Amines and polymeric phenols and usage thereof as curing agents in one component epoxy resin compositions

Patent metadata

Field	Value
Publication number	US-9546243-B2
Application number	US-201313944312-A
Country	US
Kind code	B2
Filing date	Jul 17, 2013
Priority date	Jul 17, 2013
Publication date	Jan 17, 2017
Grant date	Jan 17, 2017

Abstract

The disclosure relates to solving problems associated with conventional latent epoxy curing agents by providing a new class of latent epoxy curing agents. In particular, the disclosure relates to epoxy curing agents with improved storage stability and low use level (e.g., less than about 10 wt % relative to the epoxy compound) by forming solid solutions of certain classes of amines in polyphenolic resins.

First claim

The invention claimed is:

1. A composition comprising dicyandimide, and a solid solution of at least one polyphenolic resin and at least one imidazole or substituted imidazoles represented by the general structure shown below:

wherein R 1 =amino alkyl substituted groups of 1-20 carbon atoms and R 2 , R 3 , and R 4 may be alkyl or aryl groups of 1-20 carbon atoms; wherein the polyphenolic resin comprises at least one phenol formaldehyde resin and wherein the solid solution has a particle size of about 2 to about 50 um.

2. The composition of claim 1 comprising 1,3-aminopropyl imidazole and polyphenolic resin.

3. The composition of claim 1 comprising 2-methylimidazole and polyphenolic resin.

4. The composition of claim 1 comprising 1,8-Diazabicyclo(5.4.0)undec-7-ene (DBU) and polyphenolic resin.

5. The composition of claim 1 comprising 2,4,6-Tris(dimethylamino)phenol and polyphenolic resin.

6. The composition of claim 1 comprising 2-Ethyl-4-methylimidazole and polyphenolic resin.

7. The composition of claim 1 wherein the polyphenolic resin comprises p-cresol-formaldehyde resins.

8. The composition of claim 1 wherein the polyphenolic resin is represented by the structure:

Wherein R1=H, alkyl or aryl, R2=an alkyl group of 1-10 carbon atoms, m=0-3, n=1-20.

9. The composition of claim 1 further comprising at least one epoxy resin and wherein the solid solution initiates curing of the epoxy resin at a temperature of about 110 to about 140C.

10. The composition of claim 1 further comprising at least one amine of a general structure represented by:

Wherein A=an alkyl, aryl, arylalkyl or cycloaliphatic group bearing at least one tertiary amine group; B=an alkyl, aryl, arylalkyl or cycloaliphatic group of 1-20 carbon atoms or a substituted alkyl, substituted arylalkyl group or substituted cycloaliphatic group; and wherein C=an alkyl, aryl, arylalkyl or cycloaliphatic group of 1-20 carbon atoms or a subsituted alkyl, substituted arylalkyl group or substituted cycloaliphatic group.

11. The composition of claim 10 wherein groups A, B, and C are linked together to form monocyclic, bicyclic or polycyclic fused-ring structures.

12. The composition of claim 10 wherein groups A, B, and C are polyethylene oxide or poly propylene oxide with greater than 0 and less than 20 EO or PO units.

13. The composition of claim 10 wherein the amine comprises Benzyl dimethylamine.

14. The composition of claim 10 wherein the amine comprises 3,3′,3″-Iminotris(N,N-dimethylpropylamine).

15. The composition of claim 10 wherein at least one of B and C comprises a tertiary amine group.

16. A composition consisting essentially of dicyandimide, and a solid solution of at least one polyphenolic resin and at least one imidazole or substituted imidazoles represented by the general structure shown below:

wherein R 1 =amino alkyl substituted groups of 1-20 carbon atoms and R 2 , R 3 , and R 4 may be alkyl or aryl groups of 1-20 carbon atoms.

17. The composition of claim 16 wherein the polyphenolic resin comprises phenol-formaldehyde.

18. The composition of claim 16 wherein the polyphenolic resin is represented by the structure:

wherein R1=H, alkyl or aryl, R2=an alkyl group of 1-10 carbon atoms, m=0-3, n=1-20.

19. A composition comprising at least one epoxy resin, dicyandimide, and a solid solution comprising at least one polyphenolic resin and at least one-imidazole or substituted imidazoles represented by the general structure shown below:

wherein R 1 =amino alkyl substituted groups of 1-20 carbon atoms and R 2 , R 3 , and R 4 may be alkyl or aryl groups of 1-20 carbon atoms; and wherein the polyphenolic resin is represented by the structure:

wherein R1=H, alkyl or aryl, R2=an alkyl group of 1-10 carbon atoms, m=0-3, n=1-20 and wherein the solid solution has a particle size of about 2 to about 50 um.

20. The composition of claim 19 wherein the ratio of solid solution to dicyandimide is about 1:10 to about 6:10.

21. The composition of claim 20 wherein the ratio of amine to phenolic resin is about 1:1 to about 1:5.

22. The composition of claim 19 wherein composition has a curing initiation temperature of about 100 to about 150 C, and a heat of reaction of about 250 to about 490 J/g.

23. The composition of claim 19 wherein the polyphenolic resin comprises at least one member selected from the group consisting of formaldehyde, acetaldehyde, benzaldehyde, furfuraldehyde, bis(4-hydroxyphenyl)methane, 4,4′-hydroxydiphenyl, bis(4-hydroxyphenyl)sulphone, 4,4′-dihydroxy-benzophenone and 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) and combinations thereof.

24. The composition of claim 19 wherein the polyphenolic resin comprises at least one member selected from the group consisting of 2-allylphenol, 4-allylphenol or polymers; copolymers of phenol substituted acrylates or phenol substituted methacrylates or polymers of vinylphenols and propenylphenols; co-polymers of unsaturated phenols with other polymerizable alkene-substituted compounds.

Assignees

• Air Prod & Chem

Inventors

• Vedage Gamini Ananda
• Lal Gauri Sankar
• Boyce Stephen Michael
• Abdourazak Atteye Houssein
• Shah Dilipkumar Nandlal

Classifications

• C08K5/3445

  Five-membered rings · CPC title

• C08L63/00

  Compositions of epoxy resins; Compositions of derivatives of epoxy resins · CPC title

• C08G59/50 Primary

  Amines · CPC title

• C08G59/621 Primary

  Phenols · CPC title

• C08K5/17

  Amines; Quaternary ammonium compounds · CPC title