing Dynamic Materials 35610.4.1 Selenium-Containing Elastomer 35610.4.2 Selenium-Containing Surface/Interface Materials 36010.4.3 Selenium-Containing Nanomaterials 36010.5 Conclusion and Outlook 362Acknowledgments 363References 36311 Poly(disulfide)s 367Raju Bej and Suhrit Ghosh11.1 Introduction 36711.2 Synthesis of Poly(disulfide)s 36911.2.1 Oxidative Polymerization of Dithiols 37011.2.2 Ring-Opening Polymerization (ROP) of Cyclic Disulfide 37411.2.3 Photo-Induced Disulfide Metathesis 37511.2.4 Fragmentation Polymerization 37511.2.5 Self-Organizing Surface-Initiated Polymerization (SOSIP) 37711.2.6 Thiol-Disulfide Exchange Reaction 37811.3 Amphiphilic PDS and Drug Delivery Application 38111.4 Cell-Penetrating Poly(disulfide)s 38811.5 Summary and Outlook 389References 38912 Reduction-Responsive Disulfide-Containing Polymers for Biomedical Applications 393Xing Wang and Decheng Wu12.1 Introduction 39312.2 Disulfide-Containing Topological Polymers 39512.2.1 Systems with the Disulfide Linkages 39512.2.2 Disulfide-Containing Linear Polymers 39512.2.2.1 Linear Polymers with Cleavable Backbones 39612.2.2.2 Linear Polymers with Cleavable Side Chains 39712.2.3 Disulfide-Containing Dendritic Polymers 39812.2.3.1 Disulfide-Containing Hyperbranched Polymers 39912.2.3.2 Disulfide-Containing Dendrimers 40012.2.4 Disulfide-Containing Polypeptides and Proteins 40112.2.5 Disulfide-Containing Polymeric Nanoparticles 40312.2.5.1 Disulfide Linker for Amphiphilic Polymers 40312.2.5.2 Disulfide Linker for Nano-Assemblies 40412.2.5.3 Controlled Fabrication of Solution Nano-Assemblies 40612.2.6 Disulfide-Containing Crosslinking Hydrogels 40712.2.6.1 Disulfide-Crosslinked Micro-/Nanogels 40712.2.6.2 Disulfide-Crosslinked Macroscopic Hydrogels 40712.2.6.3 Disulfide-Crosslinked Natural Hydrogels 41012.3 Disulfide-Containing Polymers for Biomedical Applications 41212.3.1 Targeted Drug Delivery 41212.3.1.1 Disulfide-Containing Nano-Assemblies for Targeted Drug Delivery 41312.3.1.2 Disulfide-Containing Nanogels for Drug Delivery 41412.3.1.3 Disulfide-Containing Hydrogels for Drug Delivery 41512.3.2 Gene Delivery 41612.3.3 Biomedical Imaging 41812.3.4 Drug Conjugates 41912.3.5 Self-healing/Self-repairing 42012.4 Summary and Perspectives 422References 424Index 429