Benzoxazine composition

Patent metadata

Field	Value
Publication number	US-10731003-B2
Application number	US-201716323568-A
Country	US
Kind code	B2
Filing date	Sep 14, 2017
Priority date	Sep 15, 2016
Publication date	Aug 4, 2020
Grant date	Aug 4, 2020

Abstract

The disclosure provides a catalyst for use with a benzoxazine resins which imparts accelerated curing at reduced temperatures. The catalyst is selected from elemental halogen or onium polyhalide compounds.

First claim

What is claimed is:

1. A polymerizable composition comprising:
a) a benzoxazine, and
b) an elemental halogen or an onium polyhalide catalyst, wherein the onium polyhalide is of the formula
Q + X (2n+1) − ,

where 1≤n≤4,
Q is onium group, selected from ammonium, sulfonium and phosphonium; and
each X is a halide, and when the composition is heated, produces a poly(benzoxazine).

2. The composition of claim 1 wherein the elemental halogen is used in amounts of 0.5 to 20% by mass relative to the total composition.

3. The composition of claim 1 wherein the onium polyhalide is used in 0.5 to 20% by mass relative to the total composition.

4. The composition of claim 1 wherein the onium polyhalide is of the formula
Q + X (2n+1) − ,
where 1≤n≤4,
Q is onium group, selected from ammonium, sulfonium and phosphonium; and
each X is a halide.

5. The composition of claim 4 wherein Q is selected from ammonium groups of the formula (R 1 ) 4 N + , sulfonium groups of the formula (R 1 ) 3 S + or phosphonium groups of the formula (R 1 ) 4 P + ,
wherein each R 1 is independently H, alkyl, aryl, or combinations thereof with the proviso that no more than one R 1 is H.

6. The composition of claim 4 wherein Q is an ammonium group selected from the group consisting of a pyridinium, pyrrolidinium or imidazolium group.

7. The composition of claim 6 wherein Q is an ammonium group selected from the group consisting of a pyridinium, pyrrolidinium or imidazolium group of the formulas:

wherein each R 1 is independently H, alkyl, aryl, or combinations thereof with the proviso that no more than one R 1 is H.

8. The composition of claim 6 wherein Q is (R 1 ) 4 N + , wherein each R 1 is independently H, alkyl, aryl, or combinations thereof with the proviso that no more than one R 1 is H.

9. The composition of claim 4 wherein subscript n is 2.

10. The composition of claim 1 wherein said benzoxazine compound comprises at least one ring of the formula:

where R is a (hetero)hydrocarbyl group.

11. The polymerizable composition of claim 10 wherein said benzoxazine is of the formula:

wherein
each R 1 is H or an alkyl group, and is the residue of an aliphatic aldehyde,
R 2 is H, a covalent bond, or a polyvalent (hetero)hydrocarbyl group, preferably H, a covalent bond or a divalent alkyl group;
R 5 is the (hetero)hydrocarbyl residue of a primary amino compound;
R 5 is the residue of a primary amino compound;
z is at least 1.

12. The polymerizable composition of claim 10 where the benzoxazine is of the formula:

wherein
each R 1 is H or an alkyl group, and is the residue of an aliphatic aldehyde,
R 2 is H, a covalent bond, a phenol or a polyvalent (hetero)hydrocarbyl group, preferably H, a covalent bond or a divalent alkyl group;
R 5 is (hetero)hydrocarbyl residue of a primary amino compound, with the proviso that R 2 is not H when subscript x is >1; and
subscript m is 1 to 4.

13. The polymerizable composition of claim 1 comprising a mixture of two or more benzoxaxines.

14. The polymerizable composition of claim 1 comprising a benzoxazines derived from poly(alkyleneoxy) diamines.

15. The polymerizable composition of claim 1 , further comprising a co-curative.

16. The polymerizable composition of claim 15 wherein the co-curative is of the formula:
R 30 —(ZH) p   (XII)

wherein, in Formula (XII):
R 30 is a (hetero)hydrocarbyl group;
each Z is independently —S— or NR 31 , where R 31 is H or a hydrocarbyl group, including aryl and alkyl; and
p is 1 to 6 (in certain embodiments, p is at least 2).

17. The polymerizable composition of claim 16 , wherein the ratio of the sum of amine and/or thiol groups from the compound R 30 —(ZH) p , to the benzoxazine groups is about 3:1 to 100:1.

18. The polymerizable composition of claim 15 wherein the co-curative is of the formula:
R 30 (NHR 31 ) p
wherein, R 30 is a (hetero)hydrocarbyl group;
R 31 is H or a hydrocarbyl group, including aryl and alkyl; and
p is 1 to 6.

19. The polymerizable composition of claim 15 wherein the co-curative is of the formula: R 30 —(SH) p
wherein, R 30 is a (hetero)hydrocarbyl group; and
p is 1 to 6.

Assignees

• 3M Innovative Properties Co

Inventors

• Sorenson Gregory P
• Gorodisher Ilya
• Webb Robert J

Classifications

• C08G14/06

  and monomers containing hydrogen attached to nitrogen · CPC title

• C09D161/34

  Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C09D161/04, C09D161/18 and C09D161/20 · CPC title

• C08G73/0233 Primary

  Polyamines derived from (poly)oxazolines, (poly)oxazines or having pendant acyl groups · CPC title