Azeotrope-like compositions of tetrafluoropropene and hydrofluorocarbons

• US 20050247905A1
• Filed: 04/29/2005
• Published: 11/10/2005
• Est. Priority Date: 04/29/2004
• Status: Active Grant

• Current Assignee: Honeywell International Inc.
• Original Assignee: Honeywell International Inc.
• Inventors: Singh, Rajiv R., Knopeck, Gary M., Pham, Hang T., Diringer, Jeremy N., Herena, Louis E.
• Granted Patent: US 7,767,638 B2
• Time in Patent Office: Days
• US Class Current: 252/67
• CPC Class Codes: A01N 29/02 Acyclic compounds or compounds containing halogen attached to an aliphatic side-chain of a cycloaliphatic ring system
• CPC Class Codes: C09K 2205/122 Halogenated hydrocarbons
• CPC Class Codes: C09K 2205/126 Unsaturated fluorinated hydrocarbons
• CPC Class Codes: C09K 2205/22 All components of a mixture being fluoro compounds
• CPC Class Codes: C09K 2205/32 The mixture being azeotropic
• CPC Class Codes: C09K 2205/34 The mixture being non-azeotropic
• CPC Class Codes: C09K 2205/40 Replacement mixtures
• CPC Class Codes: C09K 23/017 Mixtures of compounds
• CPC Class Codes: C09K 3/30 for aerosols aerosol containers B65D83/14
• CPC Class Codes: C09K 5/045 containing only fluorine as halogen
• CPC Class Codes: C11D 7/5018 Halogenated solvents
• CPC Class Codes: C11D 7/505 Mixtures of (hydro)fluorocarbons
• CPC Class Codes: F25B 1/00 Compression machines, plants or systems with non-reversible cycle F25B3/00, F25B5/00, F25B6/00, F25B7/00, F25B9/00 take precedence
• CPC Class Codes: F25B 31/002 Lubrication

Abstract

Provided are azeotrope-like compositions comprising tetrafluoropropene and hydrofluorocarbons and uses thereof, including use in refrigerant compositions, refrigeration systems, blowing agent compositions, and aerosol propellants.

Claims

1. An azeotrope-like composition comprising effective amounts of trans-1,3,3,3-pentafluoropropane (transHFO-1234ze) and a compound selected from the group consisting of 1,1-difluoroethane (“

HFC-152a”

), 1,1,1,2,3,3,3-heptafluoropropane (“

HFC-227ea”

), 1,1,1,2,-tetraafluoethane (“

HFC-134a”

), 1,1,1,2,2-pentafluoroethane (“

HFC-125”

) and combinations of two or more of these.

2. The azeotrope-like composition of claim 1 comprising effective amounts of transHFO-1234ze and a component selected from the group consisting of 1,1-difluoroethane (“

HFC-152a”

), 1,1,1,2,3,3,3-heptafluoropropane (“

HFC-227ea”

), 1,1,1,2,-tetraafluoethane (“

HFC-134a”

), and 1,1,1,2,2-pentafluoroethane (“

HFC-125”

).

3. The azeotrope-like composition of claim 1 which consists essentially of from greater than zero to about 75 weight percent transHFO-1234ze and from about 25 to less than 100 weight percent of HFC-134a.

4. The azeotrope-like composition of claim 1 which consists essentially of from greater than zero to about 60 weight percent transHFO-1234ze and from about 40 to less than 100 weight percent of HFC-134a.

5. The azeotrope-like composition of claim 1 which consists essentially of from about 1 to about 40 weight percent transHFO-1234ze and from about 60 to about 99 weight percent of HFC-134a.

6. The azeotrope-like composition of claim 1 which consists essentially of from about 5 to about 35 weight percent transHFO-1234ze and from about 65 to about 95 weight percent of HFC-134a.

7. An azeotrope-like composition in accordance with claim 1 having a boiling point of from about −

26°

C. to about −

23°

C. at a pressure of about 14.4 psia.

8. An azeotrope-like composition in accordance with claim 6 having a boiling point of from about −

26□

C to about −

23□

C at a pressure of about 14.4 psia.

9. The azeotrope-like composition of claim 1 which consists essentially of from greater than zero to about 75 weight percent transHFO-1234ze and from about 25 to less than 100 weight percent of HFC-125.

10. The azeotrope-like composition of claim 1 which consists essentially of from greater than zero to about 60 weight percent transHFO-1234ze and from about 40 to less than 100 weight percent of HFC-125.

11. The azeotrope-like composition of claim 1 which consists essentially of from about 1 to about 40 weight percent transHFO-1234ze and from about 60 to about 99 weight percent of HFC-125.

12. The azeotrope-like composition of claim 1 which consists essentially of from about 2 to about 15 weight percent transHFO-1234ze and from about 85 to about 98 weight percent of HFC-125.

13. An azeotrope-like composition in accordance with claim 12 having a boiling point of from about −

26□

C to about −

23□

C at a pressure of about 14.4 psia.

14. The azeotrope-like composition of claim 1 which consists essentially of from greater than zero to about 75 weight percent transHFO-1234ze and from about 25 to less than 100 weight percent of HFC-152a.

15. The azeotrope-like composition of claim 1 which consists essentially of from greater than zero to about 50 weight percent transHFO-1234ze and from about 50 to less than 100 weight percent of HFC-152a.

16. The azeotrope-like composition of claim 1 which consists essentially of from about 15 to about 30 weight percent transHFO-1234ze and from about 70 to about 85 weight percent of HFC-152a.

17. An azeotrope-like composition in accordance with claim 16 having a boiling point of from about −

26□

C to about −

23□

C at a pressure of about 14.4 psia.

18. The azeotrope-like composition of claim 1 which consists essentially of from greater than zero to about 75 weight percent HFC-227ea and from about 25 to less than 100 weight percent of transHFO-1234ze.

19. The azeotrope-like composition of claim 1 which consists essentially of from greater than zero to about 50 weight percent HFC-227ea and from about 50 to less than 100 weight percent of transHFO-1234ze.

20. The azeotrope-like composition of claim 1 which consists essentially of from about 5 to about 35 weight percent HFC-2227ea and from about 65 to about 95 weight percent of transHFO-1234ze.

21. An azeotrope-like composition in accordance with claim 20 having a boiling point of from about −

17□

C to about −

19□

C at a pressure of about 14.4 psia.

22. A composition comprising the composition of claim 1 and at least one adjuvant selected from the group consisting of supplemental lubricants, compatibilizers, surfactants, supplemental flame suppressants, solubilizing agents, dispersing agents, cell stabilizers, cosmetics, polishing agents, medicaments, cleaners, fire retarding agents, colorants, chemical sterilants, stabilizers, polyols, polyol premix components and combinations of two or more of these.

23. A heat transfer composition comprising the composition of claim 22 and wherein said adjuvant comprises at least one lubricant.

24. The heat transfer composition of claim 23 wherein said supplemental lubricant is selected from the group consisting of mineral oil, silicone oil, polyalkyl benzenes (PABs), polyol esters (POEs), polyalkylene glycols (PAGs), polyalkylene glycol esters (PAG esters), polyvinyl ethers (PVEs), poly(alpha-olefins) (PAOs), and combinations of these.

25. The heat transfer composition of claim 24 wherein said adjuvant further includes at least one compatibilizer.

26. The heat transfer composition of claim 25 comprising from about 0.5 to about 5 percent by weight of said at least one compatibilizer.

27. The heat transfer composition of claim 24 wherein said supplemental lubricant(s) together are present in an amount of from about 5 to about 50 percent by weight of the heat transfer composition.

28. The heat transfer composition of claim 23 comprising one or more supplemental flame suppressants.

29. The heat transfer composition of claim 28 wherein said one or more flame suppressant(s) together are present in an amount of from about 0.5% to about 30% by weight of the heat transfer composition.

30. A heat transfer composition comprising an azeotrope-like composition of claim 1.

31. A heat transfer composition comprising at least about 50% by weight of the composition of claim 1.

32. A refrigerant comprising the heat transfer composition of claim 31.

33. A refrigeration system comprising a heat transfer composition of claim 32.

34. A refrigeration system of claim 33 selected from group consisting of automotive air conditioning systems, residential air conditioning systems, commercial air conditioning systems, residential refrigerator systems, residential freezer systems, commercial refrigerator systems, commercial freezer systems, chiller air conditioning systems, chiller refrigeration systems, heat pump systems, and combinations of two or more of these.

35. A blowing agent comprising an azeotrope-like composition of claim 1.

36. A blowing agent comprising at least about 5% by weight of the azeotrope-like composition of claim 1.

37. A foamable composition comprising one or more components capable of forming foam and the azeotrope-like composition of claim 1.

38. The foamable composition of claim 37 wherein said one or more components capable of forming foam comprise one or more components capable of forming foam selected from the group consisting of thermoplastic foams, polystyrene foams, polyethylene foams, low density polyethylene foams, extruded thermoplastic foams, polyurethane foams, and polyisocyanurate foams.

39. The foamable composition of claim 38 further comprising at least one additive selected from the group consisting of dispersing agents, cell stabilizers, surfactants, flame retardants and combinations of two or more of these.

40. A foam formed from the foamable composition of claim 37.

41. A closed cell foam comprising the foam of claim 40.

42. A method of replacing an existing refrigerant contained in a refrigerant system comprising removing at least a portion of said existing refrigerant from said system and replacing at least a portion of said existing refrigerant by introducing into said system a refrigerant composition comprising the composition of claim 1.

43. The method of claim 42 wherein said existing refrigerant is selected from the group consisting of HFC-134a, R-12, R-500, HFC-152a, and HFC-22 and combinations of these,

44. The method of claim 42 wherein said existing refrigerant system comprises at least a first compressor having a first displacement and further comprising the step of removing said first compressor from the system and inserting in said system at least a second compressor having a larger displacement than said first compressor.

45. The method of claim 42 wherein said existing refrigerant system is selected from the group consisting of automotive air conditioning systems, residential air conditioning systems, commercial air conditioning systems, residential refrigerator systems, residential freezer systems, commercial refrigerator systems, commercial freezer systems, chiller air conditioning systems, chiller refrigeration systems, heat pump systems, and combinations of two or more of these.

46. The method of claim 42 wherein said refrigerant in accordance with claim 1 has a Global Warming Potential (GWP) of not greater than about 1000.

47. A sprayable composition comprising a material to be sprayed and a propellant comprising an azeotrope-like composition of claim 1.

48. The sprayable composition of claim 47 in the form of an aerosol.

49. The sprayable composition of claim 48 wherein said material to be sprayed is selected from the group consisting of cosmetics, cleaning solvent, lubricants and medicinal materials.

50. The sprayable composition of claim 49 comprising a medicinal material and wherein said medicinal material is a drug or a biologically active material.

51. A method of sterilizing an article comprising contacting said article with a composition comprising the composition of claim 1.

52. A method for cooling an article which comprises condensing a composition of claim 1 and thereafter evaporating said composition in the vicinity of the article to be cooled.

53. A method for heating an article which comprises condensing a composition of claim 1 in the vicinity of the article to be heated and thereafter evaporating said composition.

54. A blowing agent comprising at least about 50% by weight of the composition of claim 1.

55. A method of sterilizing an article comprising contacting said article with a composition comprising the composition of claim 1.

56. A sprayable composition comprising a material to be sprayed and a propellant comprising a composition of claim 1.

57. A sprayable composition according to claim 56 wherein the sprayable composition is an aerosol.

58. The sprayable composition of claim 56 wherein said material to be sprayed is selected from the group consisting of cosmetics, cleansers, polishing agents, and medicinal materials.

59. The sprayable composition of claim 58 comprising a medicinal material and wherein said medicinal material is a drug or a biologically active material.