At least trifunctional epoxy resin reacted with solid rubber mixed with epoxy resin and curing agent

• US 6,013,730 A
• Filed: 07/28/1997
• Issued: 01/11/2000
• Est. Priority Date: 06/07/1994
• Status: Expired due to Term

• Current Assignee: Cytec Technology Corp. (Syensqo SA)
• Original Assignee: Fiberite, Inc. (Syensqo SA)
• Inventors: Maskell, Robin K., Ciriscioli, Peter R., Lucas, Scott D., Jenkins, Stephen D., McGrail, Patrick T., Carter, Jeffrey T.
• Primary Examiner(s): Sellers, Robert E.
• Application Number:
  US08/750,394
• Time in Patent Office: 897 Days
• Field of Search: 525/113, 525/119, 523/428, 428/290, 428/413, 428/417
• US Class Current: 525/113
• CPC Class Codes: C08G 59/38 together with di-epoxy compounds
• CPC Class Codes: C08J 2363/00 Characterised by the use of epoxy resins; Derivatives of epoxy resins
• CPC Class Codes: C08J 3/243 Two or more independent types of crosslinking for one or more polymers
• CPC Class Codes: C08L 2666/08 Homopolymers or copolymers according to C08L7/00 - C08L21/00; Derivatives thereof
• CPC Class Codes: C08L 63/00 Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• CPC Class Codes: Y10T 428/24994 Fiber embedded in or on the surface of a polymeric matrix
• CPC Class Codes: Y10T 428/24995 Two or more layers
• CPC Class Codes: Y10T 428/31511 Of epoxy ether
• CPC Class Codes: Y10T 428/31525 Next to glass or quartz
• CPC Class Codes: Y10T 442/697 Containing at least two chemically different strand or fiber materials

Abstract

A curable composition and a method of making it comprises reacting in the presence of a catalyst epoxy resin(s) having at least 0.05% by weight of epoxy resin oligomer with a solid rubber which is swellable or soluble in the reaction mixture and possessing at least 1% by weight of reactive groups, in a rubber:epoxy resin(s) weight ratio of between 1:1 and 1:20, wherein said epoxy resin(s) comprises (a) at least one epoxy resin having an epoxy functionality of greater than three and (b) at least one second epoxy resin having a functionality of greater than one but not more than three; heating to effect the reaction, cooling to substantially ambient temperature, and adding any remaining portion of epoxy resin and curing agent(s).

Claims

1. A curable composition comprising an epoxy resin system, wherein said epoxy resin system comprises:

an epoxy resin comprising at least one first epoxy resin component and at least one second epoxy resin component, at least one curing agent for said epoxy resin, and a reaction product formed in situ by prereaction between a solid rubber and at least a proportion of said at least one first epoxy resin component in a rubber to first epoxy resin component weight ratio of between 1;

1 and 1;

20,

wherein each of said at least one first epoxy resin component comprises monomers having an epoxy functionality of greater than 3 and at least 0.05 wt % of oligomers of said monomers, and wherein each of said at least one first epoxy resin component is independently a polyglycidyl derivative or an oligomer of a polyglycidyl derivative of at least one compound selected from the group consisting of aromatic diamines, aromatic monoprimary amines and aminophenols,

wherein each of said at least one second epoxy resin component has an epoxy functionality of greater than 1 but no more than 3, and

wherein said solid rubber has at least 1 wt % of reactive groups, and wherein said solid rubber is swellable or soluble in a reaction mixture in which said reaction product is formed.

2. A curable composition according to claim 1 wherein said rubber to first epoxy resin component weight ratio is between 1:

2.5 and 1;

17.

3. A curable composition according to claim 2 wherein said rubber to first epoxy resin component weight ratio is between 1:

2.5 and 1;

16.5.

4. A curable composition according to claim 1 wherein said second epoxy resin component is a polyglycidyl derivative or an oligomer of a polyglycidyl derivative of at least one compound selected from the group consisting of aromatic diamines, aromatic monoprimary amines, aminophenols, polyhydric phenols, polyhydric alcohols, and polycarboxylic acids.

5. A curable composition according to claim 1 wherein said first epoxy resin component is selected from the group consisting of monomers and oligomers of N,N,N¹,N¹ -tetraglycidyl diaminodiphenylmethane and N,N,N¹,N¹ -tetraglycidyl-bis (4-amino-3,5-dimethylphenyl)-1, 4-diisopropylbenzene, and combinations thereof.

6. A curable composition according to claim 5, wherein said first epoxy resin component is selected from the group consisting of monomers and oligomers of N,N,N¹,N¹ -tetraglycidyl diaminodiphenylmethane.

7. A curable composition according to claim 1, wherein said at least one curing agent comprises 4-4'"'"'-diaminodiphenylsulphone as a first curing agent, and said solid rubber comprises a solid acrylonitrile/butadiene/methacrylic acid rubber.

8. A curable composition according to claim 5, wherein said at least one curing agent further comprises dicyanodiamide as a second curing agent.

9. A curable composition according to claim 1, further comprising reinforcement fibers impregnated by said epoxy resin system.

10. A curable composition according to claim 9, wherein said reinforcement fibers comprise at least 20% by volume of the curable composition.

11. A curable composition according to claim 7, further comprising reinforcement fibers impregnated by said epoxy resin system.

12. A curable composition according to claim 11, wherein said reinforcement fibers comprise at least 20% by volume of the curable composition.

13. A curable composition according to claim 8, further comprising reinforcement fibers impregnated by said epoxy resin system.

14. A curable composition according to claim 13, wherein said reinforcement fibers comprise at least 20% by volume of the curable composition.

15. A prepreg comprising a curable composition according to claim 9.

16. A prepreg comprising a curable composition according to claim 10.

17. A prepreg comprising a curable composition according to claim 11.

18. A prepreg comprising a curable composition according to claim 12.

19. A prepreg comprising a curable composition according to claim 13.

20. A prepreg comprising a curable composition according to claim 14.

21. A process for making a curable composition according to claim 1 comprising forming a reaction mixture of said rubber, at least a proportion of said at least one first epoxy resin component, a catalyst capable of promoting a reaction between epoxy groups and the reactive groups of said rubber, and a polar solvent, wherein said rubber, said first epoxy resin component, and said catalyst comprise between 25 and 75 wt % of the reaction mixture, heating the reaction mixture to effect said reaction, cooling the resultant mixture to substantially ambient temperature and adding said second epoxy resin component, any remaining proportion of said first epoxy resin component, and said at least one curing agent to the resultant mixture and substantially removing the solvent therefrom.

22. A process according to claim 21 in which said rubber, said first epoxy resin component and said catalyst comprise between 35 and 65 wt % of the reaction mixture.

23. A process according to claim 21 in which said rubber, said first epoxy resin component and said catalyst comprise between 40 and 50 wt % of the reaction mixture.

24. A process according to claim 21 in which the mixture is heated to a temperature in the range 40°

C. to 80°

C., optionally under reflux.

25. A process according to claim 21 in which the catalyst is selected from the group consisting of alkyl triphenyl phosphonium iodide, bromide and chloride, wherein the alkyl is selected from the group consisting of methyl, ethyl, propyl, n-butyl, isobutyl, n-pentyl and n-decyl, triphenyl phosphine, stannous octoate, boron trifluoride.

26. A process according to claim 25 wherein the catalyst is ethyl triphenyl phosphonium iodide.

27. A process for making a curable composition according to claim 1 comprising forming a reaction mixture of said rubber, at least a proportion of said at least one first epoxy resin component, a catalyst capable of promoting a reaction between epoxy groups and the reactive groups of said rubber, and a polar solvent, wherein said rubber, said first epoxy resin component, and said catalyst comprise between 25 and 75 wt % of the reaction mixture, heating the reaction mixture to effect said reaction, adding to the reaction mixture said second epoxy resin component and any remaining proportion of said first epoxy resin component, cooling the resultant mixture to substantially ambient temperature, and adding said at least one curing agents to the resultant mixture and substantially removing the solvent therefrom.