HANDBOOK OF RING-OPENING POLYMERIZATION

This comprehensive, truly one-stop reference discusses monomers, methods, stereochemistry, industrial applications and more. Chapters written by internationally acclaimed experts in their respective fields cover both basic principles and up-to-date information, ranging from the controlled ring-opening polymerization methods to polymer materials of industrial interest. All main classes of monomers including heterocyclics, cyclic olefins and alkynes, and cycloalkanes, are discussed separately as well as their specificities regarding the ring-opening polymerization techniques, the mechanisms, the degree of control, the properties of the related polymers and their applications. The two last chapters are devoted to the implementation of green chemistry in ring-opening polymerization processes.
Of much interest to chemists in academia and industry.

Philippe Dubois received his PhD degree from University of Liege. In 1997 he moved to University of Mons-Hainaut (UMH) where he obtained the chair of macromolecular chemistry and directed the Laboratory of Polymeric and Composite Materials. He has co-authored more than 350 peer-reviewed publications and is co-inventor of 40 patents. He co-edited 5 books. In 2007 he became Director of of The Center of Innovation and Research in Materials and Polymers (CIRMAP) at UMH. He is currently past-president of the Belgian Royal Chemical Society (president in 2006-2007) and scientific director of Materia Nova research center in Mons.

Olivier Coulembier received his PhD degree from University of Mons-Hainaut, Belgium in 2005 and joined the University of Stanford (United States) for his postdoctoral research in 2006. He is currently Research Associate by Belgian F.R.S.-FNRS in the Laboratory of Polymeric and Composite Materials (Professor Philippe Dubois) at University of Mons-Hainaut. His main activities are focused on the (non)organometallic ring-opening polymerization of cyclic monomers. He has authored 24 scientific papers in international journals.

Jean-Marie Raquez, PhD in chemistry um UMH, Belgium, is currently postdoctoral researcher by Belgian F.R.S.-FNRS and works in the Laboratory of Polymeric and Composites Materials (Professor Philippe Dubois) at University of Mons-Hainaut (UMH) in Mons, Belgium. He has authored 12 scientific papers and 5 US patents in Materials Technology including macromolecular synthesis and reactive processing. In 2004, he joined the Michigan State University, USa, for his postdoctoral research.

Preface.

List of Contributors.

1 Thermodynamics and Kinetics of Ring-Opening Polymerizatio (Andrzej Duda and Adam Kowalski).

1.1 Introduction.

1.2 Thermodynamics of the Ring-Opening Polymerization.

1.2.1 Equilibrium Monomer Concentration: Ceiling/Floor Temperatures.

1.2.2 Selected Particular Cases.

1.2.2.1 Polymerization in Heterogeneous Systems.

1.2.2.2 Monomer–Polymer–Solvent Interactions.

1.2.2.3 Thermodynamics of Oligomerization.

1.2.3 Thermodynamics of Macrocyclization.

1.2.4 Equilibrium Copolymerization.

1.2.5 Molar Mass Distribution in the Equilibrium Polymerization.

1.3 Kinetics of Ring-Opening Polymerization.

1.3.1 Thermodynamic and Kinetic Polymerizability.

1.3.2 Kinetics of Living Polymerization.

1.3.2.1 Kinetic Criteria of Living Polymerization.

1.3.2.2 Active Center Interconversions and the Determination of Absolute Rate Constants.

1.3.2.3 Departure from Livingness: Kinetics of Selected Side Reactions.

1.3.2.4 Kinetics of Copolymerization.

1.4 Concluding Remarks.

References.

2 General Mechanisms in Ring-Opening Polymerization (Takeshi Endo).

2.1 Introduction.

2.2 Anionic Ring-Opening Polymerization.

2.2.1 General Mechanism.

2.2.2 Activated Monomer Mechanism.

2.3 Cationic Ring-Opening Polymerization.

2.3.1 General Mechanism.

2.3.2 Activated Monomer Mechanism.

2.3.3 Isomerization Polymerization.

2.4 Radical Ring-Opening Polymerization.

2.5 Summary and Prospects.

References.

3 Siloxane-Containing Polymers (François Ganachaud and Sylvie Boileau).

3.1 Introduction.

3.2 Polydimethylsiloxanes.

3.2.1 Anionic Polymerization.

3.2.1.1 General Considerations.

3.2.1.2 Recent Advances.

3.2.2 Cationic Polymerization.

3.2.2.1 General Considerations.

3.2.2.2 Recent Advances.

3.2.3 Emulsion Polymerization.

3.2.3.1 General Considerations.

3.2.3.2 Recent Advances.

3.2.4 Other Processes.

3.3 Functional Silicones.

3.3.1 Anionic Polymerization.

3.3.1.1 Homopolymerization of Symmetrical Cyclosiloxanes.

3.3.1.2 Homopolymerization of Asymmetrical Cyclosiloxanes.

3.3.1.3 Copolymerization.

3.3.2 Cationic Polymerization.

3.3.2.1 Homopolymerization of Symmetrical Cyclosiloxanes.

3.3.2.2 Homopolymerization of Asymmetrical Cyclosiloxanes.

3.3.2.3 Copolymerization.

3.3.3 Emulsion Polymerization.

3.4 Polycarbosiloxanes.

3.4.1 Five-Atom Rings.

3.4.2 Larger Cyclocarbosiloxanes.

3.5 Summary and Prospects.

Acknowledgments.

References.

4 Sulfur–Nitrogen–Phosphorus-Containing Polymers (Frederick F. Stewart and Eric S. Peterson).

4.1 Introduction.

4.2 Mechanism and Methods in Ring-Opening Polymerization (ROP) of Halogenated Cyclotriphosphazenes.

4.3 Ring-Opening Polymerization and Chemistry of Nonhalogenated Phosphazene Rings.

4.4 Incorporation of Sulfur into Phosphazene Ring Systems, and Their Polymerization Chemistry.

4.4.1 Thiophosphazenes.

4.4.2 Thionylphosphazenes.

4.5 Summary and Prospects.

Acknowledgments.

References.

5 Polymerization of Cyclic Depsipeptides, Ureas and Urethanes(Pieter J. Dijkstra).

5.1 Introduction.

5.2 Polydepsipeptides.

5.3 Monomers.

5.4 Ring-Opening Polymerization.

5.5 Enzymatic Polymerization.

5.6 Ring Expansion.

5.7 Polyureas.

5.8 Polyurethanes.

5.9 Summary and Prospects.

References.

6 Polyethers and Polyoxazolines (Richard Hoogenboom).

6.1 Introduction.

6.2 Polyethers.

6.2.1 Poly(ethylene Oxide).

6.2.2 Poly(oxetane).

6.2.3 Poly(tetrahydrofuran).

6.3 Polyoxazolines.

6.4 Summary and Prospects.

Acknowledgments.

References.

7 Polyamides (Jan Roda).

7.1 Introduction.

7.2 Mechanism of the Anionic Polymerization of Lactams.

7.3 Initiators for the Anionic Polymerization of Lactams.

7.4 Activators for Anionic Polymerization of Lactams.

7.4.1 N-Acyllactams.

7.4.2 N-Carbamoyllactams.

7.4.3 Special Activators.

7.5 Nonactivated Polymerization.

7.6 Cyclic Oligomers of å-Caprolactam

7.7 Block Copolymers of Lactams.

7.8 Anionic Copolymerization of å-Caprolactam with ù-Laurolactam.

7.9 Copolymerization of Lactams with Lactones (å-Caprolactone).

7.10 Powdered Polyamide.

7.11 Nanocomposites.

7.12 Anionic Polymerization of 2-Pyrrolidone.

7.13 Summary and Prospects.

Acknowledgments.

References.

8 Ring-Opening Metathesis Polymerization (Michael R. Buchmeiser).

8.1 General Introduction.

8.2 Introduction to Ring-Opening Metathesis Polymerization (ROMP).

8.3 Well-Defi ned Catalysts for ROMP.

8.3.1 Schrock-Type Initiators.

8.3.2 Grubbs-Type Initiators.

8.4 ‘Living’ ROMP.

8.4.1 ROMP with Schrock Initiators.

8.4.2 ROMP with Grubbs-Type Initiators.

8.5 Selected Recent Applications and Developments.

8.5.1 Novel Catalysts for ROMP.

8.5.2 ROMP of High and Low Ring-Strain Monomers.

8.5.3 Stereoselective and Regioselective ROMP.

8.5.4 Mechanistic Investigations.

8.5.5 Alternating Copolymerizations.

8.5.6 Changes in Polymerization Mechanism.

8.5.7 Materials Science.

8.5.8 ROMP in Water and in Ionic Liquids.

8.5.9 Computational Studies.

8.6 Summary and Prospects.

References.

9 Polyesters from β-Lactones (Olivier Coulembier and Philippe Dubois).

9.1 Introduction.

9.2 â-Lactones Preparation.

9.3 Ionic Polymerization.

9.3.1 Anionic Processes.

9.3.2 Carbocationic Process.

9.4 Coordination Process.

9.5 Carbene-Based Polymerization.

9.6 Enzymatic Polymerization.

9.7 Illustrative Experimental Section.

9.7.1 Anionic Ring-Opening Polymerization of Benzyl â-Malolactonate.

9.7.2 Synthesis of Poly([R,S]-â-Butyrolactone), á-Methoxy, ù-Carboxylic Acid from Commercially Available 5-Methoxy-1,3,4-Triphenyl-4,5- Dihydro-1H-1,2-Triazol-5-Ylidene Carbene.

References.

10 Polyesters from Dilactones (Odile Dechy-Cabaret, Blanca Martin-Vaca, and Didier Bourissou).

10.1 Introduction.

10.2 General Concepts and ROP Promoted by Metallic Catalysts/Initiators.

10.2.1 O-Donor Ligands.

10.2.2 N-Donor Ligands.

10.2.3 N,O-Donor Ligands.

10.3 Recent Advances in ROP.

10.3.1 Metal-Free ROP.

10.3.1.1 Nucleophilic/Basic Catalysts.

10.3.1.2 Cationic Polymerization.

10.3.1.3 Bifunctional Catalysts.

10.3.2 Stereocontrolled ROP.

10.3.2.1 rac-Lactide.

10.3.2.2 meso-Lactide.

10.4 Macromolecular Engineering.

10.4.1 ‘Modifi ed’ PLGAs: Alternative Monomers to Lactide and Glycolide.

10.4.2 Macromolecular Architectures.

10.4.2.1 Linear Block Copolymers.

10.4.2.2 Grafted Block Copolymers.

10.4.2.3 Star and Dendritic Polymers.

10.5 Applications.

10.6 Summary and Prospects.

Acknowledgments.

References.

11 Polyesters from Large Lactones (Ann-Christine Albertsson, Indra K. Varma, and Rajiv K. Srivastava).

11.1 Introduction.

11.2 Controlled Synthesis of Linear Polyesters.

11.2.1 Nonenzymatic Methods of Polymerization.

11.2.2 Enzymatic Methods of Polymerization.

11.2.2.1 The Mechanism of Enzyme-Catalyzed ROP.

11.2.3 Copolyesters.

11.2.4 Functionalized Polyesters.

11.2.5 Chemospecifi c Polymerization.

11.2.6 Enantioselective Polymerization.

11.3 Physical Properties of Polymers.

11.4 Summary and Prospects.

References.

12 Polycarbonates (Helmut Keul).

12.1 Introduction.

12.2 Polymerization of Cyclic Carbonates: Homopolymers and Block Copolymers.

12.2.1 Initiation.

12.2.1.1 Alkali Metal-Based and Metal-Free Initiators.

12.2.1.2 Initiators for a Coordination–Insertion Mechanism.

12.2.2 Chain Propagation.

12.2.2.1 Alkali Metal Alcoholate and Phenolate Active Sites.

12.2.2.2 Metal-Free Active Sites: Site Transformation from Group Transfer Polymerization to Anionic Metal-Free Polymerization.

12.2.2.3 Magnesium, Aluminum and Zinc Alcoholate Active Sites.

12.2.3 Monomers and Homopolymers.

12.2.4 Block Copolymers Comprising a Polycarbonate Block.

12.2.5 Copolymerization of Cyclic Carbonates with Lactones.

12.3 Summary and Prospects.

References.

13 Polymerization of Cycloalkanes (Jacques Penelle).

13.1 Introduction.

13.2 General Overview and Thermodynamic Requirements.

13.3 Structure–Reactivity Relationships Based on a Comprehensive Survey of the Current Literature.

13.3.1 The Polymerization of Monocyclic Alkanes.

13.3.1.1 Cyclopropane Rings.

13.3.1.2 Cyclobutane Rings.

13.3.2 The Polymerization of Polycyclic Rings.

13.3.3 Unusual Examples.

13.4 Summary and Prospects.

References.

14 Metal-Free Catalysis in Ring-Opening Polymerization (Andrew P. Dove).

14.1 Introduction.

14.2 Nucleophilic ROP.

14.2.1 Tertiary Amines and Phosphines.

14.2.2 N-Heterocyclic Carbenes.

14.2.3 Supramolecular Activation.

14.2.4 Other Nucleophilic ROP Catalysts.

14.3 Metal-Free Ionic ROP.

14.3.1 Cationic.

14.3.2 Anionic.

14.4 Summary and Prospects.

References.

15 Enzyme-Mediated Ring-Opening Polymerization (Andreas Heise, Christopher J. Duxbury, and Anja R. A. Palmans).

15.1 Introduction.

15.2 Characteristics of Enzymatic ROP.

15.3 Classes of Monomer.

15.3.1 Lactones.

15.3.1.1 Substituted Lactones.

15.3.2 Lactides/Glycolide/Depsipeptides and Cyclic Diesters.

15.3.3 Cyclic Carbonates and Cyclic Phosphates.

15.4 Polymer Architectures Employing Enzymatic ROP.

15.4.1 Block Copolymers.

15.4.2 Graft Copolymers.

15.4.3 Branched and Crosslinked Polymers.

15.5 Summary and Prospects.

References.

Index.