Compositions containing fluorine substituted olefins

• US 8,065,882 B2
• Filed: 03/26/2009
• Issued: 11/29/2011
• Est. Priority Date: 10/25/2002
• Status: Expired due to Term

• Current Assignee: Honeywell International Inc.
• Original Assignee: Honeywell International Inc.
• Inventors: Thomas, Raynond H., Singh, Rajiv R., Pham, Hang T., Shankland, Ian, Wilson, David P.
• Primary Examiner(s): KHAN, AMINA S
• Application Number:
  US12/412,342
• Publication Number:
  US 20090278076A1
• Time in Patent Office: 978 Days
• Field of Search: 252/67, 252/68, 252/71, 252/78.1, 62/6, 624/01, 624/98
• US Class Current: 62/6
• CPC Class Codes: A01N 29/00 Biocides, pest repellants or attractants, or plant growth regulators containing halogenated hydrocarbons
• CPC Class Codes: A23L 27/202 Aliphatic compounds
• CPC Class Codes: A23V 2002/00 Food compositions, function of food ingredients or processes for food or foodstuffs
• CPC Class Codes: A61K 47/06 Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
• CPC Class Codes: A61K 9/008 comprising drug dissolved or suspended in liquid propellant for inhalation via a pressurized metered dose inhaler [MDI]
• CPC Class Codes: A61L 2/18 Liquid substances or solutions comprising solids or dissolved gases
• CPC Class Codes: A62D 1/00 Fire-extinguishing compositions; Use of chemical substances in extinguishing fires fireproof paints C09D5/18; fireproofing materials C09K21/00
• CPC Class Codes: A62D 1/0028 Liquid extinguishing substances A62D1/0092 takes precedence
• CPC Class Codes: A62D 1/0057 Polyhaloalkanes A62D1/005 takes precedence
• CPC Class Codes: B01J 31/0231 Halogen-containing compounds
• CPC Class Codes: B01J 37/03 Precipitation; Co-precipitation
• CPC Class Codes: B01J 37/035 Precipitation on carriers
• CPC Class Codes: C07C 21/18 containing fluorine
• CPC Class Codes: C08J 2203/164 Perhalogenated unsaturated hydrocarbons, e.g. F2C=CF2
• CPC Class Codes: C08J 2207/04 Aerosol, e.g. polyurethane foam spray
• CPC Class Codes: C08J 2325/06 Polystyrene
• CPC Class Codes: C08J 9/146 only fluorine as halogen atoms
• CPC Class Codes: C09D 7/20 Diluents or solvents
• CPC Class Codes: C09K 21/08 containing halogen
• CPC Class Codes: C09K 2205/12 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 2205/24 : Only one single fluoro component present
• CPC Class Codes: C09K 3/00 : Materials not provided for elsewhere
• 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: C11B 9/0007 : Aliphatic compounds
• CPC Class Codes: C11D 17/0043 : For use with aerosol devices
• CPC Class Codes: C11D 2111/22 : Electronic devices, e.g. PCBs or semiconductors
• CPC Class Codes: C11D 3/245 : containing fluorine
• CPC Class Codes: Y02A 40/963 : Off-grid food refrigeration

Abstract

Disclosed are the use of fluorine substituted olefins, including tetra- and penta-fluoropropenes, in a variety of applications, including connection with blowing agents, foams, foamable compositions, foaming methods, heat transfer compositions and methods, propellants, and solvating methods.

Claims

1. A method of transferring heat to or from a fluid or body to provide cooling of air in an automobile, said method comprising;

(a) providing a heat transfer system comprising an automobile air conditioning system;

(b) providing in said system a heat transfer composition comprising at least one lubricant and at least one -fluoroalkene of Formula II;

2. The method of claim 1 wherein said unsaturated terminal carbon has one F substituent.

3. The method of claim 1 wherein n is 0.

4. The method of claim 3 wherein said unsaturated terminal carbon has no F substituent.

5. The method of claim 1 wherein each substituent on the unsaturated terminal carbon is H.

6. The method of claim 1 wherein n is 1.

7. The method of claim 1 wherein said fluoroalkene of Formula II comprises 1,1,1,2-tetrafluoropropene (HFO-1234yf).

8. The method of claim 1 wherein said fluoroalkene of Formula II comprises 1,3,3,3-tetrafluoropropene (HFO-1234ze).

9. The method of claim 1 wherein said fluoroalkene of Formula II comprises trans 1,3,3,3-tetrafluoropropene (HFO-1234ze).

10. The method of claim 1 comprising conditioning the air in an automobile comprising:

(a) providing a vapor compression air conditioning system having at least one compressor, at least one condenser and a heat transfer composition in said system, said heat transfer composition comprising 1,1,1,2-tetrafluoropropene (HFO-1234yf) in an amount of from about 5% by weight to about 99% by weight of the heat transfer composition; and

(b) operating said condenser in a temperature range that includes about 150°

F.

11. The method of claim 1 wherein said at least one fluoroalkene consists essentially of 1,1,1,2-tetrafluoropropene (HFO-1234yf).

12. The method of claim 1 wherein said lubricant is present in the composition in an amount of from about 30 to about 50% by weight of the heat transfer composition based on the total weight of said lubricant and said compound(s) of Formula II.

13. The method of claim 1 wherein said lubricant is selected from the group consisting of polyol esters, polyalkylene glycols, polyalkylene silicon oils, mineral oils, alkyl benzenes, poly(alpha-olefins) and combinations of these.

14. The method of claim 1 wherein said lubricant comprises at least one polyalkylene glycol.

15. The method of claim 1 wherein said lubricant comprises polyalkylene glycol ester.

16. The method of claim 1 wherein said heat transfer composition has a Global Warming Potential (GWP) of not greater than about 150.

17. The method of claim 1 wherein said heat transfer composition has a Global Warming Potential (GWP) of not greater than about 75.

18. The method of claim 1 wherein said heat transfer composition has an ozone depletion potential (ODP) of not greater than about 0.05.

19. The method of claim 1 wherein said heat transfer composition has an ozone depletion potential (ODP) of not greater than about 0.02.

20. The method of claim 1 wherein said heat transfer composition has an ozone depletion potential (ODP) of not greater than about zero.

22. The method of claim 1 wherein said compound of Formula II is present in the composition in an amount of at least about 50% by weight.

23. The method of claim 1 wherein said compound of Formula II is present in the composition in an amount of at least about 70% by weight.

24. The method of claim 1 wherein said heat transfer composition further comprises one or more of the following:

difluoromethane (HFC-32);

pentafluoroethane (HFC-125);

1,1,2,2-tetrafluoroethane (HFC-134);

1,1,1,2-tetrafluoroethane (HFC-134a);

difluoroethane (HFC-152a);

1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea);

1,1,1,3,3,3-hexafluoropropane (HFC-236fa);

1,1,1,3,3-pentafluoropropane (HFC-245fa);

1,1,1,3,3-pentafluorobutane (HFC-365mfc);

water; and

CO₂.

25. The method of claim 1 wherein said heat transfer composition further comprises a flammability suppressant.

26. The method of claim 25 wherein said flammability suppressant comprises CF3I.

27. The method of claim 1 wherein said lubricant comprises an alkyl benzene.

28. The method of claim 1 wherein said lubricant comprises an ester oil.

29. The method of claim 1 wherein said lubricant comprises a poly(alpha-olefin) oil.

30. The method of claim 1 wherein said heat transfer composition has one liquid phase at at least one temperature between about −

50°

C. and +70°

C.

31. The method of claim 1 wherein said heat transfer composition is stable when in contact with aluminum, steel and copper under the conditions of use in said air conditioning systems.

32. The method of claim 1 wherein heat transfer composition comprises from about 5% by weight to about 95% by weight of 1,1,1,2-tetrafluoropropene (HFO-1234yf).

21. The method claim wherein said compound of Formula II is present in the composition in an amount of from about 5% by weight to about 95% by weight.

33. A method of providing an air conditioning system for conditioning the air in an automobile comprising:

(a) providing in the automobile a vapor compression air conditioning system having at least one compressor and at least one condenser; and

(b) providing a refrigerant in said system for cooling the air in the automobile, said refrigerant comprising from about 5% by weight to about 99% by weight of 1,1,1,2-tetrafluoropropene (HFO-1234yf).

34. The method of claim 33 wherein said refrigerant further comprises at least one lubricant comprising a polyalkylene glycol.

35. The method of claim 34 wherein said refrigerant has one liquid phase at at least one temperature between about −

50°

C. and +70°

C. and wherein said refrigerant has a a capacity relative to HFC-134a of about 1, a Coefficient of Performance (COP) relative to HFC-134a of about 1 and a Global Warming Potential (GWP) of not greater than about 75.

36. A method for cooling air in an automobile by use of an automobile air conditioning system, said method comprising providing in said automobile air conditioning system a heat transfer composition comprising at least one tetrafluoropropene according to Formula II:

37. The method of claim 36 wherein said tetrafluoropropene comprises 1,1,1,2-tetrafluoropropene (HFO-1234yf).

38. The method of claim 37 wherein said heat transfer composition comprises from about 5% by weight to about 95% by weight of 1,1,1,2-tetrafluoropropene (HFO-1234yf).

39. The method of claim 37 wherein said tetrafluoropropene consists essentially of 1,1,1,2-tetrafluoropropene (HFO-1234yf).

40. The method of claim 36 wherein said heat transfer composition further comprises at least one lubricant.

41. The method of claim 40 wherein said lubricant is selected from the group consisting of polyol esters, polyalkylene glycols, polyalkylene silicon oils, mineral oils, alkyl benzenes, poly(alpha-olefins) and combinations of these.

42. The method of claim 40 wherein said at least one lubricant comprises at least one polyalkylene glycol.

43. The method of claim 40 wherein said at least one lubricant comprises polyalkylene glycol ester.

44. The method of claim 41 wherein said heat transfer composition has one liquid phase at at least one temperature between about −

50°

C. and +70°

C. and wherein said heat transfer composition has a capacity relative to HFC-134a of about 1 and a Coefficient of Performance (COP) relative to HFC-134a of about 1.

45. The method of claim 44 wherein said 1,1,1,2-tetrafluoropropene (HFO-1234yf) is present in the composition in an amount of at least about 70% by weight.

46. The method of claim 45 wherein said heat transfer composition further comprises one or more of the following:

difluoromethane (HFC-32);

pentafluoroethane (HFC-125);

1,1,2,2-tetrafluoroethane (HFC-134);

1,1,1,2-tetrafluoroethane (HFC-134a);

difluoroethane (HFC-152a);

1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea);

1,1,1,3,3,3-hexafluoropropane (HFC-236fa);

1,1,1,3,3-pentafluoropropane (HFC-245fa);

1,1,1,3,3-pentafluorobutane (HFC-365mfc);

water; and

CO₂.

47. A method for cooling the air in an automobile comprising:

(a) providing in said automobile a vapor compression air conditioning system having at least one compressor and at least one condenser operable in a temperature range that includes about 150°

F.; and

(b) providing a heat transfer fluid in said system, said heat transfer fluid comprising 1,1,1,2-tetrafluoropropene (HFO-1234yf) in an amount of from about 5% by weight to about 99% by weight of the heat transfer fluid.

48. The method of claim 47 wherein said heat transfer fluid has a capacity relative to HFC-134a of about 1 and a Coefficient of Performance (COP) relative to HFC-134a of about 1.

49. The method of claim 47 wherein said heat transfer fluid further comprises at least one lubricant selected from the group consisting of polyol esters, polyalkylene glycols, polyalkylene silicon oils, mineral oils, alkyl benzenes, poy(alpha-olefins) and combinations of these.

50. A method of conditioning the air in an automobile using an automobile air conditioning system including at least one compressor and at least one evaporator, said method comprising:

(a) utilizing in said system a heat transfer fluid comprising 1,1,1,2-tetrafluoropropene (HFO-1234yf) in an amount of from about 5% by weight to about 99% by weight of the heat transfer fluid; and

(b) using said heat transfer fluid to absorb heat from the air in the automobile by evaporating in said evaporator said heat transfer fluid to produce a vapor comprising said HFO-1234yf;

(c) compressing at least a portion of said vapor from said step (b) in said at least one compressor to produce a relatively elevated pressure vapor comprising HFO-1234yf; and

(d) removing heat from said relatively elevated pressure vapor by condensing said vapor.

51. The method of claim 50 wherein said heat transfer fluid further comprises at least one lubricant selected from the group consisting of polyol esters, polyalkylene glycols, polyalkylene silicon oils, mineral oils, alkyl benzenes, poy(alpha-olefins) and combinations of these and wherein said system further comprises a condenser operated in a temperature range that includes about 150°

F.

52. The method of claim 51 wherein said heat transfer fluid has a Global Warming Potential (GWP) of not greater than about 75.