Polybenzoxazine composition

Patent metadata

Field	Value
Publication number	US-9416302-B2
Application number	US-201314419050-A
Country	US
Kind code	B2
Filing date	Sep 24, 2013
Priority date	Sep 28, 2012
Publication date	Aug 16, 2016
Grant date	Aug 16, 2016

Abstract

A polymerizable composition comprising a benzoxazine compound and a catalyst is described. The polymerizable composition may be cured to produce compositions useful in coating, sealants, adhesive and many other applications.

First claim

What is claimed is:

1. A polymerizable composition comprising:
a) a benzoxazine, and
b) a catalyst selected from elemental sulfur, elemental selenium, and sulfides or selenides of Group V or VI elements.

2. The polymerizable composition of claim 1 comprising 0.1 to 10 mole percent of said catalyst.

3. The polymerizable composition of claim 1 further comprising a toughening agent.

4. The polymerizable composition of claim 1 , wherein said toughening agent is present at between about 3% and 35% by weight of the benzoxazine.

5. The polymerizable composition of claim 1 , wherein said toughening agent is a polymeric compound having both a rubbery phase and a thermoplastic phase.

6. The polymerizable composition of claim 5 , wherein said toughening agent is a graft polymer having a polymerized, diene, rubbery core and a shell grafted thereto of an acrylic acid ester, a methacrylic acid ester, a monovinyl aromatic hydrocarbon, or a mixture thereof.

7. The polymerizable composition of claim 6 , wherein said rubbery core comprises polymerized butadiene or a polymerized mixture of butadiene and styrene.

8. The polymerizable composition of claim 6 , wherein said shell comprises a methacrylic acid ester.

9. The polymerizable composition of claim 8 , wherein said methacrylic acid ester comprises a C 1 -C 4 alkyl substituted methacrylate.

10. The polymerizable composition of claim 6 , wherein said shell comprises a monovinyl aromatic hydrocarbon.

11. The polymerizable composition of claim 10 , wherein said monovinyl aromatic hydrocarbon is selected from styrene, alpha-methylstyrene, vinyltoluene, vinylxylene, ethylvinylbenzene, isopropylstyrene, chlorostyrene, dichlorostyrene, and ethylchlorostyrene.

12. The polymerizable composition of claim 5 , wherein said toughening agent is a core-shell polymer wherein the core is a rubbery polyacrylate polymer having a glass transition temperature below about 0° C. and the shell is grafted thereto and is a thermoplastic polyacrylate polymer having a glass transition temperature above about 25° C.

13. The polymerizable composition of claim 12 , wherein said core is selected from polybutylacrylate and polyisooctylacrylate and said shell is polymethylmethacrylate.

14. The polymerizable composition of claim 6 , wherein said toughening agent is an elastomeric particle having a T g below about 25° C. that is a polymerized mixture of free-radical polymerizable monomers and a polymeric stabilizer that is soluble in the polymerizable composition.

15. The polymerizable composition of claim 6 , wherein the toughening agent comprises nucleophilic reactive groups that may ring open a portion of the benzoxazine.

16. The polymerizable composition of claim 1 comprising a mixture of benzoxaxines derived from both aliphatic and aryl amines.

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

18. The polymerized composition of claim 1 comprising one or more polymers of the formula:

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;
R 5 is the (hetero)hydrocarbyl residue of a primary amino compound, R 5 (NH 2 ) m , where m is 1-4; and
y+z is at least 2, and
the residue of the catalyst.

19. The polymerized composition of claim 18 , wherein R 5 is a poly(alkyleneoxy) group.

20. The polymerized composition of claim 18 , wherein R 5 comprises a mixture of aryl groups and aliphatic groups.

21. The polymerizable composition of claim 1 , further comprising a reactive diluent.

22. The polymerizable composition of claim 21 wherein the reactive diluent is of the formula:
R 8 —(ZH) p ,

where
R 8 is the (hetero)hydrocarbyl group,
Z is —S—or —NR 9 , where each R 9 is H or a hydrocarbyl group, and
p is at least 2.

23. The polymerizable composition of claim 22 , wherein the ratio of the sum of amine or thiol groups from the compound R 8 —(ZH) p , to the benzoxazine groups is about 3:1 to 100:1.

24. The polymerizable composition of claim 1 , further comprising a film-forming polymer or oligomer.

25. The polymerizable composition of claim 24 , wherein the film-forming polymer is present in amounts of 1 to 75 wt %, relative to the benzoxazine.

26. The polymerizable composition of claim 1 further comprising an epoxy resin.

Assignees

• 3M Innovative Properties Co

Inventors

• Salnikov Dmitriy
• Gorodisher Ilya
• Webb Robert J

Classifications

• C08L51/04

  grafted on to rubbers · CPC title

• C08G65/26

  from cyclic ethers and other compounds · CPC title

• C08G73/06

  Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule · CPC title

• C08G65/2612

  containing aromatic or arylaliphatic hydroxyl groups · CPC title

• C08K5/357

  Six-membered rings · CPC title