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Table of Contents

Cover image

Front matter

Copyright

Contributors

Preface

Chapter 1. Overview and Historical Background of Polybenzoxazine Research

1. Introduction

2. Benzoxazine chemistry

3. Polymerization mechanisms

4. Unique properties of benzoxazines and polybenzoxazines

5. Molecular origin of unusual properties

6. Historical development of monomeric benzoxazines

7. Recent development of high molecular weight benzoxazines

8. Benzoxazines combined with other polymerizing groups

9. Various technologies attractive for applications

10. Characterization of benzoxazines

11. Conclusion

Chapter 2. Benzoxazine Chemistry in Solution and Melt

1. Synthesis of benzoxazine monomers in homogeneous solution

2. Synthesis of benzoxazine monomers in heterogeneous solution

3. Synthesis of benzoxazine monomers by melt or high solid methods

4. Benzoxazine ring formation mechanism

5. Conclusion

Chapter 3. Molecular Modeling

1. Introduction

2. Chemical reaction

3. Structure analysis

4. Structure-property relationship

5. Summary and remarks

Chapter 4. Mono-Substituted Phenol-Based Benzoxazines

1. Chemistry and development of benzoxazines

2. Ring opening reaction of mono-substituted phenol-based benzoxazines: dimerization of benzoxazines and its self-termination

3. Single crystallography of monofunctional benzoxazine dimer

4. Asymmetric reaction of monofunctional benzoxazine dimer

5. Benzoxazine dimer and its metal ion complexation

6. Conclusions

Chapter 5. Using Molecular Simulation to Predict the Physical and Mechanical Properties of Polybenzoxazines

1. Introduction

2. Materials and methods

3. Results and discussion

4. Conclusions

Chapter 6. Chemorheology of Benzoxazine-based Resins

1. Introduction

2. Chemorheology of benzoxazine-based resins

3. Gelation of benzoxazine-based resins investigated by FTMS

4. Conclusion

Chapter 7. Polymerization Kinetics

1. Introduction

2. Kinetic analysis of resin polymerization reaction

3. Conclusions

Chapter 8. Electrochemical Polymerization of Benzoxazines

1. Introduction

2. Experimental

3. Electrochemical polymerization of benzoxazines

4. Conclusions

Chapter 9. Light-Induced Reactions of Benzoxazines and Derivatives

1. Introduction

2. Free radical systems

3. Cationic systems

4. Photodimerization

5. UV stability of benzoxazine resins

6. Conclusion

Chapter 10. Effect of Neighboring Groups on Enhancing Benzoxazine Autocatalytic Polymerization

1. Introduction

2. Polymerization mechanism of benzoxazine monomers

3. Substituted benzoxazine monomers

4. Carboxylic acid functional benzoxazine monomers

5. Hydroxyl-functional benzoxazine monomers

6. Conclusion

Chapter 11. Catalytic Opening of Lateral Benzoxazine Rings by Thiols

1. Introduction

2. Experimental

3. Results and discussion

4. Proposed colbert reaction mechanism

5. Linear aromatic polymers

6. Conclusion

Chapter 12. Hydrogen Bonding of Polybenzoxazines

1. Introduction

2. Structure of hydrogen bonding

3. Conclusion

Chapter 13. Thermal Properties Enhancement of Polybenzoxazines

1. Introduction

2. Polymerization of benzoxazine monomers

3. Polybenzoxazine thermal stability

4. Additional cross-linking sites in benzoxazine structure

5. Alkyne functional benzoxazine

6. Alkene-functional benzoxazine

7. Nitrile-functional benzoxazine monomers

8. Maleimide-functional benzoxazine monomers

9. Epoxy functional benzoxazine

10. Methacrylate-functional benzoxazine

11. Conclusion

Chapter 14. Thermal Degradation Mechanisms of Polybenzoxazines

1. Introduction

2. Thermal characteristics of polybenzoxazines

3. Conclusions

Chapter 15. Various Approaches for Main-Chain Type Benzoxazine Polymers

1. Introduction

2. Polymeric mannich base condensation

3. Polymers with mannich condensation of ab-type

4. Chain extension through reactive benzoxazine monomers

5. Conclusion

Chapter 16. Side- and End-Chain Benzoxazine Functional Polymers

1. Introduction

2. Side-chain benzoxazine functional polymers

3. Benzoxazine telechelics

4. Conclusions

Chapter 17. Supramolecular Chemistry of Benzoxazines

1. Concept of supramolecules

2. Resembled structure of benzoxazine and calixarenes

3. Supramolecular structures of benzoxazine dimers

4. Molecular designs and syntheses of benzoxazine dimer-based macrocycles

5. Benzoxazine dimer-based macrocycles

6. Inclusion phenomena of macrocyclic compounds

7. Conclusions

Chapter 18. Main-Chain Type Benzoxazine Oligomers

1. Introduction

2. Synthesis of bisphenol F-Based MCBOs

3. Polymerization behavior of MCBOs

4. Thermal stability of cross-linked MCBOs

5. Viscoelastic properties of MCBOs

6. Viscosity study of MCBOs

7. Conclusions

Chapter 19. Study of a Cardanol-Based Benzoxazine as Reactive Diluent and Toughening Agent of Conventional Benzoxazines

1. Introduction

2. Experimental

3. Results and discussion

4. Conclusion

Chapter 20. Polybenzoxazine/Polyimide Alloys

1. Introduction

2. Polybenzoxazine/pi alloy

3. Effect of preparation method on the properties of poly(ba-a)/pi alloy [17]

4. Polybenzoxazine-poly(imide-siloxane) alloys [19]

5. Conclusions

Chapter 21. Polybenzoxazine/Polyurethane Alloys

1. Introduction

2. Different approaches for the preparation of polybenzoxazine/Polyurethane alloys

3. Conclusion

Chapter 22. The Blends of a Silicon-Containing Arylacetylene Resin and an Acetylene-Functional Benzoxazine

1. Introduction

2. Experimental

3. Properties of blend resins

4. Properties of fiber-reinforced blend resin composites

5. Conclusion

Chapter 23. Polybenzoxazine/Polysiloxane Hybrids

1. Introduction

2. Polybenzoxazine-PDMS hybrid [22]

3. Hybridization with polysiloxanes having a phenyl group as the pendant [23]

4. Polybenzoxazine-poly(dimethylsiloxane-co-diphenylsiloxane) hybrids [24]

5. High-molecular-weight polybenzoxazine prepolymers containing polysiloxane

6. Conclusions

Chapter 24. Poly(Benzoxazine/Bisoxazoline)

1. Introduction

2. Experimental

3. Results and discussion

4. Conclusion

Chapter 25. Morphology and Properties of Polybenzoxazine Blends

1. Introduction

2. Miscibility of polybenzoxazine blends

3. Morphology and properties of polybenzoxazine blends

4. Conclusion

Chapter 26. Porous Materials from Polybenzoxazine

1. Introduction

2. Traditional phenolic-based porous carbon via sol-gel process

3. Porous materials and porous carbon from polybenzoxazine

4. Summary

Chapter 27. Spherical Polybenzoxazine Resin

1. Introduction

2. Experimental

3. Results and discussion

4. Conclusion

Chapter 28. Polybenzoxazine/Fiber Composites

1. Introduction

2. Processing of polybenzoxazine/fiber composites

3. Interface modification of polybenzoxazine/fiber composites

4. Properties and application of polybenzoxazine/fiber composites

Chapter 29. Polybenzoxazine-Clay Nanocomposites

1. Introduction

2. Polybenzoxazines

3. Polybenzoxazine nanocomposites

4. Montmorillonite

5. Synthesis of polybenzoxazine-clay nanocomposites

6. Polymerization behavior of benzoxazines

7. Structure characterization

8. Surface energy properties

9. Viscoelastic properties

10. Thermal stability

11. Conclusions

Chapter 30. Polybenzoxazine-POSS Nanocomposites

1. Introduction

2. Preparation of PBZ-POSS nanocomposties

3. Properties of PBZ-POSS nanocomposites

4. Conclusions and future directions

Chapter 31. Polybenzoxazine-CNT Nanocomposites

1. Introduction

2. Characterization of modified MWNT

3. The preparation of polybenzoxazine-CNT nanocomposites

4. Properties of polybenzoxazine-CNT nanocomposites

5. Conclusion

Chapter 32. Polybenzoxazines with Enhanced Flame Retardancy

1. Introduction

2. Flame retardants: mechanism and environmental concerns

3. Heteroelement-containing polybenzoxazines

4. Conclusion

Chapter 33. Surface Properties of Polybenzoxazines

1. Introduction

2. Surface properties of polybenzoxazines

3. Conclusions

Chapter 34. Advanced Benzoxazine Chemistries Provide Improved Performance in a Broad Range of Applications*

1. Introduction

2. Benzoxazine chemistry

3. Cured characteristics

4. Applications

5. Conclusion

Chapter 35. Benzoxazines for Industrial Applications Comparison with Other Resins, Formulation and Toughening Know-How, and Water-Based Dispersion Technology

1. Introduction and comparison with other resins

2. Chemistry variations, chemical engineering, and tailoring of desired properties

3. Benzoxazine resins in fiber reinforced plastics and water-based dispersions

4. Conclusions

Chapter 36. Polybenzoxazine-Based Composites for Increased Dielectric Constant

1. Polybenzoxazines and their composites

2. Performances of polybenzoxazines and their dielectric properties

3. Dielectric properties in solid materials

4. Dielectric properties of polymer-ceramic composites

5. Dielectric properties of polybenzoxazine-ceramic composites

6. Enhancement of dielectric properties by surface modification of ceramic fillers in composites

7. Conclusion

Chapter 37. Preparation of Polybenzoxazine-Ni-Zn Ferrite Nanocomposites and Their Magnetic Property

1. Introduction

2. Experimental methods

3. Results and discussion

4. Conclusion and future direction

Chapter 38. 1H-NMR Spectra

Chapter 39. IR Spectra

Chapter 40. Raman Spectra

Chapter 41. DSC Thermograms

Chapter 42. TGA Thermograms

Chapter 43. DMA Spectra

Index

Front matter

Handbook of Benzoxazine Resins

Handbook of Benzoxazine Resins

Edited by

Hatsuo Ishida, Department of Macromolecular Science and Engineering, Case Western Reserve University, Cleveland, Ohio, USA

and

Tarek Agag, Department of Macromolecular Science and Engineering, Case Western Reserve University, Cleveland, Ohio USA

Amsterdam • Boston • Heidelberg • London • New York • Oxford Paris • San Diego • San Francisco • Sydney • Tokyo

Copyright

Elsevier

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Contributors

Numbers in parentheses indicate the pages on which the authors' contributions begin

Tarek Agag193263309355379495

Department of Macromolecular Science and Engineering, Case Western Reserve University, 10900 Euclid Avenue, Cleveland, Ohio 44106–7202, USA

Chemistry Department, Faculty of Science, Tanta University, Tanta 31527, Egypt

Ahmed Akelah495

Chemistry Department, Faculty of Science, Tanta University, Tanta 31527, Egypt

Saeed Alhassan309

Department of Chemical Engineering, Case Western Reserve University, Cleveland, Ohio, USA

Wanchat Bangsen143

Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn University, Bangkok, Thailand

Mohamed Baqar193

Department of Chemical Engineering, Case Western Reserve University, Cleveland, Ohio 44106–7202, USA

V. Cádiz557

Departament de Química Analítica i Química Orgànica, Universitat Rovira i Virgili, Campus Sescelades, Marcel.lí Domingo s/n, 43007 Tarragona, Spain

Pietro Campaner365

Cimteclab S.p.A., Area Science Park, Padriciano 99, 34012, Trieste, Italy

Thanyalak Chaisuwan457

The Petroleum and Petrochemical College, Chulalongkorn University, Soi Chula 12, Phayathai Rd., Bangkok 10330, Thailand

Feng-Chih Chang579

Institute of Applied Chemistry, National Chiao Tung University, Hsin Chu, Taiwan

Qianqian Chang469

College of Science, Huazhong Agricultural University, Wuhan, Hubei 430070, People's Republic of China

Mohammad Chaudhari595

Huntsman Advanced Materials, The Woodlands, Texas, USA

Wei Chen175

Department of Polymer Science and Engineering, Nanjing University, 22 Hankou Road, Nanjing, Jiangsu 210093, P.R. China

Suwabun Chirachanchai111331

The Petroleum and Petrochemical College, Chulalongkorn University, Phyathai Road, Pathumwan, Bangkok 10330, Thailand

Center for Petroleum, Petrochemicals, and Advanced Materials, Chulalongkorn University, Phyathai Road, Pathumwan, Bangkok 10330, Thailand

Luminita Cianga183

Istanbul Technical University, Faculty of Science and Letters, Chemistry Department, Maslak, TR-34469, Istanbul, Turkey

Daniele D'Amico365

Cimteclab S.p.A., Zona Industriale, SP 362, 73010, Soleto (Lecce), Italy

Robert J. DeVoe211

3M Corporate Research Materials Laboratory, 3M Center Building 201-1C-18, St. Paul, MN 55144-1000, USA

Lei Du405

Key Laboratory for Specially Functional Polymeric Materials and Related Technology of the Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, P R China

Burcin Gacal183

Istanbul Technical University, Faculty of Science and Letters, Chemistry Department, Maslak, TR-34469, Istanbul, Turkey

M. Galià557

Departament de Química Analítica i Química Orgànica, Universitat Rovira i Virgili, Campus Sescelades, Marcel.lí Domingo s/n, 43007 Tarragona, Spain

Yu Gao405

Key Laboratory for Specially Functional Polymeric Materials and Related Technology of the Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, P R China

Samuel Geiger263

Department of Macromolecular Science and Engineering, Case Western Reserve University, 10900 Euclid Avenue, Cleveland, Ohio 44106–7202, USA

Narendra Nath Ghosh641

Chemistry Department, Birla Institute of Technology and Science, Pilani, K K Birla Goa Campus, Zuarinagar, Goa 403726, India

Ilya Gorodisher211

3M Corporate Research Materials Laboratory, 3M Center Building 201-1C-18, St. Paul, MN 55144-1000, USA

Yi Gu103481

State Key Laboratory of Polymer Materials Engineering, College of Polymer Science and Engineering, Sichuan University, Chengdu 610065, People's Republic of China

Jale Hacaloğlu287

Department of Chemistry, Middle East Technical University, Ankara, 06531, Turkey

Stephen A. Hall127

Chemical Sciences Division, Faculty of Health and Medical Sciences, University of Surrey, Guildford, Surrey, GU2 7XH, U.K.

Ian Hamerton127

Chemical Sciences Division, Faculty of Health and Medical Sciences, University of Surrey, Guildford, Surrey, GU2 7XH, U.K.

Brendan J. Howlin127

Chemical Sciences Division, Faculty of Health and Medical Sciences, University of Surrey, Guildford, Surrey, GU2 7XH, U.K.

Farong Huang405

Key Laboratory for Specially Functional Polymeric Materials and Related Technology of the Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, P R China

Jianxiang Huang405

Key Laboratory for Specially Functional Polymeric Materials and Related Technology of the Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, P R China

Hatsuo Ishida 385193237263287309355621

Department of Macromolecular Science and Engineering, Case Western Reserve University, 10900 Euclid Avenue, Cleveland, Ohio 44106–7202, USA

Chanchira Jubsilp143157

Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn University, Bangkok, Thailand

Department of Chemical Engineering, Faculty of Engineering, Srinakharinwirot University, Nakhonnayok 26120, Thailand

Fatmanur Kasapoglu183

Istanbul Technical University, Faculty of Science and Letters, Chemistry Department, Maslak, TR-34469, Istanbul, Turkey

Takehiro Kawauchi379415

Department of Environmental and Life Sciences, Toyohashi University of Technology, Hibarigaoka, Tempaku-cho, Toyohashi, 441–8580, Japan

HoDong Kim237

Department of Fiber System Engineering, Dankook University, 126 Jukjeon-dong, Suji-gu, Yongin-si, Gyeonggi-do, Korea

Hajime Kimura429

Thermosetting Resin Lab, Organic Materials Research Division, Osaka Municipal Technical Research Institute, 1-6-50, Morinomiya, Joto-ku, Osaka 536-8553, Japan

Baris Kiskan183319

Istanbul Technical University, Faculty of Science and Letters, Chemistry Department, Maslak, TR-34469, Istanbul, Turkey

Stefan Kreiling605

Henkel AG & Co. KGaA (Henkel), Adhesive Technologies R&D, Henkelstrasse 67, D-40191 Düsseldorf, Germany

Pathomkorn Kunopast143

Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn University, Bangkok, Thailand

Shiao-Wei Kuo579

Department of Materials and Optoelectronic Science, National Sun Yat-Sen University, Kaohsiung, Taiwan

Katharina Landfester605

Max-Planck-Institute for Polymer Research (MPI-P), Ackermannweg 10, D-55128 Mainz, Germany

Apirat Laobuthee111

Department of Materials Engineering, Faculty of Engineering, Kasetsart University, Phahonyotin Road, Chatuchak, Bangkok 10900, Thailand

Ming Li103

State Key Laboratory of Polymer Materials Engineering, College of Polymer Science and Engineering, Sichuan University, Chengdu 610065, Peoples Republic of China

Jia Liu355

Department of Macromolecular Science and Engineering, Case Western Reserve University, Cleveland, OH, USA

Jin-Ping Liu85

Department of Macromolecular Science and Engineering, Case Western Reserve University, Cleveland, Ohio 44106-7202, USA

G. Lligadas557

Departament de Química Analítica i Química Orgànica, Universitat Rovira i Virgili, Campus Sescelades, Marcel.lí Domingo s/n, 43007 Tarragona, Spain

Luigia Longo365

Cimteclab S.p.A., Zona Industriale, SP 362, 73010, Soleto (Lecce), Italy

Hathaikarn Manuspiya621

Petroleum and Petrochemical College, Chulalongkorn University, Pathumwan, Bangkok 10330, Thailand

Akihiro Matsumoto429

Thermosetting Resin Lab, Organic Materials Research Division, Osaka Municipal Technical Research Institute, 1-6-50, Morinomiya, Joto-ku, Osaka 536-8553, Japan

Lisa McNamara127

Chemical Sciences Division, Faculty of Health and Medical Sciences, University of Surrey, Guildford, Surrey, GU2 7XH, U.K.

Amy L. Mitchell127

Chemical Sciences Division, Faculty of Health and Medical Sciences, University of Surrey, Guildford, Surrey, GU2 7XH, U.K.

Keiko Ohtsuka429

Thermosetting Resin Lab, Organic Materials Research Division, Osaka Municipal Technical Research Institute, 1-6-50, Morinomiya, Joto-ku, Osaka 536-8553, Japan

Suttinun Phongtamrug111331

Department of Industrial Chemistry, Faculty of Applied Science, King Mongkut's University of Technology North Bangkok, Bangsue, Bangkok 10800, Thailand

Syed Qutubuddin193309

Department of Chemical Engineering, Case Western Reserve University, Cleveland, Ohio 44106–7202, USA

Department of Macromolecular Science and Engineering, Case Western Reserve University, Cleveland, Ohio 44106–7202, USA

Amit Balsing Rajput641

Chemistry Department, Birla Institute of Technology and Science, Pilani, K K Birla Goa Campus, Zuarinagar, Goa 403726, India

Qi-chao Ran481

State Key Laboratory of Polymer Materials Engineering, College of Polymer Science and Engineering, Sichuan University, Chengdu 610065, People's Republic of China

Sarawut Rimdusit143157

Polymer Engineering Laboratory, Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn University, Bangkok 10300, Thailand

J.C. Ronda557

Departament de Química Analítica i Química Orgànica, Universitat Rovira i Virgili, Campus Sescelades, Marcel.lí Domingo s/n, 43007 Tarragona, Spain

Christian Sawaryn605

Henkel AG & Co. KGaA (Henkel), Adhesive Technologies R&D, Henkelstrasse 67, D-40191, Düsseldorf, Germany

Max-Planck-Institute for Polymer Research (MPI-P), Ackermannweg 10, D-55128 Mainz, Germany

Rainer Schönfeld605

Henkel AG & Co. KGaA (Henkel), Adhesive Technologies R&D, Henkelstrasse 67, D-40191 Düsseldorf, Germany

David Schiraldi309

Department of Chemical Engineering, Case Western Reserve University, Cleveland, Ohio, USA

Department of Macromolecular Science and Engineering, Case Western Reserve University, Cleveland, Ohio, USA

Cristina Stifani365

Cimteclab S.p.A., Zona Industriale, SP 362, 73010, Soleto (Lecce), Italy

Andreas Taden605

Henkel AG & Co. KGaA (Henkel), Adhesive Technologies R&D, Henkelstrasse 67, D-40191, Düsseldorf, Germany

Max-Planck-Institute for Polymer Research (MPI-P), Ackermannweg 10, D-55128 Mainz, Germany

Tsutomu Takeichi157379415

Department of Environmental and Life Sciences, Toyohashi University of Technology, Hibarigaoka, Tempaku-cho, Toyohashi 441–8580, Japan

Antonella Tarzia365

Cimteclab S.p.A., Zona Industriale, SP 362, 73010, Soleto (Lecce), Italy

Mehmet Atilla Tasdelen183

Istanbul Technical University, Faculty of Science and Letters, Chemistry Department, Maslak, TR-34469, Istanbul, Turkey

Kohji Tashiro111331

Department of Future Industry-Oriented Basic Science and Materials, Toyota Technological Institute, Tempaku, Nagoya 468-8511, Japan

Selena Tiburzio365

Cimteclab S.p.A., Area Science Park, Padriciano 99, 34012, Trieste, Italy

Roger Tietze595

Huntsman Advanced Materials, The Woodlands, Texas, USA

Tamer Uyar287

UNAM-Institute of Materials Science and Nanotechnology, Bilkent University, Ankara, 06800, Turkey

Chih-Feng Wang579

Department of Materials Science and Engineering, I-Shou University, Kaohsiung, Taiwan

Jing Wang541

Key Laboratory of Carbon Fiber and Functional Polymers, Ministry of Education, College of Material Science and Engineering, Beijing University of Chemical Technology, Beijing, China

Lei Wang445517

Department of Polymer Science and Engineering and State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, Shanghai 200240, P. R. China

Key Laboratory of Carbon Fiber and Functional Polymers, Ministry of Education, College of Material Science and Engineering, Beijing University of Chemical Technology, 15 Beisanhuan East Road, Chaoyang District, Beijing, 100029, China

Robert J. Webb211

3M Corporate Research Materials Laboratory, 3M Center Building 201-1C-18, St. Paul, MN 55144-1000, USA

Riwei Xu517541

Key Laboratory of Carbon Fiber and Functional Polymers, Ministry of Education, College of Material Science and Engineering, Beijing University of Chemical Technology, 15 Beisanhuan East Road, Chaoyang District, Beijing, 100029, China

Youmiao Xu469

College of Science, Huazhong Agricultural University, Wuhan, Hubei 430070, People's Republic of China

Yang Xue469

College of Science, Huazhong Agricultural University, Wuhan, Hubei 430070, People's Republic of China

Yusuf Yagci183319

Istanbul Technical University, Faculty of Science and Letters, Chemistry Department, Maslak, TR-34469, Istanbul, Turkey

Hamid Yeganeh389

Polyurethane Department, Faculty of Polymer Science, Iran Polymer and Petrochemical Institute, Tehran, Iran

Dingsheng Yu517541

Key Laboratory of Carbon Fiber and Functional Polymers, Ministry of Education, College of Material Science and Engineering, Beijing University of Chemical Technology, 15 Beisanhuan East Road, Chaoyang District, Beijing, 100029, China

Rentong Yu445

Department of Polymer Science and Engineering and State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, Shanghai 200240, P. R. China

Chongyin Zhang445

Department of Polymer Science and Engineering and State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, Shanghai 200240, P. R. China

Pengli Zhang541

Key Laboratory of Carbon Fiber and Functional Polymers, Ministry of Education, College of Material Science and Engineering, Beijing University of Chemical Technology, Beijing, China

Sixun Zheng445

Department of Polymer Science and Engineering and State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, Shanghai 200240, P. R. China

Xinsheng Zheng469

College of Science, Huazhong Agricultural University, Wuhan, Hubei 430070, People's Republic of China

Yan Zhou405

Key Laboratory for Specially Functional Polymeric Materials and Related Technology of the Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, P R China

Preface

After nearly two decades of active research on polybenzoxazines as advanced thermoset polymers, it is a pleasure to finally see the publication of Handbook of Benzoxazine Resins. The numbers of polybenzoxazine researchers, published papers, and filed patents have been increasing exponentially in the past decade. Polybenzoxazines have become one of a rare few new polymers commercialized in the past 30 years.

As a result of this strong interest in polybenzoxazines, the usefulness of organizing a conference solely dedicated to this new class of polymers became obvious. The First International Symposium on Polybenzoxazines was organized and held in San Francisco in March of 2010 during the Annual Spring Meeting of the American Chemical Society. It was the first time the majority of researchers on polybenzoxazines from both academia and industry gathered together. After this successful and fruitful gathering, there were suggestions to publish the proceedings of the conference. However, the proceedings book containing the collective articles presented in the symposium is in no way near the satisfactory depth and breadth of subjects that are needed not only by the current polybenzoxazine research community but also for those who are interested in starting in this new, exciting field of study.

It was envisioned that a handbook of collective review articles, containing the most recent research directions on polybenzoxazines, would be the best option for further advancement of the field. The notion of a collective book by the polybenzoxazine community, while a challenging task, strongly appealed to the editors.

With the current activities of academic and industrial researchers, the field is expected to grow fast in the next few years. As a result, this handbook was written with the contributions of the entire body of active scientists engaging in polybenzoxazine research, utilizing the most current knowledge available. The purposeful naming of this handbook, Benzoxazine Resins, rather than Polybenzoxazines, indicates that precursors of polybenzoxazines are also of interest.

The handbook has been divided into 10 parts. Part I offers general overview of the various research directions in the field. This overview was designed to offer a broad perspective of the field at a glance and realize the advantages of this new class of polymers. It is not a replacement for the chapters in other parts, as they cover their individual subjects in more depth. Part II collects mostly the subjects related to the chemistry of polybenzoxazine precursors and their polymerization process, while Part III discusses the structure and properties of cross-linked polybenzoxazines. Part IV is on a more recent topic of high molecular weight precursors, including the main-chain type benzoxazine polymers as a new generation of polybenzoxazine precursors. While Part V, on polybenzoxazines derived from natural resources, has only one chapter, it is a section which should generate considerable interest and future growth in a world that is becoming more environmentally conscious. Parts VI, VII, and VIII are on heterogeneous materials using polybenzoxazine as a matrix or blend partner. Finally, since polybenzoxazines are a relatively new class of polymers, Part IX discusses their potential future applications, rather than current real world applications. This handbook also attempts to provide spectral data using various techniques in Part X for selected benzoxazine monomers and their polymers. This data is to aid novice researchers or to act as reference data for the experienced. In future editions of this handbook, the collection of the data will be enriched and added in a more systematic way.

In addition to review articles, there are some chapters that resemble original research articles. These chapters focus on novel and interesting subjects that we deemed a worthy inclusion in this handbook. Many of these chapters offer original data in addition to citation of the published data. It is also worth noting that with the future growth of the field in consideration, the structures of the chapters were arranged to accommodate new topics as they should arise.

Finally, upon completion of this handbook, the authors wish to thank strong encouragement and hard work of Dr. Kostas Marinakis, Senior Acquisition Editor, Dr. Anita Koch, Associate Acquisition Editor, and Mageswaran Babusivakumar, Project Manager of Elsevier to publish this as a comprehensive handbook. Hearty thanks are also due to the strong support of our family members who endured negligence of family duties during the time of editing.

Hatsuo Ishida

Department of Macromolecular Science and Engineering Case Western Reserve University, Cleveland, Ohio 44106

Tarek Agag

Department of Macromolecular Science and Engineering, Case Western Reserve University, Cleveland, Ohio 44106

On leave from Tanta University, Egypt

Chapter 1. Overview and Historical Background of Polybenzoxazine Research

Hatsuo Ishida (email: hxi3@cwru.edu )

Department of Macromolecular Science and Engineering, Case Western Reserve University, 10900 Euclid Avenue, Cleveland, Ohio 44106-7202, USA

Historical development of benzoxazine resin synthesis and properties of polybenzoxazines are reviewed. Benzoxazine chemistry offers unique properties that can seldom be observed in other polymers, including extremely rich molecular design flexibility, near-zero shrinkage upon polymerization, fast development of properties at low conversion, one of the highest char yield among processable resins, low water absorption despite having many hydrophilic groups, and excellent physical and mechanical properties. This overview first discusses various unusual properties and their molecular origin, hydrogen bonding. It also presents many benzoxazine monomers, main-chain type polybenzoxazines, side-chain type polybenzoxazines, and telechelics. Modification of properties via blending, making composites and nanocomposites, and functionalization is also discussed. Attempts are made to introduce acceleration of polymerization rate without added initiators or catalysts. Areas where there is a strong possibility of application are also introduced. Finally, characterization techniques, including FTIR, NMR, DSC, TGA, MS, and DMA, with specific examples for benzoxazine studies are presented.

1. Introduction

1.1. Nomenclature

Benzoxazine is a molecule where an oxazine ring (a heterocyclic six-membered ring with oxygen and nitrogen atom) is attached to a benzene ring. There are several benzoxazine structures depending on the position of the heteroatoms ( Figure 1 ). For example, the traditional naming of the structure a is a 1,3-benzoxazine (3,4-dihydro-3-methyl-2H-1,3-benzoxazine), whereas structure b is a 3,1-benzoxazine. The numbering is made in such a way that the oxygen position precedes the nitrogen. Thus, structure c is a 1,4-benzoxazine. This is because the benzoxazine was originally the compound with a double bond, such as in structure d. The word, dihydro, indicates the hydrogenated version of benzoxazine d. It is the 1,3-benzoxazines that are the subject of interest for development of polymeric materials as this class of benzoxazines readily polymerizes via cationic ring-opening polymerization. The IUPAC name avoids the reversing of 1,3 into 3,1 from the structure a into b. Instead, the position of the oxygen is indicated by [e] for structure a and [d] for structure b by alphabetically counting the atoms in the oxazine ring.

While the accurate naming must still follow IUPAC notation, it is very complex and impractical for routine use. Thus, a convention has been developed to abbreviate the name of the benzoxazine. Capital letters are used for the abbreviated phenolic component whereas lower case characters are used for the abbreviated amine component. To describe the benzoxazine name, these two abbreviated names are connected with a hyphen. As the flexibility of aldehyde is not rich and it is unusual for aldehyde other than formaldehyde to be used, omitting the name of formaldehyde will not usually lead to confusion. Thus, a popular benzoxazine monomer synthesized from bisphenol-A (abbreviated as BA) and aniline (abbreviated as a) has an abbreviated monomeric benzoxazine name of BA-a. When it is polymerized, one can simply describe this as poly(BA-a). Using poly(BA-a) instead of PBA-a will avoid the misunderstanding of the phenolic component that might come from a compound that can be abbreviated as PBA.

Naming of polybenzoxazine is very complex due to the rich variety of structures from similar raw materials available. The cross-linked polybenzoxazine derived from bisphenol-A and aniline-based monomeric benzoxazine (BA-a) is expressed as poly(BA-a) as described above. However, this abbreviation cannot be used to describe the main-chain type benzoxazine polymers (MCBP) that will be discussed in a later section. Instead, the uncross-linked, main-chain type polybenzoxazine derived from bisphenol-A (BA) and methylenedianiline (mda) is abbreviated as MCBP(BA-mda) to distinguish it from poly(BA-a).

1.2. Historical Development of Benzoxazines and Polybenzoxazines

The history of small molecular weight benzoxazines dates back to more than 60 years ago. Holly and Cope first reported the synthesis of benzoxazine in 1944 [ 1 ]. In the 1950s and 1960s, Burke et al. contributed significantly to the fundamental understanding of the small molecular weight benzoxazine chemistry [ [2] , [3] , [4] , [5] , [6] , [7] , [8] and [9] ]. It was Schreiber in his patents in the early 1970s who reported the synthesis of small oligomes as a modifier for epoxy resin, though no details of the oligomer properties were reported [ 10 , 11 ]. In the 1980s, Higginbottom in his quest to develop a coating system was the first to develop a cross-linked polybenzoxazines based on a multifunctional benzoxazines, though again no polybenzoxazine properties were reported in his patents [ [12] , [13] and [14] ]. Around the same time, Riese et al. studied the reaction kinetics of benzoxaine oligomer formation using mostly the monofunctional benzoxazines, showing that large molecular weight linear polybenzoxazines cannot be obtained from monofunctional benzoxazines. Several monomers studied showed the molecular weights roughly between a few hundreds to a few thousands upon polymerization [ 15 ]. In 1988, Turpin and Thrane reported in their patent the self-curable benzoxazine functional cathodic electrocoat resin formulation [ 16 ]. They described the use of both multifunctional phenols and multifunctional amines as the raw materials for small molecular weight benzoxazine resins. It is as recently as in 1994 that the study on polybenzoxazine properties was reported for the first time by Ning and Ishida [ 17 ], despite its long history of discovery of small molecular weight benzoxazine in 1944, possibility of polymerizing it in 1973, and utilization of a cross-linked polybenzoxazine in 1985.

In the early days of polybenzoxazine development, it was thought to be an attractive candidate for replacing the traditional condensation chemistry phenolic resins, as the ring-opening approach eliminated almost all the shortcomings associated with the condensation chemistry approach. However, it is now recognized that polybenzoxazine is not to be considered as simply a replacement material for the traditional phenolic resins, but as a class of materials that goes far beyond those materials, such as phenolics, epoxies, and bismaleimides. Benzoxazine resins have a wide range of mechanical and physical properties that can be tailored to various needs, reflecting the extremely rich molecular design flexibility. The material property balance of polybenzoxazines is excellent. Good thermal, chemical, electrical, mechanical, and physical properties make them attractive alternatives to existing applications. Additional new applications can be developed by utilizing unique properties of polybenzoxazines that have not been often observed by other well-known polymers. Those properties include near-zero shrinkage, very high char yield, fast development of mechanical properties as a function of conversion, glass transitions much higher than curing temperatures, excellent electrical properties, and low water uptake despite having many hydrophilic groups. They can be synthesized from inexpensive raw materials and polymerized by a ring-opening addition reaction, yielding no reaction by-product. The superb molecular design flexibility of the polybenzoxazines allows the properties of the polymerized materials to be tailored in a wide range of properties for the specific requirements of individual applications. The purpose of this chapter is to introduce this new class of polymers as alternatives to traditional phenolics, polyesters, vinyl esters, epoxies, bismaleimides, cyanate esters, and polyimides, and further provide inspirations for developing applications beyond those developed for well-known commercial polymers. In this review, references for the first discovery are preferentially cited as much as possible to the authors' knowledge to give proper credit for the pioneering works.

A number of review articles on the development of polybenzoxazines have been reported [ [18] , [19] , [20] , [21] , [22] , [23] , [24] , [25] , [26] , [27] , [28] , [29] , [30] , [31] , [32] , [33] , [34] , [35] , [36] and [37] ]. In this article, the subject of benzoxazine resins (unpolymerized precursors) as well as cross-linked polybenzoxazines will be covered as wide as possible with special emphasis on the unique properties of benzoxazine and polybenzoxazine properties.

2. Benzoxazine chemistry

The basic chemistry of benzoxazine resins is described as follows. These resins can be readily synthesized by a combination of a phenolic derivative, formaldehyde, and a primary amine ( Figure 2 ).

where X and R′ are substituents. R′ includes a group such as CH 3, C 2H 5, and benzene. Two examples of bifunctional benzoxazine resins are shown in Figure 3 .

where R is a group, such as CH 3 and other aliphatic groups, or substituted benzene rings, and X is a group, such as -, CH 2, C(CH 3) 2, C(CF 3) 2, C=O, SO 2. Any combination of a bifunctional phenol and primary amine can be used. In a similar manner, any combination of a bifunctional amine and mono-functional phenol can also be used as shown in Class B example, though the structure of the cross-linked polymer is somewhat different. Naturally, multifunctional amines or phenolic derivatives can also be used to synthesize multifunctional benzoxazines [ 38 ].

Benzoxazine monomers crystallize if they are pure. Benzoxazine monomers tend to retain a small amount of solvents and impurities rather tenaciously and thus purification can sometimes be difficult. Upon polymerization, polybenzoxazine exhibits amorphous structure as they are cross-linked. Crystal structures of some monomeric benzoxazines and dimeric compounds have been reported [ [39] , [40] , [41] , [42] , [43] and [44] ] ( Figure 4 ; Table 1 , Table 2 and Table 3 ).

It has been found that the six-membered heterocycle has an irregular chair structure with some ring strain, which provides the driving force for ring-opening polymerization. However, the ring strain is not substantial, making the polymerization temperature somewhat higher in comparison to epoxies.

A more recent concept of benzoxazine resins involves the use of a difunctional phenolic compound and a diamine, yielding a linear polymer having oxazine rings in the main chain as in Class C below; however, due to the reactivity on the benzene rings, a small number of branching can take place. The oxazine rings can be used to form crosslinking networks. This class of materials will be described in Section 7 of this chapter ( Figure 5 ).

Hundreds of papers on benzoxazine resins and their polymers have been reported to date. Those papers can be roughly classified as in Table 4 .

The synthesized compound is then subjected to thermally accelerated, cationic ring-opening polymerization with or without an added initiator. If the initiation takes place with a labile proton initiator, such as phenol, it leads to a polymer with a phenolic structure. On the other hand, if a nonlabile proton initiator, such as Lewis acid, is used to polymerize at a relatively low temperature, it could lead to an arylether structure. However, the arylether structure is thermally unstable and can undergo structural transformation to the phenolic-type at an elevated temperature ( Figure 6 ).

It should be cautioned that benzoxazine polymerization is not thermal polymerization as this term implies the thermal cleavage of a bond followed by free radical polymerization by the newly formed free radicals. The polymerization takes place by simple heating because the monomer typically contains a small amount of a cationic initiator, such as phenolic raw materials and benzoxazine oligomers, as an impurity. Heating simply increases the rate of polymerization. Thus, it should be more appropriately called thermally accelerated (or activated) polymerization if the effect of temperature needs to be mentioned. The ring opening polymerization is readily achieved by heating the purified monomer, typically at temperatures in the range between 160 and 220 °C [ 45 ], and gelation takes place in a matter of minutes to tens of minutes at these temperatures if no initiators and/or catalysts are added. However, the polymerization rate, thus the adopted temperature, depends on the purity of the benzoxazine resin produced. The higher the purity, the higher the polymerization temperature needed.

Differential scanning calorimetric (DSC) study of the conversion of a benzoxazine resin as a function of the polymerization time and temperature has been reported [ 46 ] ( Figure 7 ).

The benzoxazine polymerization is autocatalyzed [ 47 ] as the newly produced phenolic structure acts as an additional initiator and catalyst. The curing kinetics of benzoxazine resins have been actively studied [ [46] , [47] , [48] , [49] , [50] , [51] , [52] , [53] , [54] , [55] and [56] ]. The mono-functional benzoxazine typically leads to a linear (or perhaps branched) polymer, though the molecular weight is on the order of a few hundreds to a few thousands [ 15 ]; however, if the benzene ring is sufficiently reactive, even a monofunctional benzoxazine resin can lead to a crosslinked polymer. Bifunctional or poly-functional benzoxazine resins lead to crosslinked polymers [ 45 ]. If the para and meta positions to the phenolic OH are available, they can also react, although the reactivity reduces in the order from the ortho to para to meta and the meta to be rather unreactive. Albeit with lower reactivities, these multiple reactive sites are one of the causes for the difficulty of developing purely linear polymers from monofunctional benzoxazines.

The rate of ring-opening polymerization is affected in a complex way from the steric hindrance and electronic properties of the surrounding groups. The steric hindrance of the radicals which is attached to the nitrogen atom has a profound effect on the monomer conversion as shown in Figure 8 [ 40 ].

Synthesis of the monomer generally shows yields of nearly 70-90% depending on the component, temperature, time, solvent, and synthetic procedure. A highly efficient solventless method for benzoxazine resin preparation is also developed [ 57 , 58 ] in addition to commonly adopted synthetic method using a solvent [ 17 , 45 ]. This solventless approach is applicable for raw materials (phenol and amine) that are both liquid, one of which is liquid, or when the combination of the solid acid and solid amine leads to reduced melting temperature less than approximately 150 °C. The liquidation temperature should be below 150 °C so as to use low synthesis temperature to minimize oligomerization and the resulting liquid needs to be reasonably low viscosity to maintain homogeneity of the reacting compounds. Monomeric benzoxazines can show low viscosity, some of which exhibit as low as 0.1-0.2 Pa.s at 100 °C [ 59 ]. A variation of the solventless method is to add small amounts of solvents. Although this high solid synthesis has the same disadvantage of eliminating solvent after the synthesis, it is more efficient in higher quantity sample preparation than the commonly used low-solid solution synthesis.

Thermal stability of this class of Mannich base polymers is excellent despite that the usual Mannich bridge, CH 2N(R) CH 2, of small molecules shows either thermal degradation or a reverse Mannich reaction at moderate temperatures. Thermogravimetric analysis (TGA) results of many polybenzoxazines do not show any evidence of low temperature thermal degradation. In fact, bifunctional polybenzoxazines start degrading around 260 °C with varying rates depending on the type of phenols used [ 60 ]. This surprisingly good thermal stability is due to the stabilization of the Mannich bridges by the very stable intramolecular hydrogen bonding between the phenolic OH and the nitrogen atom of the Mannich bridge [ 61 ].

While the uses of phenolic derivatives, formaldehyde, and amines are not immune to the toxicity argument, the release of by-products, such as phenol, formaldehyde or amine, during benzoxazine polymerization is substantially less than those released during the polymerization process of traditional phenolic resins. Furthermore, the ring opening polymerization mechanism produces no water unlike the water-producing condensation polymerization of ordinary phenolic resins.

The mechanical and physical properties of benzoxazine resins strongly depend on the choice of components and vary widely. Ordinary performance materials such as bisphenol-A-based polybenzoxazines favorably compare with the traditional phenolic and advanced epoxy resins, whereas high performance polybenzoxazines are comparable to bismaleimides and polyimides but typically with lower raw material costs. Some properties of bisphenol-A and methylamine based polybenzoxazine (hereinafter abbreviated as BA-m) and bisphenol-A and aniline-based polybenzoxazine (abbreviated as BA-a) are compared with an epoxy and traditional phenolic resin in Table 5 [ 62 ].

A higher performance polybenzoxazine based on 4,4′-dihydroxybenzophenone and aniline (abbreviated as 44O-a) benzoxazine is also compared with a thermosetting polyimide resin (PMR-15) in Table 6 [ 63 ].

3. Polymerization mechanisms

The ring-opening polymerization of benzoxazine is thought to proceed via ionic mechanism and some attempts to study the mechanism have been reported [ 15 , [64] , [65] , [66] , [67] , [68] , [69] and [70] ]. Following are some of the mechanisms proposed in references 15 (A), 65 (B), 68 (C), 69 (D), and [ 70 ] (E) ( Figure 9 ).

While the iminium ion mechanism seems to explain many observed phenomena, it still lacks total consistency. Due to the extremely complex reaction by-products formation, the polymerization mechanism of benzoxazine resin has been elusive. In fact, using exactly the same monomer, a phenolic-based Mannich polymer and nonphenolic, arylether-based Mannich base polymer can be produced, depending on the initiation mode [ 68 ]. This arylether structure can then be converted into the phenolic structure with Mannich base in usual polybenzoxazines upon heat treatment around 160 °C [ 69 ].

Various sites of benzene rings can react with varying degrees of reactivity. This complicates the polymerization mechanism study. However, this rich reactivity can be utilized regioselectively to improve the mechanical and thermal properties. By simply using a methyl substituted aniline instead of aniline, Tg of the bisphenol-A based polybenzoxazines increased substantially from 170 to 245 °C [ 71 , 72 ] as shown in Table 7 . Such secondary crosslinking mechanism has been strongly supported by pyrolysis-MS [ 75 , 76 ] and solid-state NMR studies [ 77 ].

Chain propagation of benzoxazine polymerization faces difficulty due to the competing intra-molecular six-membered ring hydrogen bonding formation [ 78 , 79 ]. It is difficult to obtain a large molecular weight linear polybenzoxazine from monofunctional benzoxazines. Therefore, as described in a later section, a hydrogen bond forming polymer as a blend partner exhibits synergism in polybenzoxazine formation, showing a greater Tg than any of the pure components used.

4. Unique properties of benzoxazines and polybenzoxazines

Benzoxazine resins as precursors for cross-linked polybenzoxazines and the resultant cross-linked polymers exhibit a number of unique properties, as described in the following sections. These properties will allow the development of unique applications, in addition to providing the opportunity to be the replacement materials for the existing polymers.

4.1. Near-Zero Volume Changes

Thermosetting resins shrink during polymerization by about 2-10% even for low shrinkage materials, while thermoplastics exhibit even higher polymerization shrinkage [ [80] , [81] and [82] ]. Superior mechanical interlocking to a substrate can be obtained by expanding polymers, which would make them ideally suited for high performance adhesives, sealants, and coatings. Elimination or reduction of interfacial residual stress benefits composites as polymerization shrinkage leads to residual stress which increases the adverse effects of moisture. Zero shrinkage materials eliminate optical distortion as well as warping of composite materials. Benzoxazine resins display near-zero shrinkage with high mechanical integrity [ [83] , [84] and [85] ]. The majority of the monomers changed their volume within ±1% upon polymerization. It should be noted that the volume of the resin actually reduced slightly during the isothermal curing at an elevated temperature. However, when the room temperature volumes before and after the polymerization are compared, very little changes in densities, and thus the volume changes, are observed. The combination of slight shrinkage at an elevated, isothermal curing temperature and eventual near-zero shrinkage at room temperature seems ideal from the viewpoint of demolding and minimization of residual stress ( Table 8 ).

4.2. Low Water Absorption

One of the common problems of polyester, vinylester, phenolic, epoxy, bismaleimide, and polyimide resins is their relatively high water up-take at saturation. Both phenolic and epoxy resin absorb as much as 3-20% by weight upon saturation [ [86] , [87] , [88] and [89] ]. This relatively high water absorption is due to the presence of polar groups in these resins. Polybenzoxazines also contain polar groups, such as phenolic OH and Mannich base, CH 2NCH 2, in each chemical repeat unit. However, contrary to what might be expected, polybenzoxazines absorb much less water than these resins. A bisphenol-A and aniline-based (abbreviated as BA-a) polybenzoxazine is saturated at 1.9% by weight and bisphenol-A and methylamine-based (abbreviated as BA-m) polymer at 1.3% by weight in water at room temperature [ 62 ] as shown in Figure 10 . No further water absorption was observed after more than 4000 days (more than 10 years). Use of phenols and amines with more hydrophobic radicals will further reduce the water up-take. This feature of low water up-take will be advantageous when dielectric constant of the polymer needs to be reduced since just 1% of water absorbed will contribute to the dielectric constant of the material roughly by 1. Another advantage of low water up-take is that the difference between the dry Tg and wet Tg is small. In an actual application of products, this is an important property.

4.3. Glass Transition Temperature ( Tg)

Cross-linked polybenzoxazines show surprisingly high glass transition temperatures ranging approximately from 160 to 400 °C. Naturally, if a sub-zero Tg is desired, it can also be designed. The apparent glass transition temperature of a thermosetting resin roughly coincides with the polymerization temperature if the polymerization is carried out below the ultimate glass transition temperature of the material. However, if the polymerization mechanism is such that local motion of a polymer chain allows further reactions or structural rearrangement of the polymer, then the Tg continues to increase beyond the polymerization temperature, Tcure. Such is the case for polybenzoxazines where there are many active sites available and the benzene rings, to which the active sites react, are also abundant. Thus, the β-transition temperature, Tβ, provides sufficient mobility for these types of reactions. Another reason is possibly its chain polymerization mechanism rather than the condensation mechanism. Yet, another possible mechanism is the structural rearrangement at elevated temperatures. A 4,4′-dihydroxybenzophenone and aniline-based benzoxazine (abbreviated as 44O-a) shows a Tg of 350 °C if it is polymerized at 290 °C for 1 hour [ 63 ]. This represents Tg > Tcure by 60 °C. Post curing at this temperature for an additional 2 h increases the Tg to 385 °C, further increasing this difference to 95 °C. Furthermore, aminophenylacetylene functional benzoxazine resins show typical Tgs of 350 °C when they are polymerized at 190 °C, representing a Tg − Tcure difference of 160 °C [ 90 ]. This large discrepancy between the Tg and Tcure offers a processing advantage since the majority of high performance resins, such as polyimides and phthalocyanine resins, are polymerized at much higher temperatures in the range of 300-410 °C.

4.4. Fast Physical and Mechanical Property Development

Condensation polymers such as epoxy resins develop physical and mechanical properties slowly at low degrees of polymerization and require a high degree of conversion to achieve good properties. Thus, the difference in degree of conversion by a few percent near the end of polymerization exhibits far more significant changes in mechanical properties than 10-20% increase in conversion around 50% degree of conversion. This is in contrast to addition polymerization where fast build-up of molecular weight at an early stage of polymerization is observed. Polybenzoxazines develop their glass transition temperatures and other mechanical properties quickly as the polymerization proceeds. For BA-a benzoxazine, 80% of the Tg development takes place at 50% conversion as shown in Figure 11 [ 91 ].

This is in strong contrast to a typical bisphenol-A type epoxy resin [ [92] , [93] and [94] ]. Approximately 25% of the ultimate Tg would be developed at the same conversion. This means that even at a relatively low conversion, the green strength of the polybenzoxazine product will be excellent, and may reduce cycle time.

4.5. Very High Char Yield

The flammability of materials has attracted industrial and academic attention as federal regulations become stricter and new technologies emerge. Materials first decompose by thermally initiated mechanisms or thermo-oxidative degradation. Small combustible fragments move to the material surface and eventually to the flame front where a rich supply of oxygen burns the flammable gases. The heat generated by this process supplies the energy necessary for further sustainable thermal degradation of the material. This cycle is repeated as the material continues to burn. One way to reduce burning is to design intrinsically high char-forming materials. Char also reduces the diffusion rate of decomposed, flammable gases toward the flame front. Thus, a high char yield polymer is desired for flame-resistant material applications. Many polymers show low char yield when the remaining weight is examined under nitrogen at 800 °C. This char yield is 5-15% for epoxy resins, and 30-55% for traditional phenolic resins. Phenolic resins show one of the highest char yields among processable polymers. Char formation usually increases with increased content of benzene groups, although there is no straightforward relationship between the benzene content and char yield. This is well expressed by the fact that despite a higher content of aliphatic groups in polybenzoxazines, their char yield, generally 35-75%, is higher than traditional phenolic resins. An important property for flammability characteristics, according to Walters and Lyon [ 95 ], is the heat release capacity for which molar group contribution can be used to calculate, thus allowing theoretical comparison of flammability. According to Walter and Lyon's method, polybenzoxazines can be inherently good flame-retardant materials as molar group contribution of hydroxyl groups, tertially amine, and benzene groups are high.

A TGA curve of the high performance polybenzoxazine based on 4,4′-dihydroxybenzophenone and aniline (abbreviated as 44O-a) is shown in Figure 12 [ 63 ].

The 5% decomposition temperature is above 400 °C. It is surprising to see that more than 60% of the weight still remains in air at 600 °C. A long-term thermal stability of the poly(44O-a) indicates the weight reduction is rather negligible until around 240-250 °C even after 200 h exposure in air [ 63 ]. At the present time, long-term durability studies of polybenzoxazines are severely lacking in the literature.

In general, thermal degradation of the polybenzoxazines which is based on bisphenol and monoamine exhibits a three-stage mechanism. The lowest temperature event is associated with the evaporation of the amine group. The detailed mechanisms of polybenzoxazine degradation have been studied by mass spectrometry and Fourier transform infrared spectroscopy (FTIR) [ 75 , 76 , [96] , [97] , [98] , [99] , [100] , [101] and [102] ]. Thus, minimizing the evaporation of the amine by adding a reactive group on the dangling amine side-chain will improve the char formation. Molecularly designed polybenzoxazines that are optimized for high char formation using acetylene, nitrile, and phthalonitrile groups exhibit very high char yield [ 90 , [103] , [104] , [105] , [106] , [107] and [108] ]. Easy processibility, relatively low cost, and high char yield are the characteristics of maleimide functional [ [109] , [110] , [111] , [112] , [113] , [114] , [115] and [116] ] and allylamine functional [ [117] , [118] , [119] , [120] , [121] , [122] , [123] , [124] and [125] ] benzoxazines. Naphthoxazines usually exhibit high char yield, though some naphthoxazines degrade at much lower temperatures than benzoxazines [ 121 , [126] , [127] and [128] ].

5. Molecular origin of unusual properties

Many of the unusual properties described above can be explained by complex hydrogen bond formation in polybenzoxazines. Almost all known forms of hydrogen bonds, including inter and intramolecular OH⋯OH, intramolecular OH⋯N six-membered hydrogen bonds, and OH⋯π interactions, are possible in polybenzoxazines. X-ray crystallographic study of model dimer [ 129 ], molecular modeling study [ 130 ], high resolution solid-state ¹H-NMR with double quantum technique [ [131] , [132] and [133] ] and FTIR study of model oligomers [ 61 , [134] , [135] , [136] , [137] , [138] and [139] ] all strongly support the formation of both inter and intra-molecular hydrogen bonds. Of particular interest is the very stable six-membered hydrogen bond shown in Figure 13 that explains the hydrophobicity, low dielectric constant, high char yield, and high modulus.

Polybenzoxazines are not reported to be semi-crystalline polymers due to the cross-linked nature, branched structures or, perhaps, with complex hydrogen bonding associations even when it is basically a linear oligomer derived from a monofunctional benzoxazine. However, X-ray study, molecular modeling [ 39 , 140 ], and high-resolution solid-state ¹H NMR with double quantum technique study [ 133 ] all point to the tendency of local helical structure formation as shown in Figure 14 . Understanding this local structure is important when considering the structure-property relationships, in particular mechanical strength, thermal stability, and diffusion properties.

The fraction of intramolecular hydrogen bonds against intermolecular hydrogen bonds depends on the nature of the amines used. A high p Ka amine, such as methylamine will have a higher intramolecular hydrogen bond fraction than a lower p Ka amine, such as aniline. However, majority of the phenolic OH groups are intramolecularly hydrogen bonded to the N atom in the Mannich base. This intramolecular hydrogen bond is so stable that even above 300 °C, it can survive if it is below the glass transition temperature of the polymer as shown in Figure 15 [ 61 ].

6. Historical development of monomeric benzoxazines

The reported monomeric-type benzoxazines are listed in Table 9 in the historical order [ [17] , [45] , [60] , [63] , [71] , [83] , [90] , [96] , [103] , [104] , [105] , [107] , [108] , [109] , [110] , [113] , [116] , [118] , [119] , [120] , [121] , [122] , [123] , [125] , [126] , [127] , [141] , [142] , [143] , [144] , [145] , [146] , [147] , [148] , [149] , [150] , [151] , [152] , [153] , [154] , [155] , [156] , [157] , [158] , [159] , [160] , [161] , [162] , [163] , [164] , [165] , [166] , [167] , [168] , [169] , [170] , [171] , [172] , [173] , [174] , [175] , [176] , [177] , [178] , [179] , [180] , [181] , [182] , [183] , [184] , [185] , [186] , [187] , [188] , [189] , [190] and [191] ]. The year the new compound was first reported in the peer-reviewed journals