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Table of Contents
Cover
Preface
Contents
Chapter 1 Nucleophilic Catalysts and Organocatalyzed Zwitterionic Ring-opening Polymerization of Heterocyclic Monomers
1.1 Introduction
1.2 Definition of ZROP
1.2.1 Pyridine-based Initiation
1.2.2 Imidazole-based Initiation
1.2.3 Amidine/Guanidine-based Initiation
1.2.4 Tertiary Amine-based Initiation
1.2.5 Phosphine-based Initiation
1.2.6 N-heterocyclic Carbene-based Initiation
Acknowledgments
References
Chapter 2 Ring-opening Polymerization Promoted by Brønsted Acid Catalysts
2.1 Introduction
2.2 Organic Acids
2.2.1 Inorganic Strong Brønsted Acids
2.2.2 Sulfonic Acids
2.2.2.1 Performances in ROP
2.2.2.2 Mechanistic Aspects
2.2.3 Sulfonamides
2.2.3.1 Performance in ROP
2.2.3.2 Mechanistic Considerations
2.2.4 Phosphoric Acids
2.2.4.1 Performance in ROP
2.2.4.2 Mechanistic Considerations
2.2.5 Carboxylic Acids
2.2.5.1 Performance in ROP
2.2.5.2 Mechanistic Considerations
2.2.6 Activated Brønsted Acids
2.2.6.1 Brønsted Acids Activated by a Hydrogen Bond Donor
2.2.6.2 Performances
2.2.6.3 Mechanistic Considerations
2.2.7 Brønsted Base Activated Brønsted Acids: Ions Pairs as Catalysts
2.2.7.1 Performances
2.2.7.2 Mechanistic Considerations
2.3 Applications of Organocatalyzed ROP Promoted by Brønsted Acids
2.3.1 Functional Group Compatibility
2.3.1.1 Functionalized/Macromolecular Initiators
2.3.1.2 Using Functionalized Monomers
2.3.2 Preparation of Copolymers
2.3.2.1 Block and Random Copolymerization Promoted by a Common Catalyst
2.3.2.2 Block Copolymerization Promoted by Different Catalysts: The Switch Catalyst Strategy
2.3.2.3 Block Copolymerization via Two Different Polymerization Methods
2.4 Conclusion
References.
Chapter 3 Bifunctional and Supramolecular Organocatalysts for Polymerization
3.1 Introduction
3.2 Dual Catalysts
3.2.1 Thiourea H-bond Donors
3.2.2 Thiourea-mediated Stereoselective ROP
3.2.3 Squaramides
3.3 Rate-accelerated Dual Catalysis
3.3.1 Internal Lewis Acid Enhanced H-bond Donors
3.3.2 Multi (Thio)urea Catalysts
3.3.3 Urea and Thiourea Anions
3.4 Non-(thio)urea Lewis Acid/Base Catalysis
3.4.1 Sulfonamides, Phosphoric and Phosphoramide H-bond Donor/Acceptors
3.4.2 Phenol and Benzyl Alcohol H-bond Donors
3.4.3 Electrostatic Monomer Activation by Cations
3.5 Bron̈sted Acid/Base Pairs
3.6 Supramolecular Catalysts
3.6.1 Betaines
3.6.2 Amino-oxazoline
3.6.3 Cyclodextrins
3.7 Conclusion
Acknowledgments
References
Chapter 4 Base Catalysts for Organopolymerization
4.1 Introduction
4.2 Amidines and Guanidines
4.2.1 Amidines-Synthesis and Properties
4.2.2 Guanidines-Synthesis and Properties
4.2.3 Amidines and Guanidines as Base Catalysts for Polymerizations
4.3 Phosphazenes
4.3.1 Synthesis and Properties
4.3.2 Phosphazenes as Base Catalysts for Polymerizations
4.4 N-heterocyclic Carbenes and N-heterocyclic Olefins
4.4.1 Properties of N-heterocyclic Carbenes
4.4.2 Properties of N-heterocyclic Olefins
4.4.3 Synthesis of NHOs and NHCs
4.4.4 NHCs as Base Catalysts for Polymerizations
4.4.5 NHOs as Base Catalysts for Polymerizations
4.5 Other Types of Organic Base Catalysts
4.6 Summary and Comparison
4.6.1 Why Use Organobase Polymerization Catalysis?
4.6.2 Selecting Organobases
4.7 Outlook
References
Chapter 5 Ring-opening Polymerization of Lactones
5.1 Introduction
5.2 Polymerization of Six- and Seven-membered Medium Size Monoesters
5.2.1 Polymerization Catalyzed by Carboxylic Acids.
5.2.2 Polymerization Catalyzed by Sulfonic and Dialkyl Phosphates
5.2.3 Polymerization Catalyzed by H-bond Donor
5.2.4 Polymerization Catalyzed by Lewis Bases
5.2.5 Dual Catalysts
5.2.6 Zwitterionic Polymerization
5.3 Polymerization of Five-membered Lactones
5.4 Polymerization of Four-membered Small-size Cyclic Monoesters
5.5 Polymerization of Large-size Macrocyclic Monoesters
5.6 Macromolecular Engineering
5.7 Conclusions
Acknowledgments
References
Chapter 6 Organic Catalysis for the Polymerization of Lactide and Related Cyclic Diesters
6.1 Introduction
6.2 Polymerization Mechanisms in the Organocatalyzed ROP of LA
6.3 Polymerization of LA Directly Induced by Single Organic Initiators
6.4 Polymerization of LA Catalyzed by Brønsted and Lewis Acids
6.5 Polymerization of LA and OCAs Catalyzed by Nitrogen-containing Brønsted/Lewis Bases
6.5.1 Polymerization of LA Catalyzed by Amines and Pyridine Derivatives
6.5.2 Polymerization of LA Catalyzed by Amidines and Guanidines
6.5.3 Polymerization of LA Catalyzed by N-heterocyclic Carbenes
6.5.4 Polymerization of OCAs Catalyzed by Pyridine Derivatives and N-heterocyclic Carbenes
6.6 Polymerization of LA Catalyzed by Phosphorus-containing Brønsted/Lewis Bases: Phosphines and Phosphazenes
6.6.1 Polymerization of LA Catalyzed by Phosphines
6.6.2 Polymerization of LA Catalyzed by Phosphazenes
6.7 Polymerization of LA Catalyzed by Mono- or Multicomponent Dual Catalytic Systems
6.7.1 Polymerization of LA Catalyzed by Monocomponent Dual Catalytic Systems
6.7.2 Polymerization of LA Catalyzed by Multicomponent Dual Catalytic Systems
6.8 Conclusion
Abbreviations
Acknowledgments
References
Chapter 7 ROP of Cyclic Carbonates
7.1 Introduction
7.2 Classical Mechanism
7.2.1 Anionic Pathway
7.2.2 Cationic Pathway.
7.2.3 Coordination-Insertion Pathway
7.3 Recent Trends in Catalysts and Initiators
7.3.1 Organometallics
7.3.1.1 Immortal ROP
7.3.1.2 Borohydride Ligand: Formation of a-hydroxy,o-formate telechelic Polycarbonates
7.3.1.3 Redox-switchable Catalyst
7.3.2 Organocatalysts
7.3.2.1 Organic Bases
7.3.2.2 Organic Acids
7.3.2.3 Conjugate Acid-Base Pairs
7.3.3 Enzymes
7.4 Regioselective ROP of Cyclic Carbonates
7.5 Copolymerization
7.5.1 Copolymerization of TMC and LLA
7.5.2 Copolymerization of TMC and CL
7.5.3 Copolymerization of TMC and Other Six-membered Cyclic Carbonates
7.6 Cyclic Carbonates as Polymerizable Monomers
7.6.1 Five-membered Cyclic Carbonates
7.6.2 Six-membered Cyclic Carbonates
7.6.3 Seven-membered Cyclic Carbonates
7.6.4 Eight-membered Cyclic Carbonates
7.6.5 Cyclic Oligo-/Polycarbonates
7.7 Conclusion
References
Chapter 8 Metal-free Polyether Synthesis by Organocatalyzed Ring-opening Polymerization
8.1 Introduction
8.2 Metal-free Synthesis of Aliphatic Polyethers by ROP of Epoxides
8.2.1 Industrial Importance
8.2.2 Brønsted and Lewis acids
8.2.3 Phosphazenes, Phosphazenium Salts, Phosphines and Phosphonium Salts
8.2.4 Dual Activation from a Phosphazene Base and a Metallic Lewis Acid
8.2.5 N-heterocyclic carbenes (NHCs) and N-heterocyclic olefins (NHOs)
8.2.6 Other Organic Salts
8.3 Recent Developments in the Synthesis of Metal-free Epoxy Resins
8.4 Conclusion
References
Chapter 9 Ring-opening Polymerization of N-carboxyanhydrides Using Organic Initiators or Catalysts
9.1 Introduction
9.2 Synthesis of NCAs, R-NCA, NTA and R-NTA Monomers
9.3 Polymerization of NCAs, NTAs, R-NCAs or R-NTAs by the Normal Amine Mechanism (NAM) and/or Activated Monomer Mechanism (AMM).
9.3.1 ROPs of NCAs by the Normal Amine Mechanism Using Protic Nucleophilic Initiators
9.3.2 Side Reactions in the ROPs of NCAs Bearing the N-H Proton
9.3.3 ROPs of NCAs Bearing the N-H Proton by the Activated Monomer Mechanism
9.3.4 Towards Controlled ROPs of NCAs Bearing the N-H Proton by Optimization of Reaction Conditions
9.3.5 Towards Controlled ROPs of NCAs Bearing the N-H Proton by Modulating the Reactivity of Propagating Species
9.3.6 Towards Controlled ROPs of NCAs Bearing the N-H Proton by Modulating the Reactivity of Propagating Species and Activation Of Monomers
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
9.3.8 Towards the Controlled ROPs of NTAs Bearing the N-H Proton by NAM
9.3.9 Towards the Controlled ROPs of R-NCAs or R-NTAs by NAM
9.3.10 Towards the Controlled ROPs of R-NCAs or R-NTAs by Activation of Alcohol Initiators
9.4 Polymerization of NCAs or R-NCAs by the Silyl Group Transfer Mechanism
9.5 Polymerization of NCAs or R-NCAs by the Zwitterionic Ring-opening Polymerization Mechanism
9.6 Concluding Remarks
Acknowledgments
References
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
10.1 C-C Bond Forming Monomer Units via Metal-free Ring-opening Polymerization Poly(cyclopropane)s
10.2 Nitrogen-containing Monomers
10.2.1 Polylactams
10.2.2 Poly(aziridine)s
10.2.3 Polyurethanes
10.3 Silicon-containing Monomers
10.3.1 Poly(cyclosiloxane)s
10.3.2 Poly(cyclocarbosiloxane)s
10.4 Phosphorus-containing Monomers.
10.4.1 Poly(phosphoric acid ester)s, Polyphosphates.
Preface
Contents
Chapter 1 Nucleophilic Catalysts and Organocatalyzed Zwitterionic Ring-opening Polymerization of Heterocyclic Monomers
1.1 Introduction
1.2 Definition of ZROP
1.2.1 Pyridine-based Initiation
1.2.2 Imidazole-based Initiation
1.2.3 Amidine/Guanidine-based Initiation
1.2.4 Tertiary Amine-based Initiation
1.2.5 Phosphine-based Initiation
1.2.6 N-heterocyclic Carbene-based Initiation
Acknowledgments
References
Chapter 2 Ring-opening Polymerization Promoted by Brønsted Acid Catalysts
2.1 Introduction
2.2 Organic Acids
2.2.1 Inorganic Strong Brønsted Acids
2.2.2 Sulfonic Acids
2.2.2.1 Performances in ROP
2.2.2.2 Mechanistic Aspects
2.2.3 Sulfonamides
2.2.3.1 Performance in ROP
2.2.3.2 Mechanistic Considerations
2.2.4 Phosphoric Acids
2.2.4.1 Performance in ROP
2.2.4.2 Mechanistic Considerations
2.2.5 Carboxylic Acids
2.2.5.1 Performance in ROP
2.2.5.2 Mechanistic Considerations
2.2.6 Activated Brønsted Acids
2.2.6.1 Brønsted Acids Activated by a Hydrogen Bond Donor
2.2.6.2 Performances
2.2.6.3 Mechanistic Considerations
2.2.7 Brønsted Base Activated Brønsted Acids: Ions Pairs as Catalysts
2.2.7.1 Performances
2.2.7.2 Mechanistic Considerations
2.3 Applications of Organocatalyzed ROP Promoted by Brønsted Acids
2.3.1 Functional Group Compatibility
2.3.1.1 Functionalized/Macromolecular Initiators
2.3.1.2 Using Functionalized Monomers
2.3.2 Preparation of Copolymers
2.3.2.1 Block and Random Copolymerization Promoted by a Common Catalyst
2.3.2.2 Block Copolymerization Promoted by Different Catalysts: The Switch Catalyst Strategy
2.3.2.3 Block Copolymerization via Two Different Polymerization Methods
2.4 Conclusion
References.
Chapter 3 Bifunctional and Supramolecular Organocatalysts for Polymerization
3.1 Introduction
3.2 Dual Catalysts
3.2.1 Thiourea H-bond Donors
3.2.2 Thiourea-mediated Stereoselective ROP
3.2.3 Squaramides
3.3 Rate-accelerated Dual Catalysis
3.3.1 Internal Lewis Acid Enhanced H-bond Donors
3.3.2 Multi (Thio)urea Catalysts
3.3.3 Urea and Thiourea Anions
3.4 Non-(thio)urea Lewis Acid/Base Catalysis
3.4.1 Sulfonamides, Phosphoric and Phosphoramide H-bond Donor/Acceptors
3.4.2 Phenol and Benzyl Alcohol H-bond Donors
3.4.3 Electrostatic Monomer Activation by Cations
3.5 Bron̈sted Acid/Base Pairs
3.6 Supramolecular Catalysts
3.6.1 Betaines
3.6.2 Amino-oxazoline
3.6.3 Cyclodextrins
3.7 Conclusion
Acknowledgments
References
Chapter 4 Base Catalysts for Organopolymerization
4.1 Introduction
4.2 Amidines and Guanidines
4.2.1 Amidines-Synthesis and Properties
4.2.2 Guanidines-Synthesis and Properties
4.2.3 Amidines and Guanidines as Base Catalysts for Polymerizations
4.3 Phosphazenes
4.3.1 Synthesis and Properties
4.3.2 Phosphazenes as Base Catalysts for Polymerizations
4.4 N-heterocyclic Carbenes and N-heterocyclic Olefins
4.4.1 Properties of N-heterocyclic Carbenes
4.4.2 Properties of N-heterocyclic Olefins
4.4.3 Synthesis of NHOs and NHCs
4.4.4 NHCs as Base Catalysts for Polymerizations
4.4.5 NHOs as Base Catalysts for Polymerizations
4.5 Other Types of Organic Base Catalysts
4.6 Summary and Comparison
4.6.1 Why Use Organobase Polymerization Catalysis?
4.6.2 Selecting Organobases
4.7 Outlook
References
Chapter 5 Ring-opening Polymerization of Lactones
5.1 Introduction
5.2 Polymerization of Six- and Seven-membered Medium Size Monoesters
5.2.1 Polymerization Catalyzed by Carboxylic Acids.
5.2.2 Polymerization Catalyzed by Sulfonic and Dialkyl Phosphates
5.2.3 Polymerization Catalyzed by H-bond Donor
5.2.4 Polymerization Catalyzed by Lewis Bases
5.2.5 Dual Catalysts
5.2.6 Zwitterionic Polymerization
5.3 Polymerization of Five-membered Lactones
5.4 Polymerization of Four-membered Small-size Cyclic Monoesters
5.5 Polymerization of Large-size Macrocyclic Monoesters
5.6 Macromolecular Engineering
5.7 Conclusions
Acknowledgments
References
Chapter 6 Organic Catalysis for the Polymerization of Lactide and Related Cyclic Diesters
6.1 Introduction
6.2 Polymerization Mechanisms in the Organocatalyzed ROP of LA
6.3 Polymerization of LA Directly Induced by Single Organic Initiators
6.4 Polymerization of LA Catalyzed by Brønsted and Lewis Acids
6.5 Polymerization of LA and OCAs Catalyzed by Nitrogen-containing Brønsted/Lewis Bases
6.5.1 Polymerization of LA Catalyzed by Amines and Pyridine Derivatives
6.5.2 Polymerization of LA Catalyzed by Amidines and Guanidines
6.5.3 Polymerization of LA Catalyzed by N-heterocyclic Carbenes
6.5.4 Polymerization of OCAs Catalyzed by Pyridine Derivatives and N-heterocyclic Carbenes
6.6 Polymerization of LA Catalyzed by Phosphorus-containing Brønsted/Lewis Bases: Phosphines and Phosphazenes
6.6.1 Polymerization of LA Catalyzed by Phosphines
6.6.2 Polymerization of LA Catalyzed by Phosphazenes
6.7 Polymerization of LA Catalyzed by Mono- or Multicomponent Dual Catalytic Systems
6.7.1 Polymerization of LA Catalyzed by Monocomponent Dual Catalytic Systems
6.7.2 Polymerization of LA Catalyzed by Multicomponent Dual Catalytic Systems
6.8 Conclusion
Abbreviations
Acknowledgments
References
Chapter 7 ROP of Cyclic Carbonates
7.1 Introduction
7.2 Classical Mechanism
7.2.1 Anionic Pathway
7.2.2 Cationic Pathway.
7.2.3 Coordination-Insertion Pathway
7.3 Recent Trends in Catalysts and Initiators
7.3.1 Organometallics
7.3.1.1 Immortal ROP
7.3.1.2 Borohydride Ligand: Formation of a-hydroxy,o-formate telechelic Polycarbonates
7.3.1.3 Redox-switchable Catalyst
7.3.2 Organocatalysts
7.3.2.1 Organic Bases
7.3.2.2 Organic Acids
7.3.2.3 Conjugate Acid-Base Pairs
7.3.3 Enzymes
7.4 Regioselective ROP of Cyclic Carbonates
7.5 Copolymerization
7.5.1 Copolymerization of TMC and LLA
7.5.2 Copolymerization of TMC and CL
7.5.3 Copolymerization of TMC and Other Six-membered Cyclic Carbonates
7.6 Cyclic Carbonates as Polymerizable Monomers
7.6.1 Five-membered Cyclic Carbonates
7.6.2 Six-membered Cyclic Carbonates
7.6.3 Seven-membered Cyclic Carbonates
7.6.4 Eight-membered Cyclic Carbonates
7.6.5 Cyclic Oligo-/Polycarbonates
7.7 Conclusion
References
Chapter 8 Metal-free Polyether Synthesis by Organocatalyzed Ring-opening Polymerization
8.1 Introduction
8.2 Metal-free Synthesis of Aliphatic Polyethers by ROP of Epoxides
8.2.1 Industrial Importance
8.2.2 Brønsted and Lewis acids
8.2.3 Phosphazenes, Phosphazenium Salts, Phosphines and Phosphonium Salts
8.2.4 Dual Activation from a Phosphazene Base and a Metallic Lewis Acid
8.2.5 N-heterocyclic carbenes (NHCs) and N-heterocyclic olefins (NHOs)
8.2.6 Other Organic Salts
8.3 Recent Developments in the Synthesis of Metal-free Epoxy Resins
8.4 Conclusion
References
Chapter 9 Ring-opening Polymerization of N-carboxyanhydrides Using Organic Initiators or Catalysts
9.1 Introduction
9.2 Synthesis of NCAs, R-NCA, NTA and R-NTA Monomers
9.3 Polymerization of NCAs, NTAs, R-NCAs or R-NTAs by the Normal Amine Mechanism (NAM) and/or Activated Monomer Mechanism (AMM).
9.3.1 ROPs of NCAs by the Normal Amine Mechanism Using Protic Nucleophilic Initiators
9.3.2 Side Reactions in the ROPs of NCAs Bearing the N-H Proton
9.3.3 ROPs of NCAs Bearing the N-H Proton by the Activated Monomer Mechanism
9.3.4 Towards Controlled ROPs of NCAs Bearing the N-H Proton by Optimization of Reaction Conditions
9.3.5 Towards Controlled ROPs of NCAs Bearing the N-H Proton by Modulating the Reactivity of Propagating Species
9.3.6 Towards Controlled ROPs of NCAs Bearing the N-H Proton by Modulating the Reactivity of Propagating Species and Activation Of Monomers
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
9.3.8 Towards the Controlled ROPs of NTAs Bearing the N-H Proton by NAM
9.3.9 Towards the Controlled ROPs of R-NCAs or R-NTAs by NAM
9.3.10 Towards the Controlled ROPs of R-NCAs or R-NTAs by Activation of Alcohol Initiators
9.4 Polymerization of NCAs or R-NCAs by the Silyl Group Transfer Mechanism
9.5 Polymerization of NCAs or R-NCAs by the Zwitterionic Ring-opening Polymerization Mechanism
9.6 Concluding Remarks
Acknowledgments
References
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
10.1 C-C Bond Forming Monomer Units via Metal-free Ring-opening Polymerization Poly(cyclopropane)s
10.2 Nitrogen-containing Monomers
10.2.1 Polylactams
10.2.2 Poly(aziridine)s
10.2.3 Polyurethanes
10.3 Silicon-containing Monomers
10.3.1 Poly(cyclosiloxane)s
10.3.2 Poly(cyclocarbosiloxane)s
10.4 Phosphorus-containing Monomers.
10.4.1 Poly(phosphoric acid ester)s, Polyphosphates.