Advanced and Emerging Polybenzoxazine Science and Technology

Dedication

Preface

Part I: Synthesis and Properties of Benzoxazine Resins

• Chapter 1: Various Synthetic Methods of Benzoxazine Monomers
  • Abstract
  • 1 Introduction
  • 2 Various Synthetic Methods Used for Benzoxazine Synthesis
  • 3 Conclusion
• Chapter 2: Catalytic Accelerated Polymerization of Benzoxazines and Their Mechanistic Considerations
  • Abstract
  • 1 Introduction
  • 2 Benzoxazine Polymerization Mechanism Consideration
  • 3 Catalysts for Accelerated Benzoxazine Polymerization
  • 4 Catalyst Effects on Polymerization Mechanism and Network Structures
  • 5 Conclusion
• Chapter 3: Molecular Designs of Benzoxazines With Enhanced Reactivity Based on Utilization of Neighboring-Group Participation and Introduction of Thioether Moiety
  • Abstract
  • 1 Introduction
  • 2 Benzoxazines Activated by Neighboring-Group Participation
  • 3 Benzoxazines Activated by a Thioether Group
  • 4 Conclusion
  • 5 Experimental
• Chapter 4: Development of New Generation Benzoxazine Thermosets Based on Smart Ortho-Benzoxazine Chemistry
  • Abstract
  • 1 Introduction
  • 2 Anomalous Isomeric Effects on the Properties of Bisphenol F-Based Benzoxazines
  • 3 Benzoxazole Resin: A Novel Class of Thermoset via Smart Ortho-Benzoxazine Chemistry
  • 4 An Ultrahigh Performance Crosslinked PBO via Thermal Conversion From Main-Chain Type Poly(Benzoxazine Amic Acid)
  • 5 Thermally Stable Polybenzoxazine via Ortho-Norbornene Functional Benzoxazine Monomers
  • 6 Molecular Understanding of the Unexpected Properties of Ortho-Functional Benzoxazine Resins
  • 7 Conclusion
• Chapter 5: Tailoring Polybenzoxazine Chemical Structure: Synthetic Approaches to Flexible Systems
  • Abstract
  • 1 Introduction
  • 2 Benzoxazine Monomers Containing Flexible Segments
  • 3 Benzoxazine Oligomers and Polymers Containing Flexible Spacers
  • 4 Conclusion
• Chapter 6: 3,4-Dihydro-1,3-2H-Benzoxazines: Uses Other Than Making Polybenzoxazines
  • Abstract
  • 1 Introduction
  • 2 Novel Luminescent Properties
  • 3 Novel Ligands for Metal Ions
  • 4 Nanoceria From Cerium-Benzoxazine Complexes
  • 5 Novel Reducing Agents Through One Electron-Donation Mechanism
  • 6 Nanometallic Silver-Coating Application
  • 7 Conclusion
• Chapter 7: Symmetric Versus Asymmetric di-Bz Monomer Design: Structure-to-Properties Relationship
  • Abstract
  • 1 Introduction
  • 2 State of the Art of Symmetric di-Bz Monomers
  • 3 Asymmetric Benzoxazines
  • 4 Conclusion

Part II: Physical and Chemical Properties of Cross-linked Polybenzoxazines

• Chapter 8: Modern Developments Using Molecular Simulation to Predict the Physical and Mechanical Properties of Polybenzoxazines
  • Abstract
  • Acknowledgments
  • 1 Introduction: The Rationale for Using Molecular Simulation
  • 2 The Methodology for Building a Realistic Structure for MM and MD Simulations
  • 3 Calculation of Physical and Mechanical Properties for Polybenzoxazines using MM Techniques
  • 4 Using MM Techniques to Examine the Influence of Hydrogen bonding in the Benzoxazine Structure
  • 5 The Methodology of MD Simulations
  • 6 Comparison of Mechanical Properties
  • 7 Calculation of Physical Properties for Oligomeric and Telechelic Polybenzoxazines using MD Techniques
  • 8 Conclusions
  • 9 Materials and Methods
• Chapter 9: Predictive Methodology and Properties of Polybenzoxazines
  • Abstract
  • Acknowledgments
  • 1 Introduction
  • 2 Basis of QSPR
  • 3 Current Applications of QSPR
  • 4 Glass Transition Temperature of Polybenzoxazines
  • 5 Char Yield
  • 6 Conclusions
• Chapter 10: Properties Enhancement Obtained in Anhydride-Modified Polybenzoxazines: Effects of Ester Functional Group on Polybenzoxazine Network
  • Abstract
  • Acknowledgments
  • 1 Introduction
  • 2 Aromatic Ester and Amide Linkage Formation in Polybenzoxazine Alloyed With Poly(Amic Acid)
  • 3 Anhydride-Modified Polybenzoxazine: An Introduction of Ester Linkages in Polybenzoxazine Network [26]
  • 4 Investigation of Types of Dianhydrides on Properties of Dianhydride-Modified Polybenzoxazine [27]
  • 5 Effects of Monoanhydrides and Dianhydrides on Properties of Polybenzoxazine [31]
  • 6 Enhanced Fire Resistance and Thermomechanical Properties Obtained in Dianhydride-Modified Polybenzoxazine Reinforced With Carbon Fiber [30]
  • 7 Future Work
  • 8 Conclusions
• Chapter 11: Thermal Degradation Mechanism of Polybenzoxazines
  • Abstract
  • Acknowledgments
  • 1 Introduction
  • 2 Thermal Degradation of Benzoxazine Models
  • 3 Thermal Degradation Mechanism of Polybenzoxazine Homopolymers
  • 4 Thermal Degradation Mechanism of Polybenzoxazines With Functional Groups
  • 5 Thermal Degradation Mechanism of Blends Based on Polybenzoxazines
  • 6 Conclusions
• Chapter 12: Mediated Surface Properties of Polybenzoxazines
  • Abstract
  • 1 Introduction
  • 2 Surface Properties of Polybenzoxazines
  • 3 Conclusions

Part III: Application of Advanced Organic Synthesis for Benzoxazine Resins

• Chapter 13: Thiol-Benzoxazine Chemistry for Macromolecular Modifications
  • Abstract
  • 1 Introduction
  • 2 Thiol-Benzoxazine Reaction in Polymer Synthesis and Modification
  • 3 Conclusion
• Chapter 14: Boron-Containing Benzoxazine Resin
  • Abstract
  • 1 Introduction
  • 2 Benzoxazine Resin Synthesized with Boric Acid
  • 3 Inorganic Boron Compound-Modified Benzoxazine
  • 4 Benzoxazine Resin Synthesized with Icosahedral Carborane
  • 5 Hyperbranched Boron Compounds Modified Benzoxazine Resin
  • 6 Conclusion
• Chapter 15: Structures of Metal-Complex Polybenzoxazines and Effect of Metal Ions on the Polymerization, Degradation, and Catalysis
  • Abstract
  • 1 Introduction
  • 2 Structures of the Fourth Period Transition Metal-Complex Polybenzoxazine and the Effect of Transition Metal Ions on Benzoxazine
  • 3 Structures of the Rare-Earth Transition Metal-Complex Polybenzoxazine and Effect of Transition Metal Ions on Benzoxazine
  • 4 Other Methods for the Preparation of Transition Metal-Complex Polybenzoxazine
  • 5 Conclusion
• Chapter 16: Development of Phosphorus-Containing Polybenzoxazines
  • Abstract
  • 1 Introduction
  • 2 Preparation Strategy
  • 3 Conclusions

Part IV: Polybenzoxazine Blends and Alloys

• Chapter 17: Benzoxazine/Cyanate Ester Alloys
  • Abstract
  • 1 Introduction
  • 2 Results and Discussion
  • 3 Conclusions
• Chapter 18: Polybenzoxazine/Bismaleimide Alloys
  • Abstract
  • 1 Introduction
  • 2 Benzoxazine/Bismaleimide Binary Alloys
  • 3 X-Functional Benzoxazine/Bismaleimide Binary Alloys
  • 4 Benzoxazine/Bismaleimide/Other Resin Tertiary Alloys
  • 5 Conclusions
• Chapter 19: Arylacetylene-Derived Resins and Functional Benzoxazines
  • Abstract
  • Acknowledgments
  • 1 Introduction
  • 2 Preparation of the Resin Blends
  • 3 Processability of Arylacetylene-Derived Resin/Benzoxazine Blends
  • 4 Curing Reaction of Benzoxazines, PSA, and Their Blends
  • 5 Thermal and Mechanical Properties of the Cured Blends
  • 6 Application of the Blends
  • 7 Conclusions
• Chapter 20: Polybenzoxazines Derived from Nitrile- and Phthalonitrile-Functional Benzoxazines and Copolymers from Benzoxazine/Phthalonitrile Resin Mixtures
  • Abstract
  • 1 Introduction
  • 2 Phenylnitrile-Functional Benzoxazine
  • 3 Phthalonitrile-Functional Benzoxazine
  • 4 Polybenzoxazine/Phthalonitrile Copolymers
  • 5 Potential Applications of Benzoxazine/Phthalonitrile Copolymers
• Chapter 21: Fluorene-Based High Molecular Weight Benzoxazine Blends
  • Abstract
  • Acknowledgments
  • 1 Introduction
  • 2 Structures and Properties of High Molecular Weight Benzoxazine Precursors
  • 3 Synthesis and Properties of Fluorene-Based Oxazine Monomers and High Molecular Weight Precursors
  • 4 Blends of Fluorene-Based High Molecular Weight Benzoxazine Precursors With Benzoxazine Monomer
  • 5 Conclusions
• Chapter 22: Polybenzoxazine/Organosiloxane
  • Abstract
  • 1 Introduction
  • 2 The Methods for the Preparation of Polybenzoxazine/Polysiloxane
  • 3 Properties of the Polybenzoxazine/Polysiloxane
  • 4 Conclusion

Part V: Biobased Polybenzoxazine Materials

• Chapter 23: Polybenzoxazine Materials From Renewable Diphenolic Acid
  • Abstract
  • 1 Introduction
  • 2 Synthesis and Characterization of DPA-Based Benzoxazine
  • 3 Curing Behavior of DPA-Based Benzoxazines
  • 4 Thermosetting Resins From MDP-a
  • 5 MDP-a Thermosetting Resins With Enhanced Flame Retardancy
  • 6 MDP-a Multi-Walled Carbon Nanotube (MWNT) Nanocomposites
  • 7 Foam Thermosets From DPA-a
  • 8 Conclusions
• Chapter 24: Cardanol-Based Benzoxazines and Their Applications
  • Abstract
  • Acknowledgments
  • 1 Introduction
  • 2 Approaches for the Preparation of Cardanol-Based Benzoxazine Monomers
  • 3 Characterization of Cardanol-Based Benzoxazine Monomers
  • 4 Composites of Cardanol-Based Benzoxazines
  • 5 Conclusions
• Chapter 25: Lignin-Based Phenols: Potential Feedstock for Renewable Benzoxazines
  • Abstract
  • Acknowledgments
  • 1 Introduction
  • 2 Vanillin
  • 3 Guaiacol
  • 4 p-Hydroxycinnamic Acid Derivatives
  • 5 p-Hydroxybenzoic Acid
  • 6 Eugenol
  • 7 Fillers for Reinforcement of Renewable Benzoxazines
  • 8 Conclusions
• Chapter 26: Chitin- and Shell-Based Benzoxazines
  • Abstract
  • Acknowledgments
  • 1 Introduction
  • 2 CT- and CTS-Based Benzoxazine Blends
  • 3 Crab- and Shell-Based Benzoxazine Composites
  • 4 Conclusions
• Chapter 27: Eugenol-Based Polybenzoxazines
  • Abstract
  • 1 Introduction
  • 2 Plant Derived Phenolics, Amines, and Paraformaldehyde as Precursors for Benzoxazine Synthesis
  • 3 Eugenol-Based Benzoxazine Monomers and Their Polymers
  • 4 Copolymers of Eugenol-Based Benzoxazines
  • 5 Bio-Based Composites of Polybenzoxazines
  • 6 Conclusions
• Chapter 28: Furan-Based Benzoxazines
  • Abstract
  • Acknowledgments
  • 1 Introduction
  • 2 Experimental
  • 3 Results and Discussion
  • 4 Conclusions

Part VI: Morphological Control of Polybenzoxazines

• Chapter 29: Reaction-Induced Phase Separation of Benzoxazine Blends
  • Abstract
  • 1 Introduction
  • 2 Benzoxazine/Poly(Ethylene Oxide) Blends
  • 3 Benzoxazine/Polycaprolactone Blends
  • 4 Benzoxazine/PSU (PES) Blends
  • 5 Benzoxazine/Polyimide Blend
  • 6 Benzoxazine/Bismaleimide Blends
  • 7 Benzoxazine/Epoxy Blends
  • 8 Benzoxazine/Cyanate Ester Blends
  • 9 Conclusion
• Chapter 30: Precision Thermoset-Spherical Nano- and Microparticles Formation in Nanoconfinement: A Model Case From Benzoxazine Polymerization in the Blend System With Aromatic Containing Thermoplastic Resin
  • Abstract
  • 1 Introduction
  • 2 Result and Discussion
  • 3 Conclusions
• Chapter 31: Polybenzoxazine for Hierarchical Nanoporous Materials
  • Abstract
  • 1 Introduction
  • 2 Sol–Gel-Derived Hierarchically Nanoporous Carbon Prepared From Polybenzoxazine
  • 3 Hierarchically Ordered Nanoporous Carbon Prepared From Polybenzoxazine via Soft-Template Route
  • 4 Hierarchically Ordered Nanoporous Carbon Prepared From Polybenzoxazine via Hard-Template Route
  • 5 Conclusions
• Chapter 32: Nanostructured Carbons and Related Materials Derived From Polybenzoxazine-Based Polymers
  • Abstract
  • 1 Introduction
  • 2 Morphology-Controllable Polybenzoxazines and Their Derived Carbons
  • 3 Heteroatom–Doped Porous Carbons Derived From Polybenzoxazines
  • 4 Conclusion and Perspective
• Chapter 33: Polybenzoxazine-Based Nanofibers by Electrospinning
  • Abstract
  • Acknowledgments
  • 1 Introduction
  • 2 Surface Modification of Nanofibrous Membranes by In Situ Polymerization of Benzoxazines
  • 3 Polybenzoxazine/Polymer Composite Nanofibers
  • 4 Polybenzoxazine-Based MCNFs
  • 5 MCPBz Nanofibers
  • 6 Summary
• Chapter 34: HCl-Catalyzed Polymerization of Benzoxazine and Chemical Transformations Along Pyrolysis to Microporous Carbons
  • Abstract
  • Acknowledgments
  • 1 Introduction
  • 2 HCl-Catalyzed Synthesis of poly(BA-a) Aerogels and Their Carbonization
  • 3 Chemical Characterization Along Polymerization, Curing, and Carbonization
  • 4 Material Properties of Poly(BA-a) Aerogels and Their Carbons
  • 5 Specific Applications of Poly(BA-a) Emerging From the H⁺-Catalyzed Synthesis and From the Microporosity of the Resulting Carbons
  • 6 Summary

Part VII: Polybenzoxazine Composites, Hybrid Materials, and Nanocomposites

• Chapter 35: Hard Armor Composites From Ballistic Fiber-Reinforced Polybenzoxazine Alloys
  • Abstract
  • Acknowledgments
  • 1 Introduction
  • 2 Standard Test Method for Ballistic Armor
  • 3 Soft Ballistic Protective Materials
  • 4 Hard Ballistic Protective Materials
  • 5 Ballistic Impact Behaviors of Aramid Fiber-Reinforced Polybenzoxazine/Polyurethane Composites and Their Characterizations
  • 6 Computer Simulation of Ballistic Impact in Composite Materials
  • 7 Future Work
  • 8 Conclusions
• Chapter 36: Polybenzoxazine/Carbon Nanotube Composites
  • Abstract
  • 1 Introduction
  • 2 Characterization of Modified MWCNT and SWCNT Through Covalent Interaction
  • 3 Preparation of Polybenzoxazine-CNT Nanocomposites Through Covalent Interaction
  • 4 Properties of Polybenzoxazine-CNT Nanocomposites Through Covalent Interaction
  • 5 Preparation of Polybenzoxazine-CNT Through Noncovalent Interaction
  • 6 Conclusion
• Chapter 37: Recent Progress in Polybenzoxazine/POSS Hybrid Materials
  • Abstract
  • Acknowledgments
  • 1 Introduction
  • 2 POSS Precursors Used in Polybenzoxazine/POSS Hybrid Materials
  • 3 Types of Polybenzoxazine/POSS Hybrid Materials
  • 4 PBZ/POSS Hybrid Materials for Different Purpose
  • 5 Summary and Perspective
• Chapter 38: Polybenzoxazine Nanocomposites: Case Study of Carbon Nanotubes
  • Abstract
  • 1 Introduction
  • 2 Polybenzoxazine/CNT Nanocomposites
  • 3 General Conclusions
• Chapter 39: Polybenzoxazine-Based Organic-Inorganic Nanohybrid Materials for High Performance Engineering Applications
  • Abstract
  • Acknowledgment
  • 1 Introduction
  • 2 Synthesis of Monomers
  • 3 Synthesis of Reinforcements
  • 4 Preparation of Polybenzoxazine Matrices and Nanocomposites
  • 5 Results and Discussion
  • 6 Conclusion
• Chapter 40: Polybenzoxazine-Clay Nanocomposites
  • Abstract
  • Acknowledgments
  • 1 Introduction
  • 2 Organophilization Process of Clay
  • 3 Methods for Preparation of Polybenzoxazine-Clay (Cationic and Anionic) Nanocomposites
  • 4 Characterization of Polybenzoxazine-Clay Nanocomposites
  • 5 Conclusions
• Chapter 41: Ceramic-Based Polybenzoxazine Micro- and Nanocomposites
  • Abstract
  • Acknowledgments
  • 1 Introduction
  • 2 Properties of Ceramic Fillers
  • 3 Preparation and Properties of Ceramic-Based Polybenzoxazine Composites
  • 4 Conclusion
• Chapter 42: Preparation of Mechanically Flexible Composites Composed of Polybenzoxazine—Linear Low-Density Polyethylene—Fumed Silica and Study of Their Properties
  • Abstract
  • 1 Introduction
  • 2 Experimental Methods
  • 3 Results and Discussion
  • 4 Conclusion

Part VIII: Polybenzoxazine Applications and Potential Applications

• Chapter 43: Benzoxazines in Proton Exchange Membrane Fuel Cells
  • Abstract
  • 1 Introduction
  • 2 Benzoxazines in Proton Exchange Membranes for Fuel Cells
  • 3 Benzoxazine-Based Polymers in Bipolar Plates for Fuel Cells
  • 4 Conclusion
• Chapter 44: Polybenzoxazine-Based Self-Lubricating and Friction Materials
  • Abstract
  • Acknowledgments
  • 1 Introduction
  • 2 Tribosystem: COF and Wear Rate
  • 3 Tribology of Polymers [5,36,39,40]
  • 4 Polybenzoxazine-Based Copolymers and Composites: COF and Specific Wear Rate
  • 5 Multi Filler-Reinforced Polybenzoxazine Composites: Self-Lubricating Phenomenon
  • 6 Polybenzoxazine-Based Composites: Automotive friction Materials
  • 7 Conclusions
• Chapter 45: Hybrid Polybenzoxazine Nanocomposites for Low-k Dielectrics
  • Abstract
  • Acknowledgment
  • 1 Introduction
  • 2 Experimental
  • 3 Curing Behavior of Benzoxazine From DSC Analysis
  • 4 Structural Behavior of Polybenzoxazine Hybrid Nanocomposites
  • 5 Analysis of Chemical Composition and Chemical Bonds of GO and GO-BPZ-PBz
  • 6 Analysis of GO Reinforced BPZ-PBz Composites by Raman Spectral Data
  • 7 Morphological Properties of Hybrid Polybenzoxazine Nanocomposites
  • 8 Thermal Properties of Polybenzoxazine and Hybrid Polybenzoxazine Nanocomposites
  • 9 Dielectric Properties of Polybenzoxazine Nanocomposites
  • 10 Conclusions
• Chapter 46: Polybenzoxazine-Based Coatings for Corrosion Protection
  • Abstract
  • Acknowledgments
  • 1 Introduction
  • 2 Corrosion Protection: Mechanism and Characterization
  • 3 Corrosion Resistance of Polybenzoxazines
  • 4 Summary and Future Direction
• Chapter 47: Polybenzoxazines as Self-Healing Materials
  • Abstract
  • 1 Introduction
  • 2 Principles of Self-Healing Materials
  • 3 Polybenzoxazine-Based Self-Healing Materials
  • 4 Conclusion
• Chapter 48: Shape Memory Polymers From Polybenzoxazine-Modified Polymers
  • Abstract
  • Acknowledgments
  • 1 Introduction
  • 2 Brief Overview of SMPs
  • 3 Parameters Relevant to SMP Characterizations
  • 4 Classification of SMPs
  • 5 SMPs From Polybenzoxazine-Modified Polymers
  • 6 Examples of Applications and Commercial Products
  • 7 Future Trends of SMP Research
  • 8 Conclusions

Part IX: Benzoxazine Resin Preparation and Spectra

• Chapter 49: Preparation of High Purity Samples, Effect of Purity on Properties, and FT-IR, Raman, ¹H and ¹³C NMR, and DSC Data of Highly Purified Benzoxazine Monomers
  • Abstract
  • 1 Introduction
  • 2 Experimental
  • 3 Synthesis of a Benzoxazine Resin That Contains Intramolecular Hydrogen Bond Using Typical Mannich Condensation
  • 4 Examples of Large Single Crystal Preparation of 6,6′-(Propane-2,2-diyl)bis(3-Phenyl-3,4-Dihydro-2H-Benzo[e][1,3]oxazine) (BA-a)
  • 5 FT-IR, Raman, ¹H and ¹³C NMR, DSC Data of Highly Purified Benzoxazine Monomers

Index