Claims
- 1. A method of uncatalyzed chain extension by Michaels addition of a bismaleimide with a polyhydric phenol consisting essentially of reacting in the absence of a catalyst the carbon-carbon double bonds of a bismaleimide selected from the group consisting of ##STR6## where R.sub.a and R.sub.b each independently is hydrogen, an alkyl or alkoxy group containing up to 4 carbon atoms, chlorine, or bromine, or R.sub.a and R.sub.b together form a fused 6-membered hydrocarbon aromatic ring, with the proviso that R.sub.a and R.sub.b are not t-butyl or t-butoxy, where X is O, S, or Se, i is 1-3, and the alkylene bridging group is optionally substituted by 1-3 methyl groups or by fluorine, with the hydroxyl groups of about 0.05 to about 2.0 molar proportion of a polyhydric phenol and recovering the chain-extended product.
- 2. The method of claim 1 where the bismaleimide is 1,2-bis(2-maleimidophenylthio)ethane.
- 3. The method of claim 1 where the polyhydric phenol is a dihydric phenol.
- 4. The method of claim 3 where the dihydric phenol is selected from the group consisting of resorcinols, pyrocatechols, hydroquinones, dihydroxynaphthalenes, and phenols of the formula ##STR7## where Y is a covalent bond or Y is selected from the group consisting of CH.sub.2, C=O, C(CH.sub.3).sub.2, C(CF.sub.3).sub.2, O, S, SO.sub.2, SO, and R.sub.c, R.sub.d are independently selected from the group consisting of hydrogen and alkyl or alkoxy containing from 1 to about 10 carbon atoms.
- 5. The method of claim 4 where the phenol has said formula where Y is a covalent bond.
- 6. The method of claim 4 where the phenol has the said formula where Y is C(CH.sub.3).sub.2 or C(CF.sub.3).sub.2.
- 7. The method of claim 1 where the polyhydric phenol is at least a trihydric phenol.
- 8. The method of claim 7 where the polyhydric phenol is selected from the group consisting of tris(hydroxyphenyl)methane, 1,1,1-tris(hydroxyphenyl)ethane, tetrakis(hydroxyphenyl)methane, 1,3,5-tris(hydroxyphenyl)benzene, 1,1,2,2-tetrakis(hydroxyphenyl)ethane, and phenolformaldehyde condensation products.
- 9. The method of claim 1 where the bismaleimide is reacted with from about 0.1 to about 1.0 molar proportion of the polyhydric phenol.
- 10. A thermosetting resin uncatalyzed reaction product by Michaels addition of the carbon-carbon double bonds of a bismaleimide selected from the group consisting of ##STR8## where R.sub.a and R.sub.b each independently is hydrogen, an alkyl or alkoxy group containing up to 4 carbon atoms, chlorine, or bromine, or R.sub.a and R.sub.b together form a fused 6-membered hydrocarbon aromatic ring, with the proviso that R.sub.a and R.sub.b are not t-butyl or t-butoxy, where X is O, S, or Se, i is 1-3, and the alkylene bridging group is optionally substituted by 1-3 methyl groups or by fluorine with the hydroxyl groups of 0.05 to about 2.0 molar proportion of a polyhydric phenol, said resin characterized by the absence of a base catalyst as a discrete nonreactive component and further characterized by having a difference of at least 100.degree. C. between melting point and onset of thermal polymerization.
- 11. The thermosetting resin of claim 10 where the bismaleimide is 1,2-bis(2-maleimidophenylthio)ethane.
- 12. The thermosetting resin of claim 10 where the polyhydric phenol is a dihydric phenol.
- 13. The thermosetting resin of claim 12 where the dihydric phenol is selected from the group consisting of resorcinols, pyrocatechols, hydroquinones, dihydroxynaphthalenes, and phenols of the formula ##STR9## where Y is a covalent bond or Y is selected from the group consisting of CH.sub.2, C=O, C(CH.sub.3).sub.2, C(CF.sub.3).sub.2, O, S, SO.sub.2, SO, and R.sub.c, R.sub.d are independently selected from the group consisting of hydrogen and alkyl or alkoxy containing from 1 to about 10 carbon atoms.
- 14. The thermosetting resin of claim 13 where the phenol has said formula where Y is a covalent bond.
- 15. The thermosetting resin of claim 13 where the phenol has the said formula where Y is C(CH.sub.3).sub.2 or C(CF.sub.3).sub.2.
- 16. The thermosetting resin of claim 10 where the polyhydric phenol is at least a trihydric phenol.
- 17. The thermosetting resin of claim 16 where the polyhydric phenol is selected from the group consisting of tris(hydroxyphenyl)methane, 1,1,1-tris(hydroxyphenyl)ethane, tetrakis(hydroxyphenyl)methane, 1,3,5-tris(hydroxyphenyl)benzene, 1,1,2,2-tetrakis(hydroxyphenyl)ethane, and phenolformaldehyde condensation products.
- 18. The thermosetting resin of claim 10 where the bismaleimide is reacted with from about 0.1 to about 1.0 molar proportion of the polyhydric phenol.
- 19. A polymer resulting from thermally curing a uncatalyzed chain-extended reaction product by Michaels addition of the carbon-carbon double bonds of a bismaleimide selected from the group consisting of ##STR10## where R.sub.a and R.sub.b each independently is hydrogen, an alkyl or alkoxy group containing up to 4 carbon atoms, chlorine, or bromine, or R.sub.a and R.sub.b together form a fused 6-membered hydrocarbon aromatic ring, with the proviso that R.sub.a and R.sub.b are not t-butyl or t-butoxy, where X is O, S, or Se, i is 1-3, and the alkylene bridging group is optionally substituted by 1-3 methyl groups or by fluorine with the hydroxyl group of 0.05 to about 2.0 molar proportion of a polyhydric phenol, said resin characterized by the absence of a base catalyst as a discrete nonreactive component and further characterized by having a difference of at least 100.degree. C. between melting point and onset of thermal polymerization.
- 20. The polymer of claim 19 where the bismaleimide is 1,2-bis(2-maleimidophenylthio)ethane.
- 21. The polymer of claim 19 where the polyhydric phenol is a dihydric phenol.
- 22. The polymer of claim 21 where the dihydric phenol is selected from the group consisting of resorcinols, pyrocatechols, hydroquinones, dihydroxynaphthalenes, and phenols of the formula ##STR11## where Y is a covalent bond or Y is selected from the group consisting of, CH.sub.2, C=O, C(CH.sub.3).sub.2, C(CF.sub.3).sub.2, O, S, SO.sub.2, SO, and R.sub.c, R.sub.d are independently selected from the group consisting of hydrogen and alkyl or alkoxy containing from 1 to about 10 carbon atoms.
- 23. The polymer of claim 22 where the phenol has said formula where Y is a covalent bond.
- 24. The polymer of claim 22 where the phenol has the said formula where Y is C(CH.sub.3).sub.2 or C(CF.sub.3).sub.2.
- 25. The polymer of claim 19 where the polyhydric phenol is at least a trihydric phenol.
- 26. The polymer of claim 25 where the polyhydric phenol is selected from the group consisting of tris(hydroxyphenyl)methane, 1,1,1-tris(hydroxyphenyl)ethane, tetrakis(hydroxyphenyl)methane, 1,3,5-tris(hydroxyphenyl)benzene, 1,1,2,2-tetrakis(hydroxyphenyl)ethane, and phenolformaldehyde condensation products.
- 27. The polymer of claim 19 where the bismaleimide is reacted with from about 0.1 to about 1.0 molar proportion of the polyhydric phenol.
REFERENCE TO RELATED APPLICATIONS
This is a continuation-in-part of U.S. patent application Ser. No. 07/306,002, filed Feb. 2, 1989, now abandoned.
US Referenced Citations (1)
Number |
Name |
Date |
Kind |
4464520 |
Adams et al. |
Aug 1984 |
|
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Non-Patent Literature Citations (3)
Entry |
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Stenzenberger et al. "Toughened Bismaleimides: Concepts, Achievements, Directions", 19th Int'l SAMPE Tech. Conf. Oct. 13-15, 1987. |
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Continuation in Parts (1)
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Number |
Date |
Country |
Parent |
306002 |
Feb 1989 |
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