1. The Chemistry and Applications of Benzoxazines
Reporter: Meng Wei Wang
Advising Prof: Ru Jong Jeng
Hatsuo Ishida and Tarek Agag, Handbook of Benzoxazine Resins

2. Outline Chemistry of benzoxazines Recent development of benzoxazines
Synthesis
Ring-opening mechanisms
Recent development of benzoxazines
Monomeric benzoxazines
Main chain type
Side chain type
Another applications for benzoxazine resins
Conclusions

3. Benzoxazine (Bz) resins
Benzene
Polybenzoxazine themosets.
1. Low cost of raw materials Low water absorption
2. No need for harsh catalysts Low surface energy
3. No by-product Superior electrical properties
4. Small shrinkage in curing Considerable flexibility in the
molecular design.
How to synthesize benzoxazines?
5,6Wang, C.-F., et al ,Angew. Chem. Int. Ed. 2006, 45, 2248.
7Ishida, H., et al ,J. Polym. Sci. Part A: Polym. Chem. 1994, 32, 1121.

4. One-pot procedure (Traditional procedure)
Brunovska, Z.; Liu, J.-P.; Ishida, H. Macromol. Chem. Phys.1999, 200, 1745.

5. Two-pot procedure
Lin. C.H., et al ,Polymer 2008, 49, 1220

6. Ring-opening mechanism of benzoxazines
What is the mechanism
of polymerization?

7. Type I - Phenoxy structure
Ishida, H., et al , Macromolecules 2000, 33, 2839.

8. Type II – Phenolic structure
Ishida, H., et al , Macromolecules 2000, 33, 2839.

9. Main chain rearrangement
Endo, T., et al , Macromolecules 2008, 41, 9030.

10. The acceleration of benzoxazine polymerization (I)
Andreu, R. et al., J. Polym. Sci., Part A: Polym. Chem. 2008, 46, 3353.
When R1 is electron-withdrawing group → Decrease in the polymerization temp.
When R2 is electron-withdrawing group → Increase in the polymerization temp.
Gu, Y. et al., J. Polym. Sci., Part A: Polym. Chem. 2011, 49, 1443.

11. The acceleration of benzoxazine polymerization (II)
Ronda, J. C., et al., J. Polym. Sci., Part A: Polym. Chem. 2008, 46, 3353.
Endo, T., Macromolecules 2010, 43, 1185.
Ishida, H., Macromolecules 2012, 45, 8119.

12. Outline Chemistry of benzoxazines Recent development of benzoxazines
Synthesis
Ring-opening mechanisms
Recent development of benzoxazines
Monomeric benzoxazines
Main chain type
Side chain type
Another applications for benzoxazine resins
Conclusions

13. Monomeric benzoxazines (I)
Bisphenol type
Diamine type
Sample
Tg (oC)
Td (oC)
Char yield (%)
P(13)
208
425 52
P(F-a)
155
314 49
Poor mechanical property
Lin. C.H., et al ,Polymer 2008, 49, 1220

14. Monomeric benzoxazines (II)
Takeichi, T., et al, Macromolecules 2001, 34, 7257.
Sample
Tg (oC)
PPa
161
PP-appe
251
PBa
171
PB-appe
318
Curing
Lin, C. H., et al, J. Polym. Sci. Part A: Polym. Chem. 2010, 48, 4555.

15. Main chain type polybenzoxazine precursors
Takeichi, T., et al, Polymer 2005, 46,
Lin. C.H., et al ,Polym. Chem. 2012, 3, 935

16. Side chain type polybenzoxazine precursors
Kimura. H., et al , J. Appl. Polym. Sci. 2001, 79, 555
Sample
Tg (oC)
Va/DGEBA
174
VBa/DGEBA
143
Endo. T., et al , J. Polym. Sci. Part A: Polym. Chem. 2011, 49, 3174

17. Outline Chemistry of benzoxazines Recent development of benzoxazines
Synthesis
Ring-opening mechanisms
Recent development of benzoxazines
Monomeric benzoxazines
Main chain type
Side chain type
Another applications for benzoxazine resins
Conclusions

18. Another applications for benzoxazine resins (I)
Ishida, H., et al., Polym. Chem. 2011, 49, 4335.
Takeichi, T., et al, Polymer 2008, 49, 1173.
Takeichi, T., et al, J. Polym. Sci. Part A: Polym. Chem. 2001, 39, 2633.

19. Another applications for benzoxazine resins (II)
Ishida, H., et al., Macromolecules 2012, 45, 8991.
Endo, T., et al .ACS Macro Lett. 2013, 2, 1.

20. Conclusions Considerable flexibility in the molecule-design Crosslink
No by-product
Future work
More functionality
Brittle
Ring-open temperature

21. Thanks for your attention.