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Abstract
In recent years polymerisation using organocatalysts has become an appealing alternative to more traditional metal-based catalysts. Conferring numerous advantages including low cost and ease of use, as well as the ability to precisely control the synthesis of advanced polymer structures, organocatalysts are increasingly used in polymer synthesis. Organic Catalysis for Polymerisation provides a holistic overview of the field, covering all process in the polymer synthesis pathway that are catalysed by organic catalysts. Sub-divided into two key sections for ease of use, the first focuses on recent developments in catalysis and the applications of catalysts to the full range of polymerisations that they have been utilised in; the second concerning monomers, arranges the field by monomer type and polymerisation mechanism. The book will therefore, provide a complimentary view of the field, providing both an overview of state-of-the-art catalyst development and also the best methodologies available to create specific polymer types. Edited by leading figures in the field and featuring contributions from researchers across the globe, this title will serve as an excellent reference for postgraduate students and researchers in both academia and industry interested in polymer chemistry, organic chemistry, catalysis and materials science.
Table of Contents
| Section Title | Page | Action | Price |
|---|---|---|---|
| Cover | Cover | ||
| Preface | vii | ||
| Contents | xi | ||
| Chapter 1 Nucleophilic Catalysts and Organocatalyzed Zwitterionic Ring-opening Polymerization of Heterocyclic Monomers | 1 | ||
| 1.1 Introduction | 1 | ||
| 1.2 Definition of ZROP | 2 | ||
| 1.2.1 Pyridine-based Initiation | 2 | ||
| 1.2.2 Imidazole-based Initiation | 10 | ||
| 1.2.3 Amidine/Guanidine-based Initiation | 12 | ||
| 1.2.4 Tertiary Amine-based Initiation | 16 | ||
| 1.2.5 Phosphine-based Initiation | 19 | ||
| 1.2.6 N-heterocyclic Carbene-based Initiation | 20 | ||
| Acknowledgments | 31 | ||
| References | 31 | ||
| Chapter 2 Ring-opening Polymerization Promoted by Brønsted Acid Catalysts | 37 | ||
| 2.1 Introduction | 37 | ||
| 2.2 Organic Acids | 39 | ||
| 2.2.1 Inorganic Strong Brønsted Acids | 39 | ||
| 2.2.2 Sulfonic Acids | 41 | ||
| 2.2.2.1 Performances in ROP | 41 | ||
| 2.2.2.2 Mechanistic Aspects | 46 | ||
| 2.2.3 Sulfonamides | 51 | ||
| 2.2.3.1 Performance in ROP | 51 | ||
| 2.2.3.2 Mechanistic Considerations | 53 | ||
| 2.2.4 Phosphoric Acids | 54 | ||
| 2.2.4.1 Performance in ROP | 54 | ||
| 2.2.4.2 Mechanistic Considerations | 58 | ||
| 2.2.5 Carboxylic Acids | 61 | ||
| 2.2.5.1 Performance in ROP | 61 | ||
| 2.2.5.2 Mechanistic Considerations | 63 | ||
| 2.2.6 Activated Brønsted Acids | 64 | ||
| 2.2.6.1 Brønsted Acids Activated by a Hydrogen Bond Donor | 64 | ||
| 2.2.6.2 Performances | 64 | ||
| 2.2.6.3 Mechanistic Considerations | 67 | ||
| 2.2.7 Brønsted Base Activated Brønsted Acids: Ions Pairs as Catalysts | 67 | ||
| 2.2.7.1 Performances | 67 | ||
| 2.2.7.2 Mechanistic Considerations | 70 | ||
| 2.3 Applications of Organocatalyzed ROP Promoted by Brønsted Acids | 71 | ||
| 2.3.1 Functional Group Compatibility | 71 | ||
| 2.3.1.1 Functionalized/Macromolecular Initiators | 71 | ||
| 2.3.1.2 Using Functionalized Monomers | 74 | ||
| 2.3.2 Preparation of Copolymers | 75 | ||
| 2.3.2.1 Block and Random Copolymerization Promoted by a Common Catalyst | 75 | ||
| 2.3.2.2 Block Copolymerization Promoted by Different Catalysts: The Switch Catalyst Strategy | 76 | ||
| 2.3.2.3 Block Copolymerization via Two Different Polymerization Methods | 77 | ||
| 2.4 Conclusion | 82 | ||
| References | 82 | ||
| Chapter 3 Bifunctional and Supramolecular Organocatalysts for Polymerization | 87 | ||
| 3.1 Introduction | 87 | ||
| 3.2 Dual Catalysts | 89 | ||
| 3.2.1 Thiourea H-bond Donors | 90 | ||
| 3.2.2 Thiourea-mediated Stereoselective ROP | 92 | ||
| 3.2.3 Squaramides | 94 | ||
| 3.3 Rate-accelerated Dual Catalysis | 94 | ||
| 3.3.1 Internal Lewis Acid Enhanced H-bond Donors | 95 | ||
| 3.3.2 Multi (Thio)urea Catalysts | 95 | ||
| 3.3.3 Urea and Thiourea Anions | 96 | ||
| 3.4 Non-(thio)urea Lewis Acid/Base Catalysis | 99 | ||
| 3.4.1 Sulfonamides, Phosphoric and Phosphoramide H-bond Donor/Acceptors | 99 | ||
| 3.4.2 Phenol and Benzyl Alcohol H-bond Donors | 100 | ||
| 3.4.3 Electrostatic Monomer Activation by Cations | 101 | ||
| 3.5 Bro¨nsted Acid/Base Pairs | 102 | ||
| 3.6 Supramolecular Catalysts | 104 | ||
| 3.6.1 Betaines | 104 | ||
| 3.6.2 Amino-oxazoline | 105 | ||
| 3.6.3 Cyclodextrins | 105 | ||
| 3.7 Conclusion | 107 | ||
| Acknowledgments | 108 | ||
| References | 108 | ||
| Chapter 4 Base Catalysts for Organopolymerization | 121 | ||
| 4.1 Introduction | 121 | ||
| 4.2 Amidines and Guanidines | 126 | ||
| 4.2.1 Amidines-Synthesis and Properties | 126 | ||
| 4.2.2 Guanidines-Synthesis and Properties | 129 | ||
| 4.2.3 Amidines and Guanidines as Base Catalysts for Polymerizations | 132 | ||
| 4.3 Phosphazenes | 147 | ||
| 4.3.1 Synthesis and Properties | 147 | ||
| 4.3.2 Phosphazenes as Base Catalysts for Polymerizations | 152 | ||
| 4.4 N-heterocyclic Carbenes and N-heterocyclic Olefins | 164 | ||
| 4.4.1 Properties of N-heterocyclic Carbenes | 164 | ||
| 4.4.2 Properties of N-heterocyclic Olefins | 167 | ||
| 4.4.3 Synthesis of NHOs and NHCs | 170 | ||
| 4.4.4 NHCs as Base Catalysts for Polymerizations | 172 | ||
| 4.4.5 NHOs as Base Catalysts for Polymerizations | 176 | ||
| 4.5 Other Types of Organic Base Catalysts | 180 | ||
| 4.6 Summary and Comparison | 182 | ||
| 4.6.1 Why Use Organobase Polymerization Catalysis? | 182 | ||
| 4.6.2 Selecting Organobases | 184 | ||
| 4.7 Outlook | 186 | ||
| References | 187 | ||
| Chapter 5 Ring-opening Polymerization of Lactones | 198 | ||
| 5.1 Introduction | 198 | ||
| 5.2 Polymerization of Six- and Seven-membered Medium Size Monoesters | 202 | ||
| 5.2.1 Polymerization Catalyzed by Carboxylic Acids | 202 | ||
| 5.2.2 Polymerization Catalyzed by Sulfonic and Dialkyl Phosphates | 205 | ||
| 5.2.3 Polymerization Catalyzed by H-bond Donor | 206 | ||
| 5.2.4 Polymerization Catalyzed by Lewis Bases | 206 | ||
| 5.2.5 Dual Catalysts | 208 | ||
| 5.2.6 Zwitterionic Polymerization | 213 | ||
| 5.3 Polymerization of Five-membered Lactones | 214 | ||
| 5.4 Polymerization of Four-membered Small-size Cyclic Monoesters | 214 | ||
| 5.5 Polymerization of Large-size Macrocyclic Monoesters | 216 | ||
| 5.6 Macromolecular Engineering | 218 | ||
| 5.7 Conclusions | 220 | ||
| Acknowledgments | 220 | ||
| References | 220 | ||
| Chapter 6 Organic Catalysis for the Polymerization of Lactide and Related Cyclic Diesters | 224 | ||
| 6.1 Introduction | 224 | ||
| 6.2 Polymerization Mechanisms in the Organocatalyzed ROP of LA | 227 | ||
| 6.3 Polymerization of LA Directly Induced by Single Organic Initiators | 229 | ||
| 6.4 Polymerization of LA Catalyzed by Brønsted and Lewis Acids | 233 | ||
| 6.5 Polymerization of LA and OCAs Catalyzed by Nitrogen-containing Brønsted/Lewis Bases | 235 | ||
| 6.5.1 Polymerization of LA Catalyzed by Amines and Pyridine Derivatives | 235 | ||
| 6.5.2 Polymerization of LA Catalyzed by Amidines and Guanidines | 238 | ||
| 6.5.3 Polymerization of LA Catalyzed by N-heterocyclic Carbenes | 242 | ||
| 6.5.4 Polymerization of OCAs Catalyzed by Pyridine Derivatives and N-heterocyclic Carbenes | 247 | ||
| 6.6 Polymerization of LA Catalyzed by Phosphorus-containing Brønsted/Lewis Bases: Phosphines and Phosphazenes | 248 | ||
| 6.6.1 Polymerization of LA Catalyzed by Phosphines | 248 | ||
| 6.6.2 Polymerization of LA Catalyzed by Phosphazenes | 249 | ||
| 6.7 Polymerization of LA Catalyzed by Mono- or Multicomponent Dual Catalytic Systems | 251 | ||
| 6.7.1 Polymerization of LA Catalyzed by Monocomponent Dual Catalytic Systems | 251 | ||
| 6.7.2 Polymerization of LA Catalyzed by Multicomponent Dual Catalytic Systems | 252 | ||
| 6.8 Conclusion | 265 | ||
| Abbreviations | 266 | ||
| Acknowledgments | 268 | ||
| References | 268 | ||
| Chapter 7 ROP of Cyclic Carbonates | 274 | ||
| 7.1 Introduction | 274 | ||
| 7.2 Classical Mechanism | 275 | ||
| 7.2.1 Anionic Pathway | 275 | ||
| 7.2.2 Cationic Pathway | 276 | ||
| 7.2.3 Coordination-Insertion Pathway | 280 | ||
| 7.3 Recent Trends in Catalysts and Initiators | 280 | ||
| 7.3.1 Organometallics | 280 | ||
| 7.3.1.1 Immortal ROP | 284 | ||
| 7.3.1.2 Borohydride Ligand: Formation of a-hydroxy,o-formate telechelic Polycarbonates | 291 | ||
| 7.3.1.3 Redox-switchable Catalyst | 292 | ||
| 7.3.2 Organocatalysts | 294 | ||
| 7.3.2.1 Organic Bases | 294 | ||
| 7.3.2.2 Organic Acids | 298 | ||
| 7.3.2.3 Conjugate Acid-Base Pairs | 301 | ||
| 7.3.3 Enzymes | 303 | ||
| 7.4 Regioselective ROP of Cyclic Carbonates | 303 | ||
| 7.5 Copolymerization | 305 | ||
| 7.5.1 Copolymerization of TMC and LLA | 305 | ||
| 7.5.2 Copolymerization of TMC and CL | 308 | ||
| 7.5.3 Copolymerization of TMC and Other Six-membered Cyclic Carbonates | 308 | ||
| 7.6 Cyclic Carbonates as Polymerizable Monomers | 308 | ||
| 7.6.1 Five-membered Cyclic Carbonates | 309 | ||
| 7.6.2 Six-membered Cyclic Carbonates | 312 | ||
| 7.6.3 Seven-membered Cyclic Carbonates | 314 | ||
| 7.6.4 Eight-membered Cyclic Carbonates | 316 | ||
| 7.6.5 Cyclic Oligo-/Polycarbonates | 316 | ||
| 7.7 Conclusion | 318 | ||
| References | 318 | ||
| Chapter 8 Metal-free Polyether Synthesis by Organocatalyzed Ring-opening Polymerization | 328 | ||
| 8.1 Introduction | 328 | ||
| 8.2 Metal-free Synthesis of Aliphatic Polyethers by ROP of Epoxides | 331 | ||
| 8.2.1 Industrial Importance | 331 | ||
| 8.2.2 Brønsted and Lewis acids | 333 | ||
| 8.2.3 Phosphazenes, Phosphazenium Salts, Phosphines and Phosphonium Salts | 338 | ||
| 8.2.4 Dual Activation from a Phosphazene Base and a Metallic Lewis Acid | 351 | ||
| 8.2.5 N-heterocyclic carbenes (NHCs) and N-heterocyclic olefins (NHOs) | 352 | ||
| 8.2.6 Other Organic Salts | 356 | ||
| 8.3 Recent Developments in the Synthesis of Metal-free Epoxy Resins | 358 | ||
| 8.4 Conclusion | 360 | ||
| References | 361 | ||
| Chapter 9 Ring-opening Polymerization of N-carboxyanhydrides Using Organic Initiators or Catalysts | 367 | ||
| 9.1 Introduction | 367 | ||
| 9.2 Synthesis of NCAs, R-NCA, NTA and R-NTA Monomers | 368 | ||
| 9.3 Polymerization of NCAs, NTAs, R-NCAs or R-NTAs by the Normal Amine Mechanism (NAM) and/or Activated Monomer Mechanism (AMM) | 369 | ||
| 9.3.1 ROPs of NCAs by the Normal Amine Mechanism Using Protic Nucleophilic Initiators | 369 | ||
| 9.3.2 Side Reactions in the ROPs of NCAs Bearing the N-H Proton | 370 | ||
| 9.3.3 ROPs of NCAs Bearing the N-H Proton by the Activated Monomer Mechanism | 372 | ||
| 9.3.4 Towards Controlled ROPs of NCAs Bearing the N-H Proton by Optimization of Reaction Conditions | 372 | ||
| 9.3.5 Towards Controlled ROPs of NCAs Bearing the N-H Proton by Modulating the Reactivity of Propagating Species | 375 | ||
| 9.3.6 Towards Controlled ROPs of NCAs Bearing the N-H Proton by Modulating the Reactivity of Propagating Species and Activation Of Monomers | 378 | ||
| 9.3.7 Towards Controlled ROPs of NCAs Bearing the N-H Proton by Activating the Alcohol Initiators and Monomers, and Modulating the Reactivity of Propagating Species | 379 | ||
| 9.3.8 Towards the Controlled ROPs of NTAs Bearing the N-H Proton by NAM | 382 | ||
| 9.3.9 Towards the Controlled ROPs of R-NCAs or R-NTAs by NAM | 383 | ||
| 9.3.10 Towards the Controlled ROPs of R-NCAs or R-NTAs by Activation of Alcohol Initiators | 385 | ||
| 9.4 Polymerization of NCAs or R-NCAs by the Silyl Group Transfer Mechanism | 388 | ||
| 9.5 Polymerization of NCAs or R-NCAs by the Zwitterionic Ring-opening Polymerization Mechanism | 392 | ||
| 9.6 Concluding Remarks | 398 | ||
| Acknowledgments | 398 | ||
| References | 398 | ||
| Chapter 10 Organocatalytic Ring-opening Polymerization Towards Poly(cyclopropane)s, Poly(lactame)s, Poly(aziridine)s, Poly(siloxane)s, Poly (carbosiloxane)s, Poly (phosphate)s, Poly (phosphonate)s, Poly(thiolactone)s, Poly (thionolactone)s and Poly (thiirane)s | 406 | ||
| 10.1 C–C Bond Forming Monomer Units via Metal-free Ring-opening Polymerization Poly(cyclopropane)s | 407 | ||
| 10.2 Nitrogen-containing Monomers | 408 | ||
| 10.2.1 Polylactams | 408 | ||
| 10.2.2 Poly(aziridine)s | 413 | ||
| 10.2.3 Polyurethanes | 419 | ||
| 10.3 Silicon-containing Monomers | 419 | ||
| 10.3.1 Poly(cyclosiloxane)s | 419 | ||
| 10.3.2 Poly(cyclocarbosiloxane)s | 424 | ||
| 10.4 Phosphorus-containing Monomers | 427 | ||
| 10.4.1 Poly(phosphoric acid ester)s, Polyphosphates | 427 | ||
| 10.4.2 Poly(phosphonic acid ester)s, Poly(phosphonate)s | 445 | ||
| 10.5 Sulfur-containing Monomers | 455 | ||
| 10.5.1 Poly(thiolactone)s and Poly(thionolactone)s | 455 | ||
| 10.5.2 Poly(thiirane)s | 459 | ||
| References | 462 | ||
| Chapter 11 Organopolymerization of Acrylic Monomers | 473 | ||
| 11.1 Introduction | 473 | ||
| 11.2 Organocatalytic Group Transfer Polymerization | 474 | ||
| 11.2.1 Organic-base-catalyzed GTP | 475 | ||
| 11.2.1.1 NHCs | 478 | ||
| 11.2.1.2 Organic Superbase | 480 | ||
| 11.2.1.3 Phosphines | 481 | ||
| 11.2.1.4 Polar Donor Solvents | 481 | ||
| 11.2.2 Organic-acid-catalyzed GTP | 482 | ||
| 11.2.2.1 Tris(pentafluorophenyl)borane (B(C6F5)3) | 484 | ||
| 11.2.2.2 Triphenylmethyl Salts | 488 | ||
| 11.2.2.3 Tris(pentafluorophenyl) Aluminum (Al(C6F5)3) | 490 | ||
| 11.2.2.4 Trifluoromethanesulfonimide (Tf2NH) | 491 | ||
| 11.2.2.5 N-(Trimethylsilyl)bis(trifluoromethanesulfonyl)imide(Me3SiNTf2) | 493 | ||
| 11.2.2.6 Pentafluorophenylbis(triflyl)methane (Tf2CHC6F5) | 494 | ||
| 11.2.2.7 List’s Sulfonimide and the Other Organic Brønsted Acids | 494 | ||
| 11.2.3 Copolymerization of Acrylic Monomers Using Organocatalyzed GTP | 496 | ||
| 11.3 Polymerization of Acrylic Monomers by OrganicLewis Pairs | 497 | ||
| 11.4 Other Types of Organopolymerization of Polar Vinyl Monomers | 510 | ||
| 11.4.1 NHC and CO2-protected NHC | 511 | ||
| 11.4.2 Phosphazene Base | 519 | ||
| 11.4.3 Organic Electron Donors | 520 | ||
| 11.4.4 N-heterocyclic olefins (NHOs) | 522 | ||
| 11.5 Summary and Outlook | 524 | ||
| References | 525 | ||
| Chapter 12 Organocatalyzed Step-growth Polymerization | 531 | ||
| 12.1 Introduction | 531 | ||
| 12.2 Step-growth Polymerization Catalyzed by Brønsted and Lewis Bases | 534 | ||
| 12.2.1 Alkyl Amines and Pyridine Derivatives | 534 | ||
| 12.2.2 Amidines and Guanidines | 539 | ||
| 12.2.3 Phosphazenes | 549 | ||
| 12.2.4 N-heterocyclic Carbenes | 552 | ||
| 12.3 Step-growth Polymerization Catalyzed by Brønsted and Lewis Acids | 556 | ||
| 12.3.1 Sulfonic and Sulfonamide Acids | 556 | ||
| 12.3.2 Phosphoric Acid and Derivatives | 567 | ||
| 12.3.3 (Thio)ureas | 569 | ||
| 12.3.4 Brønsted Acid Ionic Liquids (BAILs) | 570 | ||
| 12.4 Step-growth Polymerization Catalyzed by Organic Ionic Salts | 574 | ||
| 12.5 Summary and Outlook | 576 | ||
| Abbreviations | 577 | ||
| Acknowledgments | 578 | ||
| References | 579 | ||
| Chapter 13 Organocatalyzed Controlled Radical Polymerizations | 584 | ||
| 13.1 Fundamentals of Organocatalyzed Controlled Radical Polymerizations | 584 | ||
| 13.1.1 Free-radical Polymerizations | 584 | ||
| 13.1.2 Controlled Radical Polymerizations | 585 | ||
| 13.1.3 Photo-mediated Controlled Radical Polymerizations | 589 | ||
| 13.1.4 Photocatalysis: Photophysical and Electrochemical Considerations | 591 | ||
| 13.2 Organocatalyzed Atom Transfer Radical Polymerization | 593 | ||
| 13.2.1 Mechanistic Cycle | 593 | ||
| 13.2.1.1 Introduction | 593 | ||
| 13.2.1.2 Activation | 594 | ||
| 13.2.1.3 Propagation | 595 | ||
| 13.2.1.4 Deactivation | 595 | ||
| 13.2.1.5 Role of Light Overall | 595 | ||
| 13.2.2 Catalyst Families | 595 | ||
| 13.2.2.1 Introduction | 595 | ||
| 13.2.2.2 PAHs | 596 | ||
| 13.2.2.3 Phenothiazines | 597 | ||
| 13.2.2.4 Phenazines | 597 | ||
| 13.2.2.5 Phenoxazines | 598 | ||
| 13.2.2.6 Carbazoles | 598 | ||
| 13.2.2.7 Summary | 598 | ||
| 13.3 Organocatalyzed Reversible Addition- Fragmentation Chain-transfer Polymerization | 599 | ||
| 13.3.1 Mechanism | 599 | ||
| 13.4 Reversible Complexation Mediated Radical Polymerization | 600 | ||
| 13.5 Future Outlook | 601 | ||
| References | 602 | ||
| Chapter 14 Organocatalysis for Depolymerisation | 607 | ||
| 14.1 Introduction | 607 | ||
| 14.2 Recycling of Commodity Polymers | 608 | ||
| 14.2.1 Organic Bases | 608 | ||
| 14.2.2 Organic Acids | 614 | ||
| 14.2.3 Alcohols and Amines | 616 | ||
| 14.2.4 Ionic Liquids and Acid-Base Salts | 619 | ||
| 14.3 Innovative Polymers and Their End-of-life Option | 625 | ||
| 14.4 Conclusion | 630 | ||
| References | 630 | ||
| Chapter 15 Organic Catalysis Outlook: Roadmap for the Future | 634 | ||
| References | 639 | ||
| Subject Index | 641 |