Oxygen scavengers independent of transition metal catalysts

• US 6,517,728 B1
• Filed: 11/29/2001
• Issued: 02/11/2003
• Est. Priority Date: 11/24/1992
• Status: Expired due to Term

• Current Assignee: Commonwealth Scientific & Industrial Research Organisation (Commonwealth Of Australia As Represented By Department Of Industry, Innovation, Climate Change, Science, Research And Tertiary Education)
• Original Assignee: Commonwealth Scientific & Industrial Research Organisation (Commonwealth Of Australia As Represented By Department Of Industry, Innovation, Climate Change, Science, Research And Tertiary Education)
• Inventors: Rooney, Michael Laurence
• Primary Examiner(s): ANTHONY, JOSEPH DAVID
• Application Number:
  US09/995,834
• Time in Patent Office: 439 Days
• Field of Search: 252/188.28, 252/188.21, 252/188.22, 252/188.23, 252/314, 252/389.2, 252/397, 252/400.2, 252/405, 252/188.25, 428/411.1, 428/516, 428/35.4, 428/35.5, 428/35.2, 502/401, 502/402, 210/750, 210/757, 206/484.1, 206/484.2, 426/107, 426/100
• US Class Current: 210/757
• CPC Class Codes: A23L 3/3436 Oxygen absorbent
• CPC Class Codes: C09K 15/08 containing a phenol or quinone moiety
• CPC Class Codes: Y10S 252/96 Surface flaw detecting compositions
• CPC Class Codes: Y10S 252/964 Leak detection
• CPC Class Codes: Y10T 428/31504 Composite [nonstructural laminate]

Abstract

A composition for reducing the concentration of molecular oxygen present in an atmosphere or liquid, comprising at least one reducible organic compound which is reduced under predetermined conditions, the reduced form of the compound being oxidizable by molecular oxygen, wherein the reduction and/or subsequent oxidation of the organic compound occurs independent of the presence of a transition metal catalyst.

Claims

1. A method of lowering the concentration of ground state molecular oxygen present in an atmosphere or liquid, said method comprising the steps of:

(i) exposing the atmosphere or liquid in substantial darkness to a solid phase composition free of ethylenically unsaturated monomers, said composition comprising a source of labile hydrogen or electrons and at least one reducible organic compound; and

(ii) treating the solid phase composition with visible or ultraviolet light of a predetermined intensity or wavelength or γ

-rays, corona discharge, an electron beam or heat so as to reduce the reducible organic compound to a reduced form oxidizable by ground state molecular oxygen such that the amount of ground state molecular oxygen present in the atmosphere or liquid is subsequently lowered through oxidation of the reduced form of the reducible organic compound;

wherein the oxidation of the reduced form of the reducible organic compound occurs regardless of the presence of a transition metal catalyst and wherein the lowering of the amount of ground state molecular oxygen continues over a period of at least 1 hour when conducted at room temperature;

and wherein the source of labile hydrogen or electrons is provided by the reducible organic compound and the reducible organic compound is dispersed in, dissolved in or covalently bonded to a polymer which does not readily donate hydrogen or electrons to the reducible organic compound.

2. The method of claim 1, wherein the solid phase composition is treated by irradiation with. light of a certain intensity or wavelength, γ

-rays, corona discharge or exposure to an electron beam.

3. The method of claim 1, wherein the solid phase composition is treated with heat.

4. The method of claim 1, wherein the reducible organic compound is selected from the group consisting of:

quinones, photoreducible dyes and carbonyl compounds which have absorbence in the UV spectrum.

5. The method of claim 1, wherein the reducible organic compound is present in a polymerised or oligomerised form.

6. The method of claim 1, wherein the polymerised organic compound comprises monomers or co-monomers which are covalently bonded to the reducible organic compound.

7. The method of claim 1, wherein the reducible organic compound is a sodium sulfonate salt of polymerised 9,10-anthraquinone, the sodium sulfonate salt providing the source of labile hydrogen or electrons.

8. The method of claim 1, further comprising a scavenging component reactive towards an activated oxygen species.

9. The method of claim 8, wherein the scavenging component is a compound selected from the group consisting of:

organic antioxidants, organic phosphites, organic phosphines, organic phosphates, hydroquinone and substituted hydroquinone, inorganic compounds, sulphur-containing compounds and nitrogen-containing compounds and their derivatives.

10. The method of claim 8, wherein the scavenging component is present in a polymerised or oligomerised form.

11. A method of claim 10, wherein the scavenging component comprises monomers or co-monomers which are covalently bonded to a compound selected from the group consisting of:

organic antioxidants, organic phosphites, organic phosphines, organic phosphates, hydroquinone and substituted hydroquinone, inorganic compounds, sulphur-containing compounds and nitrogen-containing compounds and their derivatives.

12. The method of claim 11, wherein the composition is a polymeric film or polymeric film layer.

13. A method of lowering the concentration of ground state molecular oxygen present in an atmosphere or liquid, said method comprising the steps of

(i) treating a solid phase composition free of ethylenically unsaturated monomers, said composition comprising a source of labile hydrogen or electrons and at least one reducible organic compound, with visible or ultraviolet light of a predetermined intensity or wavelength or γ

-rays, corona discharge, an electron beam, or heat so as to reduce the reducible organic compound to a reduced form oxidizable by ground state molecular oxygen; and

(ii) exposing the atmosphere or liquid in substantial darkness to said treated solid phase composition such that the amount of ground state molecular oxygen present in the atmosphere or liquid is lowered through oxidation of the reduced form of the reducible organic compound;

wherein the oxidation of the reduced form of the reducible organic compound occurs regardless of the presence of a transition metal catalyst and wherein the lowering of the amount of ground state molecular oxygen continues over a period of at least 1 hour when conducted at room temperature,

and wherein the source of labile hydrogen or electrons is provided by the reducible organic compound and the reducible organic compound is dispersed in, dissolved in or covalently bonded to a polymer which does not readily donate hydrogen or electrons to the reducible organic compound.

14. The method of claim 13, wherein the solid phase composition is treated by irradiation with light of a certain intensity or wavelength, γ

-rays, corona discharge or exposure to an electron beam.

15. The method of claim 13, wherein the solid phase composition is treated with heat.

16. The method of claim 13, wherein the reducible organic compound is selected from the group consisting of quinones, photoreducible dyes and carbonyl compounds which have absorbence in the UV spectrum.

17. The method of claim 13, wherein the composition is a polymeric film or polymeric film layer.

18. The method of claim 13, wherein the reducible organic compound is a sodium sulfonate salt of polymerised 9,10-anthraquinone, the sodium sulfonate salt providing the source of labile hydrogen or electrons.

19. The method of claim 13, wherein the reducible organic compound is present in a polymerised or oligomerised form.

20. The method of claim 19, wherein the polymerised organic compound comprises monomers or co-monomers which are covalently bonded to the reducible organic compound.

21. The method of claim 13, further comprising a scavenging component reactive towards an activated oxygen species.

22. The method of claim 21, wherein the scavenging component is a compound selected from the group consisting of organic antioxidants, organic phosphites, organic phosphines, organic phosphates, hydroquinone and substituted hydroquinone, inorganic compounds, sulphur-containing compounds and nitrogen-containing compounds and their derivatives.

23. The method of claim 13, wherein the scavenging component is present in a polymerised or oligomerised form.

24. The method of claim 23, wherein the scavenging component comprises monomers or co-monomers which are covalently bonded to a compound selected from the group consisting of:

organic antioxidants, organic phosphites, organic phosphines, organic phosphates, hydroquinone and substituted hydroquinone, inorganic compounds, and nitrogen-containing compounds and their derivatives.

25. A method of preventing the transmission of ground state molecular oxygen through a package, said method comprising the steps of:

(i) forming a package from a packaging material or polymeric film, said packaging material or polymeric film comprising a solid phase composition free of ethylenically unsaturated monomers, said composition comprising a source of labile hydrogen or electrons and at least one reducible organic compound; and

(ii) treating the package with visible or ultraviolet light of a predetermined intensity or wavelength or γ

-rays, corona discharge, an electron beam, or heat so as to reduce the at least one reducible organic compound to a reduced form oxidizable by ground state molecular oxygen;

wherein subsequent oxidation of the reduced form of the reducible organic compound by ground state molecular oxygen occurs regardless of the presence of a transition metal catalyst and wherein the oxidation of the reduced form of the reducible organic compound occurs in substantial darkness for a period of at least 1 hour when conducted at room temperature,

and wherein the source of labile hydrogen or electrons is provided by the reducible organic compound and the reducible organic compound is dispersed in, dissolved in or covalently bonded to a polymer which does not readily donate hydrogen or electrons to the reducible organic compound.

26. The method of claim 25, wherein the package is treated by irradiation with light of a certain intensity or wavelength, γ

-rays, corona discharge or exposure to an electron beam.

27. The method of claim 25, wherein the package is treated with heat.

28. The method of claim 25, wherein the reducible organic compound is selected from the group consisting of:

quinones, photoreducible dyes and carbonyl compounds which have absorbence in the UV spectrum.

29. The method of claim 25, wherein the reducible organic compound is present in a polymerised or oligomerised form.

30. The method of claim 25, wherein the polymerised organic compound comprises monomers or co-monomers which are covalently bonded to the reducible organic compound.

31. The method of claim 25, wherein the package comprises a polymeric film.

32. The method of claim 25, wherein the scavenging component comprises monomers or co-monomers which are covalently bonded to a compound selected from the group consisting of:

organic antioxidants, organic phosphites, organic phosphines, organic phosphates, hydroquinone and substituted hydroquinone, inorganic compounds, sulphur-containing compounds and nitrogen-containing compounds and their derivatives.

33. The method of claim 32, wherein the reducible organic compound is a sodium sulfonate salt of polymerised 9,10-anthraquinone, the sodium sulfonate salt providing the source of labile hydrogen or electrons.

34. The method of claim 25, further comprising a scavenging component reactive towards an activated oxygen species.

35. The method of claim 34, wherein the scavenging component is a compound selected from the group consisting of:

organic antioxidants, organic phosphites, organic phosphines, organic phosphates, hydroquinone and substituted hydroquinone, inorganic compounds, sulphur-containing compounds and nitrogen-containing compounds and their derivatives.

36. The method of claim 34, wherein the scavenging component is present in a polymerised or oligomerised form.