Mannich based adducts as water based epoxy curing agents with fast cure capabilities for green concrete application

• US 20040176502A1
• Filed: 03/04/2003
• Published: 09/09/2004
• Est. Priority Date: 03/04/2003
• Status: Active Grant

• Current Assignee: Evonik Operations GmbH (Rag-Stiftung)
• Original Assignee: Air Products and Chemicals Incorporated (Linde Plc)
• Inventors: Cook, Michael, Raymond, William R.
• Granted Patent: US 6,916,505 B2
• Time in Patent Office: Days
• US Class Current: 523/416
• CPC Class Codes: C04B 28/02 containing hydraulic cements other than calcium sulfates
• CPC Class Codes: C04B 41/009 characterised by the material treated
• CPC Class Codes: C04B 41/4578 Coating or impregnating of green ceramics or unset concrete
• CPC Class Codes: C04B 41/4853 Epoxides
• CPC Class Codes: C04B 41/63 Macromolecular compounds
• CPC Class Codes: C08G 59/184 with amines
• CPC Class Codes: C08G 59/623 Aminophenols
• CPC Class Codes: C08L 63/00 Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Abstract

A water-soluble composition including a water soluble polyamine adduct which is a reaction product of: (a) an alkoxy group modified polyepoxide resin containing an average of at least 1.5 epoxide groups per molecule; and (b) a Mannich base polyamine. The Mannich base polyamine is a reaction product of a polyamine containing at least two amino groups with a N-Mannich condensate prepared from a reaction of a phenolic compound, an aldehyde, and a secondary amine wherein the secondary amine of the N-Mannich condensate is replaced by one of the at least two amino groups of the polyamine, and wherein the ratio of the Mannich base polyamine to the alkoxy group modified polyepoxide resin contains an excess of an active amine hydrogen relative to epoxide groups so that the water soluble polyamine adduct has an amine hydrogen equivalent weight of at most 1000 based on solids content.

Claims

1. A water-soluble composition comprising a water soluble polyamine adduct which is a reaction product of:

(a) an alkoxy group modified polyepoxide resin containing an average of at least 1.5 epoxide groups per molecule; and

(b) a Mannich base polyamine, wherein the Mannich base polyamine is a reaction product of a polyamine containing at least two amino groups with a N-Mannich condensate prepared from a reaction of a phenolic compound, an aldehyde, and a secondary amine; and

provided that the secondary amine of the N-Mannich condensate is replaced by one of the at least two amino groups of the polyamine, the polyamine boils at a higher temperature than the secondary amine, and at least one of the at least two amino groups of the polyamine is a primary or a secondary amino group; and

wherein the ratio of the Mannich base polyamine to the alkoxy group modified polyepoxide resin contains an excess of an active amine hydrogen relative to epoxide groups so that the water soluble polyamine adduct has an amine hydrogen equivalent weight (AHEW) of at most 1000 based on solids content.

2. The water-soluble composition of claim 1, wherein the alkoxy group modified polyepoxide resin is a member selected from the group consisting of

(i) a reaction product of a polyether polyol containing at least 2 OH groups and a polyalkoxy chain with a polyepoxide resin containing an average of at least 1.5 epoxide groups per molecule;

(ii) a reaction product of a polyepoxide resin containing an average of at least 1.5 epoxide groups per molecule with a polyalkoxy monoamine containing a polyalkoxy chain, wherein the polyalkoxy monoamine has the following structure;

where R is H or C₁ to C₁₂ alkyl, X is a C₂H₄, C₃H₆, or C₄H₈ alkyl group, Y is a C₂H₄, C₃H₆, or C₄H₈ alkyl group, and n is a number of repeats sufficient to produce the polyalkoxy monoamine having a molecular weight of from about 200 to about 4000;

(iii) a polyglycidyl ether of a polyether polyol containing at least 2 OH groups and a polyalkoxy chain; and

(iv) a diglycidyl ether derivative of an alkoxylated diphenol containing an average of at least 1.5 epoxide groups per molecule.

3. The water-soluble composition of claim 2, wherein the polyether polyol in (i) has a molecular weight from about 200 to about 4000.

4. The water-soluble composition of claim 3, wherein the molecular weight of the polyether polyol in (i) is from 800 to 1200.

5. The water-soluble composition of claim 2, wherein the polyalkoxy chain of the polyether polyol in (i) is a member selected from the group consisting of polyethylene oxide, polypropylene oxide, polybutylene oxide, and polytetrahydrofuran.

6. The water-soluble composition of claim 5, wherein the alkoxy group of the polyether polyol in (i) is polyethylene oxide or polypropylene oxide.

7. The water-soluble composition of claim 2, wherein the polyepoxide resin in (i) is at least one of bisphenol-A epoxy resin and bisphenol-F epoxy resin.

8. The water-soluble composition of claim 2, wherein a molar ratio of the polyether polyol to the polyepoxide resin in (i) is from about {fraction (1/1.5)} to about {fraction (1/10)}.

9. The water-soluble composition of claim 8, wherein the molar ratio of the polyether polyol to the polyepoxide resin in (i) is from ½

to ¼

.

10. The water-soluble composition of claim 2, wherein the polyalkoxy monoamine in (ii) has a molecular weight from about 800 to about 1200.

11. The water-soluble composition of claim 2, wherein the polyalkoxy chain of the polyalkoxy monoamine in (ii) is a member selected from the group consisting of polyethylene oxide, polypropylene oxide, polybutylene oxide, and polytetrahydrofuran.

12. The water-soluble composition of claim 11, wherein the polyalkoxy chain of the polyalkoxy monoamine in (ii) is polyethylene oxide or polypropylene oxide.

13. The water-soluble composition of claim 2, wherein the polyalkoxy chain of the polyether polyol in (iii) is a member selected from the group consisting of polyethylene oxide, polypropylene oxide, polybutylene oxide, and polytetrahydrofuran.

14. The water-soluble composition of claim 2, wherein the polyglycidyl ether of the polyether polyol in (iii) has a molecular weight from about 200 to about 4000.

15. The water-soluble composition of claim 14, wherein the polyglycidyl ether of the polyether polyol in (iii) has a molecular weight from 800 to 1200.

16. The water-soluble composition of claim 2, wherein the alkoxylated diphenol in (iv) has a structure:

17. The water-soluble composition of claim 16, wherein n+m=4 to 10.

18. The water-soluble composition of claim 2, wherein the diphenol is resorcinol, bisphenol-A, or bisphenol-F.

19. The water-soluble composition of claim 1, wherein the alkoxy group modified polyepoxide resin is reacted with the Mannich base polyamine at an epoxy equivalenVamine equivalent ratio of about ⅓

to about {fraction (1/12)}.

20. The water-soluble composition of claim 19, wherein the epoxy equivalentlamine equivalent ratio is from about ¼

to about ⅙

.

21. The water-soluble composition of claim 1, wherein the secondary amine a member selected from the group consisting of dimethylamine, diethylamine, dipropylamine, and dibutylamine.

22. The water-soluble composition of claim 1, wherein the polyamine further comprises an alkoxylate group.

23. The water-soluble composition of claim 1, wherein the polyamine is a member selected from the group consisting of an aliphatic polyamine, an arylaliphatic polyamine, a cycloaliphatic polyamine, an aromatic polyamine, a heterocyclic polyamine, and a polyalkoxypolyamine.

24. The water-soluble composition of claim 23, wherein the polyamine is a member selected from the group consisting of diethylenetriamine, triethylenetetramine, 1,3-bisaminocyclohexylamine, isophorone diamine, N-aminoethylpiperazine, 4,7-dioxadecane-1,10-diamine, 1-propanamine,3,3′

-(oxybis(2,1-ethanediyloxy))bis-, poly(oxy(methyl-1,2-ethanediyl)), alpha-(2-aminomethylethyl)omega-(2-aminomethylethoxy), triethyleneglycoldiamine, and poly(oxy(methyl-1,2-ethanediyl))alpha,alpha′

-(oxy(di-2,1-ethanediyl))bis(omega-(aminomethylethoxy)).

25. The water-soluble composition of claim 1, wherein the N-Mannich condensate and the polyamine are reacted at an active site/mole ratio of about 0.8 to about 2.

27. The water-soluble composition of claim 1, wherein the N-Mannich condensate has at least two active sites.

28. The water-soluble composition of claim 27, wherein the N-Mannich condensate is 2,4,6-tris-(dimethylaminomethyl)phenol.

29. The water-soluble composition of claim 1, wherein the water soluble polyamine adduct is diluted with water to form a polyamine adduct solution.

30. The water-soluble composition of claim 1, wherein consisting essentially of the water soluble polyamine adduct.

31. The water-soluble composition of claim 1, wherein the AHEW is at most 350 based on solids content.

32. The water-soluble composition of claim 1, wherein the AHEW is at most 200 based on solids content.

33. The water-soluble composition of claim 1, wherein the water-soluble polyamine adduct is diluted with water to at least 20 wt % to form a single phase at a temperature of 20°

C., provided that water is essentially free of an organic co-solvent.

34. The water-soluble composition of claim 33, wherein the water-soluble polyamine adduct is diluted with water to at least 10 wt %.

35. A composition comprising a product of reaction of a water-soluble composition of claim 1 and a polyepoxide resin containing an average of at least 1.5 epoxide groups per molecule, wherein the composition is capable of hardening.

36. The composition of claim 35, wherein the polyepoxide resin is at least one of bisphenol-A epoxy resin and bisphenol-F epoxy resin.

37. The composition of claim 35 adapted to be used as a primer, a coating, a curing compound, and/or a sealant for a concrete.

38. The composition of claim 35 adapted to be applied to wet concrete to provide a cured concrete, wherein the composition remains attached to the cured concrete and functions as both a curing compound and a primer.

39. A process for preparing a water-soluble composition of claim 1 comprising:

(a) producing a N-Mannich condensate by reacting a phenolic compound, an aldehyde, and a secondary amine;

(b) producing a Mannich base polyamine, wherein the Mannich base polyamine is a reaction product of a polyamine containing at least two amino groups with a N-Mannich condensate prepared from a reaction of a phenolic compound, an aldehyde, and a secondary amine; and

provided that the secondary amine of the N-Mannich condensate is replaced by one of the at least two amino groups of the polyamine, the polyamine boils at a higher temperature than the secondary amine, and at least one of the at least two amino groups of the polyamine is a primary or a secondary amino group; and

(c) reacting the Mannich base polyamine with an alkoxy group modified polyepoxide resin containing an average of at least 1.5 epoxide groups per molecule, wherein the ratio of the Mannich base polyamine to the alkoxy group modified polyepoxide resin contains an excess of an active amine hydrogen relative to epoxide groups so that the water soluble polyamine adduct has an amine hydrogen equivalent weight (AHEW) of at most 1000 based on solids content.

40. The process of claim 39, further comprising diluting the water-soluble composition with water.

41. The process of claim 39, further comprising diluting the Mannich base polyamine with an organic solvent to form an azeotropic mixture with water, azeotropically removing the organic solvent, and adding water in an amount sufficient to adjust a polyamine adduct solution to from about 10 to about 90 wt % solids.

42. The process of claim 39, water is added in an amount sufficient to adjust the polyamine adduct solution to 50-80 wt % solids.

46. A process of treating a concrete, comprising:

curing the concrete using a curing compound to provide a cured concrete wherein the concrete has set; and

/or

priming the concrete using a primer to provide a primed concrete, wherein at least one of the curing compound or the primer comprises the composition of claim 35.

47. The process of claim 46, wherein the curing compound and the primer comprise the composition of claim 35 provided that the curing compound remains attached to the cured concrete and functions as both the curing compound and the primer.

48. The process of claim 46, wherein the water-soluble composition is formed by reacting:

(a) a Mannich base polyamine, wherein the Mannich base polyamine is a polyetherpolyamine; and

(b) an alkoxy group modified polyepoxide resin containing an average of at least 1.5 epoxide groups per molecule, wherein the alkoxy group modified polyepoxide resin is a member selected from the group consisting of;

i) a reaction product of a polyether polyol containing at least 2 OH groups and a polyalkoxy chain and a polyepoxide resin containing an average of at least 1.5 epoxide groups per molecule; and

ii) a reaction product of a polyepoxide resin containing an average of at least 1.5 epoxide groups per molecule with a polyalkoxy monoamine containing a polyalkoxy chain, wherein the polyalkoxy monoamine has the following structure;

where R is H or C₁ to C₁₂ alkyl, X is a C₂H₄, C₃H₆, or C₄H₈ alkyl group, Y is a C₂H₄, C₃H₆, or C₄H₈ alkyl group, and n is a number of repeats sufficient to produce the polyalkoxy monoamine having a molecular weight of from about 200 to about 4000.

26. The water-soluble composition of claim 26, wherein the active site/mole ratio is about 0.8 to about 1.2.

43. A primer for concrete comprising a product of reaction of a polyepoxide resin containing an average of at least 1.5 epoxide groups per molecule and a water-soluble composition, wherein the water-soluble composition is formed by:

(a) reacting a phenolic compound, an aldehyde and secondary amine to form a N-Mannich condensate;

(b) forming a Mannich base polyamine, wherein the Mannich base polyamine is a reaction product of a polyamine containing at least two amino groups with a N-Mannich condensate prepared from a reaction of a phenolic compound, an aldehyde, and a secondary amine; and

provided that the secondary amine of the N-Mannich condensate is replaced by one of the at least two amino groups of the polyamine, the polyamine boils at a higher temperature than the secondary amine, and at least one of the at least two amino groups of the polyamine is a primary or a secondary amino group; and

(c) reacting the Mannich base polyamine with an alkoxy group modified polyepoxide resin containing an average of at least 1.5 epoxide groups per molecule to form the polyamine adduct, wherein the primer is adapted to be applied on concrete that has set.

44. The primer for concrete of claim 43, wherein the Mannich base polyamine is a polyetherpolyamine and the alkoxy group modified polyepoxide resin containing an average of at least 1.5 epoxide groups per molecule is a member selected from the group consisting of:

i) a reaction product of a polyether polyol containing at least 2 OH groups and a polyalkoxy chain and a polyepoxide resin containing an average of at least 1.5 epoxide groups per molecule; and

ii) a reaction product of a polyepoxide resin containing an average of at least 1.5 epoxide groups per molecule with a polyalkoxy monoamine containing a polyalkoxy chain, wherein the polyalkoxy monoamine has the following structure;

where R is H or C₁ to C₁₂ alkyl, X is a C₂H₄, C₃H₆, or C₄H₈ alkyl group, Y is a C₂H₄, C₃H₆, or C₄H₈ alkyl group, and n is a number of repeats sufficient to produce the polyalkoxy monoamine having a molecular weight of from about 200 to about 4000.

45. The primer for concrete of claim 43, wherein the polyepoxide resin is at least one of bisphenol-A epoxy resin and bisphenol-F epoxy resin.