Preface xiii 1 Organocatalyzed Ring-Opening Polymerization of Cyclic Esters Toward Degradable Polymers 1 Feng Li, Takuya Isono, and Toshifumi Satoh 1.1 General Introduction 1 1.2 Polymerization Mechanism 3 1.2.1 Nucleophilic Catalysts 3 1.2.2 Base Catalysts 4 1.2.

3 Acid Catalysts 6 1.2.4 Ionic Catalysts 7 1.2.5 Bifunctional and Multifunctional Catalysts 9 1.3 Recent Trends in Organocatalyst Development 10 1.3.1 Higher Catalytic Efficiency 11 1.

3.2 Higher Selectivity 12 1.3.3 Higher-Temperature Tolerance 17 1.3.4 Safety Considerations 19 1.4 Toward Higher Degradability and Recyclability 21 1.4.

1 Incorporation of Chemically Labile Moieties into Polymer Chains for Higher Degradability 22 1.4.2 Development of Novel Chemically Recyclable Polyesters 25 1.5 Summary and Outlook 29 References 30 2 Organocatalyzed Copolymerization of CO 2 with Epoxide Toward Polycarbonate Synthesis 45 Xiaoshuang Feng and Yves Gnanou 2.1 Introduction 45 2.2 Discovery of TEB Catalyzed CO2 /Epoxides Copolymerization 46 2.3 Development of TEB Catalyzed CO2 /Epoxides Copolymerization 50 2.4 Synthesis of CO2 -Based Block Copolymers 55 2.

4.1 One-Step Ter-, Quater-Polymerization 55 2.4.2 Polycarbonate Block Copolymers from Orthogonal Polymerization 58 2.4.3 All-Polycarbonate Block Copolymers 60 2.4.4 CO2 -Based Triblock Copolymers 62 2.

5 Bifunctional Organoboron Catalysts 65 2.5.1 9-BBN Tethered with Ammonium Cations 65 2.5.2 9-BBN Tethered with Phosphonium Cations 67 2.5.3 Borinane Tethered with Ammonium Cations 68 2.6 Conclusions 69 References 70 3 Organocatalyzed Ring-Opening Copolymerization of Cyclic Anhydride and Cyclic Ether (Acetal) 79 Xun Zhang, Chengjian Zhang, and Xinghong Zhang 3.

1 Introduction 79 3.2 The Copolymerization of Epoxide with Cyclic Anhydride 81 3.2.1 The Scope of Epoxides and Cyclic Anhydrides 81 3.2.2 Metal Catalysts 82 3.2.3 Organocatalysts 85 3.

2.3.1 Organic Bases 86 3.2.3.2 Bicomponent Lewis Pair 88 3.2.3.

3 Bifunctional Lewis Pair 92 3.3 The Copolymerization of Oxetane with Cyclic Anhydride 95 3.4 The Copolymerization of Tetrahydrofuran with Cyclic Anhydride 97 3.5 The Copolymerization of Cyclic Acetal (Aldehyde) with Cyclic Anhydride 100 3.6 Polyester-Based Block Copolymer 103 3.7 Conclusions and Outlook 105 References 107 4 Organocatalysts for the Preparation of Degradable and Closed-Loop Recyclable Polyesters 115 Yong Shen and Zhibo li 4.1 Introduction 115 4.2 Catalytic Mechanism of Various Organocatalysts 116 4.

2.1 Electrophilic Monomer Activation Mechanism 116 4.2.2 Nucleophilic Monomer Activation Mechanism 117 4.2.3 Chain-End Activation Mechanism 117 4.2.4 Bifunctional Activation Mechanism 118 4.

3 Organocatalytic ROP of Lactones or Lactides 119 4.3.1 γ-Butyrolactone and its Derivatives 119 4.3.2 δ-Valerolactone and ε-Caprolactone 124 4.3.3 δ-Valerolactone Derivatives 129 4.3.

4 Lactide 131 4.3.5 Large-Membered Lactones 135 4.4 Summary and Perspective 136 References 137 5 Organo-Catalyst Catalyzed Ring Opening Polymerization of N-Carboxyanhydrides 147 Chongyi Chen and Zhibo li 5.1 Introduction 147 5.2 Organo-Catalysts for NCA Ring Opening Polymerization 149 5.2.1 Organo-Catalysts Before 2010 149 5.

2.2 Amine-Based Organo-Catalysts 150 5.2.3 Other Organo-Catalysts 156 5.2.4 Autocatalysis of NCA Ring Opening Polymerization 160 5.3 Conclusions and Future Prospects 165 Abbreviations 166 References 166 6 Organocatalyst Catalyzed Ring Opening Polymerization of O(S)-Carboxyanhydride to Produce High Performance Poly(thio)esters 173 Yinuo Zhu and Youhua Tao 6.1 Introduction 173 6.

2 Synthesis and Purification of O(S)-Carboxyanhydride Monomers 175 6.3 The Racemization of α-Proton 175 6.4 Organocatalyst for OCA Polymerization 176 6.4.1 ROP Catalyzed by DMAP 176 6.4.2 ROP Catalyzed by N-Heterocyclic Carbenes 178 6.4.

3 ROP Catalyzed by Acid/Base Adducts 178 6.4.4 Thiourea-Based Organocatalysts for OCAs Polymerization 179 6.5 Organocatalyst for SCA Polymerization 182 6.6 Conclusion and Perspective 185 References 186 7 Organocatalyzed Stereoselective Ring-Opening (Co)Polymerization 191 Shaofeng Liu and Daniel Taton 7.1 Introduction 191 7.2 Mechanisms in the Organocatalyzed Stereoselective ROP 192 7.3 Organic Acids for Stereoselective ROP of rac-LA 193 7.

4 Organic Bases for Stereoselective ROP of rac-LA 196 7.4.1 N-Heterocyclic Carbenes (NHCs) 196 7.4.2 Amidines and Guanidines 198 7.4.3 Phosphazenes 198 7.5 Dual Organocatalysts 200 7.

5.1 Mono-Component Bifunctional Organocatalysts 200 7.5.2 Bi-Component Organocatalysts 203 7.6 Organocatalysts for Stereoselective ROP of Other Cyclic Monomers 211 7.7 Conclusion 212 Acknowledgements 213 References 213 8 Ring-Opening Polymerization of Epoxides Through Organocatalysis 219 Lijun Liu, Yuxuan Zhou, Xingyu Tang, and Junpeng Zhao 8.1 Introduction 219 8.2 Catalyst and Mechanism 220 8.

2.1 Single-Component Catalyst 221 8.2.1.1 Base 221 8.2.1.2 Acid 223 8.

2.2 Two-Component Catalyst 225 8.3 Synthesis of Functionalized Polyether 227 8.3.1 End-Group Functionalization 228 8.3.2 Pendant-Group Functionalization 230 8.4 Synthesis of Polyether-Based Block Copolymer 232 8.

4.1 One-Pot Two-Step Block Copolymerization 232 8.4.2 One-Step Block Copolymerization 236 8.5 Conclusion and Outlook 240 References 240 9 Organo-Borane Catalysis for Ring Opening Polymerization of Epoxides 253 Xiaowu Wang and Zhibo li 9.1 Introduction 253 9.2 Fundamentals of Borane Compounds 253 9.2.

1 General Characteristics of Boron and Boranes 253 9.2.2 Bond Length and Strengths 254 9.2.3 Characterization 255 9.2.4 Lewis Acidity of (Organo)Borane 255 9.3 Et3B-Mediated ROP of Epoxides 256 9.

3.1 Introduction of ROP of Epoxides 256 9.3.2 Et3B -Based Binary Lewis Pair Systems in the ROP of Epoxides 258 9.3.3 Mechanism of Et3B Mediated ROP of Epoxides 260 9.3.4 Poly(alkylene oxide) Structures: Novel and Innovative Polyether Architectures 261 9.

4 Modified Organoborane Mediated ROP of Epoxides 264 9.4.1 One-Component Ammonium Borane-Based Lewis Pair Systems Mediated ROP of Epoxides 265 9.4.2 One-Component Phosphonium Borane-Based Lewis Pair Systems Mediated ROP of Epoxides 269 9.4.3 Silicon-Based Borane Lewis Pair System 272 9.4.

4 Macromolecular Organoborane Mediated ROP of Epoxides 272 9.4.5 Poly(alkylene oxide) Structures: Innovative Polyether Architectures 274 9.5 Chiral Organoborane Mediated Asymmetric ROP of Epoxides 279 9.6 Conclusion and Outlook 281 References 283 10 Organocatalyst for Ring-Opening Polymerization of Cyclosiloxanes Toward Polysiloxanes 289 Na Zhao, Yuetao liu, and Zhibo li 10.1 Introduction 289 10.2 Anionic ROP of Cyclosiloxanes 291 10.3 Phosphazene-Catalyzed Anionic ROP of Cyclosiloxanes 291 10.

3.1 Schwesinger''s Phosphazene Bases 293 10.3.2 Phosphazenium Hydroxide P5OH 293 10.3.3 Cyclic Trimeric Phosphazene Base (CTPB) 295 10.3.4 Trisphosphazene Base - C3N3 -Me-P3 297 10.

3.5 Guanidinophosphazene - HTGCP 297 10.4 Guanidines-Catalyzed Anionic ROP of Cyclosiloxanes 297 10.5 Phosphorus Ylides-Catalyzed Anionic ROP of Cyclosiloxanes 302 10.6 NHC-Catalyzed Anionic ROP of Cyclosiloxanes 303 10.7 Conclusion 304 References 305 11 Organic Lewis Pair in Polymer Synthesis 309 Mingqian Wang, Zhiqiang Ding, Bin Wang, and Yuesheng li 11.1 Lewis Pair Catalytic Ring-Opening Polymerization of Cyclic Esters 309 11.2 Mechanisms for Lewis Pair-Catalyzed ROP of Cyclic Esters 310 11.

3 Lewis Pairs Used for ROP of Cyclic Ester 311 11.3.1 Organoboron-Based Lewis Pair 311 11.3.2 Organoaluminum-Based Lewis Pair 313 11.3.3 Organozinc-Based Lewis Pair 315 11.3.

4 Metal Halide-Based LPs 318 References 322 12 Organocatalysts for Radical Polymerization 325 Chenyu Wu, Qiang Ma, Baoshan Hou, Zhilei Wang, Zikuan Wang, and Saihu Liao 12.1 Photocontrolled Organocatalyzed Radical Polymerization 325 12.2 Organocatalyzed Atom Transfer Radical Polymerization (O-ATRP) 328 12.2.1 Mechanism of O-ATRP 328 12.2.2 Polynuclear Aromatic Hydrocarbons 328 12.2.

3 Phenothiazine Derivatives 329 12.2.4 Dihydrophenazine Derivatives 330 12.2.5 Phenoxazine Derivatives 331 12.2.6 Dimethylacridine Derivatives 332 12.2.

7 Organic Donor-Acceptor Scaffolds 333 12.2.8 Heteroatom-Doped Anthanthrene Derivatives 334 12.2.9 Other Classes 335 12.3 Photoinduced Electron/Energy Transfer Reversible Addition-Fragmentation Chain Transfer (PET-RAFT) 337 12.3.1 Mechanism of PET-RAFT 337 12.

3.2 Porphyrin Derivatives 338 12.3.3 Fluorescein Derivatives 340 12.3.4 Phthalocyanine Derivatives 340 12.3.5 Other Classes 340 12.

4 Structure-Property-Performance Relationships 341 12.4.1 Structure-Property-Relations.