Signal activated decontaminating coating

• US 20070114121A1
• Filed: 06/21/2006
• Published: 05/24/2007
• Est. Priority Date: 06/21/2005
• Status: Active Grant

• Current Assignee: Crosslink Polymer Research
• Original Assignee: Crosslink
• Inventors: Hou, Shifeng, Ding, Yiwei, Bashkin, James, Kinlen, Patrick
• Granted Patent: US 7,993,495 B2
• Time in Patent Office: Days
• US Class Current: 204/175
• CPC Class Codes: A61L 2/03 Electric current
• CPC Class Codes: A61L 2/16 using chemical substances
• CPC Class Codes: A61L 2/232 layered or coated
• CPC Class Codes: A62D 2101/02 Chemical warfare substances, e.g. cholinesterase inhibitors
• CPC Class Codes: A62D 2203/10 Apparatus specially adapted for treating harmful chemical agents; Details thereof
• CPC Class Codes: A62D 3/38 by oxidation; by combustion
• CPC Class Codes: B01J 2231/70 Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
• CPC Class Codes: B01J 2531/72 Manganese
• CPC Class Codes: B01J 2531/842 Iron
• CPC Class Codes: B01J 31/006 comprising organic radicals, e.g. TEMPO
• CPC Class Codes: B01J 31/0208 Ketones or ketals
• CPC Class Codes: B01J 31/184 mixed aromatic/aliphatic ring systems, e.g. indoline
• CPC Class Codes: C01B 15/00 Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
• CPC Class Codes: C01B 15/01 Hydrogen peroxide
• CPC Class Codes: C01B 15/0295 by electrical discharge
• CPC Class Codes: C09D 105/04 Alginic acid; Derivatives thereof

Abstract

A method is provided for decontaminating a surface that is susceptible to contamination by a contaminant by applying to the surface a coating which produces a decontaminating agent for the contaminant in response to a signal, connecting the electroactive coating to a source of a signal, and when the surface is contaminated, applying the signal to the electroactive coating, thereby producing one or more decontaminating agents which neutralize or destroy the contaminant. Coatings for practicing the method and articles that have been protected by the novel coatings are also provided.

Claims

1. A method of producing activated peroxides in a coating, the method comprising

providing a coating comprising a peroxide source and a peroxide activating catalyst;

causing the peroxide source to produce a peroxide; and

contacting the peroxide with the catalyst to produce activated peroxide.

2. The method according to claim 1, wherein the peroxide source comprises:

a reservoir of a peroxide;

or

a signal activated peroxide producing system.

3. The method according to claim 2, wherein the peroxide comprises hydrogen peroxide and the peroxide source comprises a signal activated peroxide producing system.

4. The method according to claim 3, wherein the signal activated peroxide producing system comprises:

a positive electrode and a negative electrode;

which are interconnected by

an electrically or ionically conductive matrix that comprises water and/or oxygen.

5. The method according to claim 4, wherein the step of causing the peroxide source to produce the hydrogen peroxide comprises providing the signal to activate the production of hydrogen peroxide.

6. The method according to claim 5, wherein the signal comprises imposing an electrical potential across the positive and the negative electrode, thereby causing the reduction of oxygen and the production of hydrogen peroxide.

7. The method according to claim 4, wherein the peroxide source further comprises a mediator which is involved in the transfer of electrons and hydrogen ions to oxygen in the formation of hydrogen peroxide.

8. The method according to claim 7, wherein the mediator comprises at least one compound that is selected from the group consisting of quinones, naphthoquinones, anthraquinones, derivatives thereof, and mixtures thereof

9. The method according to claim 1, wherein peroxide activating catalyst comprises at least one compound that is selected from the group consisting of complexes of ethylenediaminetetraacetic acid with metals, EDTA/Fe complexes, tetraaminomacrocyclic ligand (TAML®

) complexes with metals, TAML®

/Fe complexes, manganese gluconate, sodium hypochlorite, N-[4-(triethylammoniomethyl)benzoyl]-caprolactam chloride, nonanoyloxybenzene sulfonate, porphyrins, phthalocyanines, ruthenium oxide, indium oxide, and quinones.

10. The method according to claim 4, wherein the electrode at which hydrogen peroxide formation occurs comprises a material that is selected from metals, platinum, gold, metal oxides, indium tin oxide, conductive metal salts, carbon, carbon/metal composites, intrinsically conductive polymers, materials that include carbon nanotubes, and mixtures of any of these materials.

11. The method according to claim 10, wherein the coating comprises a gel structure.

12. The method according to claim 1, wherein the coating is permeable to water vapor and oxygen.

13. The method according to claim 1, wherein the coating is sufficiently permeable to activated hydrogen peroxide to permit the diffusion of activated hydrogen peroxide to a surface of the coating, whereby the activated hydrogen can contact a contaminant that is present on the surface.

14. The method according to claim 1, wherein the coating comprises a polymer layer and/or a gel and wherein the peroxide activating catalyst is chemically linked to the polymer layer and/or the gel.

15. The method according to claim 4, wherein at least one of the positive electrode or the negative electrode has a coating comprising a fluorinated sulfonic acid copolymer.

16. A method of decontaminating a surface that is susceptible to contamination with a contaminant, the method comprising:

applying to the surface a coating which produces a decontaminating agent for the contaminant when an electrical potential is applied to the coating;

connecting the electroactive coating to a source of an electrical potential; and

when the surface is contaminated,

applying an electrical potential to the electroactive coating, thereby producing the decontaminating agent and destroying the contaminant.

17. The method according to claim 16, wherein the surface comprises an outer surface of a material that is selected from metal, plastic, wood, fabric, glass, paper, clay, ceramic, or a mixture of any of these.

18. The method according to claim 16, wherein the contaminant comprises a chemical warfare agent, a biological warfare agent, a bacterial toxin, a disease causing microorganism, or a mixture of any of these.

19. The method according to claim 16, wherein the contaminant comprises antrax, botulinum toxin, plague, a virus that is harmful to humans or animals, a disease causing organism, or a mixture of any of these.

20. The method according to claim 16, wherein the contaminant comprises a vesicant, a type G nerve gas, a type V nerve gas, or a mixture of any of these.

21. The method according to claim 16, wherein the contaminant comprises, o-alkyl phosphonofluoridates, sarin GB) and soman (GD), o-alkyl phophoramidocyanidates, tabun (GA), o-alkyl, s-2-dialkyl aminoethyl alkylphosphonothiolates and corresponding alkylated or protonated salts, VX, 2-chloroethylchloromethylsulfide, bis(2-chloroethyl)sulfide, bis(2-chloroethylthio)methane, 1,2-bis(2-chloroethylthio)ethane, 1,3-bis(2-chloroethylthio)-n-propane, 1,4-bis(2-chloroethylthio)-n-butane, 1,5-bis(2-chloroethylthio)-n-pentane, bis(2-chloroethylthiomethyl)ether, bis(2-chloroethylthioethyl)ether, Lewisites, 2-chlorovinyldichioroarsine, bis(2-chlorovinyl)chloroarsine, tris(2-chlorovinyl)arsine, bis(2-chloroethyl)ethylamine, bis(2-chloroethyl)methylamine, saxitoxin, ricin, alkyl phosphonyidifluoride, alkyl phosphonites, chlorosarin, chlorosoman, amiton, 1,1,3,3,3,-pentafluoro-2-(trifluoromethyl)-1-propene, 3-quinuclidinyl benzilate, methylphosphonyl dichloride, dimethyl methylphosphonate, dialkyl phosphoramidic dihalides, dialkyl phosphoramidates, arsenic trichloride, diphenyl hydroxyacetic acid, quinuclidin-3-ol, dialkyl aminoethyl-2-chlorides, dialkyl aminoethan-2-ols, dialkyl aminoethane-2-thiols, thiodiglycols, pinacolyl alcohols, phosgene, cyanogen chloride, hydrogen cyanide, chloropicrin, phosphorous oxychloride, phosphorous trichloride, phosphorus pentachloride, alkyl phosphites, sulfur monochloride, sulfur dichloride, thionyl chloride, or mixtures of any of these.

22. The method according to claim 16, wherein the decontaminating agent comprises a reactive oxygen species, a nucleophilic agent, or a mixture of these.

23. The method according to claim 16, wherein the decontaminating agent comprises hypochlorites, sodium hypochlorite, chlorine, potassium peroxymonosulfate, ammonium persulfate, ammonium peroxymonosulfate, peroxydisulfate, permanganates, potassium permanaganate, peroxides, hydrogen peroxide, or a mixture of any of these.

24. The method according to claim 16, further comprising the step of ceasing the application of an electrical potential to the electroactive coating, thereby ceasing the production of the decontaminating agent.

25. The method according to claim 24, where the coating is exposed to air and further comprising permitting oxygen to enter the coating from the air.

26. The method according to claim 25, further comprising permitting water vapor to enter the coating.

27. The method according to claim 26, further comprising repeating the step of applying an electrical potential to the electroactive coating, thereby producing the decontaminating agent and destroying the contaminant.

28. The method according to claim 16, wherein the step of applying an electrical potential comprises attaching the positive and the negative electrodes to a source of direct current.

29. The method according to claim 28, wherein the direct current is provided at a voltage of between about −

10 volts and +50 volts versus a Ag/AgCl electrode.

30. The method according to claim 16, wherein the step of applying the coating to the surface comprises applying one or more layers to the surface in one or a series of steps.

31. The method according to claim 30, wherein the surface is a surface of a flexible material that is a fabric or a film, and the layers are applied by screen printing.

32. A coating for a surface, wherein the coating comprises a peroxide source and a peroxide activating catalyst in a durable matrix.

33. The coating according to claim 32, wherein the durable matrix comprises a material that is water insoluble and is sufficiently adherent to the surface to remain on the surface during normal usage.

34. The coating according to claim 32, wherein the peroxide source comprises:

a reservoir of a peroxide;

or

a signal activated peroxide producing system.

35. The coating according to claim 32, wherein the peroxide comprises hydrogen peroxide and the peroxide source comprises a signal activated peroxide producing system.

36. The coating according to claim 35, wherein the signal activated peroxide producing system comprises:

a positive electrode and a negative electrode;

which are interconnected by

an electrically or ionically conductive medium that comprises water and/or oxygen.

37. The coating according to claim 36, wherein the system further comprises a positive electrode lead that interconnects the positive electrode with the positive pole of a source of an electrical potential and a negative electrode lead that interconnects the negative electrode with the negative pole of a source of an electrical potential.

38. The coating according to claim 37, further comprising a switch located in the positive electrode lead or the negative electrode lead and which can control whether an electrical potential is applied to the electrodes.

39. The coating according to claim 36, wherein the signal activated peroxide producing system further comprises a mediator which is involved in the transfer of electrons and hydrogen ions to oxygen in the formation of hydrogen peroxide.

40. The coating according to claim 39, wherein the mediator comprises a compound that can be reversibly oxidized and reduced and can transfer hydrogen ions and electrons in a chemical reaction.

41. The coating according to claim 40, wherein the mediator comprises at least one compound that is selected from the group consisting of quinones, anthraquinones, and mixtures thereof

42. The coating according to claim 32, wherein peroxide activating catalyst comprises at least one compound that is selected from the group consisting of complexes of ethylenediaminetetraacetic acid with metals, EDTA/Fe complexes, tetraaminomacrocyclic ligand (TAML®

) complexes with metals, TAML®

/Fe complexes, manganese gluconate, sodium hypochlorite, N-[4-(triethylammoniomethyl)benzoyl]-caprolactam chloride, nonanoyloxybenzene sulfonate, porphyrins, phthalocyanines, ruthenium oxide, indium oxide, and quinones.

43. The coating according to claim 36, wherein the electrode at which hydrogen peroxide formation occurs comprises a material that is selected from metals, platinum, gold, metal oxides, indium tin oxide, conductive metal salts, carbon, carbon/metal composites, intrinsically conductive polymers, materials that include carbon nanotubes, and mixtures of any of these materials.

44. The coating according to claim 33, wherein the coating comprises a gel structure.

45. The coating according to claim 33, wherein the coating is permeable to water vapor and oxygen.

46. The coating according to claim 33, wherein the coating is sufficiently permeable to activated hydrogen peroxide to permit the diffusion of activated hydrogen peroxide to a surface of the coating, whereby the activated hydrogen can contact a contaminant that is present on the surface.

47. The coating according to claim 32, comprising:

a positive electrode and a negative electrode;

which are interconnected by

a water insoluble matrix which is electrically conductive or ionically conductive;

a mediator that is selected from quinone or anthraquinone and which is present in the matrix or bound to an electrode;

a peroxide activating catalyst that is selected from EDTA/Fe complex or TAML/metal complex; and

electrode leads for interconnecting the positive electrode and the negative electrode with a source of electrical potential.

48. The system method according to claim 32, wherein the coating comprises a polymer layer or a gel and wherein the peroxide activating catalyst is chemically linked to the polymer layer and/or the gel.

52. An article that is coated with the coating of claim 32.

53. A sensor-activated decontaminating coating system comprising:

an electroactivated decontaminating coating according to claim 32;

a source of an electrical potential;

electrode leads interconnecting the source of an electrical potential and the electrodes of the coating;

a switch that is located in an electrical lead and which controls the application of an electrical potential to the coating; and

a sensor that controls the operation of the switch.

54. The system according to claim 53, where the sensor can sense the presence of a contaminant.

55. The system according to claim 54, wherein the sensor can sense the presence of a chemical warfare agent and/or a biological warfare agent.

49. An electroactivated decontaminating coating comprising a coating which produces a decontaminating agent for a contaminant that is in contact with the coating, where the decontaminating agent is produced when an electrical potential is applied to the coating.

50. A method of making an electroactivated decontaminating coating for a surface that is susceptible to contamination with a contaminant, the method comprising:

applying at least one positive electrode and at least one negative electrode to the surface; and

applying a layer comprising a matrix that is electrically conductive or ionically conductive over the positive electrode and the negative electrode, wherein the matrix contains a peroxide activating catalyst and is permeable to oxygen, water vapor, and hydrogen peroxide.

51. The method according to claim 50, wherein a peroxide activating mediator is provided that is either bound to an electrode or distributed throughout the matrix, or both.

56. An electroactivated decontaminating coating comprising:

a polymer coating containing a stable oxidizing catalyst capable of activating hydrogen peroxide to activated hydrogen peroxide, which coating is in contact with;

two or more flexible polymer electrodes and a supporting electrolyte gel.