Curable benzoxazine compositions with improved thermal stability

Patent metadata

Field	Value
Publication number	US-10023698-B2
Application number	US-201515515162-A
Country	US
Kind code	B2
Filing date	Dec 8, 2015
Priority date	Dec 18, 2014
Publication date	Jul 17, 2018
Grant date	Jul 17, 2018

Abstract

A curable benzoxazine composition is described wherein the benzoxazine is derived from an aryl amine having a b.p.>200° C. The curable compositions are more thermally stable and have reduced weight loss and by-products upon cure.

First claim

What is claimed is:

1. A curable composition comprising a curable benzoxazine of the formula:

where
each R 1 is an alkyl or H;
each R 2 is an H, an alkyl, an aryl or a benzoxazine group;
y is 1 to 4
R aryl is derived from an aryl amine having a boiling point greater than 200° C.;
N-Bz represents a nitrogen-linked benzoxazine group, and
z is 0 to 3; and
a curative selected from the group of a thiol compounds, amine compounds, and a combination thereof.

2. The curable composition of claim 1 wherein the benzoxazine is derived from bisphenol-A.

3. The curable composition of claim 1 wherein R aryl is derived from an aryl amine having a boiling point greater than 210° C.

4. The curable composition of claim 1 wherein R aryl is derived from an aryl diamine and z is 1.

5. The curable composition of claim 1 wherein R aryl is selected from phenyl, napthyl, anthracenyl and biphenyl, each optionally substituted with one or more alkyl or aryl groups.

6. The curable composition of claim 1 , wherein z is 0 or 1.

7. The curable composition of claim 1 derived from a phenol having a b.p.>200° C.

8. The curable composition of claim 1 further comprising a polyfunctional curative.

9. The curable composition of claim 1 further comprising a toughening agent.

10. The curable composition of claim 9 , wherein said toughening agent is present at between about 3% and 35% by weight relative to the benzoxazine.

11. The curable composition of claim 1 , further comprising a co-catalyst.

12. The curable composition of claim 11 wherein the co-catalyst is an acid catalyst.

13. The curable composition of claim 12 wherein the acid catalyst is a blocked acid catalyst.

14. The curable composition of claim 13 wherein the blocked acid catalyst is a tosylate.

15. The curable composition of claim 1 wherein the thiol curative is a polythiol.

16. The curable composition of claim 1 wherein the amine curative is a polyamine.

17. The curable composition of claim 1 wherein the curative is of the formula:
R 30 —(ZH) p

wherein,
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.

18. The curable composition of claim 17 wherein p is 2 to 6.

19. The curable composition of claim 17 wherein the molar amounts ratio of benzoxazine groups to the “Z” groups, is 3:2 to 100:1.

20. The curable composition of claim 17 wherein the molar amounts ratio of benzoxazine groups to the “Z” groups, is 4:1 to 50:1.

21. The curable composition of claim 1 wherein the curative is present in an amount of at least 5 wt. %, to 60% of the benzoxazine equivalent.

22. The curable composition of claim 1 further comprising an epoxy resin.

23. The curable composition of claim 22 wherein the epoxy resin is used in amounts of 3 to 35 wt. % relative to the benzoxazine.

Assignees

• 3M Innovative Properties Co

Inventors

• Gorodisher Ilya
• Sorenson Gregory P
• Mccormick Mark
• Huikko Katri M
• Webb Robert J

Classifications

• C09D179/02

  Polyamines · CPC title

• C08G73/0233 Primary

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

• C07D265/16

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