Amide-containing self-emulsifying epoxy curing agent

• US 5,576,416 A
• Filed: 12/13/1994
• Issued: 11/19/1996
• Est. Priority Date: 12/13/1994
• Status: Expired due to Fees

• Current Assignee: Air Products and Chemicals Incorporated (Linde Plc)
• Original Assignee: Air Products and Chemicals Incorporated (Linde Plc)
• Inventors: Walker, Frederick H.
• Primary Examiner(s): Marquis, Melvyn I.
• Assistant Examiner(s): AYLWARD, DAVID E
• Application Number:
  US08/355,149
• Time in Patent Office: 707 Days
• Field of Search: 523/404, 528/335, 528/339.3, 528/340, 554/25, 554/106, 554/112
• US Class Current: 528/340
• CPC Class Codes: C08G 69/34 using polymerised unsaturated fatty acids
• CPC Class Codes: C08G 69/40 Polyamides containing oxygen in the form of ether groups C08G69/12, C08G69/32 take precedence
• CPC Class Codes: C08L 63/00 Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• CPC Class Codes: C08L 77/00 Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain of polyhydrazides C08L79/06; of polyamideimides or polyamide acids C08L79/08; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 77/08 from polyamines and polymerised unsaturated fatty acids

Abstract

A new epoxy hardener composition is the product of the reaction of (A) a poly(alkylene oxide) monoamine or diamine with a molecular weight (Mn) of about 500 to 3000 and (B) a di- or polycarboxylic acid, in a ratio of moles of carboxylic acid to equivalents of amine of about 1:1 to 6:1 to yield an intermediate (C), which in a second step is reacted with (D) a di- or polyamine. The compositions of the invention are excellent emulsifiers of liquid epoxy resins in aqueous media without the addition of added surfactants or acidic compounds, and can be used to prepare water resistant water-borne coatings and related products from both liquid and solid epoxy resins, that possess long pot lives and contain relatively small amounts of volatile organic compounds.

Claims

1. An epoxy hardener composition comprising the reaction product of (A) a poly(alkylene oxide) mono- or diamine having a number average molecular weight (Mn) of 500 to 3000 and (B) a polycarboxylic acid in a ratio of moles of polycarboxylic acid to equivalents of amine of about 1:

1 to 6;

1 to yield an intermediate (C) which is reacted with (D) a polyamine which is selected from the group consisting of aliphatic diamines and polyamines, araliphatic diamines and polyamines, aromatic diamines and polyamines, cycloaliphatic diamines and polyamines, heterocyclic diamines and polyamines, and mixtures thereof, the amount of the poly(alkylene oxide) monoamine or diamine used to produce intermediate (C) being sufficient to provide a stable solution or emulsion of the epoxy hardener composition in an aqueous medium.

2. The epoxy hardener composition of claim 1 in which the amount of the poly(alkylene oxide) monoamine or diamine used to produce intermediate (C) comprises 15 to 40 wt % of the epoxy hardener composition.

3. The epoxy hardener composition of claim 1 in which the amount of the poly(alkylene oxide) monoamine or diamine used to produce intermediate (C) comprises 18 to 25 wt % of the epoxy hardener composition.

4. The epoxy hardener composition of claim 1 in which the ratio of moles of polycarboxylic acid to equivalents of amine in the production of intermediate (C) ranges from 1.3:

1 to 2.6;

1.

5. The epoxy hardener composition of claim 2 in which the ratio of moles of polycarboxylic acid to equivalents of amine in the production of intermediate (C) ranges from 1.3:

1 to 2.6;

1.

6. The epoxy hardener composition of claim 1 in which component (A) is a poly(alkylene oxide) monoamine.

7. The epoxy hardener composition of claim 1 in which the polycarboxylic acid is a dicarboxylic acid containing 3 to 12 carbon atoms.

8. The epoxy hardener composition of claim 1 in which the polycarboxylic acid is a dimer fatty acid.

9. The epoxy hardener composition of claim 1 in which polyamine (D) is 4,4'"'"'-diaminodicyclohexyl methane.

10. The epoxy hardener composition of claim 1 in which polyamine (D) is a mixture of methylene bridged poly(cyclohexyl-aromatic)amines.

26. The epoxy hardener composition of claim 1 in which the ratio of moles of polycarboxylic acid to equivalents of amine in the production of intermediate (C) ranges from 1.3:

1 to 6;

1.

27. The epoxy hardener composition of claim 1 in which polyamine (D) is selected from the group consisting of polyethylene amines, 1,2-propylenediamine, 1,3-propylenediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,3-pentanediamine, 1,6-hexanediamine, 3,3,5-trimethyl-1,6-hexanediamine, 3,5,5-trimethyl-1,6-hexanediamine, 2-methyl-1,5-pentanediamine, bis-(3-aminopropyl)amine, N,N'"'"'-bis-(3-aminopropyl)-1,2-ethanediamine, N-(3-aminopropyl)-1,2-ethanediamine, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, aminoethylpiperazine, meta-xylylenediamine, phenylenediamine, 4,4'"'"'-diaminodiphenylmethane, toluenediamine, isophoronediamine, 3,3'"'"'-dimethyl-4,4'"'"'-diaminodicyclohexylmethane, 4,4'"'"'-diaminodicyclohexylmethane, 2,4'"'"'-diaminodicyclohexyl methane, the mixture of methylene bridged poly(cyclohexyl-aromatic)amines, polyaminoamides, and mixtures thereof.

11. An epoxy hardener composition comprising the reaction product of (A) a poly(alkylene oxide) mono- or diamine having a number average molecular weight (Mn) of 500 to 3000 and (B) a dicarboxylic acid in a ratio of moles of dicarboxylic acid to equivalents of amine of about 1.3:

1 to 6;

1 to yield an intermediate (C) which is reacted with (D) a polyamine which is selected from the group consisting of aliphatic diamines and polyamines, araliphatic diamines and polyamines, aromatic diamines and polyamines, cycloaliphatic diamines and polyamines, heterocyclic diamines and polyamines and mixtures thereof, the amount of the poly(alkylene oxide) monoamine or diamine used to produce intermediate (C) being 15 to 40 wt % of the epoxy hardener composition.

12. The epoxy hardener composition of claim 11 in which the amount of the poly(alkylene oxide) monoamine or diamine used to produce intermediate (C) comprises 18 to 25 wt % of the epoxy hardener composition.

13. The epoxy hardener composition of claim 11 in which the ratio of moles of dicarboxylic acid to equivalents of amine in the production of intermediate (C) ranges from 1.3:

1 to 2.6;

1.

14. The epoxy hardener composition of claim 11 in which component (A) is a poly(alkylene oxide) monoamine.

15. The epoxy hardener composition of claim 11 in which the dicarboxylic acid contains 3 to 12 carbons atoms.

16. The epoxy hardener composition of claim 11 in which the dicarboxylic acid is a dimer fatty acid.

17. The epoxy hardener composition of claim 13 in which polyamine (D) is 4,4'"'"'-diaminodicyclohexyl methane.

18. The epoxy hardener composition of claim 13 in which polyamine (D) is a mixture of methylene bridged poly(cyclohexyl-aromatic)amines.

24. The epoxy hardener composition of claim 17 in which the poly(alkylene oxide) monoamine is a monoamine terminated block copolymer of propylene oxide and ethylene oxide having an Mn of about 1200 based on its amine titer.

28. The epoxy hardener composition of claim 11 in which polyamine (D) is selected from the group consisting of polyethylene amines, 1,2-propylenediamine, 1,3-propylenediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,3-pentanediamine, 1,6-hexanediamine, 3,3,5-trimethyl-1,6-hexanediamine, 3,5,5,-trimethyl-1,6-hexanediamine, 2-methyl-1,5-pentanediamine, bis-(3-aminopropyl)amine, N,N'"'"'-bis-(3-aminopropyl)- 1,2-ethanediamine, N-(3-aminopropyl)-1,2-ethanediamine, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, aminoethylpiperazine, meta-xylylenediamine, phenylenediamine, 4,4'"'"'-diaminodiphenylmethane, toluenediamine, isophoronediamine, 3,3'"'"'-dimethyl-4,4'"'"'-diaminodicyclohexylmethane, 4,4'"'"'-diaminodicyclohexylmethane, 2,4'"'"'-diaminodicyclohexyl methane, the mixture of methylene bridged poly(cyclohexyl-aromatic)amines, polyaminoamides, and mixtures thereof.

19. An epoxy hardener composition comprising the reaction product of (A) a poly(alkylene oxide) monoamine having a number average molecular weight (Mn) of 800 to 1500 and (B) a dicarboxylic acid in a ratio of moles of dicarboxylic acid to equivalents of amine of about 1.3:

1 to 2.6;

1 to yield an intermediate (C) which is reacted with (D) a polyamine, the amount of the poly(alkylene oxide) monoamine used to produce intermediate (C) being 18 to 25 wt % of the epoxy hardener composition.

20. The epoxy hardener composition of claim 19 in which polyamine (D) is 4,4'"'"'-diaminodicyclohexyl methane.

21. The epoxy hardener composition of claim 19 in which polyamine (D) is a mixture of methylene bridged poly(cyclohexyl-aromatic)amines.

22. The epoxy hardener composition of claim 19 in which the poly(alkylene oxide) monoamine is a monoamine terminated block copolymer of propylene oxide and ethylene oxide having an Mn of about 1200 based on its amine titer.

23. The epoxy hardener composition of claim 19 in which the dicarboxylic acid (B) is selected from the group consisting of a dicarboxylic acid containing 3 to 12 carbons atoms and a dimer fatty acid.

25. The epoxy hardener composition of claim 20 in which the dicarboxylic acid (B) is selected from the group consisting of a dicarboxylic acid containing 3 to 12 carbons atoms and a dimer fatty acid.

29. An epoxy hardener composition comprising the reaction product of (A) a poly(alkylene oxide) monoamine having an number average molecular weight (Mn) of 500 to 3000 and (B) a polycarboxylic acid in a ratio of moles of polycarboxylic acid to equivalents of monoamine of about 1:

1 to 6;

1 to yield an intermediate (C) which is reacted with (D) a polyamine, the amount of the poly(alkylene oxide) monoamine used to produce intermediate (C) being sufficient to provide a stable solution or emulsion of the epoxy hardener composition in an aqueous medium.