Corrosion resistant structural foam

• US 6,218,442 B1
• Filed: 08/15/2000
• Issued: 04/17/2001
• Est. Priority Date: 08/27/1998
• Status: Expired due to Fees

• Current Assignee: Henkel Corporation (Henkel AG & Co KGaA)
• Original Assignee: Henkel Corporation (Henkel AG & Co KGaA)
• Inventors: Harrison, Bruce Lee, Hilborn, Bradley L.
• Primary Examiner(s): Foelak, Morton
• Application Number:
  US09/638,352
• Time in Patent Office: 245 Days
• Field of Search: 523/219, 521/85, 521/93, 521/107, 521/124, 521/135, 521/178
• US Class Current: 521/85
• CPC Class Codes: C08J 2363/00 Characterised by the use of epoxy resins; Derivatives of epoxy resins
• CPC Class Codes: C08J 9/0052 Organo-metallic compounds
• CPC Class Codes: C08J 9/103 Azodicarbonamide
• CPC Class Codes: C08J 9/32 from compositions containing microballoons, e.g. syntactic foams
• CPC Class Codes: C08K 5/0091 Complexes with metal-heteroatom-bonds
• CPC Class Codes: C08L 63/00 Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• CPC Class Codes: C23F 15/00 Other methods of preventing corrosion or incrustation

Abstract

Titanates and zirconates bearing organic substituents can act as corrosion inhibitors when added to foamable compositions based on thermosettable synthetic resins such as epoxy resins. Combinations of organometallates containing certain specific types of substituents provide synergistic improvements in the properties of structural reinforcement foams obtained by heating and curing the foamable compositions.

Claims

1. A foamable composition comprising

a) one or more thermosettable synthetic resins;

b) one or more curatives;

c) one or more blowing agents; and

d) one or more organometallate compounds selected from the group consisting of organic titanates and organic zirconates in an amount effective to reduce corrosion of a metal surface in contact with a foam produced from said foamable composition as compared to a foam produced from an analogous foamable composition not containing any of said organometallate compounds.

2. The foamable composition of claim 1 comprising at least one organic titanate and at least one organic zirconate.

3. The foamable composition of claim 1 comprising at least one organic titanate which is an amine adduct of a tetrasubstituted titanate.

4. The foamable composition of claim 1 comprising at least one organic titanate containing a phosphorus-containing substituent bonded to titanium.

5. The foamable composition of claim 1 comprising at least one organic titanate or organic zirconate containing at least one neoalkoxy substituent bonded to titanium or zirconium.

6. The foamable composition of claim 1 comprising at least one organic titanate which is a phosphite adduct of a tetrasubstituted titanate.

7. The foamable composition of claim 1 comprising,

a) at least one organic titanate selected from the group consisting of amine adducts of tetrasubstituted titanates and organic titanates containing at least one phosphato or pyrophosphato substituent bonded to titanium;

b) at least one organic titanate different from the organic titanate of (a) selected from the group consisting of organic titanates containing at least one neoalkoxy substituent bonded to titanium and phosphite adducts of tetrasubstituted titanates; and

c) at least one organic zirconate selected from the group consisting of organic zirconates containing at least one neoalkoxy substituent bonded to zirconium and organic zirconates containing at least one benzoate substituent or derivative thereof bonded to zirconium.

8. The foamable composition of claim 1 wherein at least one of the thermosettable synthetic resins is an epoxy resin.

9. The foamable composition of claim 1 wherein at least one of the thermosettable synthetic resins is a glycidyl ether of a polyhydric phenol.

10. The foamable composition of claim 1 wherein at least one of the blowing agents is a chemical blowing agent.

11. The foamable composition of claim 1 wherein at least one of the curatives is a nitrogen-containing compound.

12. The foamable composition of claim 1 additionally comprising hollow glass microspheres.

13. The foamable composition of claim 1 additionally comprising at least one additive selected from the group consisting of fillers, flexibilizing/toughening agents, blowing agent activators, thixotropic/rheological control agents, colorants, silanes, and stabilizers.

14. The foamable composition of claim 1 wherein the organometallate compounds are present in an amount totalling from about 0.1 weight % to about 2 weight % based on the overall weight of the foamable composition.

15. A foam obtained by heating and curing the foamable composition of claim 1.

16. A composite comprised of a solid article and the foam of claim 15.

17. A foamable dough useful for producing a structural reinforcement foam, said foamable dough comprising

a) from about 35 weight % to about 85 weight % of one or more epoxy resins, wherein at least one of said epoxy resins is a glycidyl ether of a polyhydric phenol;

b) from about 0.5 weight % to about 10 weight % of one or more chemical blowing agents;

c) from about 0.1 weight % to about 15 weight % of one or more curatives, wherein at least one of said curatives is a nitrogen-containing compound;

d) one or more fillers, wherein from about 5 weight % to about 50 weight % of the foamable dough is comprised of hollow glass microspheres; and

e) from about 0.1 weight % to about 2 weight % total of at least two different organometallate compounds selected from the group consisting of;

(i) amine adducts of tetrasubstituted titanates;

(ii) organic titanates containing at least one phosphato or pyrophosphato substituent bonded to titanium;

(iii) organic titanates containing at least one neoalkoxy substituent bonded to titanium;

(iv) phosphite adducts of tetrasubstituted titanates;

(v) organic zirconates containing at least one neoalkoxy substituent bonded to zirconium; and

(vi) organic zirconates containing at least one benzoate substituent or derivative thereof bonded to zirconium, wherein said organometallate compounds are present in an amount effective to reduce corrosion of a metal surface in contact with the structural reinforcement foam produced from said foamable dough as compared to a foam produced from an analogous foamable dough not containing any of said organometallate compounds.

18. The foamable dough of claim 17 comprising at least one organometallate compound from group (i) or (ii), at least one organometallate compound from group (iii) or (iv), and at least one organometallate compound from group (v) or (vi).

19. The foamable dough of claim 17 additionally comprising glass fibers.

20. The foamable dough of claim 17 wherein at least one of the chemical blowing agents is selected from the group consisting of azodicarbonamide and sulfonyl hydrazides.

21. The foamable dough of claim 17 wherein at least one of the curatives is dicyandiamide.

22. The foamable dough of claim 17 wherein a urea is present as a blowing agent activator.

23. The foamable dough of claim 17 additionally comprising at least one additive selected from the group consisting of flexibilizing/toughening agents, colorants, silanes, stabilizers, and thixotropic/rheological control agents.

24. The foamable dough of claim 17 wherein the polyhydric phenol is bisphenol A.

25. The foamable dough of claim 17 wherein the epoxy resins contain about 2 epoxy groups per molecule and have epoxy equivalent weights of from about 150 to about 1000.

26. A structural reinforcement foam obtained by heating and curing the foamable dough of claim 17.

27. A composite comprised of a ferrous article and the structural reinforcement foam of claim 26.