the chemistry and applications of benzoxazines reporter: meng wei wang advising prof: ru jong jeng...
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![Page 1: The Chemistry and Applications of Benzoxazines Reporter: Meng Wei Wang Advising Prof: Ru Jong Jeng Hatsuo Ishida and Tarek Agag, Handbook of Benzoxazine](https://reader035.vdocuments.us/reader035/viewer/2022070403/56649f335503460f94c4f203/html5/thumbnails/1.jpg)
The Chemistry and Applications of Benzoxazines
Reporter: Meng Wei Wang
Advising Prof: Ru Jong Jeng
Hatsuo Ishida and Tarek Agag, Handbook of Benzoxazine Resins
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Outline
Chemistry of benzoxazines Synthesis Ring-opening mechanisms
Recent development of benzoxazines Monomeric benzoxazines Main chain type Side chain type
Another applications for benzoxazine resins Conclusions
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Benzoxazine (Bz) resins
1. Low cost of raw materials 5. Low water absorption2. No need for harsh catalysts 6. Low surface energy 3. No by-product 7. Superior electrical properties4. Small shrinkage in curing 8. Considerable flexibility in the molecular design.
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.
R1
NOR2
R1
OH
N
R2n
Benzene
Oxazine
Polybenzoxazine themosets.
How to synthesize benzoxazines?
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One-pot procedure (Traditional procedure)R1
N
O
R1 OH + 2 CH2O + H2N
n NH2 + (CH2O)n70oC
n
NHCH2OH
NHCH2OH
3N
N N+ 3 H2O
70oC
Brunovska, Z.; Liu, J.-P.; Ishida, H. Macromol. Chem. Phys.1999, 200, 1745.
Mechanism:
N N
NN
OH OH
1/3
N
OH
OH
NOH
N
OO
H
HO H
+ HO
H
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Two-pot procedure
XH2N NH2 C
O
HH4 OH2
XN NO
O
dioxane
XHN NHHO
OH
XH2N NH2C
OHO
HXN N
HO
OH
C
H
H
S
O
O
CH3
CH3
O O
OO
2DMF
NaBH4
ethanol
CHCl3
C
O
HH
X (gel or insoluble product)
X =
for(1, 5, 9, 13)
for(2, 6, 10, 14)
for(3, 7, 11, 15)
for(4, 8, 12, 16)
(1-4) (5-8)
(9-12)
(13-16)
Lin. C.H., et al ,Polymer 2008, 49, 1220
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Ring-opening mechanism of benzoxazines
What is the mechanism of polymerization?
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Type I - Phenoxy structure
Ishida, H., et al , Macromolecules 2000, 33, 2839.
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Type II – Phenolic structure
Ishida, H., et al , Macromolecules 2000, 33, 2839.
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Main chain rearrangement
Endo, T., et al , Macromolecules 2008, 41, 9030.
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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.
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The acceleration of benzoxazine polymerization (II)
Endo, T., Macromolecules 2010, 43, 1185.
Ronda, J. C., et al., J. Polym. Sci., Part A: Polym. Chem. 2008, 46, 3353.
Ishida, H., Macromolecules 2012, 45, 8119.
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Outline
Chemistry of benzoxazines Synthesis Ring-opening mechanisms
Recent development of benzoxazines Monomeric benzoxazines Main chain type Side chain type
Another applications for benzoxazine resins Conclusions
![Page 13: The Chemistry and Applications of Benzoxazines Reporter: Meng Wei Wang Advising Prof: Ru Jong Jeng Hatsuo Ishida and Tarek Agag, Handbook of Benzoxazine](https://reader035.vdocuments.us/reader035/viewer/2022070403/56649f335503460f94c4f203/html5/thumbnails/13.jpg)
Monomeric benzoxazines (I)
NOR
R'
R'
OH
N
R
R'
OH
n
Lin. C.H., et al ,Polymer 2008, 49, 1220
Sample Tg (oC) Td (oC) Char yield (%)
P(13) 208 425 52
P(F-a) 155 314 49
Poor mechanical property
Bisphenol type Diamine type
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Monomeric benzoxazines (II)
Curing
Sample Tg (oC)
PPa 161
PP-appe 251
PBa 171
PB-appe 318
Takeichi, T., et al, Macromolecules 2001, 34, 7257.
Lin, C. H., et al, J. Polym. Sci. Part A: Polym. Chem. 2010, 48, 4555.
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Main chain type polybenzoxazine precursors
Takeichi, T., et al, Polymer 2005, 46, 12172.
Lin. C.H., et al ,Polym. Chem. 2012, 3, 935
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Side chain type polybenzoxazine precursors
Sample Tg (oC)
Va/DGEBA 174
VBa/DGEBA 143
Kimura. H., et al , J. Appl. Polym. Sci. 2001, 79, 555
Endo. T., et al , J. Polym. Sci. Part A: Polym. Chem. 2011, 49, 3174
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Outline
Chemistry of benzoxazines Synthesis Ring-opening mechanisms
Recent development of benzoxazines Monomeric benzoxazines Main chain type Side chain type
Another applications for benzoxazine resins Conclusions
![Page 18: The Chemistry and Applications of Benzoxazines Reporter: Meng Wei Wang Advising Prof: Ru Jong Jeng Hatsuo Ishida and Tarek Agag, Handbook of Benzoxazine](https://reader035.vdocuments.us/reader035/viewer/2022070403/56649f335503460f94c4f203/html5/thumbnails/18.jpg)
Another applications for benzoxazine resins (I)
Takeichi, T., et al, J. Polym. Sci. Part A: Polym. Chem. 2001, 39, 2633.
Ishida, H., et al., Polym. Chem. 2011, 49, 4335.
Takeichi, T., et al, Polymer 2008, 49, 1173.
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Another applications for benzoxazine resins (II)Ishida, H., et al., Macromolecules 2012, 45, 8991.
Endo, T., et al .ACS Macro Lett. 2013, 2, 1.
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Conclusions
Considerable flexibility in the molecule-design Crosslink No by-product
Future work More functionality Brittle Ring-open temperature
R1
NOR2
R1
OH
N
R2n
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Thanks for your attention.