This handbook provides a wide overview of the field, fundamental understanding of the synthetic methods and structure/property correlation, as well as studies related to applications in a wide range of subjects. The handbook also provides 1H and 13C NMR spectra, FTIR spectra, DSC and TGA thermograms to aid in research activities. Additional tables on key NMR and FTIR frequencies unique to benzoxazine, heat of polymerization, Tg, and char yield will greatly aid in the choice of proper benzoxazine for a specific application.
1. 1. Introduction 2. 2. Benzoxazine chemistry 3. 3. Polymerization mechanisms 4. 4. Unique properties of benzoxazines and polybenzoxazines 5. 5. Molecular origin of unusual properties 6. 6. Historical development of monomeric benzoxazines 7. 7. Recent development of high molecular weight benzoxazines 8. 8. Benzoxazines combined with other polymerizing groups 9. 9. Various technologies attractive for applications 10. 10. Characterization of benzoxazines 11. 11. Conclusion 12. Chapter 2. Benzoxazine Chemistry in Solution and Melt 13. 1. Synthesis of benzoxazine monomers in homogeneous solution 14. 2. Synthesis of benzoxazine monomers in heterogeneous solution 15. 3. Synthesis of benzoxazine monomers by melt or high solid methods 16. 4. Benzoxazine ring formation mechanism 17. 5. Conclusion 18. Chapter 3. Molecular Modeling 19. 1. Introduction 20. 2. Chemical reaction 21. 3. Structure analysis 22. 4. Structure-property relationship 23. 5. Summary and remarks 24. Chapter 4. Mono-Substituted Phenol-Based Benzoxazines 25. 1. Chemistry and development of benzoxazines 26. 2. Ring opening reaction of mono-substituted phenol-based benzoxazines: dimerization of benzoxazines and its self-termination 27. 3. Single crystallography of monofunctional benzoxazine dimer 28. 4. Asymmetric reaction of monofunctional benzoxazine dimer 29. 5. Benzoxazine dimer and its metal ion complexation 30. 6. Conclusions 31. Chapter 5. Using Molecular Simulation to Predict the Physical and Mechanical Properties of Polybenzoxazines 32. 1. Introduction 33. 2. Materials and methods 34. 3. Results and discussion 35. 4. Conclusions 36. Chapter 6. Chemorheology of Benzoxazine-based Resins 37. 1. Introduction 38. 2. Chemorheology of benzoxazine-based resins 39. 3. Gelation of benzoxazine-based resins investigated by FTMS 40. 4. Conclusion 41. Chapter 7. Polymerization Kinetics 42. 1. Introduction 43. 2. Kinetic analysis of resin polymerization reaction 44. 3. Conclusions 45. Chapter 8. Electrochemical Polymerization of Benzoxazines 46. 1. Introduction 47. 2. Experimental 48. 3. Electrochemical polymerization of benzoxazines 49. 4. Conclusions 50. Chapter 9. Light-Induced Reactions of Benzoxazines and Derivatives 51. 1. Introduction 52. 2. Free radical systems 53. 3. Cationic systems 54. 4. Photodimerization 55. 5. UV stability of benzoxazine resins 56. 6. Conclusion 57. Chapter 10. Effect of Neighboring Groups on Enhancing Benzoxazine Autocatalytic Polymerization 58. 1. Introduction 59. 2. Polymerization mechanism of benzoxazine monomers 60. 3. Substituted benzoxazine monomers 61. 4. Carboxylic acid functional benzoxazine monomers 62. 5. Hydroxyl-functional benzoxazine monomers 63. 6. Conclusion 64. Chapter 11. Catalytic Opening of Lateral Benzoxazine Rings by Thiols 65. 1. Introduction 66. 2. Experimental 67. 3. Results and discussion 68. 4. Proposed colbert reaction mechanism 69. 5. Linear aromatic polymers 70. 6. Conclusion 71. Chapter 12. Hydrogen Bonding of Polybenzoxazines 72. 1. Introduction 73. 2. Structure of hydrogen bonding 74. 3. Conclusion 75. Chapter 13. Thermal Properties Enhancement of Polybenzoxazines 76. 1. Introduction 77. 2. Polymerization of benzoxazine monomers 78. 3. Polybenzoxazine thermal stability 79. 4. Additional cross-linking sites in benzoxazine structure 80. 5. Alkyne functional benzoxazine 81. 6. Alkene-functional benzoxazine 82. 7. Nitrile-functional benzoxazine monomers 83. 8. Maleimide-functional benzoxazine monomers 84. 9. Epoxy functional benzoxazine 85. 10. Methacrylate-functional benzoxazine 86. 11. Conclusion 87. Chapter 14. Thermal Degradation Mechanisms of Polybenzoxazines 88. 1. Introduction 89. 2. Thermal characteristics of polybenzoxazines 90. 3. Conclusions 91. Chapter 15. Various Approaches for Main-Chain Type Benzoxazine Polymers 92. 1. Introduction 93. 2. Polymeric mannich base condensation 94. 3. Polymers with mannich condensation of ab-type 95. 4. Chain extension through reactive benzoxazine monomers 96. 5. Conclusion 97. Chapter 16. Side- and End-Chain Benzoxazine Functional Polymers 98. 1. Introduction 99. 2. Side-chain benzoxazine functional polymers 100. 3. Benzoxazine telechelics 101. 4. Conclusions 102. Chapter 17. Supramolecular Chemistry of Benzoxazines 103. 1. Concept of supramolecules 104. 2. Resembled structure of benzoxazine and calixarenes 105. 3. Supramolecular structures of benzoxazine dimers 106. 4. Molecular designs and syntheses of benzoxazine dimer-based macrocycles 107. 5. Benzoxazine dimer-based macrocycles 108. 6. Inclusion phenomena of macrocyclic compounds 109. 7. Conclusions 110. Chapter 18. Main-Chain Type Benzoxazine Oligomers 111. 1. Introduction 112. 2. Synthesis of bisphenol F-Based MCBOs 113. 3. Polymerization behavior of MCBOs 114. 4. Thermal stability of cross-linked MCBOs 115. 5. Viscoelastic properties of MCBOs 116. 6. Viscosity study of MCBOs 117. 7. Conclusions 118. Chapter 19. Study of a Cardanol-Based Benzoxazine as Reactive Diluent and Toughening Agent of Conventional Benzoxazines 119. 1. Introduction 120. 2. Experimental 121. 3. Results and discussion 122. 4. Conclusion 123. Chapter 20. Polybenzoxazine/Polyimide Alloys 124. 1. Introduction 125. 2. Polybenzoxazine/pi alloy 126. 3. Effect of preparation method on the properties of poly(ba-a)/pi alloy [17] 127. 4. Polybenzoxazine-poly(imide-siloxane) alloys [19] 128. 5. Conclusions 129. Chapter 21. Polybenzoxazine/Polyurethane Alloys 130. 1. Introduction 131. 2. Different approaches for the preparation of polybenzoxazine/Polyurethane alloys 132. 3. Conclusion 133. Chapter 22. The Blends of a Silicon-Containing Arylacetylene Resin and an Acetylene-Functional Benzoxazine 134. 1. Introduction 135. 2. Experimental 136. 3. Properties of blend resins 137. 4. Properties of fiber-reinforced blend resin composites 138. 5. Conclusion 139. Chapter 23. Polybenzoxazine/Polysiloxane Hybrids 140. 1. Introduction 141. 2. Polybenzoxazine-PDMS hybrid [22] 142. 3. Hybridization with polysiloxanes having a phenyl group as the pendant [23] 143. 4. Polybenzoxazine-poly(dimethylsiloxane-co-diphenylsiloxane) hybrids [24] 144. 5. High-molecular-weight polybenzoxazine prepolymers containing polysiloxane 145. 6. Conclusions 146. Chapter 24. Poly(Benzoxazine/Bisoxazoline) 147. 1. Introduction 148. 2. Experimental 149. 3. Results and discussion 150. 4. Conclusion 151. Chapter 25. Morphology and Properties of Polybenzoxazine Blends 152. 1. Introduction 153. 2. Miscibility of polybenzoxazine blends 154. 3. Morphology and properties of polybenzoxazine blends 155. 4. Conclusion 156. Chapter 26. Porous Materials from Polybenzoxazine 157. 1. Introduction 158. 2. Traditional phenolic-based porous carbon via sol-gel process 159. 3. Porous materials and porous carbon from polybenzoxazine 160. 4. Summary 161. Chapter 27. Spherical Polybenzoxazine Resin 162. 1. Introduction 163. 2. Experimental 164. 3. Results and discussion 165. 4. Conclusion 166. Chapter 28. Polybenzoxazine/Fiber Composites 167. 1. Introduction 168. 2. Processing of polybenzoxazine/fiber composites 169. 3. Interface modification of polybenzoxazine/fiber composites 170. 4. Properties and application of polybenzoxazine/fiber composites 171. Chapter 29. Polybenzoxazine-Clay Nanocomposites 172. 1. Introduction 173. 2. Polybenzoxazines 174. 3. Polybenzoxazine nanocomposites 175. 4. Montmorillonite 176. 5. Synthesis of polybenzoxazine-clay nanocomposites 177. 6. Polymerization behavior of benzoxazines 178. 7. Structure characterization 179. 8. Surface energy properties 180. 9. Viscoelastic properties 181. 10. Thermal stability 182. 11. Conclusions 183. Chapter 30. Polybenzoxazine-POSS Nanocomposites 184. 1. Introduction 185. 2. Preparation of PBZ-POSS nanocomposties 186. 3. Properties of PBZ-POSS nanocomposites 187. 4. Conclusions and future directions 188. Chapter 31. Polybenzoxazine-CNT Nanocomposites 189. 1. Introduction 190. 2. Characterization of modified MWNT 191. 3. The preparation of polybenzoxazine-CNT nanocomposites 192. 4. Properties of polybenzoxazine-CNT nanocomposites 193. 5. Conclusion 194. Chapter 32. Polybenzoxazines with Enhanced Flame Retardancy 195. 1. Introduction 196. 2. Flame retardants: mechanism and environmental concerns 197. 3. Heteroelement-containing polybenzoxazines 198. 4. Conclusion 199. Chapter 33. Surface Properties of Polybenzoxazines 200. 1. Introduction 201. 2. Surface properties of polybenzoxazines 202. 3. Conclusions 203. Chapter 34. Advanced Benzoxazine Chemistries Provide Improved Performance in a Broad Range of Applications* 204. 1. Introduction 205. 2. Benzoxazine chemistry 206. 3. Cured characteristics 207. 4. Applications 208. 5. Conclusion 209. Chapter 35. Benzoxazines for Industrial Applications Comparison with Other Resins, Formulation and Toughening Know-How, and Water-Based Dispersion Technology 210. 1. Introduction and comparison with other resins 211. 2. Chemistry variations, chemical engineering, and tailoring of desired properties 212. 3. Benzoxazine resins in fiber reinforced plastics and water-based dispersions 213. 4. Conclusions 214. Chapter 36. Polybenzoxazine-Based Composites for Increased Dielectric Constant 215. 1. Polybenzoxazines and their composites 216. 2. Performances of polybenzoxazines and their dielectric properties 217. 3. Dielectric properties in solid materials 218. 4. Dielectric properties of polymer-ceramic composites 219. 5. Dielectric properties of polybenzoxazine-ceramic composites 220. 6. Enhancement of dielectric properties by surface modification of ceramic fillers in composites 221. 7. Conclusion 222. Chapter 37. Preparation of Polybenzoxazine-Ni-Zn Ferrite Nanocomposites and Their Magnetic Property 223. 1. Introduction 224. 2. Experimental methods 225. 3. Results and discussion 226. 4. Conclusion and future direction 227. Chapter 38. 1H-NMR Spectra 228. Chapter 39. IR Spectra 229. Chapter 40. Raman Spectra 230. Chapter 41. DSC Thermograms 231. Chapter 42. TGA Thermograms 232. Chapter 43. DMA Spectra 233. Index
This handbook provides a wide overview of the field, fundamental understanding of the synthetic methods and structure/property correlation, as well as studies related to applications in a wide range of subjects. The handbook also provides 1H and 13C NMR spectra, FTIR spectra, DSC and TGA thermograms to aid in research activities. Additional tables on key NMR and FTIR frequencies unique to benzoxazine, heat of polymerization, Tg, and char yield will greatly aid in the choice of proper benzoxazine for a specific application.
1. 1. Introduction 2. 2. Benzoxazine chemistry 3. 3. Polymerization mechanisms 4. 4. Unique properties of benzoxazines and polybenzoxazines 5. 5. Molecular origin of unusual properties 6. 6. Historical development of monomeric benzoxazines 7. 7. Recent development of high molecular weight benzoxazines 8. 8. Benzoxazines combined with other polymerizing groups 9. 9. Various technologies attractive for applications 10. 10. Characterization of benzoxazines 11. 11. Conclusion 12. Chapter 2. Benzoxazine Chemistry in Solution and Melt 13. 1. Synthesis of benzoxazine monomers in homogeneous solution 14. 2. Synthesis of benzoxazine monomers in heterogeneous solution 15. 3. Synthesis of benzoxazine monomers by melt or high solid methods 16. 4. Benzoxazine ring formation mechanism 17. 5. Conclusion 18. Chapter 3. Molecular Modeling 19. 1. Introduction 20. 2. Chemical reaction 21. 3. Structure analysis 22. 4. Structure-property relationship 23. 5. Summary and remarks 24. Chapter 4. Mono-Substituted Phenol-Based Benzoxazines 25. 1. Chemistry and development of benzoxazines 26. 2. Ring opening reaction of mono-substituted phenol-based benzoxazines: dimerization of benzoxazines and its self-termination 27. 3. Single crystallography of monofunctional benzoxazine dimer 28. 4. Asymmetric reaction of monofunctional benzoxazine dimer 29. 5. Benzoxazine dimer and its metal ion complexation 30. 6. Conclusions 31. Chapter 5. Using Molecular Simulation to Predict the Physical and Mechanical Properties of Polybenzoxazines 32. 1. Introduction 33. 2. Materials and methods 34. 3. Results and discussion 35. 4. Conclusions 36. Chapter 6. Chemorheology of Benzoxazine-based Resins 37. 1. Introduction 38. 2. Chemorheology of benzoxazine-based resins 39. 3. Gelation of benzoxazine-based resins investigated by FTMS 40. 4. Conclusion 41. Chapter 7. Polymerization Kinetics 42. 1. Introduction 43. 2. Kinetic analysis of resin polymerization reaction 44. 3. Conclusions 45. Chapter 8. Electrochemical Polymerization of Benzoxazines 46. 1. Introduction 47. 2. Experimental 48. 3. Electrochemical polymerization of benzoxazines 49. 4. Conclusions 50. Chapter 9. Light-Induced Reactions of Benzoxazines and Derivatives 51. 1. Introduction 52. 2. Free radical systems 53. 3. Cationic systems 54. 4. Photodimerization 55. 5. UV stability of benzoxazine resins 56. 6. Conclusion 57. Chapter 10. Effect of Neighboring Groups on Enhancing Benzoxazine Autocatalytic Polymerization 58. 1. Introduction 59. 2. Polymerization mechanism of benzoxazine monomers 60. 3. Substituted benzoxazine monomers 61. 4. Carboxylic acid functional benzoxazine monomers 62. 5. Hydroxyl-functional benzoxazine monomers 63. 6. Conclusion 64. Chapter 11. Catalytic Opening of Lateral Benzoxazine Rings by Thiols 65. 1. Introduction 66. 2. Experimental 67. 3. Results and discussion 68. 4. Proposed colbert reaction mechanism 69. 5. Linear aromatic polymers 70. 6. Conclusion 71. Chapter 12. Hydrogen Bonding of Polybenzoxazines 72. 1. Introduction 73. 2. Structure of hydrogen bonding 74. 3. Conclusion 75. Chapter 13. Thermal Properties Enhancement of Polybenzoxazines 76. 1. Introduction 77. 2. Polymerization of benzoxazine monomers 78. 3. Polybenzoxazine thermal stability 79. 4. Additional cross-linking sites in benzoxazine structure 80. 5. Alkyne functional benzoxazine 81. 6. Alkene-functional benzoxazine 82. 7. Nitrile-functional benzoxazine monomers 83. 8. Maleimide-functional benzoxazine monomers 84. 9. Epoxy functional benzoxazine 85. 10. Methacrylate-functional benzoxazine 86. 11. Conclusion 87. Chapter 14. Thermal Degradation Mechanisms of Polybenzoxazines 88. 1. Introduction 89. 2. Thermal characteristics of polybenzoxazines 90. 3. Conclusions 91. Chapter 15. Various Approaches for Main-Chain Type Benzoxazine Polymers 92. 1. Introduction 93. 2. Polymeric mannich base condensation 94. 3. Polymers with mannich condensation of ab-type 95. 4. Chain extension through reactive benzoxazine monomers 96. 5. Conclusion 97. Chapter 16. Side- and End-Chain Benzoxazine Functional Polymers 98. 1. Introduction 99. 2. Side-chain benzoxazine functional polymers 100. 3. Benzoxazine telechelics 101. 4. Conclusions 102. Chapter 17. Supramolecular Chemistry of Benzoxazines 103. 1. Concept of supramolecules 104. 2. Resembled structure of benzoxazine and calixarenes 105. 3. Supramolecular structures of benzoxazine dimers 106. 4. Molecular designs and syntheses of benzoxazine dimer-based macrocycles 107. 5. Benzoxazine dimer-based macrocycles 108. 6. Inclusion phenomena of macrocyclic compounds 109. 7. Conclusions 110. Chapter 18. Main-Chain Type Benzoxazine Oligomers 111. 1. Introduction 112. 2. Synthesis of bisphenol F-Based MCBOs 113. 3. Polymerization behavior of MCBOs 114. 4. Thermal stability of cross-linked MCBOs 115. 5. Viscoelastic properties of MCBOs 116. 6. Viscosity study of MCBOs 117. 7. Conclusions 118. Chapter 19. Study of a Cardanol-Based Benzoxazine as Reactive Diluent and Toughening Agent of Conventional Benzoxazines 119. 1. Introduction 120. 2. Experimental 121. 3. Results and discussion 122. 4. Conclusion 123. Chapter 20. Polybenzoxazine/Polyimide Alloys 124. 1. Introduction 125. 2. Polybenzoxazine/pi alloy 126. 3. Effect of preparation method on the properties of poly(ba-a)/pi alloy [17] 127. 4. Polybenzoxazine-poly(imide-siloxane) alloys [19] 128. 5. Conclusions 129. Chapter 21. Polybenzoxazine/Polyurethane Alloys 130. 1. Introduction 131. 2. Different approaches for the preparation of polybenzoxazine/Polyurethane alloys 132. 3. Conclusion 133. Chapter 22. The Blends of a Silicon-Containing Arylacetylene Resin and an Acetylene-Functional Benzoxazine 134. 1. Introduction 135. 2. Experimental 136. 3. Properties of blend resins 137. 4. Properties of fiber-reinforced blend resin composites 138. 5. Conclusion 139. Chapter 23. Polybenzoxazine/Polysiloxane Hybrids 140. 1. Introduction 141. 2. Polybenzoxazine-PDMS hybrid [22] 142. 3. Hybridization with polysiloxanes having a phenyl group as the pendant [23] 143. 4. Polybenzoxazine-poly(dimethylsiloxane-co-diphenylsiloxane) hybrids [24] 144. 5. High-molecular-weight polybenzoxazine prepolymers containing polysiloxane 145. 6. Conclusions 146. Chapter 24. Poly(Benzoxazine/Bisoxazoline) 147. 1. Introduction 148. 2. Experimental 149. 3. Results and discussion 150. 4. Conclusion 151. Chapter 25. Morphology and Properties of Polybenzoxazine Blends 152. 1. Introduction 153. 2. Miscibility of polybenzoxazine blends 154. 3. Morphology and properties of polybenzoxazine blends 155. 4. Conclusion 156. Chapter 26. Porous Materials from Polybenzoxazine 157. 1. Introduction 158. 2. Traditional phenolic-based porous carbon via sol-gel process 159. 3. Porous materials and porous carbon from polybenzoxazine 160. 4. Summary 161. Chapter 27. Spherical Polybenzoxazine Resin 162. 1. Introduction 163. 2. Experimental 164. 3. Results and discussion 165. 4. Conclusion 166. Chapter 28. Polybenzoxazine/Fiber Composites 167. 1. Introduction 168. 2. Processing of polybenzoxazine/fiber composites 169. 3. Interface modification of polybenzoxazine/fiber composites 170. 4. Properties and application of polybenzoxazine/fiber composites 171. Chapter 29. Polybenzoxazine-Clay Nanocomposites 172. 1. Introduction 173. 2. Polybenzoxazines 174. 3. Polybenzoxazine nanocomposites 175. 4. Montmorillonite 176. 5. Synthesis of polybenzoxazine-clay nanocomposites 177. 6. Polymerization behavior of benzoxazines 178. 7. Structure characterization 179. 8. Surface energy properties 180. 9. Viscoelastic properties 181. 10. Thermal stability 182. 11. Conclusions 183. Chapter 30. Polybenzoxazine-POSS Nanocomposites 184. 1. Introduction 185. 2. Preparation of PBZ-POSS nanocomposties 186. 3. Properties of PBZ-POSS nanocomposites 187. 4. Conclusions and future directions 188. Chapter 31. Polybenzoxazine-CNT Nanocomposites 189. 1. Introduction 190. 2. Characterization of modified MWNT 191. 3. The preparation of polybenzoxazine-CNT nanocomposites 192. 4. Properties of polybenzoxazine-CNT nanocomposites 193. 5. Conclusion 194. Chapter 32. Polybenzoxazines with Enhanced Flame Retardancy 195. 1. Introduction 196. 2. Flame retardants: mechanism and environmental concerns 197. 3. Heteroelement-containing polybenzoxazines 198. 4. Conclusion 199. Chapter 33. Surface Properties of Polybenzoxazines 200. 1. Introduction 201. 2. Surface properties of polybenzoxazines 202. 3. Conclusions 203. Chapter 34. Advanced Benzoxazine Chemistries Provide Improved Performance in a Broad Range of Applications* 204. 1. Introduction 205. 2. Benzoxazine chemistry 206. 3. Cured characteristics 207. 4. Applications 208. 5. Conclusion 209. Chapter 35. Benzoxazines for Industrial Applications Comparison with Other Resins, Formulation and Toughening Know-How, and Water-Based Dispersion Technology 210. 1. Introduction and comparison with other resins 211. 2. Chemistry variations, chemical engineering, and tailoring of desired properties 212. 3. Benzoxazine resins in fiber reinforced plastics and water-based dispersions 213. 4. Conclusions 214. Chapter 36. Polybenzoxazine-Based Composites for Increased Dielectric Constant 215. 1. Polybenzoxazines and their composites 216. 2. Performances of polybenzoxazines and their dielectric properties 217. 3. Dielectric properties in solid materials 218. 4. Dielectric properties of polymer-ceramic composites 219. 5. Dielectric properties of polybenzoxazine-ceramic composites 220. 6. Enhancement of dielectric properties by surface modification of ceramic fillers in composites 221. 7. Conclusion 222. Chapter 37. Preparation of Polybenzoxazine-Ni-Zn Ferrite Nanocomposites and Their Magnetic Property 223. 1. Introduction 224. 2. Experimental methods 225. 3. Results and discussion 226. 4. Conclusion and future direction 227. Chapter 38. 1H-NMR Spectra 228. Chapter 39. IR Spectra 229. Chapter 40. Raman Spectra 230. Chapter 41. DSC Thermograms 231. Chapter 42. TGA Thermograms 232. Chapter 43. DMA Spectra 233. Index
