Halogenated benzoxazine for use in the synthesis of polybenzoxazine

Patent metadata

Field	Value
Publication number	US-10975044-B2
Application number	US-201716616266-A
Country	US
Kind code	B2
Filing date	May 24, 2017
Priority date	May 24, 2017
Publication date	Apr 13, 2021
Grant date	Apr 13, 2021

Abstract

A halogenated benzoxazine compound, which can be used in particular as monomer in the synthesis of polybenzoxazine, corresponds to the formula:

in which: each benzene nucleus of the two oxazine rings bears at least one halogen (represented by the symbol Hal), in particular bromine, chlorine or fluorine; and Z 1 and Z 2 , which are identical or different, represent an aliphatic, at least divalent, bonding group comprising at least one carbon atom and optionally at least one heteroatom chosen from O, S, N and P.

First claim

The invention claimed is:

1. A halogenated benzoxazine compound corresponding to the formula:
(A)

in which:
Hal represents at least one halogen;
each benzene nucleus of the two oxazine rings bears at least one halogen; and
Z 1 and Z 2 , which are identical or different, represent an aliphatic, at least divalent, bonding group comprising at least one carbon atom and optionally at least one heteroatom chosen from O, S, N and P.

2. The halogenated benzoxazine compound according to claim 1 , wherein Z 1 and Z 2 , which are identical or different, represent an aliphatic group comprising from 1 to 12 carbon atoms.

3. The halogenated benzoxazine compound according to claim 2 , wherein Z 1 and Z 2 , which are identical or different, represent a (poly)alkylene sequence comprising from 1 to 8 carbon atoms.

4. The halogenated benzoxazine compound according to claim 3 corresponding to the formula:

in which x 1 and x 2 , which are identical or different, represent an integer from 1 to 8.

5. The halogenated benzoxazine compound according to claim 1 , wherein Hal represents bromine, chlorine or fluorine.

6. The halogenated benzoxazine compound according to claim 1 , wherein each benzene nucleus of the two oxazine rings bears a single halogen.

7. The halogenated benzoxazine compound according to claim 6 , wherein the halogen borne by each benzene nucleus of the two oxazine rings is located in the para position with respect to the oxygen of the oxazine ring.

8. The halogenated benzoxazine compound according to claim 1 , wherein Hal represents bromine.

9. The halogenated benzoxazine compound according to claim 4 corresponding to the formula:

in which x 1 and x 2 , which are identical or different, represent an integer from 1 to 8.

10. The halogenated benzoxazine compound according to claim 9 corresponding to the formula:

11. A polybenzoxazine made by polycondensation of at least one compound corresponding to the formula:

in which:
Hal represents at least one halogen;
each benzene nucleus of the two oxazine rings bears at least one halogen; and
Z 1 and Z 2 , which are identical or different, represent an aliphatic, at least divalent, bonding group comprising at least one carbon atom and optionally at least one heteroatom chosen from O, S, N and P.

12. The polybenzoxazine according to claim 11 made by polycondensation of a compound corresponding to formula (A), as a first monomer, with at least an aromatic diol or thiol compound, as a second monomer.

13. The polybenzoxazine according to claim 12 , wherein the aromatic diol or thiol compound corresponds to the formula (B):
HX 1 —Ar 1 —Z 3 —Ar 2 —X 2 H

in which:
X 1 and X 2 , which are identical or different, represent O or S;
Ar 1 and Ar 2 , which are identical or different, represent a phenylene group; and
Z 3 represents O or (S) n , n representing an integer equal to or greater than 1.

14. The polybenzoxazine according to claim 13 , wherein the aromatic diol or thiol compound corresponds to at least one of the formulae (B-1), (B-2) or (B-3):

15. The polybenzoxazine according to claim 11 , wherein each benzene nucleus of the two oxazine rings bears a single halogen.

16. A process for the synthesis of a polybenzoxazine comprising the step of:
polycondensating a compound corresponding to the formula:

in which:
Hal represents at least one halogen;
each benzene nucleus of the two oxazine rings bears at least one halogen; and
Z 1 and Z 2 , which are identical or different, represent an aliphatic, at least divalent, bonding group comprising at least one carbon atom and optionally at least one heteroatom chosen from O, S, N and P.

17. The process according to claim 16 , wherein the compound corresponding to formula (A), as a first monomer, is polycondensated with at least an aromatic diol or thiol compound, as a second monomer.

18. The process according to claim 17 , wherein the aromatic diol or thiol compound corresponds to the formula (B):
HX 1 —Ar 1 —Z 3 —Ar 2 —X 2 H

in which:
X 1 and X 2 , which are identical or different, represent O or S;
Ar 1 and Ar 2 , which are identical or different, represent a phenylene group; and
Z 3 represents O or (S) n , n representing an integer equal to or greater than 1.

19. The process according to claim 18 , wherein the aromatic diol or thiol compound corresponds to at least one of formulae (B-1), (B-2) or (B-3) below:

20. The process according to claim 16 , wherein each benzene nucleus of the two oxazine rings bears a single halogen.

Assignees

• Michelin & Cie

Inventors

• Fedurco Milan
• Ribezzo Marco

Classifications

• C07D265/16 Primary

  with only hydrogen or carbon atoms directly attached in positions 2 and 4 · CPC title

• C07D263/62 Primary

  having two or more ring systems containing condensed 1,3-oxazole rings · CPC title