Borated benzoxazine for use in the synthesis of polybenzoxazine

Patent metadata

Field	Value
Publication number	US-10800795-B2
Application number	US-201816617650-A
Country	US
Kind code	B2
Filing date	May 28, 2018
Priority date	May 31, 2017
Publication date	Oct 13, 2020
Grant date	Oct 13, 2020

Abstract

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

in which: Z represents an at least divalent, aliphatic, cycloaliphatic or aromatic, bonding group comprising at least one carbon atom and optionally at least one heteroatom chosen from O, S and P; and R 1 , R 2 , R 3 and R 4 , which are identical or different, represent hydrogen or an alkyl comprising from 1 to 12 carbon atoms, it being possible for R 1 and R 2 , on the one hand, and R 3 and R 4 , on the other hand, optionally to form a heterocycle with the two oxygen atoms and the boron atom to which they are respectively bonded.

First claim

The invention claimed is:

1. A borated benzoxazine compound corresponding to the formula:

in which:
Z represents an at least divalent aliphatic, cycloaliphatic or aromatic bonding group comprising at least one carbon atom and optionally at least one heteroatom chosen from O, S and P; and
R 1 , R 2 , R 3 and R 4 , which are identical or different, represent hydrogen or an alkyl comprising from 1 to 12 carbon atoms, it being possible for R 1 and R 2 , or R 3 and R 4 , or both R 1 and R 2 , and R 3 and R 4 , optionally to form a heterocycle with the two oxygen atoms and the boron atom to which they are respectively bonded.

2. The borated benzoxazine compound according to claim 1 , wherein Z comprises an aromatic group comprising from 6 to 30 carbon atoms.

3. The borated benzoxazine compound according to claim 2 corresponding to the formula (A-1):

4. The borated benzoxazine compound according to claim 1 , wherein Z represents an aliphatic group comprising from 1 to 20 or a cycloaliphatic group comprising from 3 to 20 and optionally at least one heteroatom chosen from O and S.

5. The borated benzoxazine compound according to claim 4 , wherein Z represents a (poly)alkylene sequence comprising from 1 to 20 carbon atoms and optionally at least one heteroatom chosen from O and S.

6. The borated benzoxazine compound according to claim 5 corresponding to one of the formulae (A-2) to (A-5):

7. The borated benzoxazine compound according to claim 1 , wherein R 1 , R 2 , R 3 and R 4 , which are identical or different, represent an alkyl.

8. The borated benzoxazine compound according to claim 7 , wherein the alkyl comprises from 1 to 8 carbon atoms.

9. The borated benzoxazine compound according to claim 1 , wherein both R 1 and R 2 , and R 3 and R 4 , form a heterocycle with the two oxygen atoms and the boron atom to which they are respectively bonded.

10. The borated benzoxazine compound according to claim 9 , wherein each heterocycle corresponds to one of the formulae (a), (b) or (c) below:

11. The borated benzoxazine compound according to claim 10 , wherein each heterocycle corresponds to the formula (a).

12. The borated benzoxazine compound according to claim 1 , wherein the boron atom 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.

13. The borated benzoxazine compound according to claim 12 corresponding to one of the formulae (A-1-a) to (A-5-a) below:

in which the symbols x and n represent an integer such that Z comprises from 1 to 20 carbon atoms.

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

in which:
Z represents an at least divalent aliphatic, cycloaliphatic or aromatic bonding group comprising at least one carbon atom and optionally at least one heteroatom chosen from O, S and P; and
R 1 , R 2 , R 3 and R 4 , which are identical or different, represent hydrogen or an alkyl comprising from 1 to 12 carbon atoms, it being possible for R 1 and R 2 , or R 3 and R 4 , or both R 1 and R 2 , and R 3 and R 4 , optionally to form a heterocycle with the two oxygen atoms and the boron atom to which they are respectively bonded;
wherein the borated benzoxazine compound corresponding to the formula (A), as a first monomer, is polycondensated with, as second monomer, at least a brominated benzoxazine having the formula (B):

in which Z′, which is identical to or different from Z, represents an at least divalent, aliphatic, cycloaliphatic or aromatic, bonding group comprising at least one carbon atom and optionally at least one heteroatom chosen from O, S and P.

15. The process according to claim 14 , wherein Z′ comprises an aromatic group comprising from 6 to 30 carbon atoms.

16. The process according to claim 14 , wherein Z′ represents a (poly)alkylene sequence comprising from 1 to 20 carbon atoms.

17. A borated benzoxazine compound corresponding to the formula:

in which:
Z represents an aliphatic, cycloaliphatic or aromatic bonding group comprising at least one carbon atom and optionally at least one heteroatom chosen from O, S and P; and
R 1 , R 2 , R 3 and R 4 , which are identical or different, represent hydrogen or an alkyl comprising from 1 to 12 carbon atoms, it being possible for R 1 and R 2 , or R 3 and R 4 , or both R 1 and R 2 , and R 3 and R 4 , optionally to form a heterocycle with the two oxygen atoms and the boron atom to which they are respectively bonded.

Assignees

• Michelin & Cie

Inventors

• Fedurco Milan
• Ribezzo Marco

Classifications

• C08G2261/344

  containing heteroatoms · CPC title

• C08G2261/76

  crosslinking · CPC title

• C07D265/16 Primary

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

• C08G2261/411

  Suzuki reactions · CPC title

• C09J179/04

  Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors · CPC title