JP6442011B2 - Compositions containing fluoroolefins and uses thereof - Google Patents

Description

  The present invention relates to a composition for use in a refrigeration, air conditioning or heat pump system, the composition comprising at least one fluoroolefin. The compositions of the present invention are useful as heat transfer fluids in processes that provide refrigeration or heat and are useful in many other uses.

(Cross-reference of related applications)
This application is based on US Provisional Patent Application No. 60 / 732,581 filed Nov. 1, 2005 and US Patent Application No. 11 / 486,791 filed Jul. 13, 2006. Insist on the interests of rights.

  The refrigeration industry has worked for the past few decades to find alternative refrigerants for ozone-depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) that are being phased out under the Montreal Protocol . The solution for most refrigerant manufacturers has been the commercialization of hydrofluorocarbon (HFC) refrigerants. The new HFC refrigerant currently being used most widely, HFC-134a, has a zero ozone depletion potential and is therefore unaffected by the phasing out of current regulations under the Montreal Protocol.

  Further environmental regulations can ultimately lead to a global phase out of certain HFC refrigerants. Currently, the automobile industry is facing regulations on global warming potential for refrigerants used in portable air conditioning. Accordingly, there is a great current need to identify new refrigerants with reduced global warming potential for the portable air conditioning market. In the future, if the regulations are more widely applied, there will be a greater need for refrigerants that can be used in all areas of the refrigeration and air conditioning industries.

Alternative refrigerants for HFC-134a currently proposed include HFC-152a, pure hydrocarbons such as butane or propane, or “natural” refrigerants such as CO ₂ . Many of these proposed alternatives are toxic, flammable, and / or have low energy efficiency. Therefore, new alternative refrigerants are being sought.

US Pat. No. 6,066,768 US patent application Ser. No. 11 / 062,044 US patent application Ser. No. 10 / 910,495 US Reissue Patent No. RE36,951 US Pat. No. 5,065,990 US Pat. No. 5,363,674 US patent application Ser. No. 11 / 367,517 US patent application Ser. No. 11 / 378,832

Genenaux et al., “Journal of Fluorine Chemistry”, Vol. 4, pages 261-270 (1974) 1990 ASHRAE Handbook, Refrigeration Systems and Applications (1990 ASHRAE Handbook, Refrigeration Systems and Applications), Chapter 8, Title “Lubricants in Refrigeration Systems. “Synthetic Lubricants and High-Performance Fluids”, R.A. L. RL Shubkin, editor, Marcel Dekker, 1993 "Journal of Fluorine Chemistry", Vol. 24, pages 93-104 (1984) "Journal of Organic Chemistry", Vol. 56, pages 3187-3189 (1991) “Journal of Fluorine Chemistry”, Vol. 125, pages 99-105 (2004)

  The present invention seeks to provide novel refrigerant and heat transfer fluid compositions that provide unique features that meet the requirements of low or zero ozone depletion potential and lower global warming potential as compared to current refrigerants. To do.

The present invention is:
(I) a fluoroolefin of formula E—R ¹ CH═CHR ² or Z—R ¹ CH═CHR ² , wherein R ¹ and R ² are independently C ₁ -C ₆ perfluoro A fluoroolefin which is an alkyl group and wherein the total number of carbons in the compound is at least 5;
(Ii) a cyclic fluoroolefin of formula cyclo- [CX = CY (CZW) _n- ], wherein X, Y, Z, and W are independently H or F, and n is A cyclic fluoroolefin that is an integer from 2 to 5; and (iii) 2,3,3-trifluoro-1-propene (CHF ₂ CF═CH ₂ ); 1,1,2-trifluoro-1-propene (CH ₃ CF = CF ₂ ); 1,2,3-trifluoro-1-propene (CH ₂ FCF═CF ₂ ); 1,1,3-trifluoro-1-propene (CH ₂ FCH═CF ₂ ); 1 , 3,3-trifluoro-1-propene (CHF ₂ CH═CHF); 1,1,1,2,3,4,4,4-octafluoro-2-butene (CF ₃ CF═CFCF ₃ ); 1,1,2,3,3,4,4,4-octafluoro-1-bute (CF ₃ CF ₂ CF═CF ₂ ); 1,1,1,2,4,4,4-heptafluoro-2-butene (CF ₃ CF═CHCF ₃ ); 1, 2, _{3, 3, 4} 1,4,4-heptafluoro-1-butene (CHF═CFCF ₂ CF ₃ ); 1,1,1,2,3,4,4-heptafluoro-2-butene (CHF ₂ CF═CFCF ₃ ); 1 , 3,3,3-tetrafluoro-2- (trifluoromethyl) -1-propene ((CF ₃ ) ₂ C═CHF); 1,1,3,3,4,4,4-heptafluoro-1 - butene _{(CF 2 = CHCF 2 CF 3} ); 1,1,2,3,4,4,4- heptafluoro-1-butene _{(CF 2 = CFCHFCF 3);} 1,1,2,3,3, 4,4 heptafluoro-1-butene _{(CF 2 = CFCF 2 CHF 2} ); 2,3,3,4,4,4- hexa Ruoro-1-butene _{(CF 3 CF 2 CF = CH} 2); 1,3,3,4,4,4- hexafluoro-1-butene _{(CHF = CHCF 2 CF 3)} ; 1,2,3,4 1,4,4-hexafluoro-1-butene (CHF = CFCHFCF ₃ ); 1,2,3,3,4,4-hexafluoro-1-butene (CHF = CFCF ₂ CHF ₂ ); 1,3,4,4-hexafluoro-2-butene (CHF ₂ CF═CFCHF ₂ ); 1,1,1,2,3,4-hexafluoro-2-butene (CH ₂ FCF═CFCF ₃ ); 1 1,1,1,2,4,4-hexafluoro-2-butene (CHF ₂ CH═CFCF ₃ ); 1,1,1,3,4,4-hexafluoro-2-butene (CF ₃ CH═CFCHF) _2); 1,1,2,3,3,4- hexafluoro-1-butene ( _{F 2 = CFCF 2 CH 2 F} ); 1,1,2,3,4,4- hexafluoro-1-butene _{(CF 2 = CFCHFCHF 2);} 3,3,3- trifluoro-2- (trifluoromethyl methyl) -1-propene _{(CH 2 = C (CF 3} ) 2); 1,1,1,2,4- pentafluoro-2-butene _{(CH 2 FCH = CFCF 3)} ; 1,1,1,3 , 4-pentafluoro-2-butene (CF ₃ CH═CFCH ₂ F); 3,3,4,4,4-pentafluoro-1-butene (CF ₃ CF ₂ CH═CH ₂ ); 1,4,4-pentafluoro-2-butene _{(CHF 2 CH = CHCF 3)} ; 1,1,1,2,3- pentafluoro-2-butene _{(CH 3 CF = CFCF 3)} ; 2,3, 3,4,4-pentafluoro-1-butene _{(CH 2 = CFCF 2 CHF 2} ); 1,1 1,2,4,4-pentafluoro-2-butene (CHF ₂ CF═CHCHF ₂ ); 1,1,2,3,3-pentafluoro-1-butene (CH ₃ CF ₂ CF═CF ₂ ); 1 1,1,2,3,4-pentafluoro-2-butene (CH ₂ FCF═CFCHF ₂ ); 1,1,3,3,3-pentafluoro-2-methyl-1-propene (CF ₂ ═C ( _{CF 3) (CH 3))} ; 2- ( difluoromethyl) -3,3,3-trifluoro-1-propene _{(CH 2 = C (CHF 2} ) (CF 3)); 2,3,4,4 , 4-pentafluoro-1-butene (CH ₂ ═CFCHFCF ₃ ); 1,2,4,4,4-pentafluoro-1-butene (CHF═CFCH ₂ CF ₃ ); 1,3,4,4 4-pentafluoro-1-butene (CHF = CHCHFCF _3); 1,3,3,4 4-pentafluoro-1-butene _{(CHF = CHCF 2 CHF 2)} ; 1,2,3,4,4- pentafluoro-1-butene (CHF = CFCHFCHF _2); 3,3,4,4- tetrafluoro 1-butene _{(CH 2 = CHCF 2 CHF 2} ); 1,1- difluoro-2- (difluoromethyl) -1-propene _{(CF 2 = C (CHF 2} ) (CH 3)); 1,3,3 , 3-tetrafluoro-2-methyl-1-propene _{(CHF = C (CF 3)} (CH 3)); 3,3- difluoro-2- (difluoromethyl) -1-propene (CH ₂ = C (CHF ₂ ) ₂ ); 1,1,1,2-tetrafluoro-2-butene (CF ₃ CF═CHCH ₃ ); 1,1,1,3-tetrafluoro-2-butene (CH ₃ CF═CHCF ₃ ) 1,1,1,2,3,4,4,5,5; 5-decafluoro-2-pentene _{(CF 3 CF = CFCF 2 CF} 3); 1,1,2,3,3,4,4,5,5,5- decafluoro-1-pentene (CF ₂ = CFCF ₂ CF ₂ CF ₃ ); 1,1,1,4,4,4-hexafluoro-2- (trifluoromethyl) -2-butene ((CF ₃ ) ₂ C═CHCF ₃ ); 1,1,1 , 2,4,4,5,5,5- nonafluoro-2-pentene _{(CF 3 CF = CHCF 2 CF} 3); 1,1,1,3,4,4,5,5,5- nonafluoro -2 - pentene _{(CF 3 CH = CFCF 2 CF} 3); 1,2,3,3,4,4,5,5,5- nonafluoro-1-pentene _{(CHF = CFCF 2 CF 2 CF} 3); 1,1 , 3,3,4,4,5,5,5-nonafluoro-1-pentene _{(CF 2 = CHCF 2 CF 2} CF 3); 1 , 1,2,3,3,4,4,5,5- nonafluoro-1-pentene _{(CF 2 = CFCF 2 CF 2} CHF 2); 1,1,2,3,4,4,5,5, 5-nonafluoro-2-pentene (CHF ₂ CF═CFCF ₂ CF ₃ ); 1,1,1,2,3,4,4,5,5-nonafluoro-2-pentene (CF ₃ CF═CFCF ₂ CHF ₂₎ ); 1,1,1,2,3,4,5,5,5-nonafluoro-2-pentene (CF ₃ CF═CFCHFCF ₃ ); 1,2,3,4,4,4-hexafluoro-3 -(Trifluoromethyl) -1-butene (CHF = CFCF (CF ₃ ) ₂ ); 1,1,2,4,4,4-hexafluoro-3- (trifluoromethyl) -1-butene (CF _{2 = CFCH (CF 3) 2)} ; 1,1,1,4,4,4- hexafluoro-2- (triphenylmethyl Oromechiru) -2-butene _{(CF 3 CH = C (CF} 3) 2); 1,1,3,4,4,4- hexafluoro-3- (trifluoromethyl) -1-butene (CF ₂ = CHCF (CF _{3) 2);} 2,3,3,4,4,5,5,5- octafluoro-1-pentene _{(CH 2 = CFCF 2 CF 2} CF 3); 1,2,3,3,4 , 4,5,5-octafluoro-1-pentene (CHF = CFCF ₂ CF ₂ CHF ₂ ); 3,3,4,4,4-pentafluoro-2- (trifluoromethyl) -1-butene (CH ₂ = C (CF ₃ ) CF ₂ CF ₃ ); 1,1,4,4,4-pentafluoro-3- (trifluoromethyl) -1-butene (CF ₂ ═CHCH (CF ₃ ) ₂ ); 1 , 3,4,4,4-pentafluoro-3- (trifluoromethyl) -1-butene (CHF) _{CHCF (CF 3) 2);} 1,1,4,4,4- pentafluoro-2- (trifluoromethyl) -1-butene _{(CF 2 = C (CF 3} ) CH 2 CF 3); 3,4 , 4,4-tetrafluoro-3- (trifluoromethyl) -1-butene ((CF ₃ ) ₂ CFCH═CH ₂ ); 3,3,4,4,5,5,5-heptafluoro-1- pentene _{(CF 3 CF 2 CF 2 CH} = CH 2); 2,3,3,4,4,5,5- heptafluoro-1-pentene _{(CH 2 = CFCF 2 CF 2} CHF 2); 1,1, 3,3,5,5,5- heptafluoro-1-butene _{(CF 2 = CHCF 2 CH 2} CF 3); 1,1,1,2,4,4,4- heptafluoro-3-methyl-2 - butene _{(CF 3 CF = C (CF} 3) (CH 3)); 2,4,4,4- tetrafluoro-3- (triphenylmethyl Ruoromechiru) 1-butene _{(CH 2 = CFCH (CF 3} ) 2); 1,4,4,4- tetrafluoro-3- (trifluoromethyl) -1-butene _{(CHF = CHCH (CF 3)} 2) 1,1,1,4-tetrafluoro-2- (trifluoromethyl) -2-butene (CH ₂ FCH═C (CF ₃ ) ₂ ); 1,1,1,3-tetrafluoro-2- ( Trifluoromethyl) -2-butene (CH ₃ CF═C (CF ₃ ) ₂ ); 1,1,1-trifluoro-2- (trifluoromethyl) -2-butene ((CF ₃ ) ₂ C═CHCH _3); 3,4,4,5,5,5- hexafluoro-2-pentene _{(CF 3 CF 2 CF = CHCH} 3); 1,1,1,4,4,4- hexafluoro-2-methyl 2-butene _{(CF 3 C (CH 3)} = CHCF 3); 3,3,4,5, , 5-hexafluoro-1-pentene _{(CH 2 = CHCF 2 CHFCF 3} ); 4,4,4- trifluoro-3- (trifluoromethyl) -1-butene _{(CH 2 = C (CF 3} ) CH 2 CF ₃ ); 1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1-hexene (CF ₃ (CF ₂ ) ₃ CF═CF ₂ ); 1,1,2,2,3,4,5,5,6,6,6- dodecafluoro-3- hexene _{(CF 3 CF 2 CF = CFCF} 2 CF 3); 1,1,1,4,4 , 4-Hexafluoro-2,3-bis (trifluoromethyl) -2-butene ((CF ₃ ) ₂ C═C (CF ₃ ) ₂ ); 1,1,1,2,3,4,5, 5,5 nonafluoro-4- (trifluoromethyl) -2-pentene _{((CF 3) 2 CFCF =} CFCF 3); 1,1,1,4 4,5,5,5-octafluoro-2- (trifluoromethyl) -2-pentene _{((CF 3) 2 C =} CHC 2 F
₅ ); 1,1,1,3,4,5,5,5-octafluoro-4- (trifluoromethyl) -2-pentene ((CF ₃ ) ₂ CFCF═CHCF ₃ ); 3,3,4 , 4,5,5,6,6,6- nonafluoro-1-hexene _{(CF 3 CF 2 CF 2 CF} 2 CH = CH 2); 4,4,4- trifluoro-3,3-bis (trifluoromethyl Methyl) -1-butene (CH ₂ ═CHC (CF ₃ ) ₃ ); 1,1,1,4,4,4-hexafluoro-2- (trifluoromethyl) -3-methyl-2-butene (( CF ₃ ) ₂ C═C (CH ₃ ) (CF ₃ )); 2,3,3,5,5,5-hexafluoro-4- (trifluoromethyl) -1-pentene (CH ₂ ═CFCF ₂ CH (CF _{3) 2);} 1,1,1,2,4,4,5,5,5- nonafluoro-3-methyl-2-pent _{(CF 3 CF = C (CH} 3) CF 2 CF 3); 1,1,1,5,5,5- hexafluoro-4- (trifluoromethyl) -2-pentene (CF ₃ CH = CHCH (CF _{3) 2);} 3,4,4,5,5,6,6,6- octafluoro-2-hexene _{(CF 3 CF 2 CF 2 CF} = CHCH 3); 3,3,4,4,5, 5,6,6-octafluoro-1-hexene (CH ₂ ═CHCF ₂ CF ₂ CF ₂ CHF ₂ ); 1,1,1,4,4-pentafluoro-2- (trifluoromethyl) -2-pentene ( (CF ₃ ) ₂ C═CHCF ₂ CH ₃ ); 4,4,5,5,5-pentafluoro-2- (trifluoromethyl) -1-pentene (CH ₂ ═C (CF ₃ ) CH ₂ C ₂ F _5); 3,3,4,4,5,5,5-heptafluoro-2-methyl-1-pentene (CF _{3 CF 2 CF 2 C (CH} 3) = CH 2); 4,4,5,5,6,6,6- heptafluoro-2-hexene _{(CF 3 CF 2 CF 2 CH} = CHCH 3); 4, 4,5,5,6,6,6- heptafluoro-1-hexene _{(CH 2 = CHCH 2 CF 2} C 2 F 5); 1,1,1,2,2,3,4- heptafluoro -3 - hexene _{(CF 3 CF 2 CF = CFC} 2 H 5); 4,5,5,5- tetrafluoro-4- (trifluoromethyl) -1-pentene _{(CH 2 = CHCH 2 CF (} CF 3) 2) 1,1,1,2,5,5,5-heptafluoro-4-methyl-2-pentene (CF ₃ CF═CHCH (CF ₃ ) (CH ₃ )); 1,1,1,3-tetra fluoro-2- (trifluoromethyl) -2-pentene _{((CF 3) 2 C =} CFC 2 H 5); 1,1,1,2 3,4,4,5,5,6,6,7,7,7- tetradecanoyl-fluoro-2-heptene _{(CF 3 CF = CFCF 2 CF} 2 C 2 F 5); 1,1,1,2, 2,3,4,5,5,6,6,7,7,7- tetradecanoyl-fluoro-3- heptene _{(CF 3 CF 2 CF = CFCF} 2 C 2 F 5); 1,1,1,3, 4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene _{(CF 3 CH = CFCF 2 CF} 2 C 2 F 5); 1,1,1,2,4, 4,5,5,6,6,7,7,7- tridecafluoro-2-heptene _{(CF 3 CF = CHCF 2 CF} 2 C 2 F 5); 1,1,1,2,2,4, 5,5,6,6,7,7,7- tridecafluoro-3-heptene _{(CF 3 CF 2 CH = CFCF} 2 C 2 F 5); 1,1,1,2,2,3,5, 5, 6, 6, 7, 7, - tridecafluoro-3-heptene _{(CF 3 CF 2 CF = CHCF} 2 C 2 F 5); fluoro selected from the group consisting of _{CF 2 = CFOCF 2 CF 3 (} PEVE) and CF ₂ = CFOCF ₃ (PMVE) Olefins;
It relates to a refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of:

The present invention is a composition comprising: (i) at least one fluoroolefin compound; and (ii) at least one flammable refrigerant;
(A) Formula A fluoroolefins E-R ¹ CH = CHR ² or ^{Z-R 1 CH = CHR 2} , wherein, R ¹ and R ² are independently perfluoro C ₁ -C ₆ A fluoroolefin which is an alkyl group;
(B) a cyclic fluoroolefin of the formula cyclo- [CX = CY (CZW) _n- ], wherein X, Y, Z and W are independently H or F, and n is A cyclic fluoroolefin that is an integer from 2 to 5; and (c) 1,2,3,3,3-pentafluoro-1-propene (CF ₃ CF═CHF); 1,1,3,3,3-penta fluoro-1-propene _{(CF 3 CH = CF 2)} ; 1,1,2,3,3- pentafluoro-1-propene _{(CHF 2 CF = CF 2)} ; 1,1,1,2,3,4 , 4,4-octafluoro-2-butene (CF ₃ CF═CFCF ₃ ); 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF ₃ CF ₂ CF═CF ₂ ); 1,1,1,2,4,4,4-heptafluoro-2-butene (CF ₃ CF═CHC F _3); 1,2,3,3,4,4,4- heptafluoro-1-butene _{(CHF = CFCF 2 CF 3)} ; 1,1,1,2,3,4,4- heptafluoro - 2-butene (CHF ₂ CF═CFCF ₃ ); 1,3,3,3-tetrafluoro-2- (trifluoromethyl) -1-propene ((CF ₃ ) ₂ C═CHF); 1,1,3 , 3,4,4,4-heptafluoro-1-butene _{(CF 2 = CHCF 2 CF 3} ); 1,1,2,3,4,4,4- heptafluoro-1-butene (CF ₂ = CFCHFCF _3); 1,1,2,3,3,4,4- heptafluoro-1-butene _{(CF 2 = CFCF 2 CHF 2} ); 2,3,3,4,4,4- hexafluoro-1- butene _{(CF 3 CF 2 CF = CH} 2); 1,3,3,4,4,4- hexafluoro-1-butene (CH = CHCF ₂ CF _3); 1,2,3,4,4,4- hexafluoro-1-butene (CHF = CFCHFCF _3); 1,2,3,3,4,4- hexafluoro-1-butene _{(CHF = CFCF 2 CHF 2)} ; 1,1,2,3,4,4- hexafluoro-2-butene _{(CHF 2 CF = CFCHF 2)} ; 1,1,1,2,3,4- hexafluoro -2-butene (CH ₂ FCF═CFCF ₃ ); 1,1,1,2,4,4-hexafluoro-2-butene (CHF ₂ CH═CFCF ₃ ); 1,1,1,3,4, 4-hexafluoro-2-butene _{(CF 3 CH = CFCHF 2)} ; 1,1,2,3,3,4- hexafluoro-1-butene _{(CF 2 = CFCF 2 CH 2} F); 1,1, 2,3,4,4-hexafluoro-1-butene (CF ₂ = CFCHFCHF ₂ ); 3,3,3-trifluoro-2- (trifluoromethyl) -1-propene (CH ₂ ═C (CF ₃ ) ₂ ); 1,1,1,2,3,4,4,5, 5,5-decafluoro-2-pentene (CF ₃ CF═CFCF ₂ CF ₃ ); 1,1,2,3,3,4,4,5,5,5-decafluoro-1-pentene (CF ₂₎ = CFCF ₂ CF ₂ CF ₃ ); 1,1,1,4,4,4-hexafluoro-2- (trifluoromethyl) -2-butene ((CF ₃ ) ₂ C═CHCF ₃ ); 1,1 , 1,2,4,4,5,5,5-nonafluoro-2-pentene (CF ₃ CF═CHCF ₂ CF ₃ ); 1,1,1,3,4,4,5,5,5-nonafluoro 2-pentene _{(CF 3 CH = CFCF 2 CF} 3); 1,2,3,3,4,4,5,5,5- nonafluoro-1-pentene ( _{CHF = CFCF 2 CF 2 CF 3} ); 1,1,3,3,4,4,5,5,5- nonafluoro-1-pentene _{(CF 2 = CHCF 2 CF 2} CF 3); 1,1,2 , 3,3,4,4,5,5- nonafluoro-1-pentene _{(CF 2 = CFCF 2 CF 2} CHF 2); 1,1,2,3,4,4,5,5,5- nonafluoro - 2-pentene (CHF ₂ CF═CFCF ₂ CF ₃ ); 1,1,1,2,3,4,4,5,5-nonafluoro-2-pentene (CF ₃ CF═CFCF ₂ CHF ₂ ); 1,1,2,3,4,5,5,5-nonafluoro-2-pentene (CF ₃ CF═CFCHFCF ₃ ); 1,2,3,4,4,4-hexafluoro-3- (trifluoro methyl) -1-butene _{(CHF = CFCF (CF 3)} 2); 1,1,2,4,4,4- hexa Ruoro-3- (trifluoromethyl) -1-butene _{(CF 2 = CFCH (CF 3} ) 2); 1,1,1,4,4,4- hexafluoro-2- (trifluoromethyl) -2 Butene (CF ₃ CH═C (CF ₃ ) ₂ ); 1,1,3,4,4,4-hexafluoro-3- (trifluoromethyl) -1-butene (CF ₂ ═CHCF (CF ₃ ) ₂ ); 2,3,3,4,4,5,5,5- octafluoro-1-pentene _{(CH 2 = CFCF 2 CF 2} CF 3); 1,2,3,3,4,4,5, 5-octafluoro-1-pentene _{(CHF = CFCF 2 CF 2 CHF} 2); 3,3,4,4,4- pentafluoro-2- (trifluoromethyl) -1-butene (CH ₂ = C (CF _{3) CF 2 CF 3);} 1,1,4,4,4- pentafluoro-3- (trifluoromethanesulfonyl Le) -1- butene _{(CF 2 = CHCH (CF 3} ) 2); 1,3,4,4,4- pentafluoro-3- (trifluoromethyl) -1-butene (CHF = CHCF (CF _{3) 2} ); 1,1,4,4,4-pentafluoro-2- (trifluoromethyl) -1-butene (CF ₂ ═C (CF ₃ ) CH ₂ CF ₃ ); Tetrafluoro-3- (trifluoromethyl) -1-butene ((CF ₃ ) ₂ CFCH═CH ₂ ); 3,3,4,4,5,5,5-heptafluoro-1-pentene (CF ₃ CF _{2 CF 2 CH = CH 2)} ; 2,3,3,4,4,5,5- heptafluoro-1-pentene _{(CH 2 = CFCF 2 CF 2} CHF 2); 1,1,3,3,5 5,5 heptafluoro-1-butene _{(CF 2 = CHCF 2 CH 2} CF 3); 1,1,1,2, 4,4,4-heptafluoro-3-methyl-2-butene (CF ₃ CF═C (CF ₃ ) (CH ₃ )); 2,4,4,4-tetrafluoro-3- (trifluoromethyl) 1-butene _{(CH 2 = CFCH (CF 3} ) 2); 1,4,4,4- tetrafluoro-3- (trifluoromethyl) -1-butene _{(CHF = CHCH (CF 3)} 2); 1 , 1,1,4-tetrafluoro-2- (trifluoromethyl) -2-butene (CH ₂ FCH═C (CF ₃ ) ₂ ); 1,1,1,3-tetrafluoro-2- (trifluoro Methyl) -2-butene (CH ₃ CF═C (CF ₃ ) ₂ ); 1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1-hexene ( _{CF 3 (CF 2) 3 CF} = CF 2); 1,1,1,2,2,3,4,5,5,6,6,6- de Kafuruoro 3- hexene _{(CF 3 CF 2 CF = CFCF} 2 CF 3); 1,1,1,4,4,4- hexafluoro-2,3-bis (trifluoromethyl) -2-butene ((CF ₃ ) ₂ C = C (CF ₃ ) ₂ ); 1,1,1,2,3,4,5,5,5-nonafluoro-4- (trifluoromethyl) -2-pentene ((CF ₃ ) ₂ CFCF = CFCF ₃ ); 1,1,1,4,4,5,5,5-octafluoro-2- (trifluoromethyl) -2-pentene ((CF ₃ ) ₂ C═CHC ₂ F ₅ ); 1,1,1,3,4,5,5,5-octafluoro-4- (trifluoromethyl) -2-pentene ((CF ₃ ) ₂ CFCF═CHCF ₃ ); 3,3,4,4 5,5,6,6,6- nonafluoro-1-hexene _{(CF 3 CF 2 CF 2 CF} 2 CH = CH 2) 4,4,4-trifluoro-3,3-bis (trifluoromethyl) -1-butene _{(CH 2 = CHC (CF 3} ) 3); 1,1,1,4,4,4- hexafluoro - 2- (trifluoromethyl) -3-methyl-2-butene ((CF ₃ ) ₂ C═C (CH ₃ ) (CF ₃ )); 2,3,3,5,5,5-hexafluoro-4 - (trifluoromethyl) -1-pentene _{(CH 2 = CFCF 2 CH (} CF 3) 2); 1,1,1,2,4,4,5,5,5- nonafluoro-3-methyl-2- Pentene (CF ₃ CF═C (CH ₃ ) CF ₂ CF ₃ ); 1,1,1,5,5,5-hexafluoro-4- (trifluoromethyl) -2-pentene (CF ₃ CH═CHCH ( CF ₃ ) ₂ ); 1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro 2- heptene _{(CF 3 CF = CFCF 2 CF} 2 C 2 F 5); 1,1,1,2,2,3,4,5,5,6,6,7,7,7- tetradecanoyl fluoro 3- heptene _{(CF 3 CF 2 CF = CFCF} 2 C 2 F 5); 1,1,1,3,4,4,5,5,6,6,7,7,7- tridecafluoro-fluoro-2 - heptene _{(CF 3 CH = CFCF 2 CF} 2 C 2 F 5); 1,1,1,2,4,4,5,5,6,6,7,7,7- tridecafluoro-2-heptene (CF ₃ CF = CHCF ₂ CF ₂ C ₂ F ₅ ); 1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF ₃ CF ₂ CH═CFCF ₂ C ₂ F ₅ ); and 1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF ₃ CF ₂ CF = Fluoroolefin selected from the group consisting of HCF ₂ C ₂ F _5);
Further relates to a composition selected from the group consisting of:

The invention further relates to a method of using a refrigerant or heat transfer fluid composition in a refrigeration, air conditioning, or heat pump apparatus, the method comprising: (a) a centrifugal compressor; (b) a multi-stage centrifugal compressor, or (c) ) Supplying said device with a single slab / single pass heat exchanger; wherein said refrigeration composition or heat transfer composition is used in said device to provide heating or cooling; and The frozen or heat transfer composition is:
(I) a fluoroolefin of formula E—R ¹ CH═CHR ² or Z—R ¹ CH═CHR ² , wherein R ¹ and R ² are independently C ₁ -C ₆ perfluoro A fluoroolefin which is an alkyl group;
(Ii) a cyclic fluoroolefin of formula cyclo- [CX = CY (CZW) _n- ], wherein X, Y, Z, and W are independently H or F, and n is A cyclic fluoroolefin which is an integer from 2 to 5; or (iii) 1,2,3,3,3-pentafluoro-1-propene (CF ₃ CF═CHF); 1,1,3,3,3-penta fluoro-1-propene _{(CF 3 CH = CF 2)} ; 1,1,2,3,3- pentafluoro-1-propene _{(CHF 2 CF = CF 2)} ; 1,2,3,3- tetrafluoro - 1-propene (CHF ₂ CF═CHF); 2,3,3,3-tetrafluoro-1-propene (CF ₃ CF═CH ₂ ); 1,3,3,3-tetrafluoro-1-propene (CF ₃ CH = CHF); 1,1,2,3- tetrafluoro-1 Ropen _{(CH 2 FCF = CF 2)} ; 1,1,3,3- tetrafluoro-1-propene _{(CHF 2 CH = CF 2)} ; 2,3,3- trifluoro-1-propene (CHF ₂ CF = CH ₂ ); 3,3,3-trifluoro-1-propene (CF ₃ CH═CH ₂ ); 1,1,2-trifluoro-1-propene (CH ₃ CF═CF ₂ ); 1,1, 3-trifluoro-1-propene (CH ₂ FCH═CF ₂ ); 1,2,3-trifluoro-1-propene (CH ₂ FCF═CHF); 1,3,3-trifluoro-1-propene ( CHF ₂ CH = CHF); 1,1,1,2,3,4,4,4- octafluoro-2-butene _{(CF 3 CF = CFCF 3)} ; 1,1,2,3,3,4, 4,4 octafluoro-1-butene _{(CF 3 CF 2 CF = CF} 2); 1,1, , 2,4,4,4-heptafluoro-2-butene _{(CF 3 CF = CHCF 3)} ; 1,2,3,3,4,4,4- heptafluoro-1-butene (CHF = CFCF ₂ CF ₃ ); 1,1,1,2,3,4,4-heptafluoro-2-butene (CHF ₂ CF═CFCF ₃ ); 1,3,3,3-tetrafluoro-2- (trifluoromethyl) -1-propene ((CF ₃ ) ₂ C═CHF); 1,1,3,3,4,4,4-heptafluoro-1-butene (CF ₂ ═CHCF ₂ CF ₃ ); 1,1,2, , 3,4,4,4-heptafluoro-1-butene _{(CF 2 = CFCHFCF 3);} 1,1,2,3,3,4,4- heptafluoro-1-butene (CF ₂ = CFCF ₂ CHF ₂ ); 2,3,3,4,4,4-hexafluoro-1-butene (CF ₃ CF ₂ CF═C H ₂ ); 1,3,3,4,4,4-hexafluoro-1-butene (CHF═CHCF ₂ CF ₃ ); 1,2,3,4,4,4-hexafluoro-1-butene ( CHF = CFCHFCF ₃ ); 1,2,3,3,4,4-hexafluoro-1-butene (CHF═CFCF ₂ CHF ₂ ); 1,1,2,3,4,4-hexafluoro-2- butene _{(CHF 2 CF = CFCHF 2)} ; 1,1,1,2,3,4- hexafluoro-2-butene _{(CH 2 FCF = CFCF 3)} ; 1,1,1,2,4,4- hexa Fluoro-2-butene (CHF ₂ CH═CFCF ₃ ); 1,1,1,3,4,4-hexafluoro-2-butene (CF ₃ CH═CFCHF ₂ ); 1,1,2,3,3 , 4-hexafluoro-1-butene _{(CF 2 = CFCF 2 CH 2} F); 1,1,2, , 4,4-hexafluoro-1-butene _{(CF 2 = CFCHFCHF 2);} 3,3,3- trifluoro-2- (trifluoromethyl) -1-propene _{(CH 2 = C (CF 3} ) 2) 1,1,1,2,4-pentafluoro-2-butene (CH ₂ FCH═CFCF ₃ ); 1,1,1,3,4-pentafluoro-2-butene (CF ₃ CH═CFCH ₂ F) ); 3,3,4,4,4-pentafluoro-1-butene (CF ₃ CF ₂ CH═CH ₂ ); 1,1,1,4,4-pentafluoro-2-butene (CHF ₂ CH═) CHCF ₃ ); 1,1,1,2,3-pentafluoro-2-butene (CH ₃ CF═CFCF ₃ ); 2,3,3,4,4-pentafluoro-1-butene (CH ₂ ═CFCF) ₂ CHF _2); 1,1,2,4,4- pentafluoro-2-butene _{CHF 2 CF = CHCHF 2);} 1,1,2,3,3- pentafluoro-1-butene _{(CH 3 CF 2 CF = CF} 2); 1,1,2,3,4- pentafluoro-2- butene _{(CH 2 FCF = CFCHF 2)} ; 1,1,3,3,3- pentafluoro-2-methyl-1-propene _{(CF 2 = C (CF 3} ) (CH 3)); 2- ( difluoromethyl ) -3,3,3-trifluoro-1-propene _{(CH 2 = C (CHF 2} ) (CF 3)); 2,3,4,4,4- pentafluoro-1-butene (CH ₂ = CFCHFCF _3); 1,2,4,4,4- pentafluoro-1-butene _{(CHF = CFCH 2 CF 3)} ; 1,3,4,4,4- pentafluoro-1-butene (CHF = CHCHFCF ₃₎ 1,3,3,4,4-pentafluoro-1-butene (CHF = CHCF ₂ CHF ₂ ); 1,2,3,4,4-pentafluoro-1-butene (CHF═CFCHFCHF ₂ ); 3,3,4,4-tetrafluoro-1-butene (CH ₂ ═CHCF ₂ CHF) ₂ ); 1,1-difluoro-2- (difluoromethyl) -1-propene (CF ₂ ═C (CHF ₂ ) (CH ₃ )); 1,3,3,3-tetrafluoro-2-methyl-1 - propene _{(CHF = C (CF 3)} (CH 3)); 2- difluoromethyl-3,3-difluoro-1-propene _{(CH 2 = C (CHF 2} ) 2); 1,1,1,2- Tetrafluoro-2-butene (CF ₃ CF═CHCH ₃ ); 1,1,1,3-tetrafluoro-2-butene (CH ₃ CF═CHCF ₃ ); 1,1,1,2,3,4, 4,5,5,5-decafluoro-2-pentene (CF ₃ CF = FCF ₂ CF _3); 1,1,2,3,3,4,4,5,5,5- decafluoro-1-pentene _{(CF 2 = CFCF 2 CF 2} CF 3); 1,1,1, 4,4,4-hexafluoro-2- (trifluoromethyl) -2-butene ((CF ₃ ) ₂ C═CHCF ₃ ); 1,1,1,2,4,4,5,5,5- nonafluoro-2-pentene _{(CF 3 CF = CHCF 2 CF} 3); 1,1,1,3,4,4,5,5,5- nonafluoro-2-pentene _{(CF 3 CH = CFCF 2 CF} 3); 1,2,3,3,4,4,5,5,5- nonafluoro-1-pentene _{(CHF = CFCF 2 CF 2 CF} 3); 1,1,3,3,4,4,5,5, 5-nonafluoro-1-pentene _{(CF 2 = CHCF 2 CF 2} CF 3); 1,1,2,3,3,4,4,5,5- Nonafuruo 1-pentene _{(CF 2 = CFCF 2 CF 2} CHF 2); 1,1,2,3,4,4,5,5,5- nonafluoro-2-pentene _{(CHF 2 CF = CFCF 2 CF} 3); 1,1,1,2,3,4,4,5,5-nonafluoro-2-pentene (CF ₃ CF═CFCF ₂ CHF ₂ ); 1,1,1,2,3,4,5,5 5-nonafluoro-2-pentene _{(CF 3 CF = CFCHFCF 3)} ; 1,2,3,4,4,4- hexafluoro-3- (trifluoromethyl) -1-butene (CHF = CFCF (CF _{3) 2} ); 1,1,2,4,4,4-hexafluoro-3- (trifluoromethyl) -1-butene (CF ₂ ═CFCH (CF ₃ ) ₂ ); 1,1,1,4,4 , 4-Hexafluoro-2- (trifluoromethyl) -2-butene (CF ₃ CH═C (C F _{3) 2);} 1,1,3,4,4,4- hexafluoro-3- (trifluoromethyl) -1-butene _{(CF 2 = CHCF (CF 3} ) 2); 2,3,3, 4,4,5,5,5-octafluoro-1-pentene _{(CH 2 = CFCF 2 CF 2} CF 3); 1,2,3,3,4,4,5,5- octafluoro-1-pentene _{(CHF = CFCF 2 CF 2 CHF} 2); 3,3,4,4,4- pentafluoro-2- (trifluoromethyl) -1-butene _{(CH 2 = C (CF 3} )
CF ₂ CF _3); 1,1,4,4,4- pentafluoro-3- (trifluoromethyl) -1-butene _{(CF 2 = CHCH (CF 3} ) 2); 1,3,4,4, 4-pentafluoro-3- (trifluoromethyl) -1-butene (CHF = CHCF (CF ₃ ) ₂ ); 1,1,4,4,4-pentafluoro-2- (trifluoromethyl) -1- butene _{(CF 2 = C (CF 3} ) CH 2 CF 3); 3,4,4,4- tetrafluoro-3- (trifluoromethyl) -1-butene _{((CF 3) 2 CFCH =} CH 2); 3,3,4,4,5,5,5-heptafluoro-1-pentene (CF ₃ CF ₂ CF ₂ CH═CH ₂ ); 2,3,3,4,4,5,5-heptafluoro- 1-pentene _{(CH 2 = CFCF 2 CF 2} CHF 2); 1,1,3,3,5,5,5- Cheb Fluoro-1-butene _{(CF 2 = CHCF 2 CH 2} CF 3); 1,1,1,2,4,4,4- heptafluoro-3-methyl-2-butene _{(CF 3 CF = C (CF} 3 ) (CH _3)); 2,4,4,4-tetrafluoro-3- (trifluoromethyl) -1-butene _{(CH 2 = CFCH (CF 3} ) 2); 1,4,4,4- tetra Fluoro-3- (trifluoromethyl) -1-butene (CHF = CHCH (CF ₃ ) ₂ ); 1,1,1,4-tetrafluoro-2- (trifluoromethyl) -2-butene (CH ₂ FCH _{= C (CF 3) 2)} ; 1,1,1,3- tetrafluoro-2- (trifluoromethyl) -2-butene _{(CH 3 CF = C (CF} 3) 2); 1,1,1- trifluoro-2- (trifluoromethyl) -2-butene _{((CF 3) 2 C =} CHC _3); 3,4,4,5,5,5- hexafluoro-2-pentene _{(CF 3 CF 2 CF = CHCH} 3); 1,1,1,4,4,4- hexafluoro-2-methyl 2-butene (CF ₃ C (CH ₃ ) ═CHCF ₃ ); 3,3,4,5,5,5-hexafluoro-1-pentene (CH ₂ ═CHCF ₂ CHFCF ₃ ); 3- (trifluoro methyl) -4,4,4-trifluoro-1-butene _{(CH 2 = C (CF 3} ) CH 2 CF 3); 1,1,2,3,3,4,4,5,5,6, 6,6-dodecafluoro-1-hexene (CF ₃ (CF ₂ ) ₃ CF═CF ₂ ); 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro 3- hexene _{(CF 3 CF 2 CF = CFCF} 2 CF 3); 1,1,1,4,4,4- hexafluoro-2,3-bis (tri Fluoromethyl) -2-butene ((CF ₃ ) ₂ C═C (CF ₃ ) ₂ ); 1,1,1,2,3,4,5,5,5-nonafluoro-4- (trifluoromethyl) -2-pentene ((CF ₃ ) ₂ CFCF═CFCF ₃ ); 1,1,1,4,4,5,5,5-octafluoro-2- (trifluoromethyl) -2-pentene ((CF ₃ ) ₂ C = CHC ₂ F ₅ ); 1,1,1,3,4,5,5,5-octafluoro-4- (trifluoromethyl) -2-pentene ((CF ₃ ) ₂ CFCF═CHCF ₃ ); 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene (CF ₃ CF ₂ CF ₂ CF ₂ CH═CH ₂ ); 4,4,4-trifluoro-3 , 1,3-bis (trifluoromethyl) -1-butene _{(CH 2 = CHC (CF 3} ) 3); 1,1,1,4,4 4-hexafluoro-3-methyl-2- (trifluoromethyl) -2-butene _{((CF 3) 2 C =} C (CH 3) (CF 3)); 2,3,3,5,5,5 - hexafluoro-4- (trifluoromethyl) -1-pentene _{(CH 2 = CFCF 2 CH (} CF 3) 2); 1,1,1,2,4,4,5,5,5- nonafluoro -3 - methyl-2-pentene _{(CF 3 CF = C (CH} 3) CF 2 CF 3); 1,1,1,5,5,5- hexafluoro-4- (trifluoromethyl) -2-pentene (CF ₃ CH = CHCH (CF ₃ ) ₂ ); 3,4,4,5,5,6,6,6-octafluoro-2-hexene (CF ₃ CF ₂ CF ₂ CF═CHCH ₃ ); 4,4,5,5,6,6- octafluoro-1-hexene _{(CH 2 = CHCF 2 CF 2} CF 2 CH _2); 1,1,1,4,4-pentafluoro-2- (trifluoromethyl) -2-pentene _{((CF 3) 2 C =} CHCF 2 CH 3); 4,4,5,5,5 - pentafluoro-2- (trifluoromethyl) -1-pentene _{(CH 2 = C (CF 3} ) CH 2 C 2 F 5); 3,3,4,4,5,5,5- heptafluoro-fluoro-2 - methyl-1-pentene _{(CF 3 CF 2 CF 2 C} (CH 3) = CH 2); 4,4,5,5,6,6,6- heptafluoro-2-hexene (CF ₃ CF ₂ CF ₂ CH = CHCH _3); 4,4,5,5,6,6,6- heptafluoro-1-hexene _{(CH 2 = CHCH 2 CF 2} C 2 F 5); 1,1,1,2,2, 3,4 heptafluoro-3- hexene _{(CF 3 CF 2 CF = CFC} 2 H 5); 4,5,5,5- tetrafluoro-4- Trifluoromethyl-1-pentene _{(CH 2 = CHCH 2 CF (} CF 3) 2); 1,1,1,2,5,5,5- heptafluoro-4-methyl-2-pentene (CF ₃ CF = CHCH (CF ₃ ) (CH ₃ )); 1,1,1,3-tetrafluoro-2-trifluoromethyl-2-pentene ((CF ₃ ) ₂ C═CFC ₂ H ₅ ); 1,1,1 , 2,3,4,4,5,5,6,6,7,7,7- tetradecanoyl-fluoro-2-heptene _{(CF 3 CF = CFCF 2 CF} 2 C 2 F 5); 1,1,1 , 2,2,3,4,5,5,6,6,7,7,7- tetradecanoyl-fluoro-3- heptene _{(CF 3 CF 2 CF = CFCF} 2 C 2 F 5); 1,1,1 , 3,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene (CF ₃ CH═CFCF ₂ CF ₂ C ₂ F _5); 1,1,1,2,4,4,5,5,6,6,7,7,7- tridecafluoro-2-heptene _{(CF 3 CF = CHCF 2 CF} 2 C 2 F 5) 1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF ₃ CF ₂ CH═CFCF ₂ C ₂ F ₅ ); 1 , 1,1,2,2,3,5,5,6,6,7,7,7- tridecafluoro-3-heptene _{(CF 3 CF 2 CF = CHCF} 2 C 2 F 5); CF 2 = A fluoroolefin selected from the group consisting of CFOCF ₂ CF ₃ (PEVE); CF ₂ ═CFOCF ₃ (PMVE) and combinations thereof;
At least one fluoroolefin selected from the group consisting of:

  The present invention relates to a composition comprising at least one fluoroolefin. By fluoroolefin is meant that any compound containing carbon, fluorine and, optionally, hydrogen or oxygen also contains at least one double bond. These fluoroolefins can be linear, branched or cyclic.

  These compositions have a variety of uses in working fluids, such as foaming agents, expansion agents, fire extinguishing agents, heat transfer media (refrigeration systems, refrigerators, air conditioning systems, heat pumps, chillers, to name a few. As a heat transfer fluid and refrigerant for use in the like.

  A heat transfer fluid (also referred to herein as a heat transfer composition or a heat transfer fluid composition) is a working fluid used to carry heat from a heat source to a heat sink.

  A refrigerant is a compound or mixture of compounds that functions as a heat transfer fluid in a cycle, where the fluid undergoes a phase change from liquid to gas reversal.

The present invention provides fluoroolefins having the formula E—R ¹ CH═CHR ² or Z—R ¹ CH═CHR ² (Formula I), wherein R ¹ and R ² are independently C ₁ it is a perfluoroalkyl group -C _6. Examples of R ¹ and R ² groups are not particularly limited, but CF ₃ , C ₂ F _5, CF ₂ CF ₂ CF ₃ , CF (CF ₃ ) ₂ , CF ₂ CF ₂ CF ₂ CF ₃ , CF (CF _{3) CF 2 CF 3, CF} 2 CF (CF 3) 2, C (CF 3) 3, CF 2 CF 2 CF 2 CF 2 CF 3, CF 2 CF 2 CF (CF 3) 2, C (CF 3) ₂ C ₂ F ₅ , CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₃ , CF (CF ₃ ) CF ₂ CF ₂ C ₂ F ₅ , and C (CF ₃ ) ₂ CF ₂ C ₂ F ₅ . In one embodiment, the fluoroolefin of formula I has at least about 3 carbon atoms in the molecule. In other embodiments, the fluoroolefin of Formula I has at least about 4 carbon atoms in the molecule. In yet other embodiments, the fluoroolefin of Formula I has at least about 5 carbon atoms in the molecule. Exemplary, non-limiting compounds of formula I are represented in Table 1.

A compound of formula I is prepared by contacting a perfluoroalkyl iodide of formula R ¹ I with a perfluoroalkyl trihydroolefin of formula R ² CH═CH ₂ to produce a trihydroiodinated perfluoroalkane of formula R ¹ CH ₂ CHIR ^2. It can be prepared by the forming process. This trihydroiodinated perfluoroalkane can then be dehydroiodinated to form R ¹ CH═CHR ² . Alternatively, the olefin R ¹ CH═CHR ² is then formed by reacting a perfluoroalkyl iodide of formula R ² I with a perfluoroalkyltrihydroolefin of formula R ¹ CH═CH _2. ¹ CHICH ₂ R ² can be prepared by dehydroiodination of trihydroiodinated perfluoroalkane.

  The step of contacting the perfluoroalkyl iodide with the perfluoroalkyltrihydroolefin combines the reactants in a suitable reaction vessel capable of operating the reactants at the reaction temperature and the product under autogenous pressure. Can be performed in batch mode. Suitable reaction vessels include those made of stainless steel, particularly of the austenitic type, and Monel® nickel-copper alloy, Hastelloy® nickel-based alloy and Inconel ( Well-known high nickel alloys such as a nickel-chromium alloy may be mentioned.

  Alternatively, the reaction can be carried out in a semi-batch mode, where the perfluoroalkyltrihydroolefin reactant is converted to a perfluoroalkyl iodide reactant at the reaction temperature by means of a suitable addition device such as a pump. Added.

  The ratio of perfluoroalkyl iodide to perfluoroalkyltrihydroolefin should be between about 1: 1 and about 4: 1, preferably about 1.5: 1 to 2.5: 1. . A ratio of less than 1.5: 1 tends to result in a large amount of 2: 1 adduct as reported by (Non-Patent Document 1).

  Preferred temperatures for the step of contacting the perfluoroalkyl iodide with the perfluoroalkyltrihydroolefin are preferably about 150 ° C to 300 ° C, preferably about 170 ° C to about 250 ° C, and most preferably about 180 ° C. It is in the range of from 0C to about 230C.

  Suitable contact times for the reaction of perfluoroalkyl iodide with perfluoroalkyltrihydroolefin are from about 0.5 hour to 18 hours, preferably from about 4 to about 12 hours.

  Trihydroiodinated perfluoroalkanes prepared by reaction of perfluoroalkyl iodides with perfluoroalkyltrihydroolefins can be used directly in the dehydroiodination step, or preferably by distillation prior to the dehydroiodination step. It can be recovered and purified.

  The dehydroiodination step is performed by contacting the trihydroiodinated perfluoroalkane with a basic substance. Suitable basic substances include alkali metal hydroxides (eg sodium hydroxide or potassium hydroxide), alkali metal oxides (eg sodium oxide), alkaline earth metal hydroxides (eg calcium hydroxide), alkalis A mixture of basic substances such as earth metal oxides (eg calcium oxide), alkali metal alkoxides (eg sodium methoxide or sodium ethoxide), aqueous ammonia, sodium amide or soda lime. Preferred basic substances are sodium hydroxide and potassium hydroxide.

  Said step of contacting the trihydroiodinated perfluoroalkane with the basic substance can be carried out in the liquid phase, preferably in the presence of a solvent capable of at least partially dissolving both reactants. Suitable solvents for the dehydroiodination step include alcohols (eg, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and tertiary butanol), nitriles (eg, acetonitrile, propionitrile, butyronitrile). , Benzonitrile, or adiponitrile), dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, or sulfolane. The choice of solvent may depend on the ease of separation from the boiling product and the trace amount of solvent product during purification. Typically, ethanol or isopropanol is a good solvent for the reaction.

  Typically, the dehydroiodination reaction can be carried out by addition in a suitable reaction vessel to one of the reactants (either basic material or trihydroiodinated perfluoroalkane). The reaction is preferably composed of glass, ceramic, or metal, and is stirred by an impeller or a stirring mechanism.

  Suitable temperatures for the dehydroiodination reaction are from about 10 ° C to about 100 ° C, preferably from about 20 ° C to about 70 ° C. The dehydroiodination reaction can be carried out at ambient pressure or under reduced or elevated pressure. Of note are dehydroiodination reactions in which the compound of Formula I is formed and distilled from the reaction vessel.

  Alternatively, the dehydroiodination reaction may be performed by converting an aqueous solution of the basic substance into one or more of trihydroiodinated perfluoroalkanes, alkanes (eg, hexane, heptane, or octane), aromatic hydrocarbons (eg, Toluene), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride, or perchloroethylene), or ethers (eg, diethyl ether, methyl t-butyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, dimethoxyethane, Diglyme or tetraglyme) and a solution in a low-polar organic solvent in the presence of a phase transfer catalyst. Suitable phase transfer catalysts include quaternary ammonium halides such as tetrabutylammonium bromide, tetrabutylammonium hydrosulfate, triethylbenzylammonium chloride, dodecyltrimethylammonium chloride, and tricaprylylmethylammonium chloride. Quaternary phosphonium salt halides (eg triphenylmethylphosphonium bromide and tetraphenylphosphonium chloride) or cyclic polyethers known in the art as crown ethers (eg 18-crown-6 and 15-crown-5) Compounds.

  Alternatively, the dehydroiodination reaction can be performed in the absence of a solvent by adding trihydroiodinated perfluoroalkane to a solid or liquid basic material.

  Suitable reaction times for the dehydroiodination reaction are from about 15 minutes to about 6 hours or more, depending on the solubility of the reactants. Typically, the dehydroiodination reaction is rapid and requires about 30 minutes to about 3 hours to complete.

  The compound of formula I can be recovered from the dehydroiodination reaction mixture, by phase separation after addition of water, by distillation, or a combination thereof.

In another embodiment of the present invention, the fluoroolefin is a cyclic fluoroolefin (cyclo- [CX = CY (CZW) _n- ] (formula II), wherein X, Y, Z, and W are independent of H and F. And n is an integer from 2 to 5). Representative cyclic fluoroolefins of formula II are listed in Table 2.

  In other embodiments, the fluoroolefin may comprise these compounds listed in Table 3.

  The compounds listed in Tables 2 and 3 are commercially available, or are known in the art, or can be prepared by the methods described herein.

1,1,1,4,4-Pentafluoro-2-butene is derived from 1,1,1,2,4,4-hexafluorobutane (CHF ₂ CH ₂ CHFCF ₃ ) from dehydrofluorine on solid KOH. Can be prepared in the gas phase at room temperature. The synthesis of 1,1,1,2,4,4-hexafluorobutane is described in U.S. Patent Publication (Patent Document 1), which is incorporated herein by reference.

1,1,1,4,4,4-hexafluoro-2-butene is transferred from 1,1,1,4,4,4-hexafluoro-2-iodobutane (CF ₃ CHICH ₂ CF ₃ ) The catalyst can be prepared at about 60 ° C. by reaction with KOH. The synthesis of 1,1,1,4,4,4-hexafluoro-2-iodobutane consists of methyl perfluoroiodide (CF ₃ I) and 3,3,3-trifluoropropene (CF ₃ CH═CH ₂ ). Can be carried out by reaction for about 8 hours at about 200 ° C. under autogenous pressure.

3,4,4,5,5,5-hexafluoro-2-pentene is a 1,1,1,2,2,3,3-heptafluoropentane (CF ₃ CF ₂ CF ₂ CH ₂ CH ₃ ) Can be prepared by dehydrofluorination with solid KOH or over a carbon catalyst at 200-300 ° C. 1,1,1,2,2,3,3-heptafluoropentane is 3,3,4,4,5,5,5-heptafluoro-1-pentene (CF ₃ CF ₂ CF ₂ CH═CH ₂ ).

1,1,1,2,3,4-Hexafluoro-2-butene is a 1,1,1,2,3,3,4-heptafluorobutane (CH ₂ FCF ₂ CHFCF ₃ ) using solid KOH. It can be prepared by dehydrofluorination.

1,1,1,2,4,4-Hexafluoro-2-butene is 1,1,1,2,2,4,4-heptafluorobutane (CHF ₂ CH ₂ CF ₂ CF ₃₎ using solid KOH. ).

1,1,1,3,4,4-Hexafluoro-2-butene is 1,1,1,3,3,4,4-heptafluorobutane (CF ₃ CH ₂ CF ₂ CHF ₂ ) using solid KOH Can be prepared by dehydrofluorination of

1,1,1,2,4-pentafluoro-2-butene is a dehydrofluorine of 1,1,1,2,2,3-hexafluorobutane (CH ₂ FCH ₂ CF ₂ CF ₃ ) using solid KOH It can be prepared by crystallization.

1,1,1,3,4-pentafluoro-2-butene is a dehydro of 1,1,1,3,3,4-hexafluorobutane (CF ₃ CH ₂ CF ₂ CH ₂ F) using solid KOH. It can be prepared by fluorination.

1,1,1,3-tetrafluoro-2-butene is obtained by reacting 1,1,1,3,3-pentafluorobutane (CF ₃ CH ₂ CF ₂ CH ₃ ) with aqueous KOH at 120 ° C. Can be prepared.

1,1,1,4,4,5,5,5-octafluoro-2-pentene is obtained from (CF ₃ CHICH ₂ CF ₂ CF ₃ ) at about 60 ° C. with a phase transfer catalyst with KOH. It can be prepared by reaction. The synthesis of 4-iodo-1,1,1,2,2,5,5,5-octafluoropentane is the synthesis of perfluoromethyl iodide (CF ₃ CF ₂ I) and 3,3,3-trifluoropropene. At about 200 ° C. under autogenous pressure for about 8 hours.

1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene is 1,1,1,2,2,5,5,6,6,6-decafluoro It can be prepared from -3-iodohexane (CF ₃ CF ₂ CHICH ₂ CF ₂ CF ₃ ) by reaction with KOH at about 60 ° C. using a phase transfer catalyst. The synthesis of 1,1,1,2,2,5,5,6,6,6-decafluoro-3-iodohexane includes perfluoromethyl iodide (CF ₃ CF ₂ I) and 3,3,4, It can be carried out by reaction of 4,4-pentafluoro-1-butene (CF ₃ CF ₂ CH═CH ₂ ) at about 200 ° C. under autogenous pressure for about 8 hours.

1,1,1,4,5,5,5-heptafluoro-4- (trifluoromethyl) -2-pentene is 1,1,1,2,5,5,5-heptafluoro-4-iodo 2- (trifluoromethyl) - pentane _{(CF 3 cHICH 2 CF (CF} 3) 2), may be prepared by dehydrofluorination of isopropanol and KOH. CF ₃ CHICH ₂ CF (CF ₃ ) ₂ is formed from the reaction of (CF ₃ ) ₂ CFI with CF ₃ CH═CH ₂ at a high temperature such as about 200 ° C.

1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene is 1,1,1,4,4,4-hexafluoro-2-butene (CF ₃ CH = CHCF ₃ ) can be prepared by reaction of tetrafluoroethylene (CF ₂ = CF ₂ ) and antimony pentafluoride (SbF ₅ ).

  2,3,3,4,4-pentafluoro-1-butene can be prepared by dehydrofluorination of 1,1,2,2,3,3-hexafluorobutane over fluorinated alumina at high temperature .

  2,3,3,4,4,5,5,5-octafluoro-1-pentene is a solid KOH of 2,2,3,3,4,4,5,5,5-nonafluoropentane. It can be prepared by dehydrofluorination.

  1,2,3,3,4,4,5,5-octafluoro-1-pentene is on fluorinated alumina of 2,2,3,3,4,4,5,5,5-nonafluoropentane And can be prepared by dehydrofluorination at elevated temperature.

  The compositions of the present invention can comprise a single compound of Formula I, Formula II, or Table 3, or can comprise a combination of said compounds. Furthermore, many of the compounds of Formula I, Formula II, and Table 3 can exist as different configurational isomers or stereoisomers. The present invention is meant to encompass all single configurational isomers, single stereoisomers or any combination thereof. For example, 1,3,3,3-tetrafluoropropene (HFC-1234ze) represents the E-isomer, Z-isomer, or any combination or mixture of both isomers in any ratio Means that. Another example is F12E, which represents the E-isomer, the Z-isomer, or a mixture of both isomers in any combination or in any ratio.

  The composition of the present invention has a zero or low ozone depletion potential and a low global warming potential (GWP). The fluoroolefins of the present invention or mixtures of fluoroolefins of the present invention and other refrigerants will have a global warming potential less than many currently used hydrofluorocarbon refrigerants. One aspect of the present invention is to provide a refrigerant having a global warming potential of less than 1000, less than 500, less than 150, less than 100, or less than 50. Another aspect of the invention is to reduce the total GWP of the refrigerant mixture by adding a fluoroolefin to the mixture.

  Compositions of the invention that are combinations or mixtures can be prepared by any convenient method of combining the desired amounts of the individual components. A preferred method is to weigh the desired component amount and then combine the components in a suitable container. If desired, stirring may be performed.

  An alternative means of forming the composition of the present invention is: (i) recovering a volume of one or more constituents of the refrigerant composition from at least one refrigerant container; (ii) said one or Sufficiently removing impurities so that a plurality of recovered components can be reused, (iii) and, optionally, all or part of the recovered volume of the components is at least one of Combining with an additional refrigerant composition or component.

  The refrigerant container can be any container that stores a refrigerant blend composition that has been used in a refrigeration apparatus, air conditioner or heat pump apparatus. The refrigerant container may be a refrigeration apparatus, an air conditioner, or a heat pump apparatus in which a refrigerant blend is used. Further, the refrigerant container can be a storage container for collecting recovered refrigerant blend components including, but not limited to, a compressed gas cylinder.

  By residual refrigerant is meant any amount of refrigerant blend or refrigerant blend component that can be removed from the refrigerant container by any method known to transfer refrigerant blends or refrigerant blend components.

  The impurity can be any component in the refrigerant blend or refrigerant blend component for its use in a refrigeration apparatus, air conditioner or heat pump apparatus. Examples of such impurities include, but are not limited to, refrigeration lubricants, refrigeration equipment, particles such as metals or elastomers that can flow out of air conditioning equipment or heat pump equipment, and refrigerant blend compositions described above. Any other contaminants that can adversely affect performance are listed.

  Such impurities can be sufficiently removed to allow reuse of the refrigerant blend or refrigerant blend component without adversely affecting performance or the equipment in which the refrigerant blend or refrigerant blend component will be used.

  In order to produce a composition that meets the required specifications for a given product, it may be necessary to provide additional refrigerant blends or refrigerant blend components to the remaining refrigerant blend or refrigerant blend components. For example, if the refrigerant blend has three components within a specified weight percent range, one or more of the components may be given to regenerate the composition within specification limits. It may be necessary to add in amounts.

The compositions of the invention that are useful as refrigerants or heat transfer fluids are:
(I) a fluoroolefin of formula E—R ¹ CH═CHR ² or Z—R ¹ CH═CHR ² , wherein R ¹ and R ² are independently C ₁ -C ₆ perfluoro A fluoroolefin which is an alkyl group and wherein the total number of carbons in the compound is at least 5;
(Ii) a cyclic fluoroolefin of formula cyclo- [CX = CY (CZW) _n- ], wherein X, Y, Z, and W are independently H or F, and n is A cyclic fluoroolefin which is an integer from 2 to 5; and (iii) 1,2,3,3,3-pentafluoro-1-propene (CF ₃ CF═CHF); 1,1,3,3,3-penta fluoro-1-propene _{(CF 3 CH = CF 2)} ; 1,1,2,3,3- pentafluoro-1-propene _{(CHF 2 CF = CF 2)} ; 1,2,3,3- tetrafluoro - 1-propene (CHF ₂ CF═CHF); 2,3,3,3-tetrafluoro-1-propene (CF ₃ CF═CH ₂ ); 1,1,2,3-tetrafluoro-1-propene (CH ₂ FCF = CF ₂ ); 1,1,3,3-tetrafluoro-1 - propene _{(CHF 2 CH = CF 2)} ; 2,3,3- trifluoro-1-propene _{(CHF 2 CF = CH 2)} ; 3,3,3- trifluoro-1-propene (CF ₃ CH = CH ₂ ); 1,1,2-trifluoro-1-propene (CH ₃ CF═CF ₂ ); 1,2,3-trifluoro-1-propene (CH ₂ FCF═CF ₂ ); 1,1,3 - trifluoro-1- propene _{(CH 2 FCH = CF 2)} ; 1,3,3- trifluoro-l-propene _{(CHF 2 CH = CHF);} 1,1,1,2,3,4,4, 4-octafluoro-2-butene _{(CF 3 CF = CFCF 3)} ; 1,1,2,3,3,4,4,4- octafluoro-1-butene _{(CF 3 CF 2 CF = CF} 2); 1,1,1,2,4,4,4-heptafluoro-2-butene (CF ₃ CF═CHCF ₃ ); 1,2,3,3,4,4,4-heptafluoro-1-butene (CHF = CFCF ₂ CF ₃ ); 1,1,1,2,3,4,4-heptafluoro-2 - butene _{(CHF 2 CF = CFCF 3)} ; 1,3,3,3- tetrafluoro-2- (trifluoromethyl) -1-propene _{((CF 3) 2 C =} CHF); 1,1,3, 3,4,4,4-heptafluoro-1-butene (CF ₂ ═CHCF ₂ CF ₃ ); 1,1,2,3,4,4,4-heptafluoro-1-butene (CF ₂ ═CFCHFCF ₃₎ ); 1,1,2,3,3,4,4-heptafluoro-1-butene (CF ₂ = CFCF ₂ CHF ₂ ); 2,3,3,4,4,4-hexafluoro-1-butene _{(CF 3 CF 2 CF = CH} 2); 1,3,3,4,4,4- hexafluoro-1-butene (CHF CHCF ₂ CF _3); 1,2,3,4,4,4- hexafluoro-1-butene (CHF = CFCHFCF _3); 1,2,3,3,4,4- hexafluoro-1-butene ( _{CHF = CFCF 2 CHF 2);} 1,1,2,3,4,4- hexafluoro-2-butene _{(CHF 2 CF = CFCHF 2)} ; 1,1,1,2,3,4- hexafluoro - 2-butene (CH ₂ FCF═CFCF ₃ ); 1,1,1,2,4,4-hexafluoro-2-butene (CHF ₂ CH═CFCF ₃ ); 1,1,1,3,4,4 - hexafluoro-2-butene _{(CF 3 CH = CFCHF 2)} ; 1,1,2,3,3,4- hexafluoro-1-butene _{(CF 2 = CFCF 2 CH 2} F); 1,1,2 , 3,4,4-Hexafluoro-1-butene (CF ₂ = CFCHFCHF ₂ ) 3,3,3-trifluoro-2- (trifluoromethyl) -1-propene (CH ₂ ═C (CF ₃ ) ₂ ); 1,1,1,2,4-pentafluoro-2-butene ( CH ₂ FCH═CFCF ₃ ); 1,1,1,3,4-pentafluoro-2-butene (CF ₃ CH═CFCH ₂ F); 3,3,4,4,4-pentafluoro-1-butene (CF ₃ CF ₂ CH═CH ₂ ); 1,1,1,4,4-pentafluoro-2-butene (CHF ₂ CH═CHCF ₃ ); 1,1,1,2,3-pentafluoro-2 - butene _{(CH 3 CF = CFCF 3)} ; 2,3,3,4,4- pentafluoro-1-butene _{(CH 2 = CFCF 2 CHF 2} ); 1,1,2,4,4- pentafluoro - 2-butene _{(CHF 2 CF = CHCHF 2)} ; 1,1,2,3,3- pentafluoro - - butene _{(CH 3 CF 2 CF = CF} 2); 1,1,2,3,4- pentafluoro-2-butene _{(CH 2 FCF = CFCHF 2)} ; 1,1,3,3,3- pentafluoro -2-methyl-1-propene _{(CF 2 = C (CF 3} ) (CH 3)); 2- ( difluoromethyl) -3,3,3-trifluoro-1-propene (CH ₂ = C (CHF ₂ ) (CF ₃ )); 2,3,4,4,4-pentafluoro-1-butene (CH ₂ ═CFCHFCF ₃ ); 1,2,4,4,4-pentafluoro-1-butene (CHF═ CFCH ₂ CF ₃ ); 1,3,4,4,4-pentafluoro-1-butene (CHF═CHCHFCF ₃ ); 1,3,3,4,4-pentafluoro-1-butene (CHF═CHCF ₂₎ CHF _2); 1,2,3,4,4- pentafluoro-1-butene (CHF = CFCHFCHF _2); 3,3,4,4- tetrafluoro-1-butene _{(CH 2 = CHCF 2 CHF 2} ); 1,1- difluoro-2- (difluoromethyl) -1-propene (CF _{2 = C (CHF 2) (CH} 3)); 1,3,3,3- tetrafluoro-2-methyl-1-propene _{(CHF = C (CF 3)} (CH 3)); 3,3- difluoro - 2- (difluoromethyl) -1-propene _{(CH 2 = C (CHF 2} ) 2); 1,1,1,2- tetrafluoro-2-butene _{(CF 3 CF = CHCH 3)} ; 1,1,1 , 3-tetrafluoro-2-butene (CH ₃ CF═CHCF ₃ ); 1,1,1,2,3,4,4,5,5,5-decafluoro-2-pentene (CF ₃ CF═CFCF ₂ CF ₃ ); 1,1,2,3,3,4,4,5,5,5-deca Fluoro-1-pentene _{(CF 2 = CFCF 2 CF 2} CF 3); 1,1,1,4,4,4- hexafluoro-2- (trifluoromethyl) -2-butene ((CF _{3) 2} C ═CHCF ₃ ); 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene (CF ₃ CF═CHCF ₂ CF ₃ ); 1,1,1,3,4,4 , 5,5,5-nonafluoro-2-pentene _{(CF 3 CH = CFCF 2 CF} 3); 1,2,3,3,4,4,5,5,5- nonafluoro-1-pentene (CHF = CFCF ₂ CF ₂ CF _3); 1,1,3,3,4,4,5,5,5- nonafluoro-1-pentene _{(CF 2 = CHCF 2 CF 2} CF 3); 1,1,2,3, 3,4,4,5,5- nonafluoro-1-pentene _{(CF 2 = CFCF 2 CF 2} CHF 2); 1,1,2 3,4,4,5,5,5- nonafluoro-2-pentene _{(CHF 2 CF = CFCF 2 CF} 3); 1,1,1,2,3,4,4,5,5- nonafluoro-2- pentene _{(CF 3 CF = CFCF 2 CHF} 2); 1,1,1,2,3,4,5,5,5- nonafluoro-2-pentene _{(CF 3 CF = CFCHFCF 3)} ; 1,2,3, 4,4,4-hexafluoro-3- (trifluoromethyl) -1-butene (CHF = CFCF (CF ₃ ) ₂ ); 1,1,2,4,4,4-hexafluoro-3- (tri Fluoromethyl) -1-butene (CF ₂ ═CFCH (CF ₃ ) ₂ ); 1,1,1,4,4,4-hexafluoro-2- (trifluoromethyl) -2-butene (CF ₃ CH═ _{C (CF 3) 2);} 1,1,3,4,4,4- hexafluoro-3- (tri Ruoromechiru) 1-butene _{(CF 2 = CHCF (CF 3} ) 2); 2,3,3,4,4,5,5,5- octafluoro-1-pentene _{(CH 2 = CFCF 2 CF 2} CF 3 ); 1,2,3,3,4,4,5,5-octafluoro-1-pentene (CHF = CFCF ₂ CF ₂ CHF ₂ ); 3,3,4,4,4-pentafluoro-2- (Trifluoromethyl) -1-butene (CH ₂ ═C (CF ₃ ) CF ₂ CF ₃ ); 1,1,4,4,4-pentafluoro-3- (trifluoromethyl) -1-butene (CF ₂ = CHCH (CF ₃ ) ₂ ); 1,3,4,4,4-pentafluoro-3- (trifluoromethyl) -1-butene (CHF═CHCF (CF ₃ ) ₂ ); 1,1,4 , 4,4-pentafluoro-2- (trifluoromethyl) -1-butene (CF ₂ = C (CF ₃ ) CH ₂ CF ₃ ); 3,4,4,4-tetrafluoro-3- (trifluoromethyl) -1-butene ((CF ₃ ) ₂ CFCH═CH ₂ ); 3,3,4 , 4,5,5,5-heptafluoro-1-pentene _{(CF 3 CF 2 CF 2 CH} = CH 2); 2,3,3,4,4,5,5- heptafluoro-1-pentene (CH _{2 = CFCF 2 CF 2 CHF 2} ); 1,1,3,3,5,5,5- heptafluoro-1-butene _{(CF 2 = CHCF 2 CH 2} CF 3); 1,1,1,2, 4,4,4-heptafluoro-3-methyl-2-butene (CF ₃ CF═C (CF ₃ ) (CH ₃ )); 2,4,4,4-tetrafluoro-3- (trifluoromethyl) 1-butene _{(CH 2 = CFCH (CF 3} ) 2); 1,4,4,4- tetrafluoro-3- (trifluoperazine Methyl) -1-butene _{(CHF = CHCH (CF 3)} 2); 1,1,1,4- tetrafluoro-2- (trifluoromethyl) -2-butene _{(CH 2 FCH = C (CF} 3) 2 ); 1,1,1,3-tetrafluoro-2- (trifluoromethyl) -2-butene (CH ₃ CF═C (CF ₃ ) ₂ ); 1,1,1-trifluoro-2- (tri Fluoromethyl) -2-butene ((CF ₃ ) ₂ C═CHCH ₃ ); 3,4,4,5,5,5-hexafluoro-2-pentene (CF ₃ CF ₂ CF═CHCH ₃ ); 1,1,4,4,4-hexafluoro-2-methyl-2-butene (CF ₃ C (CH ₃ ) ═CHCF ₃ ); 3,3,4,5,5,5-hexafluoro-1- pentene _{(CH 2 = CHCF 2 CHFCF 3} ); 4,4,4- trifluoro-3- (tri Ruoromechiru) 1-butene _{(CH 2 = C (CF 3} ) CH 2 CF 3); 1,1,2,3,3,4,4,5,5,6,6,6- dodecafluoro-1- Hexene (CF ₃ (CF ₂ ) ₃ CF═CF ₂ ); 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene (CF ₃ CF ₂ CF = CFCF ₂ CF ₃ ); 1,1,1,4,4,4-hexafluoro-2,3-bis (trifluoromethyl) -2-butene ((CF ₃ ) ₂ C═C (CF ₃ ) ₂ ); 1,1,1,2,3,4,5,5,5-nonafluoro-4- (trifluoromethyl) -2-pentene ((CF ₃ ) ₂ CFCF═CFCF ₃ ); 1,1, 1,4,4,5,5,5-octafluoro-2- (trifluoromethyl) -2-pentene ((CF ₃ ) ₂ C═CHC ₂ F ₅ ); 1 , 1,1,3,4,5,5,5-octafluoro-4- (trifluoromethyl) -2-pentene ((CF ₃ ) ₂ CFCF═CHCF ₃ ); 3,3,4,4,5 , 5,6,6,6- nonafluoro-1-hexene _{(CF 3 CF 2 CF 2 CF} 2 CH = CH 2); 4,4,4- trifluoro-3,3-bis (trifluoromethyl) -1 - butene _{(CH 2 = CHC (CF 3} ) 3); 1,1,1,4,4,4- hexafluoro-2- (trifluoromethyl) -3-methyl-2-butene ((CF _{3) 2 C = C (CH 3) (} CF 3)); 2,3,3,5,5,5- hexafluoro-4- (trifluoromethyl) -1-pentene _{(CH 2 = CFCF 2 CH (} CF 3) ₂ ); 1,1,1,2,4,4,5,5,5-nonafluoro-3-methyl-2-pentene (CF ₃ CF = C (CH ₃ ) CF ₂ CF ₃ ); 1,1,1,5,5,5-hexafluoro-4- (trifluoromethyl) -2-pentene (CF ₃ CH═CHCH (CF ₃ ) _2); 3,4,4,5,5,6,6,6- octafluoro-2-hexene _{(CF 3 CF 2 CF 2 CF} = CHCH 3); 3,3,4,4,5,5, 6,6-octafluoro-hexene _{(CH 2 = CHCF 2 CF 2} CF 2 CHF 2); 1,1,1,4,4- pentafluoro-2- (trifluoromethyl) -2-pentene ((CF _{3) 2 C = CHCF 2 CH} 3); 4,4,5,5,5- pentafluoro-2- (trifluoromethyl) -1-pentene _{(CH 2 = C (CF 3} ) CH 2 C 2 F 5 ); 3,3,4,4,5,5,5-heptafluoro-2-methyl-1-pentene (CF ₃ CF ₂ ); CF ₂ C (CH ₃ ) ═CH ₂ ); 4,4,5,5,6,6,6-heptafluoro-2-hexene (CF ₃ CF ₂ CF ₂ CH═CHCH ₃ ); , 5,6,6,6- heptafluoro-1-hexene _{(CH 2 = CHCH 2 CF 2} C 2 F 5); 1,1,1,2,2,3,4- heptafluoro-3- hexene ( _{CF 3 CF 2 CF = CFC 2} H 5); 4,5,5,5- tetrafluoro-4- (trifluoromethyl) -1-pentene _{(CH 2 = CHCH 2 CF (} CF 3) 2); 1, 1,1,2,5,5,5-heptafluoro-4-methyl-2-pentene (CF ₃ CF═CHCH (CF ₃ ) (CH ₃ )); 1,1,1,3-tetrafluoro-2 -(Trifluoromethyl) -2-pentene ((CF ₃ ) ₂ C═CFC ₂ H ₅ ); 1,1,1,2,3,4 , 4,5,5,6,6,7,7,7- tetradecanoyl-fluoro-2-heptene _{(CF 3 CF = CFCF 2 CF} 2 C 2 F 5); 1,1,1,2,2,3 , 4,5,5,6,6,7,7,7- tetradecanoyl-fluoro-3- heptene _{(CF 3 CF 2 CF = CFCF} 2 C 2 F 5); 1,1,1,3,4,4 , 5,5,6,6,7,7,7- tridecafluoro-2-heptene _{(CF 3 CH = CFCF 2 CF} 2 C 2 F 5); 1,1,1,2,4,4,5 , 5,6,6,7,7,7- tridecafluoro-2-heptene _{(CF 3 CF = CHCF 2 CF} 2 C 2 F 5); 1,1,1,2,2,4,5,5 , 6,6,7,7,7- tridecafluoro-3-heptene _{(CF 3 CF 2 CH = CFCF} 2 C 2 F 5); 1,1,1,2,2,3,5,5,6 , 6,7,7,7-tri Kafuruoro 3- heptene _{(CF 3 CF 2 CF = CHCF} 2 C 2 F 5); CF 2 = CFOCF 2 CF 3 (PEVE) and CF ₂ = CFOCF ₃ fluoroolefin selected from the group consisting of (PMVE);
At least one fluoroolefin selected from the group consisting of:

The invention further relates to a composition comprising at least one fluoroolefin and at least one combustible refrigerant or heat transfer fluid, wherein the fluoroolefin is:
(I) a fluoroolefin of formula E—R ¹ CH═CHR ² or Z—R ¹ CH═CHR ² , wherein R ¹ and R ² are independently C ₁ -C ₆ perfluoro A fluoroolefin which is an alkyl group and wherein the total number of carbons in the compound is at least 5;
(Ii) a cyclic fluoroolefin of formula cyclo- [CX = CY (CZW) _n- ], wherein X, Y, Z, and W are independently H or F, and n is A cyclic fluoroolefin which is an integer from 2 to 5; and (iii) 1,2,3,3,3-pentafluoro-1-propene (CF ₃ CF═CHF); 1,1,3,3,3-penta fluoro-1-propene _{(CF 3 CH = CF 2)} ; 1,1,2,3,3- pentafluoro-1-propene _{(CHF 2 CF = CF 2)} ; 1,2,3,3- tetrafluoro - 1-propene (CHF ₂ CF═CHF); 2,3,3,3-tetrafluoro-1-propene (CF ₃ CF═CH ₂ ); 1,1,2,3-tetrafluoro-1-propene (CH ₂ FCF = CF ₂ ); 1,1,3,3-tetrafluoro-1 - propene _{(CHF 2 CH = CF 2)} ; 2,3,3- trifluoro-1-propene _{(CHF 2 CF = CH 2)} ; 3,3,3- trifluoro-1-propene (CF ₃ CH = CH ₂ ); 1,1,2-trifluoro-1-propene (CH ₃ CF═CF ₂ ); 1,2,3-trifluoro-1-propene (CH ₂ FCF═CF ₂ ); 1,1,3 - trifluoro-1- propene _{(CH 2 FCH = CF 2)} ; 1,3,3- trifluoro-l-propene _{(CHF 2 CH = CHF);} 1,1,1,2,3,4,4, 4-octafluoro-2-butene _{(CF 3 CF = CFCF 3)} ; 1,1,2,3,3,4,4,4- octafluoro-1-butene _{(CF 3 CF 2 CF = CF} 2); 1,1,1,2,4,4,4-heptafluoro-2-butene (CF ₃ CF═CHCF ₃ ); 1,2,3,3,4,4,4-heptafluoro-1-butene (CHF = CFCF ₂ CF ₃ ); 1,1,1,2,3,4,4-heptafluoro-2 - butene _{(CHF 2 CF = CFCF 3)} ; 1,3,3,3- tetrafluoro-2- (trifluoromethyl) -1-propene _{((CF 3) 2 C =} CHF); 1,1,3, 3,4,4,4-heptafluoro-1-butene (CF ₂ ═CHCF ₂ CF ₃ ); 1,1,2,3,4,4,4-heptafluoro-1-butene (CF ₂ ═CFCHFCF ₃₎ ); 1,1,2,3,3,4,4-heptafluoro-1-butene (CF ₂ = CFCF ₂ CHF ₂ ); 2,3,3,4,4,4-hexafluoro-1-butene _{(CF 3 CF 2 CF = CH} 2); 1,3,3,4,4,4- hexafluoro-1-butene (CHF CHCF ₂ CF _3); 1,2,3,4,4,4- hexafluoro-1-butene (CHF = CFCHFCF _3); 1,2,3,3,4,4- hexafluoro-1-butene ( _{CHF = CFCF 2 CHF 2);} 1,1,2,3,4,4- hexafluoro-2-butene _{(CHF 2 CF = CFCHF 2)} ; 1,1,1,2,3,4- hexafluoro - 2-butene (CH ₂ FCF═CFCF ₃ ); 1,1,1,2,4,4-hexafluoro-2-butene (CHF ₂ CH═CFCF ₃ ); 1,1,1,3,4,4 - hexafluoro-2-butene _{(CF 3 CH = CFCHF 2)} ; 1,1,2,3,3,4- hexafluoro-1-butene _{(CF 2 = CFCF 2 CH 2} F); 1,1,2 , 3,4,4-Hexafluoro-1-butene (CF ₂ = CFCHFCHF ₂ ) 3,3,3-trifluoro-2- (trifluoromethyl) -1-propene (CH ₂ ═C (CF ₃ ) ₂ ); 1,1,1,2,4-pentafluoro-2-butene ( CH ₂ FCH═CFCF ₃ ); 1,1,1,3,4-pentafluoro-2-butene (CF ₃ CH═CFCH ₂ F); 3,3,4,4,4-pentafluoro-1-butene (CF ₃ CF ₂ CH═CH ₂ ); 1,1,1,4,4-pentafluoro-2-butene (CHF ₂ CH═CHCF ₃ ); 1,1,1,2,3-pentafluoro-2 - butene _{(CH 3 CF = CFCF 3)} ; 2,3,3,4,4- pentafluoro-1-butene _{(CH 2 = CFCF 2 CHF 2} ); 1,1,2,4,4- pentafluoro - 2-butene _{(CHF 2 CF = CHCHF 2)} ; 1,1,2,3,3- pentafluoro - - butene _{(CH 3 CF 2 CF = CF} 2); 1,1,2,3,4- pentafluoro-2-butene _{(CH 2 FCF = CFCHF 2)} ; 1,1,3,3,3- pentafluoro -2-methyl-1-propene _{(CF 2 = C (CF 3} ) (CH 3)); 2- ( difluoromethyl) -3,3,3-trifluoro-1-propene (CH ₂ = C (CHF ₂ ) (CF ₃ )); 2,3,4,4,4-pentafluoro-1-butene (CH ₂ ═CFCHFCF ₃ ); 1,2,4,4,4-pentafluoro-1-butene (CHF═ CFCH ₂ CF ₃ ); 1,3,4,4,4-pentafluoro-1-butene (CHF═CHCHFCF ₃ ); 1,3,3,4,4-pentafluoro-1-butene (CHF═CHCF ₂₎ CHF _2); 1,2,3,4,4- pentafluoro-1-butene (CHF = CFCHFCHF _2); 3,3,4,4- tetrafluoro-1-butene _{(CH 2 = CHCF 2 CHF 2} ); 1,1- difluoro-2- (difluoromethyl) -1-propene (CF _{2 = C (CHF 2) (CH} 3)); 1,3,3,3- tetrafluoro-2-methyl-1-propene _{(CHF = C (CF 3)} (CH 3)); 3,3- difluoro - 2- (difluoromethyl) -1-propene _{(CH 2 = C (CHF 2} ) 2); 1,1,1,2- tetrafluoro-2-butene _{(CF 3 CF = CHCH 3)} ; 1,1,1 , 3-tetrafluoro-2-butene (CH ₃ CF═CHCF ₃ ); 1,1,1,2,3,4,4,5,5,5-decafluoro-2-pentene (CF ₃ CF═CFCF ₂ CF ₃ ); 1,1,2,3,3,4,4,5,5,5-deca Fluoro-1-pentene _{(CF 2 = CFCF 2 CF 2} CF 3); 1,1,1,4,4,4- hexafluoro-2- (trifluoromethyl) -2-butene ((CF _{3) 2} C ═CHCF ₃ ); 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene (CF ₃ CF═CHCF ₂ CF ₃ ); 1,1,1,3,4,4 , 5,5,5-nonafluoro-2-pentene _{(CF 3 CH = CFCF 2 CF} 3); 1,2,3,3,4,4,5,5,5- nonafluoro-1-pentene (CHF = CFCF ₂ CF ₂ CF _3); 1,1,3,3,4,4,5,5,5- nonafluoro-1-pentene _{(CF 2 = CHCF 2 CF 2} CF 3); 1,1,2,3, 3,4,4,5,5- nonafluoro-1-pentene _{(CF 2 = CFCF 2 CF 2} CHF 2); 1,1,2 3,4,4,5,5,5- nonafluoro-2-pentene _{(CHF 2 CF = CFCF 2 CF} 3); 1,1,1
, 2,3,4,4,5,5-nonafluoro-2-pentene (CF ₃ CF═CFCF ₂ CHF ₂ ); 1,1,1,2,3,4,5,5,5-nonafluoro-2 - pentene _{(CF 3 CF = CFCHFCF 3)} ; 1,2,3,4,4,4- hexafluoro-3- (trifluoromethyl) -1-butene _{(CHF = CFCF (CF 3)} 2); 1, 1,2,4,4,4- hexafluoro-3- (trifluoromethyl) -1-butene _{(CF 2 = CFCH (CF 3} ) 2); 1,1,1,4,4,4- hexafluoro -2- (trifluoromethyl) -2-butene (CF ₃ CH═C (CF ₃ ) ₂ ); 1,1,3,4,4,4-hexafluoro-3- (trifluoromethyl) -1- butene _{(CF 2 = CHCF (CF 3} ) 2); 2,3,3,4,4,5,5,5- octene Fluoro-1-pentene _{(CH 2 = CFCF 2 CF 2} CF 3); 1,2,3,3,4,4,5,5- octafluoro-1-pentene _{(CHF = CFCF 2 CF 2 CHF} 2); 3,3,4,4,4-pentafluoro-2- (trifluoromethyl) -1-butene (CH ₂ ═C (CF ₃ ) CF ₂ CF ₃ ); 1,1,4,4,4-penta fluoro-3- (trifluoromethyl) -1-butene _{(CF 2 = CHCH (CF 3} ) 2); 1,3,4,4,4- pentafluoro-3- (trifluoromethyl) -1-butene ( CHF = CHCF (CF ₃ ) ₂ ); 1,1,4,4,4-pentafluoro-2- (trifluoromethyl) -1-butene (CF ₂ ═C (CF ₃ ) CH ₂ CF ₃ ); 3 , 4,4,4-Tetrafluoro-3- (trifluoromethyl) -1-butene _{((CF 3) 2 CFCH =} CH 2); 3,3,4,4,5,5,5- heptafluoro-1-pentene _{(CF 3 CF 2 CF 2 CH} = CH 2); 2,3,3 , 4,4,5,5-heptafluoro-1-pentene _{(CH 2 = CFCF 2 CF 2} CHF 2); 1,1,3,3,5,5,5- heptafluoro-1-butene (CF _{2 = CHCF 2 CH 2 CF 3)} ; 1,1,1,2,4,4,4- heptafluoro-3-methyl-2-butene _{(CF 3 CF = C (CF} 3) (CH 3)); 2 4,4,4-tetrafluoro-3- (trifluoromethyl) -1-butene _{(CH 2 = CFCH (CF 3} ) 2); 1,4,4,4- tetrafluoro-3- (trifluoromethyl ) -1-butene (CHF = CHCH (CF ₃ ) ₂ ); 1,1,1,4-tetrafluoro-2- (tri Fluoromethyl) -2-butene (CH ₂ FCH═C (CF ₃ ) ₂ ); 1,1,1,3-tetrafluoro-2- (trifluoromethyl) -2-butene (CH ₃ CF═C (CF ₃ ) ₂ ); 1,1,1-trifluoro-2- (trifluoromethyl) -2-butene ((CF ₃ ) ₂ C═CHCH ₃ ); 3,4,4,5,5,5-hexa Fluoro-2-pentene (CF ₃ CF ₂ CF═CHCH ₃ ); 1,1,1,4,4,4-hexafluoro-2-methyl-2-butene (CF ₃ C (CH ₃ ) ═CHCF ₃ ) 3,3,4,5,5,5-hexafluoro-1-pentene (CH ₂ ═CHCF ₂ CHFCF ₃ ); 4,4,4-trifluoro-3- (trifluoromethyl) -1-butene ( _{CH 2 = C (CF 3)} CH 2 CF 3); 1,1,2,3,3,4,4,5, , 6,6,6 dodecafluoro-1-hexene _{(CF 3 (CF 2) 3} CF = CF 2); 1,1,1,2,2,3,4,5,5,6,6,6 - dodecafluoro-3- hexene _{(CF 3 CF 2 CF = CFCF} 2 CF 3); 1,1,1,4,4,4- hexafluoro-2,3-bis (trifluoromethyl) -2-butene ( (CF ₃ ) ₂ C═C (CF ₃ ) ₂ ); 1,1,1,2,3,4,5,5,5-nonafluoro-4- (trifluoromethyl) -2-pentene ((CF ₃ ) ₂ CFCF = CFCF ₃ ); 1,1,1,4,4,5,5,5-octafluoro-2- (trifluoromethyl) -2-pentene ((CF ₃ ) ₂ C═CHC ₂ F ₅ ); 1,1,1,3,4,5,5,5- octafluoro-4- (trifluoromethyl) -2-pentene ((CF _{3 2} CFCF = CHCF _3); 3,3,4,4,5,5,6,6,6- nonafluoro-1-hexene _{(CF 3 CF 2 CF 2 CF} 2 CH = CH 2); 4,4,4 - trifluoro-3,3-bis (tri fluoromethyl) -1-butene _{(CH 2 = CHC (CF 3} ) 3); 1,1,1,4,4,4- hexafluoro-2- (trifluoromethyl methyl) -3-methyl-2-butene _{((CF 3) 2 C =} C (CH 3) (CF 3)); 2,3,3,5,5,5- hexafluoro-4- (trifluoromethyl ) 1-pentene _{(CH 2 = CFCF 2 CH (} CF 3) 2); 1,1,1,2,4,4,5,5,5- nonafluoro-3-methyl-2-pentene (CF ₃ CF = C (CH ₃ ) CF ₂ CF ₃ ); 1,1,1,5,5,5-hexafluoro-4- (trifluoromethyl) ) -2- pentene _{(CF 3 CH = CHCH (CF} 3) 2); 3,4,4,5,5,6,6,6- octafluoro-2-hexene _{(CF 3 CF 2 CF 2 CF} = CHCH ₃ ); 3,3,4,4,5,5,6,6-octafluoro 1-hexene (CH ₂ ═CHCF ₂ CF ₂ CF ₂ CHF ₂ ); 1,1,1,4,4-penta Fluoro-2- (trifluoromethyl) -2-pentene ((CF ₃ ) ₂ C═CHCF ₂ CH ₃ ); 4,4,5,5,5-pentafluoro-2- (trifluoromethyl) -1- Pentene (CH ₂ ═C (CF ₃ ) CH ₂ C ₂ F ₅ ); 3,3,4,4,5,5,5-heptafluoro-2-methyl-1-pentene (CF ₃ CF ₂ CF ₂ C _{(CH 3) = CH 2)} ; 4,4,5,5,6,6,6- heptafluoro-2-hexene (CF ₃ C _{2 CF 2 CH = CHCH 3)} ; 4,4,5,5,6,6,6- heptafluoro-1-hexene _{(CH 2 = CHCH 2 CF 2} C 2 F 5); 1,1,1,2 , 2,3,4-heptafluoro-3-hexene (CF ₃ CF ₂ CF═CFC ₂ H ₅ ); 4,5,5,5-tetrafluoro-4- (trifluoromethyl) -1-pentene (CH ₂ = CHCH ₂ CF (CF ₃ ) ₂ ); 1,1,1,2,5,5,5-heptafluoro-4-methyl-2-pentene (CF ₃ CF═CHCH (CF ₃ ) (CH ₃ ) ); 1,1,1,3-tetrafluoro-2- (trifluoromethyl) -2-pentene ((CF ₃ ) ₂ C═CFC ₂ H ₅ ); 1,1,1,2,3,4, 4,5,5,6,6,7,7,7- tetradecanoyl-fluoro-2-heptene _{(CF 3 CF = CFCF 2 CF} 2 ₂ F _5); 1,1,1,2,2,3,4,5,5,6,6,7,7,7- tetradecanoyl-fluoro-3- heptene _{(CF 3 CF 2 CF = CFCF} 2 C ₂ F ₅ ); 1,1,1,3,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene (CF ₃ CH═CFCF ₂ CF ₂ C ₂ F _5); 1,1,1,2,4,4,5,5,6,6,7,7,7- tridecafluoro-2-heptene _{(CF 3 CF = CHCF 2 CF} 2 C 2 F 5) 1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF ₃ CF ₂ CH═CFCF ₂ C ₂ F ₅ ); 1 , 1,1,2,2,3,5,5,6,6,7,7,7- tridecafluoro-3-heptene _{(CF 3 CF 2 CF = CHCF} 2 C 2 F 5); CF 2 = CFOCF ₂ CF ₃ (P EVE) and a fluoroolefin selected from the group consisting of CF ₂ ═CFOCF ₃ (PMVE);
Selected from the group consisting of

  A particularly important utility in compositions comprising at least one flammable refrigerant and at least one fluoroolefin is those fluoroolefins that are themselves nonflammable. It is believed that the flammability of fluoroolefins is related to the number of fluorine atoms and the number of hydrogen atoms in the molecule. The following formula provides a flammability factor that can be calculated as an indicator of the predicted flammability:

In the formula:
F = number of fluorine atoms in the molecule; and H = number of hydrogen atoms in the molecule.

  As certain compounds were experimentally determined to be flammable, a cut-off for the non-flammable fluoroolefin flammability factor was determined. Fluoroolefins comprise an electronic ignition source under conditions specified by ASHRAE (American Society of Heating, Refrigeration and Air-Conditioning Engineers, Inc.) Standard 34-2001. By testing under the American Society of Testing and Materials E681-01, it can be determined whether it is flammable or non-flammable. Such a flammability test is performed with 101 kPa (14.7 psia) and a specific compound along with the compound of interest to determine the lower explosion limit (LFL) and / or the upper explosion limit (UFL) of the test compound in air. Performed in air at temperatures (often 100 ° C. (212 ° F.)) and at various concentrations.

  Flammability factors for a number of fluoroolefins are listed in Table 4 along with experimental determinations of flammability or nonflammability. It is therefore possible to predict for other fluoroolefins of the present disclosure what would be most useful in combination with the combustible refrigerants of the present disclosure as in fact non-flammable fluoroolefins.

  The fluoroolefins listed in Table 4 can be determined to be flammable or nonflammable based on the value of the flammability coefficient. If the flammability factor is found to be 0.70 or greater, the fluoroolefin can be expected to be non-flammable. If the flammability factor is less than 0.70, the fluoroolefin can be predicted to be flammable.

In another embodiment of the invention, the fluoroolefin used in the composition with the flammable refrigerant is:
(A) Formula A fluoroolefins E-R ¹ CH = CHR ² or ^{Z-R 1 CH = CHR 2} , wherein, R ¹ and R ² are independently perfluoro C ₁ -C ₆ A fluoroolefin which is an alkyl group;
(B) a cyclic fluoroolefin of the formula cyclo- [CX = CY (CZW) _n- ], wherein X, Y, Z and W are independently H or F, and n is 2 to 5 And a cyclic fluoroolefin having a flammability coefficient of 0.70 or more; and (c) 1,2,3,3,3-pentafluoro-1-propene (CF ₃ CF═CHF); 1,3,3,3-pentafluoro-1-propene (CF ₃ CH═CF ₂ ); 1,1,2,3,3-pentafluoro-1-propene (CHF ₂ CF═CF ₂ ); 1,1,2,3,4,4,4-octafluoro-2-butene (CF ₃ CF═CFCF ₃ ); 1,1,2,3,3,4,4,4-octafluoro-1- Butene (CF ₃ CF ₂ CF═CF ₂ ); 1,1,1,2,4,4,4-heptafluoro 2-butene _{(CF 3 CF = CHCF 3)} ; 1,2,3,3,4,4,4- heptafluoro-1-butene _{(CHF = CFCF 2 CF 3)} ; 1,1,1,2, 3,4,4-heptafluoro-2-butene (CHF ₂ CF═CFCF ₃ ); 1,3,3,3-tetrafluoro-2- (trifluoromethyl) -1-propene ((CF ₃ ) ₂ C = CHF); 1,1,3,3,4,4,4- heptafluoro-1-butene _{(CF 2 = CHCF 2 CF 3} ); 1,1,2,3,4,4,4- heptafluoro 1-butene _{(CF 2 = CFCHFCF 3);} 1,1,2,3,3,4,4- heptafluoro-1-butene _{(CF 2 = CFCF 2 CHF 2} ); 2,3,3,4, 4,4-hexafluoro-1-butene _{(CF 3 CF 2 CF = CH} 2); 1,3,3,4,4,4- Kisafuruoro butene _{(CHF = CHCF 2 CF 3)} ; 1,2,3,4,4,4- hexafluoro-1-butene (CHF = CFCHFCF _3); 1,2,3,3,4,4 - hexafluoro-1-butene _{(CHF = CFCF 2 CHF 2)} ; 1,1,2,3,4,4- hexafluoro-2-butene _{(CHF 2 CF = CFCHF 2)} ; 1,1,1,2 3,1,4-hexafluoro-2-butene (CH ₂ FCF═CFCF ₃ ); 1,1,1,2,4,4-hexafluoro-2-butene (CHF ₂ CH═CFCF ₃ ); 1,1 , 1,3,4,4- hexafluoro-2-butene _{(CF 3 CH = CFCHF 2)} ; 1,1,2,3,3,4- hexafluoro-1-butene (CF ₂ = CFCF ₂ CH ₂ F); 1,1,2,3,4,4-hexafluoro-1- Ten _{(CF 2 = CFCHFCHF 2);} 3,3,3- trifluoro-2- (trifluoromethyl) -1-propene _{(CH 2 = C (CF 3} ) 2); 1,1,1,2,3 , 4,4,5,5,5-decafluoro-2-pentene _{(CF 3 CF = CFCF 2 CF} 3); 1,1,2,3,3,4,4,5,5,5- decafluoro 1-pentene _{(CF 2 = CFCF 2 CF 2} CF 3); 1,1,1,4,4,4- hexafluoro-2- (trifluoromethyl) -2-butene ((CF _{3) 2} C = CHCF ₃ ); 1,1,1,2,4,4,5,5,5-nonafluoro- ₂ -pentene (CF ₃ CF═CHCF ₂ CF ₃ ); 1,1,1,3,4,4, 5,5,5-nonafluoro-2-pentene (CF ₃ CH═CFCF ₂ CF ₃ ); 1,2,3,3,4,4,5,5 5-nonafluoro-1-pentene _{(CHF = CFCF 2 CF 2 CF} 3); 1,1,3,3,4,4,5,5,5- nonafluoro-1-pentene _{(CF 2 = CHCF 2 CF 2} CF _3); 1,1,2,3,3,4,4,5,5- nonafluoro-1-pentene _{(CF 2 = CFCF 2 CF 2} CHF 2); 1,1,2,3,4,4, 5,5,5-nonafluoro-2-pentene _{(CHF 2 CF = CFCF 2 CF} 3); 1,1,1,2,3,4,4,5,5- nonafluoro-2-pentene (CF ₃ CF = CFCF ₂ CHF ₂ ); 1,1,1,2,3,4,5,5,5-nonafluoro-2-pentene (CF ₃ CF═CFCHFCF ₃ ); 1,2,3,4,4,4- hexafluoro-3- (trifluoromethyl) -1-butene _{(CHF = CFCF (CF 3)} 2) 1,1,2,4,4,4- hexafluoro-3- (trifluoromethyl) -1-butene _{(CF 2 = CFCH (CF 3} ) 2); 1,1,1,4,4,4- Hexafluoro-2- (trifluoromethyl) -2-butene (CF ₃ CH═C (CF ₃ ) ₂ ); 1,1,3,4,4,4-hexafluoro-3- (trifluoromethyl)- 1-butene _{(CF 2 = CHCF (CF 3} ) 2); 2,3,3,4,4,5,5,5- octafluoro-1-pentene _{(CH 2 = CFCF 2 CF 2} CF 3); 1 , 2,3,3,4,4,5,5-octafluoro-1-pentene (CHF = CFCF ₂ CF ₂ CHF ₂ ); 3,3,4,4,4-pentafluoro-2- (trifluoro methyl) -1-butene _{(CH 2 = C (CF 3} ) CF 2 CF 3); 1,1,4,4,4- pen Fluoro-3- (trifluoromethyl) -1-butene _{(CF 2 = CHCH (CF 3} ) 2); 1,3,4,4,4- pentafluoro-3- (trifluoromethyl) -1-butene ( CHF = CHCF (CF ₃ ) ₂ ); 1,1,4,4,4-pentafluoro-2- (trifluoromethyl) -1-butene (CF ₂ ═C (CF ₃ ) CH ₂ CF ₃ ); 3 , 4,4,4-tetrafluoro-3- (trifluoromethyl) -1-butene ((CF ₃ ) ₂ CFCH═CH ₂ ); 3,3,4,4,5,5,5-heptafluoro- 1-pentene _{(CF 3 CF 2 CF 2 CH} = CH 2); 2,3,3,4,4,5,5- heptafluoro-1-pentene _{(CH 2 = CFCF 2 CF 2} CHF 2); 1, 1,3,3,5,5,5-heptafluoro-1-butene (CF ₂ ═CHCF ₂ CH ₂ CF _3); 1,1,1,2,4,4,4- heptafluoro-3-methyl-2-butene _{(CF 3 CF = C (CF} 3) (CH 3)); 2,4, 4,4-tetrafluoro-3- (trifluoromethyl) -1-butene _{(CH 2 = CFCH (CF 3} ) 2); 1,4,4,4- tetrafluoro-3- (trifluoromethyl) -1 - butene _{(CHF = CHCH (CF 3)} 2); 1,1,1,4- tetrafluoro-2- (trifluoromethyl) -2-butene _{(CH 2 FCH = C (CF} 3) 2); 1, 1,1,3-tetrafluoro-2- (trifluoromethyl) -2-butene (CH ₃ CF═C (CF ₃ ) ₂ ); 1,1,2,3,3,4,4,5,5 , 6,6,6 dodecafluoro-1-hexene _{(CF 3 (CF 2) 3} CF = CF 2); 1,1,1,2,2 3,4,5,5,6,6,6- dodecafluoro-3- hexene _{(CF 3 CF 2 CF = CFCF} 2 CF 3); 1,1,1,4,4,4- hexafluoro -2, 3-bis (trifluoromethyl) -2-butene ((CF ₃ ) ₂ C═C (CF ₃ ) ₂ ); 1,1,1,2,3,4,5,5,5-nonafluoro-4- (Trifluoromethyl) -2-pentene ((CF ₃ ) ₂ CFCF═CFCF ₃ ); 1,1,1,4,4,5,5,5-octafluoro-2- (trifluoromethyl) -2- Pentene ((CF ₃ ) ₂ C═CHC ₂ F ₅ ); 1,1,1,3,4,5,5,5-octafluoro-4- (trifluoromethyl) -2-pentene ((CF ₃ ) ₂ CFCF = CHCF _3); 3,3,4,4,5,5,6,6,6- nonafluoro-1-hexene (CF _{3 F 2 CF 2 CF 2 CH =} CH 2); 4,4,4- trifluoro-3,3-bis (trifluoromethyl) -1-butene _{(CH 2 = CHC (CF 3} ) 3); 1,1 , 1,4,4,4-hexafluoro-2- (trifluoromethyl) -3-methyl-2-butene ((CF ₃ ) ₂ C═C (CH ₃ ) (CF ₃ )); 3,5,5,5- hexafluoro-4- (trifluoromethyl) -1-pentene _{(CH 2 = CFCF 2 CH (} CF 3) 2); 1,1,1,2,4,4,5, 5,5 nonafluoro-3-methyl-2-pentene _{(CF 3 CF = C (CH} 3) CF 2 CF 3); 1,1,1,5,5,5- hexafluoro-4- (trifluoromethyl ) -2-pentene (CF ₃ CH═CHCH (CF ₃ ) ₂ ); 1,1,1,2,3,4,4,5,5,6,6 , 7,7,7-tetradecafluoro-2-heptene (CF ₃ CF═CFCF ₂ CF ₂ C ₂ F ₅ ); 1,1,1,2,2,3,4,5,5,6,6 , 7,7,7- tetra deca fluoro-3- heptene _{(CF 3 CF 2 CF = CFCF} 2 C 2 F 5); 1,1,1,3,4,4,5,5,6,6,7 , 7,7-Tridecafluoro-2-heptene (CF ₃ CH═CFCF ₂ CF ₂ C ₂ F ₅ ); 1,1,1,2,4,4,5,5,6,6,7,7 , 7-Tridecafluoro- ₂ -heptene (CF ₃ CF═CHCF ₂ CF ₂ C ₂ F ₅ ); 1,1,1,2,2,4,5,5,6,6,7,7,7 - tridecafluoro-3-heptene _{(CF 3 CF 2 CH = CFCF} 2 C 2 F 5); and 1,1,1,2,2,3,5,5,6,6,7,7,7- Tridecafluoro- - fluoroolefin selected from the group consisting of heptene _{(CF 3 CF 2 CF = CHCF} 2 C 2 F 5);
A fluoroolefin selected from the group consisting of

In still other embodiments, the fluoroolefins of the present disclosure that may be particularly useful in combination with a flammable refrigerant are:
(A) Formula A fluoroolefins E-R ¹ CH = CHR ² or ^{Z-R 1 CH = CHR 2} , wherein, R ¹ and R ² are independently perfluoro C ₁ -C ₆ A fluoroolefin which is an alkyl group and has a flammability coefficient of 0.70 or more; and (b) a cyclic fluoroolefin of the formula cyclo- [CX = CY (CZW) _n- ], wherein X, Y , Z and W are independently H or F, n is an integer of 2 to 5, and the flammability coefficient is 0.70 or more;
It may be at least one fluoroolefin selected from the group consisting of

  The flammability factor provides a basis for predicting the flammability of certain fluoroolefin compounds, while certain isomers with a given molecular reaction formula are flammable while other isomers are non-flammable There may be certain variables such as the position of the hydrogen atom on the molecule that will cause this. Thus, the flammability factor can only be used as a tool for predicting flammability characteristics.

  The combustible refrigerants of the present invention comprise any compound that can be shown to propagate a flame when mixed with air under certain conditions of temperature, pressure and composition. The combustible refrigerant comprises an electronic ignition source under conditions specified by ASHRAE (American Society of Heating, Refrigeration and Air-Conditioning Engineers, Inc.) Standard 34-2001, It can be identified by testing under ASTM (American Society of Testing and Materials E681-01. Such a flammability test is a test of the lower explosive limit (LFL) in air of test compounds and 101 kPa (14.7 psia) and specified temperature (typically 100 ° C. (212 ° F.), or about 23 ° C., together with refrigerant, to determine the upper explosion limit (UFL) 73 is a ° F) room temperature), at various concentrations, it is carried out in air.

  As a practical matter, refrigerants can be distinguished as flammable upon leakage from refrigeration or air conditioning equipment and if they can ignite in contact with an ignition source. The composition of the present invention is unlikely to ignite during such leaks.

The combustible refrigerant of the present invention includes hydrofluorocarbon (HFC), fluoroolefin, fluoroether, hydrocarbon ether, hydrocarbon, ammonia (NH ₃ ), and combinations thereof.

  The combustible HFC refrigerant is not particularly limited: difluoromethane (HFC-32), fluoromethane (HFC-41), 1,1,1-trifluoroethane (HFC-143a), 1,1,2-trimethyl. Fluoroethane (HFC-143), 1,1-difluoroethane (HFC-152a), fluorethane (HFC-161), 1,1,1-trifluoropropane (HFC-263fb), 1,1,1,3, 3-pentafluoropropane (HFC-365mfc), and combinations thereof. These flammable HFC refrigerants are commercially available products available from a number of suppliers such as chemical synthesis companies, or can be prepared by synthetic processes disclosed in the art.

  The flammable refrigerant of the present invention is not particularly limited: 1,2,3,3-tetrafluoro-1-propene (HFC-1234ye); 1,3,3,3-tetrafluoro-1-propene (HFC-) 1234ze); 2,3,3,3-tetrafluoro-1-propene (HFC-1234yf); 1,1,2,3-tetrafluoro-1-propene (HFC-1234yc); 1,1,3,3 Tetrafluoro-1-propene (HFC-1234zc); 2,3,3-trifluoro-1-propene (HFC-1243yf); 3,3,3-trifluoro-1-propene (HFC-1243zf); 1 1,1,2-trifluoro-1-propene (HFC-1243yc); 1,1,3-trifluoro-1-propene (HFC-1243zc); 1,2,3-trif Oro-1-propene (HFC-1243ye); and 1,3,3 further comprising a-trifluoro-1-fluoroolefin containing propene (HFC-1243ze).

The combustible refrigerant of the present invention further includes a fluoroether that also contains at least one ether group oxygen atom, which is a compound similar to a hydrofluorocarbon. Representative fluoroether refrigerants include, but are not limited to, commercially available C ₄ F ₉ OC ₂ H ₅ .

  The combustible refrigerant of the present invention further includes a hydrocarbon refrigerant. Typical hydrocarbon refrigerants are not particularly limited, but propane, propylene, cyclopropane, n-butane, isobutane, n-pentane, 2-methylbutane (isopentane), cyclobutane, cyclopentane, 2,2-dimethylpropane, 2,2-dimethylbutane, 2,3-dimethylbutane, 2,3-dimethylpentane, 2-methylhexane, 3-methylhexane, 2-methylpentane, 3-ethylpentane, 3-methylpentane, cyclohexane, n- Examples include heptane, methylcyclopentane, and n-hexane. Flammable hydrocarbon refrigerants are available from several commercial suppliers.

The combustible refrigerants of the present invention are hydrocarbons such as dimethyl ether (DME, CH ₃ OCH ₃ ) and methyl t-butyl ether (MTBE, (CH ₃ ) ₃ COCH ₃ ), both of which are available from several commercial suppliers. Further includes ether.

The combustible refrigerant of the present invention further contains ammonia (NH ₃ ), which is a commercially available compound.

  The flammable refrigerants of the present invention may have two or more flammable refrigerants (eg, when identified under the ASTM conditions described herein, or as a matter of fact, so that the entire mixture is still considered a flammable refrigerant) A mixture of two or more refrigerants, such as a mixture of two HFCs or one HFC and a hydrocarbon) or a mixture comprising a flammable refrigerant and a non-flammable refrigerant.

  Examples of non-flammable refrigerants that can be combined with other refrigerants of the present invention include R-134a, R-134, R-23, R125, R-236fa, R-245fa, and HCFC-22 / HFC-152a / HCFC-124 mixture (known by ASHRAE type, R401 or R-401A, R-401B, and R-401C), HFC-125 / HFC-143a / HFC-134a (ASHRAE type, R-404 or R- 404A), HFC-32 / HFC-125 / HFC-134a (known by ASHRAE type, R407 or R407A, R-407B, and R-407C), HCFC-22 / HFC-143a / HFC-125 (ASHRAE type, R408 or R-408A HCFC-22 / HCFC-124 / HCFC-142b (known by ASHRAE type: R-409 or R-409A), HFC-32 / HFC-125 (known by ASHRAE type R-410A) ), And HFC-125 / HFC-143a (ASHRAE type: known by R-507 or R507A) and carbon dioxide.

Examples of mixtures of two or more of the flammable refrigerant, propane / isobutane; HFC-152a / isobutane, R32 / propane; and the HFC / carbon dioxide mixtures such and HFC-152a / CO _2; R32 / isobutane.

  One aspect of the present invention is to provide a non-flammable refrigerant having a global warming potential of less than 150, preferably less than 50. Another aspect of the invention is to reduce the flammability of the flammable refrigeration mixture by adding a non-flammable fluoroolefin to the mixture.

  It can be shown that while certain refrigerants are flammable, it is possible to produce a non-flammable refrigerant composition by adding other non-flammable compounds to the flammable refrigerant. Examples of such non-flammable refrigerant blends include R-410A (HFC-32 is a flammable refrigerant, HFC-125 is non-flammable), and R-407C (HFC-32 is a flammable refrigerant). However, HFC-125 and HFC-134a are not flammable).

  A composition of the present invention useful as a refrigerant or heat transfer fluid comprising at least one fluoroolefin and at least one combustible refrigerant contains an effective amount of the fluoroolefin and results in ASTM E681-01 results. A composition that is non-combustible can be produced.

  Compositions of the present invention comprising at least one flammable refrigerant and at least one fluoroolefin contain from about 1 weight percent to about 99 weight percent fluoroolefin and from about 99 weight percent to about 1 weight percent flammable refrigerant. obtain.

  In other embodiments, the composition of the present invention may contain from about 10 weight percent to about 80 weight percent fluoroolefin and from about 90 weight percent to about 20 weight percent flammable refrigerant. In yet other embodiments, the compositions of the present invention may contain from about 20 weight percent to about 70 weight percent fluoroolefin and from about 80 weight percent to about 30 weight percent flammable refrigerant.

  Of particular interest are embodiments of the present disclosure in which the fluoroolefin comprises HFC-1225ye and the flammable refrigerant comprises HFC-32 (difluoromethane). As determined by ASTM 681-01, compositions containing 37 weight percent or less HFC-32 were found to be non-flammable, and compositions containing 38 weight percent or more HFC-32 were found to be flammable. The present disclosure provides a non-flammable composition comprising about 1.0 weight percent to about 37.0 weight percent HFC-32 and about 99.0 weight percent to about 63 weight percent HFC-1225ye.

  Also of particular interest are embodiments of the present disclosure in which the composition comprises HFC-1225ye, HFC-32 and HFC-125. This composition of the present invention comprises from about 20 weight percent to about 95 weight percent HFC-1225ye, from about 1.0 weight percent to about 65 weight percent HFC-32, and from about 1.0 weight percent to about 40 weight percent. Of HFC-125. In other embodiments, the composition comprises from about 30 weight percent to about 90 weight percent HFC-1225ye, from about 5.0 weight percent to about 55 weight percent HFC-32, and from about 1.0 weight percent to about 35 weight percent. Contains weight percent HFC-125. In yet other embodiments, the composition comprises from about 40 weight percent to about 85 weight percent HFC-1225ye, from about 10 weight percent to about 45 weight percent HFC-32, and from about 1.0 weight percent to about 28 weight percent. Of HFC-125. These compositions containing less than about 40 weight percent HFC-32 are expected to be non-flammable compositions. This explosion limit can vary from less than about 45 weight percent HFC-32 to less than about 37 weight percent HFC-32 depending on the relative ratio of HFC-1225ye and HFC-125 present in the composition.

  In other embodiments of particular interest, the flammable refrigerant comprises HFC-1243zf and non-flammable fluoroolefins intended to reduce the flammability of the overall composition. The composition can comprise from about 1.0 weight percent to about 99 weight percent HFC-1243zf and from about 99 weight percent to about 1.0 weight percent HFC-1225ye. Alternatively, the composition can comprise from about 40 weight percent to about 70 weight percent HFC-1243zf and from about 60 weight percent to about 30 weight percent HFC-1225ye.

  In other embodiments of particular interest, the composition comprises about 1.0 weight percent to about 98 weight percent HFC-1243zf; about 1.0 weight percent to about 98 weight percent HFC-1225ye; and about 1.0 weight Percent to about 50 weight percent HFC-125. Alternatively, the composition may comprise about 40 weight percent to about 70 weight percent HFC-1243zf; about 20 weight percent to about 60 weight percent HFC-1225ye; and about 1.0 weight percent to about 10 weight percent HFC. -125 is included.

  In other embodiments of particular interest, the composition comprises about 1.0 weight percent to about 98 weight percent HFC-1243zf; about 1.0 weight percent to about 98 weight percent HFC-1225ye; and about 1.0 weight Percent to about 50 weight percent HFC-32. Alternatively, the composition may comprise about 40 weight percent to about 70 weight percent HFC-1243zf; about 20 weight percent to about 60 weight percent HFC-1225ye; and about 1.0 weight percent to about 10 weight percent HFC. Includes -32.

  In yet another embodiment of particular interest, the composition comprises from about 1.0 weight percent to about 97 weight percent HFC-1243zf; from about 1.0 weight percent to about 97 weight percent HFC-1225ye; Percent to about 50 weight percent HFC-125; and about 1.0 weight percent to about 50 weight percent HFC-32. Alternatively, the composition may comprise about 40 weight percent to about 70 weight percent HFC-1243zf; about 20 weight percent to about 60 weight percent HFC-1225ye; and about 1.0 weight percent to about 10 weight percent HFC. -125; and from about 1.0 weight percent to about 10 weight percent HFC-32.

  The present invention further relates to a method for reducing the flammability of a flammable refrigerant, the method comprising combining the flammable refrigerant with at least one fluoroolefin. The amount of fluoroolefin added should be an effective amount to produce a non-flammable composition as determined by ASTM 681-01.

  The composition of the present invention can be used in combination with a desiccant to assist in the removal of moisture in refrigeration, air conditioning, or heat pump systems. The desiccant can be composed of molecular sieve based activated alumina, silica gel, or zeolite. Exemplary molecular sieves include MOLSIV XH-7, XH-6, XH-9, and XH-11 (UOP LLC of Des Plaines, IL). For refrigerants having a small molecular size, HFC-32, XH-11 desiccant and the like are preferred.

  The composition of the present invention may further comprise at least one lubricant. The lubricants of the present invention include those that are preferred for use in refrigeration or air conditioning equipment. Among these, the lubricant is easily used in a compression refrigeration apparatus using a chlorofluorocarbon refrigerant. Such lubricants and their properties are discussed in (Non-Patent Document 2), incorporated herein by reference. The lubricant of the present invention may include what is commonly known as “mineral oil” in the field of compression refrigeration lubrication. Mineral oils are one or more characterized by paraffins (ie linear and branched-carbon-chain, saturated hydrocarbons), naphthenes (ie cyclic paraffins) and aromatics (ie alternating double bonds). Unsaturated, cyclic hydrocarbons containing rings). The lubricants of the present invention further include those commonly known as “synthetic oils” in the field of compression refrigeration lubrication. Synthetic oils include alkylaryls (ie, linear and branched alkylalkylbenzenes), synthetic paraffins and naphthenes, and poly (alpha olefins). Representative conventional lubricants of the present invention are commercially available BVM100N (paraffinic mineral oil purchased from BVA Oils), Suniso® 3GS and Suniso®. 5GS (a naphthenic mineral oil purchased from Crompton Co.), Suntex (R) 372LT (a naphthenic mineral oil purchased from Pennzoil), Calumet (R) RO-30 (a naphthenic mineral oil purchased from Calumet Lubricants), Zerol (R) 75, Zerol (R) 150 and Zerol (R) Is a 500 (Shreveport Chemicals (linear alkyl benzene was purchased from Shrieve Chemicals)) and HAB22 (Nippon Oil Corporation (Nippon Oil) was purchased from the branch alkyl benzene).

  The lubricants of the present invention further include those designed for use with hydrofluorocarbon refrigerants and those miscible with the refrigerants of the present invention under the operating conditions of compression refrigeration and air conditioning equipment. Such lubricants and their properties are discussed in (Non-Patent Document 3). Such lubricants include, but are not limited to, polyol esters (POE) such as Castrol® 100 (Castol of United Kingdom), Dow (Midland, Michigan) Polyalkylene glycols (PAG) such as RL-488A from Dow Chemical (Midland, Michigan), and polyvinyl ether (PVE).

  The lubricant of the present invention is selected by considering the requirements of a given compressor and the environment in which the lubricant will be exposed.

  Commonly used refrigeration system additives can optionally be added to the compositions of the present invention to enhance lubricity and system stability, if desired. These additives are generally known within the field of refrigeration compressor lubrication, and are antiwear agents, super pressure lubricants, corrosion and oxidation inhibitors, metal surface deactivators, foaming and antifoam control. Agents, leakage detection agents and the like. In general, these additives are present only in small amounts relative to the overall lubricant composition. These are typically used at concentrations from less than about 0.1% to about 3% of each additive. These additives are selected based on individual system requirements. Some typical examples of such additives may include, but are not limited to, lubricity enhancing additives such as alkyl or aryl esters of phosphoric acid and alkyl or aryl esters of thiophosphoric acid. In addition, metal dialkyl dithiophosphates (eg, zinc dialkyl dithiophosphate or ZDDP, Lubrizol 1375) and other members of this family of chemicals can be used in the compositions of the present invention. Other anti-wear additives include natural product oils and asymmetric polyhydroxyl lubricant additives such as Synergol TMS (International Lubricants). Similarly, stabilizers such as antioxidants, free radical scavengers, and water scavengers (dry compounds) can be utilized. Such additives include, but are not limited to, nitromethane, hindered phenols (such as butylated hydroxytoluene or BHT), hydroxylamines, thiols, phosphites, epoxides or lactones. The water scavenger is not particularly limited, and includes orthoesters such as trimethyl orthoformate, -triethyl, or -tripropyl. A single additive or a combination thereof may be used.

  In one embodiment, the present invention relates to thiophosphoric acid, butylated triphenyl phosphorothioate, organophosphate, dialkylthiophosphate, terpene, terpenoid, fullerene, functionalized perfluoropolyether, polyoxyalkylated fragrance. Group consisting of group compounds, epoxide, fluorinated epoxide, oxetane, ascorbic acid, thiol, lactone, thioether, nitromethane, alkylsilane, benzophenone derivative, aryl sulfide, divinyl terephthalate, diphenyl terephthalate, alkylamine, hindered amine antioxidant, and phenol A composition comprising at least one fluoroolefin selected from and at least one stabilizer is provided. Alkylamines can include triethylamine, tributylamine, diisopropylamine, triisopropylamine, triisobutylamine, and other members of this family of alkylamine compounds.

  In other embodiments, the stabilizers of the present invention may include specific combinations of stabilizers. One combination of particularly interesting stabilizers comprises at least one terpene or terpenoid. These terpenes or terpenoids can be combined with at least one compound selected from epoxides, fluorinated epoxides, and oxetanes.

  Terpenes are hydrocarbon compounds characterized by a structure containing two or more isoprene (2-methyl-1,3-butadiene) repeat units. Terpenes may be acyclic or cyclic. Representative terpenes include, but are not limited to, myrcene (2-methyl-6-methyl-enocta-1,7-diene), allocymene, β-osmene, teleben, limonene (or d-limonene), retinal, pinene ( Or α-pinene), menthol, geraniol, farnesol, phytol, vitamin A, terpinene, δ-3-carene, terpinolene, ferrandolene, Fenken, and mixtures thereof. Terpene stabilizers are commercially available, can be prepared by methods known in the art, or are isolated from natural sources.

  Terpenoids are natural products and related compounds characterized by structures containing two or more isoprene repeating units and optionally containing oxygen. Representative terpenoids include lycopene (CAS registry number [502-65-8]), β-carotene (CAS registry number [7235-40-7]), and xanthophylls, ie, zeaxanthin (CAS registry number [144-68). -3]); retinoids such as hepaxanthin (CAS registry number [512-39-0]) and isotretinoin (CAS registry number [4759-48-2]); abietane (CAS registry number) [640-43-7]); Ambrosan (CAS registration number [24749-18-6]); Aristolan (CAS registration number [29788-49-6]); Atisan (CAS registration number [24379-83-7) ] Bayeran (CAS registration number [2359-83-3]), Bissabo (CAS registration number [29799-19-7]); Bornan (CAS registration number [464-15-3]); Caryophyllan (CAS registration number [20479-00-9]); Sedran (CAS registration number [13567- 54-9]); Damaran (CAS registration number [545-22-2]); Doriman (CAS registration number [5951-58-6]); Eremophilan (CAS registration number [3242-05-5]); Eudesman (CAS registration number [473-11-0]); Fencan (CAS registration number [6248-88-0]); Gammaselan (CAS registration number [559-65-9]); Germaclan (CAS registration number [645- 10-3]); diban (CAS registration number [6902-95-0]); grayanoxan (CAS registration number [39907-73- 8]); Guyan (CAS registration number [489-80-5]); Himacaran (CAS registration number [20479-45-2]); Hopan (CAS registration number [471-62-5]); Humulan (CAS registration) No. [430-19-3]); Cowlan (CAS registration number [1573-40-6]); Rabdan (CAS registration number [561-90-0]); Lanostane (CAS registration number [474-20-4]) Lupine (CAS registration number [464-99-3]); p-menthane (CAS registration number [99-82-1]); Oleanan (CAS registration number [471-67-0]); Ophioborane (CAS registration) Number [20098-65-1]); Picrasan (CAS registration number [35732-97-9]); Pimaran (CAS registration number [30257-03-5]); (CAS registration number [473-55-2]); Podocarpan (CAS registration number [471-78-3]); Protostane (CAS registration number [70050-78-1]); Losan (CAS registration number [6812] Taxane (CAS registration number [1605-68-1]); Tujan (CAS registration number [471-12-5]); trichothecan (CAS registration number [24706-08-9]); Ulsan (CAS registration number [464-93-7]). The terpenoids of the present invention are commercially available, can be prepared by methods known in the art, or can be isolated from natural sources.

  In one embodiment, the terpene or terpenoid stabilizer can be combined with at least one epoxide. Exemplary epoxides include 1,2-propylene oxide (CAS registry number [75-56-9]); 1,2-butylene oxide (CAS registry number [106-88-7]); or mixtures thereof. Can be mentioned.

In other embodiments, the terpenes or terpenoid stabilizers of the present invention can be combined with at least one fluorinated epoxide. The fluorinated epoxides of the present invention can be represented by formula 3, wherein each of R ^{2 to} R ⁵ is H, alkyl of 1 to 6 carbon atoms or fluoroalkyl of 1 to 6 carbon atoms. Provided that at least one of R ^{2 to} R ⁵ is a fluoroalkyl group.

  Representative fluorinated epoxide stabilizers include, but are not limited to, trifluoromethyloxirane and 1,1-bis (trifluoromethyl) oxirane. Such compounds can be prepared by methods known in the art, for example, by the methods described in (Non-patent document 4), (Non-patent document 5), and (Non-patent document 6). .

In other embodiments, the terpenes or terpenoid stabilizers of the present invention can be combined with at least one oxetane. The oxetane stabilizer of the present invention can be a compound with one or more oxetane groups, represented by Formula 4, wherein R _{1 to} R ₆ are the same or different and are hydrogen, alkyl or substituted alkyl, It is possible to select from aryl or substituted aryl.

  Representative oxetane stabilizers include, but are not limited to, 3-ethyl-3-hydroxymethyl-oxetane such as OXT-101 (Toagosei Co., Ltd); OXT-211 (Toagosei) 3-ethyl-3-((phenoxy) methyl) -oxetane such as Toagosei Co., Ltd .; and 3-ethyl-such as OXT-212 (Toagosei Co., Ltd.) 3-((2-ethyl-hexyloxy) methyl) -oxetane.

  Another embodiment of particular interest is a combination of stabilizers comprising fullerenes. The fullerene stabilizer may be combined with at least one compound selected from the group consisting of epoxides, fluorinated epoxides, and oxetanes. Epoxides, fluorinated epoxides, and oxetanes for combination with fullerenes have already been described herein for combinations with terpenes or terpenoids.

  Another embodiment of particular interest is a combination of stabilizers comprising phenol. The fullerene stabilizer may be combined with at least one compound selected from the group consisting of epoxides, fluorinated epoxides, and oxetanes. Epoxides, fluorinated epoxides, and oxetanes for combination with phenol have already been described herein for combinations with terpenes or terpenoids.

  Phenol stabilizers include 2,6-di-tert-butyl-4-methylphenol; 2,6-di-tert-butyl-4-ethylphenol; 2,4-dimethyl-6-tetrabutylphenol; tocopherol and the like. Hydroquinone and alkylated hydroquinone, including alkylated monophenols, t-butyl hydroquinone, other derivatives of hydroquinone, 4,4'-thio-bis (2-methyl-6-tert-butylphenol); 4,4'- Hydroxylated thiodiphenyl ethers including thiobis (3-methyl-6-tetrabutylphenol); 2,2′-thiobis (4methyl-6-tert-butylphenol) and the like, 4,4′-methylenebis (2,6-di-tert) -Butylphenol); 4,4'-bis (2,6-di-tert) Butylphenol); 2,2'- or 4,4-biphenoldiol derivatives; 2,2'-methylenebis (4-ethyl-6-tertbutylphenol); 2,2'-methylenebis (4-methyl-6-tertbutylphenol) ); 4,4-butylidenebis (3-methyl-6-tert-butylphenol); 4,4-isopropylidenebis (2,6-di-tert-butylphenol); 2,2′-methylenebis (4-methyl-6) -Nonylphenol); 2,2'-isobutylidenebis (4,6-dimethylphenol; 2,2'-methylenebis (alkylidene-bisphenol including 4-methyl-6-cyclohexylphenol, 2,2'-methylenebis (4 -Ethyl-6-tert-butylphenol); butylated hydroxyltol 2,2- or 4,4-biphenyldiol containing benzene (BHT), 2,6-di-tert-α-dimethylamino-p-cresol, 4,4-thiobis (6-tert-butyl-m-cresol) Bisphenol containing heteroatoms including; acylaminophenol; 2,6-di-tert-butyl-4 (N, N′-dimethylaminomethylphenol); bis (3-methyl-4-hydroxy-5-tert) One or more substituted or unsubstituted cyclic, linear, or branched aliphatic substituents, such as sulfides including -butylbenzyl) sulfide; bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide and the like Any substituted or unsubstituted phenolic compound containing phenol containing

In one embodiment of the invention, the combination of a terpene or terpenoid, or a stabilizer comprising fullerene or phenol, with at least one compound selected from the group consisting of epoxides, fluorinated epoxides, and oxetanes is:
Areoxalyl bis (benzylidene) hydrazide (CAS Registry Number 6629-10-3);
N, N′-bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamoylhydrazine) (CAS Registry Number 32687-78-8);
2,2′-oxamidobis-ethyl- (3,5-d-tert-butyl-4-hydroxyhydrocinnamate) (CAS Registry Number 70331-94-1);
N, N ′-(disalicylidene) -1,2-propanediamine (CAS Registry Number 94-91-1); and ethylenediaminetetraacetic acid (CAS Registry Number 60-00-4) and salts thereof An additional stabilizer compound selected from can further be included.

  In another embodiment of the present invention, these combinations of a stabilizer comprising terpene or terpenoid, or fullerene or phenol, and at least one compound selected from the group consisting of epoxides, fluorinated epoxides, and oxetanes are , Triethylamine; tributylamine; triisopropylamine; diisobutylamine; triisopropylamine; triisobutylamine; and at least one alkylamine selected from the group consisting of hindered amine antioxidants.

The composition of the present invention may further comprise a compound or composition that is a tracer, and includes a hydrofluorocarbon (HFC), a deuterated hydrocarbon, a deuterated hydrofluorocarbon, a perfluorocarbon, a fluoroether, a brominated compound, an iodide compound. , Alcohol, aldehyde, ketone, nitrous oxide (N ₂ O), and combinations thereof. The tracer used in the present invention is a composition different from that used as a refrigerant or a heat transfer fluid, and as described in US Pat. To the heat transfer composition is added in a predetermined amount that can detect any dilution, contamination or other denaturation of the composition.

  Exemplary tracer compounds for use in the present compositions are listed in Table 5.

  The compounds listed in Table 5 are commercially available (from chemical suppliers) or can be prepared by processes known in the art.

  A single tracer compound can be used in combination with a refrigeration / heating fluid in the compositions of the invention, or multiple tracer compounds can be combined in any proportion to serve as a tracer blend. Tracer blends can contain multiple tracer compounds from the same class of compounds or multiple tracer compounds from different classes of compounds. For example, the tracer blend may contain two or more deuterated hydrofluorocarbons, or one deuterated hydrofluorocarbon in combination with one or more perfluorocarbons.

  In addition, some of the compounds in Table 4 exist as multiple isomers such as structure or optics. A single isomer or multiple isomers of the same compound can be used in any proportion to prepare the tracer compound. Furthermore, single or multiple isomers of a given compound can be combined with any number of other compounds in any proportion to serve as a tracer blend.

  The tracer compound or tracer blend may be present in the composition at a total concentration of about 50 parts per million (ppm) to about 1000 ppm. Preferably, the tracer compound or tracer blend is present at a total concentration of about 50 ppm to about 500 ppm, and most preferably the tracer compound or tracer blend is present at a total concentration of about 100 ppm to about 300 ppm.

  The composition of the present invention may further comprise an ultraviolet (UV) dye and optionally a solubilizer. The UV dye is a refrigerant composition or heat transfer fluid by allowing someone to observe the fluorescence of the dye in the refrigerant or heat transfer fluid composition at or near the leak point of the device in a refrigeration, air conditioning, or heat pump device. It is a useful component for detecting leakage. The fluorescence of the dye may be observed under ultraviolet light. Solubilizers may be necessary due to the low solubility of such UV dyes in some refrigerants and heat transfer fluids.

  By “ultraviolet” dye is meant a UV fluorescent composition that absorbs light in the ultraviolet or “near” ultraviolet region of the electromagnetic spectrum. Under irradiation with UV light that emits radiation having a wavelength between 10 nanometers and 750 nanometers, the fluorescence provided by the UV fluorescent dye can be detected. Therefore, if such a refrigerant or heat transfer fluid containing a UV fluorescent dye leaks from a given location in a refrigeration, air conditioning, or heat pump device, the fluorescence is detected at or near the leak point. It is possible. Such UV fluorescent dyes are not particularly limited, and include naphthalimide, perylene, coumarin, anthracene, phenanthracene, xanthene, thioxanthene, naphthoxanthene, fluororesin, and derivatives of these dyes or combinations thereof. It is done. The solubilizer of the present invention is composed of hydrocarbon, hydrocarbon ether, polyoxyalkylene glycol ether, amide, nitrile, ketone, chlorocarbon, ester, lactone, aryl ether, fluoroether and 1,1,1-trifluoroalkane. At least one compound selected from the group consisting of:

  The hydrocarbon solubilizer of the present invention comprises a hydrocarbon containing linear, branched or cyclic alkanes or alkenes containing not more than 16 carbon atoms and not containing other functional groups but only hydrogen. Including. Exemplary hydrocarbon solubilizers include propane, propylene, cyclopropane, n-butane, isobutane, n-pentane, octane, decane, and hexadecane. It should be noted that when the refrigerant is a hydrocarbon, the solubilizer cannot be the same hydrocarbon.

  The hydrocarbon ether solubilizer of the present invention comprises an ether such as dimethyl ether (DME) containing only carbon, hydrogen and oxygen.

The polyoxyalkylene glycol ether solubilizer of the present invention has the formula R ¹ [(OR ² ) _x OR ³ ] _y (wherein x is an integer from 1 to 3; y is an integer from 1 to 4; R ¹ is selected from hydrogen and an aliphatic hydrocarbon radical having 1 to 6 carbon atoms and a y-bonding site; R ² is selected from an aliphatic hydrocarbylene radical having ² to 4 carbon atoms R ³ is selected from hydrogen and aliphatic and alicyclic hydrocarbon radicals having 1 to 6 carbon atoms; at least one of R ¹ and R ³ is said hydrocarbon radical) Wherein the polyoxyalkylene glycol ether has a molecular weight of about 100 to about 300 atomic mass units. As used herein, a binding site means a radical site that can be used to form a covalent bond with another radical. A hydrocarbylene radical means a divalent hydrocarbon radical. In the present invention, preferred polyoxyalkylene glycol ether solubilizers are represented by R ¹ [(OR ² ) _x OR ³ ] _y : x is preferably 1-2; y is preferably 1; ^{1 to} R ³ are preferably independently selected from hydrogen and an aliphatic hydrocarbon radical having 1 to 4 carbon atoms; R ² is preferably 2 or 3 carbon atoms, most preferably Selected from aliphatic hydrocarbylene radicals having 3 carbon atoms; the polyoxyalkylene glycol ether molecular weight is preferably from about 100 to about 250 atomic mass units, most preferably from about 125 to about 250 atomic mass units. R ^{1 to} R ³ hydrocarbon radicals having ¹ to 6 carbon atoms can be linear, branched or cyclic. Exemplary R ^{1 to} R ³ hydrocarbon radicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, and cyclohexyl. It is done. If the free hydroxyl radicals on the polyoxyalkylene glycol ether solubilizer can be incompatible with a structured compression refrigeration device material (eg, Mylar®), R ¹ -R ³ are Preference is given to aliphatic hydrocarbon radicals having 1 to 4 carbon atoms, most preferably 1 carbon atom. R ² aliphatic hydrocarbylene radicals having ² to 4 carbon atoms form repeating oxyalkylene radicals — (OR ² ) _x —, which are oxyethylene radicals, oxypropylene radicals, and oxybutylene radicals. including. The oxyalkylene radicals containing R ² in one polyoxyalkylene glycol ether solubilizer molecule may be the same, or one molecule may contain different R ² oxyalkylene groups. The polyoxyalkylene glycol ether solubilizer preferably comprises at least one oxypropylene group. When R ¹ is an aliphatic or alicyclic hydrocarbon radical having ¹ to 6 carbon atoms and a y-bonding site, the group can be linear, branched or cyclic. Exemplary R ¹ aliphatic hydrocarbon radicals having two binding sites include, for example, ethylene, propylene, butylene, pentylene, hexylene, cyclopentylene, and cyclohexylene. Representative R ¹ aliphatic hydrocarbon radicals having three or four binding sites include polyalcohols such as trimethylolpropane, glycerin, pentaerythritol, 1,2,3-trihydroxycyclohexane and 1,3,5. -Residues derived from trihydroxycyclohexane by removing their hydroxyl groups.

Representative polyoxyalkylene glycol ether solubilizers include, but are not limited to, CH ₃ OCH ₂ CH (CH ₃ ) O (H or CH ₃ ) (propylene glycol methyl (or dimethyl) ether), CH ₃ O [CH ₂ CH (CH ₃ ) O] ₂ (H or CH ₃ ) (dipropylene glycol methyl (or dimethyl) ether), CH ₃ O [CH ₂ CH (CH ₃ ) O] ₃ (H or CH ₃ ) (tripropylene Glycol methyl (or dimethyl ether), C ₂ H ₅ OCH ₂ CH (CH ₃ ) O (H or C ₂ H ₅ ) (propylene glycol ethyl (or diethyl) ether), C ₂ H ₅ O [CH ₂ CH ( CH ₃₎ O] ₂ (H or C ₂ H ₅₎ (dipropylene glycol ethyl (or diethyl) _{ether), C 2 H 5 O [} CH 2 CH CH ₃₎ O] ₃ (H or C ₂ H ₅₎ (tripropylene glycol ethyl (or diethyl) _{ether), C 3 H 7 OCH 2} CH (CH 3) O (H or C ₃ H ₇₎ (propylene glycol n - propyl (or di -n- propyl) _{ether), C 3 H 7 O [} CH 2 CH (CH 3) O] 2 (H or C ₃ H ₇₎ (dipropylene glycol n- propyl (or di -n- propyl) _{ether), C 3 H 7 O [} CH 2 CH (CH 3) O] 3 (H or C ₃ H ₇₎ (tripropylene glycol n- propyl (or di -n- propyl) ether), C ₄ H _{9 OCH 2 CH (CH 3)} OH ( propylene glycol n- butyl _{ether), C 4 H 9 O [} CH 2 CH (CH 3) O] 2 (H or C ₄ H ₉₎ (dipropylene glycol n- butyl (or -N- butyl) _{ether), C 4 H 9 O [} CH 2 CH (CH 3) O] 3 (H or C ₄ H ₉₎ (tripropylene glycol n- butyl (or di -n- butyl) ether), (CH ₃ ) ₃ COCH ₂ CH (CH ₃ ) OH (propylene glycol t-butyl ether), (CH ₃ ) ₃ CO [CH ₂ CH (CH ₃ ) O] ₂ (H or (CH ₃ ) ₃ ) (dipropylene Glycol t-butyl (or di-t-butyl) ether), (CH ₃ ) ₃ CO [CH ₂ CH (CH ₃ ) O] ₃ (H or (CH ₃ ) ₃ ) (tripropylene glycol t-butyl (or di -t- butyl) _{ether), C 5 H 11 OCH 2} CH (CH 3) OH ( propylene glycol n- pentyl _{ether), C 4 H 9 OCH 2} CH (C 2 H 5) OH ( butylene glycol n- butyl _{Ether), C 4 H 9 O [} CH 2 CH (C 2 H 5) O] 2 H ( dibutylene glycol n- butyl ether), trimethylolpropane tri -n- butyl ether _{(C 2 H 5 C (CH} 2 O ( _{CH 2) 3 CH 3) 3} ) and trimethylolpropane di -n- butyl ether _{(C 2 H 5 C (CH} 2 OC (CH 2) 3 CH 3) 2 CH 2 OH) can be mentioned.

The amide solubilizers of the present invention have the formula R ¹ C (O) NR ² R ³ and cyclo- [R ⁴ C (O) N (R ⁵ ) —] (wherein R ¹ , R ² , R ³ and R ⁵ is independently selected from aliphatic and alicyclic hydrocarbon radicals having 1 to 12 carbon atoms; R ⁴ is selected from aliphatic hydrocarbylene groups having 3 to 12 carbon atoms Wherein the amide has a molecular weight of from about 100 to about 300 atomic mass units. The molecular weight of the amide is preferably from about 160 to about 250 atomic mass units. R ¹ , R ² , R ³ and R ⁵ optionally contain a substituted hydrocarbon radical, ie a non-hydrocarbon substituent selected from halogen (eg fluorine, chlorine) and alkoxide (eg methoxy). Groups can be included. R ¹ , R ² , R ³ and R ⁵ are optionally heteroatom-substituted hydrocarbon radicals, ie atomic nitrogen (aza-), oxygen (oxa-) or sulfur (thia-) in the radical chain. May contain radicals that are otherwise comprised of carbon atoms. Normally, no more than 3 non-hydrocarbon substituents and heteroatoms, and preferably no more than 1 will be present for every 10 carbon atoms in R ^1-3 and such non-hydrocarbon substituents The presence of any and heteroatoms must be considered in the application of the molecular weight limits described above. Preferred amide solubilizers are composed of carbon, hydrogen, nitrogen and oxygen. Exemplary R ¹ , R ² , R ³ and R ⁵ aliphatic and alicyclic hydrocarbon radicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, Neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers. A preferred embodiment of amide solubilizing agents of the formula cyclo above - those which may be represented by R ⁴ in hydrocarbylene radical _{^{(CR 6 R 7) n -}} [R 4 C (O) N (R 5)] In other words, the formula cyclo-[(CR ⁶ R ⁷ ) _n C (O) N (R ⁵ ) —] (wherein the stated values for molecular weight apply, n is an integer from 3 to 5 R ⁵ is a saturated hydrocarbon radical containing 1 to 12 carbon atoms, and R ⁶ and R ⁷ are independently according to the rules defined above for R ^1-3 (for each n ) Is selected). In the lactam represented by the formula: cyclo-[(CR ⁶ R ⁷ ) _n C (O) N (R ⁵ ) —], all R ⁶ and R ⁷ are preferably hydrogen, or of n-methylene units. Contains a single saturated hydrocarbon radical, and R ⁵ is a saturated hydrocarbon radical containing 3 to 12 carbon atoms. For example, 1- (saturated hydrocarbon radical) -5-methylpyrrolidin-2-one.

  Exemplary amide solubilizers include, but are not limited to, 1-octylpyrrolidin-2-one, 1-decylpyrrolidin-2-one, 1-octyl-5-methylpyrrolidin-2-one, 1-butylcaprolactam, 1-cyclohexylpyrrolidin-2-one, 1-butyl-5-methylpiperidin-2-one, 1-pentyl-5-methylpiperidin-2-one, 1-hexylcaprolactam, 1-hexyl-5-methylpyrrolidin-2-one 5-methyl-1-pentylpiperidi-2-one, 1,3-dimethylpiperidi-2-one, 1-methylcaprolactam, 1-butyl-pyrrolidin-2-one, 1,5-dimethylpiperidi-2-one, 1- Decyl-5-methylpyrrolidin-2-one, 1-dodecylpyrrolidi-2-one, N, N-dibutylformamide And N, include N- diisopropyl acetamide.

The ketone solubilizer of the present invention has the formula R ¹ C (O) R ² , wherein R ¹ and R ² are independently aliphatic, alicyclic and aryl carbonized having 1 to 12 carbon atoms. Selected from hydrogen radicals), wherein the ketone has a molecular weight of about 70 to about 300 atomic mass units. R ¹ and R ² in the ketone are preferably independently selected from aliphatic and alicyclic hydrocarbon radicals having 1 to 9 carbon atoms. The molecular weight of the ketone is preferably about 100 to 200 atomic mass units. R ¹ and R ² together can form a connected hydrocarbylene radical and can form a 5-, 6-, or 7-membered cyclic ketone, such as cyclopentanone, cyclohexanone, and cycloheptanone. . R ¹ and R ² can optionally include a substituted hydrocarbon radical, ie, a radical containing a non-hydrocarbon substituent selected from halogen (eg, fluorine, chlorine) and alkoxide (eg, methoxy). R ¹ and R ² optionally contain a heteroatom-substituted hydrocarbon radical, ie atomic nitrogen (aza-), oxygen (keto-, oxa-) or sulfur (thia-) in the radical chain. , Otherwise it may contain radicals composed of carbon atoms. Usually, no more than 3 non-hydrocarbon substituents and heteroatoms, and preferably no more than 1 will be present for every 10 carbon atoms in R ¹ and R ² and such non-hydrocarbon substituents And the presence of heteroatoms must be considered in the application of the molecular weight limits described above. Representative R ¹ and R ² aliphatic, alicyclic and aryl hydrocarbon radicals in general formula R ¹ C (O) R ² include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert -Butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers, and phenyl, benzyl, cumenyl, mesityl, tolyl, xylyl and phenethyl Is mentioned.

  Representative ketone solubilizers include, but are not limited to, 2-butanone, 2-pentanone, acetophenone, butyrophenone, hexanophenone, cyclohexanone, cycloheptanone, 2-heptanone, 3-heptanone, 5-methyl-2- Hexanone, 2-octanone, 3-octanone, diisobutyl ketone, 4-ethylcyclohexanone, 2-nonanone, 5-nonanone, 2-decanone, 4-decanone, 2-decanone, 2-tridecanone, dihexyl ketone and dicyclohexyl ketone. .

The nitrile solubilizers of the present invention are represented by the formula R ¹ CN, wherein R ¹ is selected from aliphatic, alicyclic or aryl hydrocarbon radicals having 5 to 12 carbon atoms. A nitrile, wherein the nitrile has a molecular weight of from about 90 to about 200 atomic mass units. R ¹ in the nitrile solubilizer is preferably selected from aliphatic and alicyclic hydrocarbon radicals having 8 to 10 carbon atoms. The molecular weight of the nitrile solubilizer is preferably about 120 to about 140 atomic mass units. R ¹ may optionally include a substituted hydrocarbon radical, ie, a radical containing a non-hydrocarbon substituent selected from halogen (eg, fluorine, chlorine) and alkoxide (eg, methoxy). R ¹ optionally contains a heteroatom-substituted hydrocarbon radical, ie atomic nitrogen (aza-), oxygen (keto-, oxa-) or sulfur (thia-) in the radical chain, and so on. Otherwise it may contain radicals composed of carbon atoms. Usually, no more than 3 non-hydrocarbon substituents and heteroatoms, and preferably no more than 1 will be present for every 10 carbon atoms in R ¹ , and any of such non-hydrocarbon substituents And the presence of heteroatoms must be considered in the application of the aforementioned molecular weight limits. Representative R ¹ aliphatic, alicyclic and aryl hydrocarbon radicals in general formula R ¹ CN include pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, Dodecyl and their configurational isomers, as well as phenyl, benzyl, cumenyl, mesityl, tolyl, xylyl and phenethyl.

  Exemplary nitrile solubilizers include, but are not limited to, 1-cyanopentane, 2,2-dimethyl-4-cyanopentane, 1-cyanohexane, 1-cyanoheptane, 1-cyanooctane, 2-cyanooctane, Examples include 1-cyanononane, 1-cyanodecane, 2-cyanodecane, 1-cyanoundecane and 1-cyanododecane.

The chlorocarbon solubilizer of the present invention has the formula RCl _x , where x is an integer selected from 1 or 2; R is an aliphatic and alicyclic hydrocarbon having 1 to 12 carbon atoms Selected from radicals), wherein the chlorocarbon has a molecular weight of from about 100 to about 200 atomic mass units. The molecular weight of the chlorocarbon solubilizer is preferably about 120 to 150 atomic mass units. Representative R aliphatic and alicyclic hydrocarbon radicals in general formula RCl _x include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert- Examples include pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers.

  Representative chlorocarbon solubilizers include, but are not limited to, 3- (chloromethyl) pentane, 3-chloro-3-methylpentane, 1-chlorohexane, 1,6-dichlorohexane, 1-chloroheptane, 1 -Chlorooctane, 1-chlorononane, 1-chlorodecane, and 1,1,1-trichlorodecane.

The ester solubilizers of the present invention have the general formula R ¹ CO ₂ R ² , wherein R ¹ and R ² are independently selected from linear and cyclic, saturated and unsaturated, alkyl and aryl radicals Including the ester represented by Preferred esters composed essentially of the elements C, H, and O have a molecular weight of about 80 to about 550 atomic mass units.

Representative esters include, but are not limited to:
_{(CH 3) 2 CHCH 2 OOC} (CH 2) 2-4 OCOCH 2 CH (CH 3) 2 ( diisobutyl dibasic ester), ethyl hexanoate, ethyl heptanoate, n- butyl propionate, n- propyl propionate, ethyl benzoate, di -n- propyl phthalate, benzoic acid ethoxyethyl ester, dipropyl carbonate, "Ekuseto (Exxate) 700" (a commercial C ₇ alkyl acetate), "Ekuseto (Exxate) 800" (commercially available C ₈ alkyl acetate), dibutyl phthalate, and acetic acid tert- butyl.

  The lactone solubilizer of the present invention comprises a lactone represented by the structures [A], [B], and [C].

These lactones contain the functional group —CO ₂ — in a ring of 6 (A), or preferably 5 atoms (B), where for structures [A] and [B] ₁ to R ₈ are independently selected from hydrogen or linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals. Each R ₁ to R ₈ can be connected to the other R ₁ to R ₈ to form a ring. The lactone is exocyclic as in structure [C], wherein R ₁ to R ₆ are independently selected from hydrogen or linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals. It may have an alkylidene group. Each R ₁ to R ₆ can be connected to the other R ₁ to R ₆ to form a ring. The lactone solubilizer has a molecular weight range of about 80 to about 300 atomic mass units, preferably about 80 to about 200 atomic mass units.

  Representative lactone solubilizers include, but are not limited to, the compounds listed in Table 6.

  Lactone solubilizers generally have a kinematic viscosity at 40 ° C. of less than about 7 centistokes. For example, γ-undecalactone has a kinematic viscosity of 5.4 centistokes and cis- (3-hexyl-5-methyl) dihydrofuran-2-one has a viscosity of 4.5 centistokes. (Both at 40 ° C.). Lactone solubilizers can be commercially available or are prepared by the method described in US Pat. No. 5,047,028 filed Aug. 3, 2004, which is incorporated herein by reference. obtain.

The aryl ether solubilizers of the present invention have the formula R ¹ OR ² , wherein R ¹ is selected from aryl hydrocarbon radicals having 6 to 12 carbon atoms; R ² is 1 to 4 carbons Selected from aliphatic hydrocarbon radicals having atoms, wherein the aryl ether has a molecular weight of from about 100 to about 150 atomic mass units. Representative R ¹ aryl radicals in the general formula R ¹ OR ² include phenyl, biphenyl, cumenyl, mesityl, tolyl, xylyl, naphthyl and pyridyl. Representative R ² aliphatic hydrocarbon radicals in the general formula R ¹ OR ² include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl. Representative aromatic ether solubilizers include, but are not limited to, methyl phenyl ether (anisole), 1,3-dimethoxybenzene, ethyl phenyl ether, and butyl phenyl ether.

The fluoroether solubilizer of the present invention has the general formula R ¹ OCF ₂ CF ₂ H where R ¹ is an aliphatic, alicyclic, and aromatic hydrocarbon having from about 5 to about 15 carbon atoms. Selected from radicals, preferably primary, linear, saturated, alkyl radicals). Exemplary fluoroether solubilizers include, but are not limited to, C ₈ H ₁₇ OCF ₂ CF ₂ H and C ₆ H ₁₃ OCF ₂ CF ₂ H. It should be noted that when the refrigerant is a fluoroether, the solubilizer cannot be the same fluoroether.

The fluoroether solubilizer can further comprise ethers derived from fluoroolefins and polyols. The fluoroolefin is of the type CF ₂ = CXY where X is hydrogen, chlorine or fluorine, and Y is chlorine, fluorine, CF ₃ or OR _{f where} R _f is CF ₃ , C ₂ F ₅ , Or C ₃ F ₇ )). Exemplary fluoroolefins are tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, and perfluoromethyl vinyl ether. The polyol can be linear or branched. Linear polyols are of the type HOCH ₂ (CHOH) _x (CRR ′) _y CH ₂ OH, where R and R ′ are hydrogen, or CH ₃ , or C ₂ H ₅ , and x is 0 An integer from ˜4, and y is an integer from 0 to 4. The branched polyol may be of the type C (OH) _t (R) _u (CH ₂ OH) _v [(CH ₂ ) _m CH ₂ OH] _{w where} R is hydrogen, CH ₃ or C ₂ H ₅ , m may be an integer from 0 to 3, t and u may be 0 or 1, and v and w may be from 0 to 4 and also t + u + v + w = 4). Typical polyols are trimethylolpropane, pentaerythritol, butanediol, and ethylene glycol.

The 1,1,1-trifluoroalkane solubilizer of the present invention has the general formula CF ₃ R ¹ , wherein R ¹ is an aliphatic and alicyclic hydrocarbon having from about 5 to about 15 carbon atoms. Selected from radicals, preferably primary, straight-chain, saturated alkyl radicals). Representative 1,1,1-trifluoroalkane solubilizers include, but are not limited to, 1,1,1-trifluorohexane and 1,1,1-trifluorododecane.

  The solubilizers of the invention can exist as a single compound or as a mixture of two or more solubilizers. A mixture of solubilizers may contain two solubilizers from the same class of compounds, such as two lactones, or from two different classes such as lactones and polyoxyalkylene glycol ethers. It may contain seed solubilizers.

  In the present compositions comprising a refrigerant and a UV fluorescent dye, or comprising a heat transfer fluid and a UV fluorescent dye, from about 0.001 weight percent to about 1.0 weight percent composition, preferably from about 0.005 weight percent to About 0.5 weight percent, and most preferably 0.01 weight percent to about 0.25 weight percent is UV dye.

  The solubility of these UV fluorescent dyes in the refrigerant and heat transfer composition may be poor. Thus, the method of introducing these dyes into refrigeration, air conditioning, or heat pump equipment has been cumbersome, expensive, and time consuming. U.S. Pat. No. 6,057,028, incorporated herein by reference, describes a method using dye powder, dye solid pellets or slurries that can be inserted into components of a refrigeration or air conditioner. As refrigerant and lubricant are circulated through the device, the dye is dissolved or dispersed and transported throughout the device. Numerous other methods for introducing dyes into refrigeration or air conditioners are described in this document.

  Ideally, the UV fluorescent dye can be dissolved in the refrigerant itself, so that no special methods are required for introduction into the refrigeration, air conditioning, or heat pump apparatus. The present invention relates to a composition comprising a UV fluorescent dye that can be introduced into a system in a refrigerant in combination with a solubilizer. The composition of the present invention will enable storage and transport of dye-containing refrigerants and heat transfer fluids while maintaining the dye in solution, even at low temperatures.

  In the present composition comprising a refrigerant, a UV fluorescent dye and a solubilizing agent, or comprising a heat transfer fluid and a UV fluorescent dye and a solubilizing agent, from about 1 to about 50 weight percent, preferably from about 2 to about 25 weight percent, and Most preferably from about 5 to about 15 weight percent of the combined composition is a solubilizer in the refrigerant or heat transfer fluid. In the composition of the present invention, the UV fluorescent dye is present in the refrigerant at a concentration of about 0.001 weight percent to about 1.0 weight percent, or of the heat transfer fluid, preferably 0.005 weight percent to about 0.5. It is present in a concentration by weight percent, and most preferably from 0.01 weight percent to about 0.25 weight percent.

  Solubilizers such as ketones can have an undesirable odor that can be masked by the addition of odor masking agents or fragrances. Typical examples of odor masking or fragrances include Evergreen, Fresh Lemon, Cherry, Cinnamon, Peppermint, Floral or Orange Peel (Floral) Orange Peel) (all of which are commercially available), and d-limonene and pinene. Such odor masking agents may be used at a concentration of about 0.001% to about 15% by weight, based on the combined weight of the odor masking agent and solubilizer.

  The invention further relates to a method of using a refrigerant or heat transfer fluid composition comprising an ultraviolet fluorescent dye for detecting leakage in a refrigeration apparatus, air conditioning apparatus, or heat pump apparatus. The presence of the dye in the composition allows detection of refrigerant leakage in refrigeration, air conditioning, or heat pump equipment. Leakage detection assists in addressing the resolution and / or prevention of inefficient operation of device or system or instrument destruction. Leak detection also assists in the inclusion of chemicals used in the operation of the device.

  The method comprises, as described herein, a refrigerant, a composition comprising an ultraviolet fluorescent dye or a composition comprising a heat transfer fluid and a UV fluorescent dye, and optionally, a solubilizer described herein. Providing to a refrigeration, air conditioning, or heat pump device, and utilizing a suitable means for detecting a UV fluorescent dye-containing refrigerant. Suitable means for detecting the dye include, but are not limited to, an ultraviolet lamp often referred to as “black light” or “blue light”. Such ultraviolet lamps are designed for the purpose of detecting UV fluorescent dyes and are commercially available from a number of suppliers. Once the ultraviolet fluorescent dye-containing composition is introduced into a refrigeration, air conditioning, or heat pump device and circulated throughout the system, the ultraviolet lamp illuminates the device and observes the fluorescence of the dye near one of the leak points Thus, it is possible to specify the leakage point or the position in the vicinity of the leakage point.

  Mechanical refrigeration is essentially a thermodynamic application, where a cooling medium, such as a refrigerant, passes through a cycle so that it can be recovered for reuse. Commonly used cycles include vapor compression, absorption, vapor jet or vapor ejector, and air.

  Vapor compression refrigeration systems include evaporators, compressors, condensers, and expansion devices. The vapor compression cycle reuses refrigerant in a multi-stage step that provides a cooling effect in one step and heat in another step. The cycle can simply be described as follows. The liquid refrigerant enters the evaporator through the expansion device, and the liquid refrigerant boils at low temperatures in the evaporator to form gas and provide cooling. The low pressure gas enters the compressor, where it is compressed to increase its pressure and temperature. High pressure (compressed) gaseous refrigerant then enters the condenser, where it is condensed and releases its heat to the environment. The refrigerant returns to the expansion device, through which the liquid is expanded from the high pressure level in the condenser to the low pressure level in the evaporator, thereby repeating the cycle.

  There are various types of compressors that can be used in refrigeration applications. Compressors generally depend on the mechanical means that compresses the fluid, as a reciprocating, rotary, jet, centrifugal, scroll, screw or axial flow, or on how the mechanical elements act on the fluid being compressed. And can be classified as volumetric (eg, reciprocal, scroll or screw) or dynamic (eg, centrifugal or jet).

  The compositions of the present invention comprising a fluoroolefin can be useful in any of the compressor types described above. The choice of refrigerant for any given compressor will depend on many factors including, for example, boiling point and vapor pressure requirements.

  Either positive displacement or dynamic compressors can be used in the process of the present invention. Centrifugal type compressors are one preferred type of instrument for certain refrigerant compositions comprising at least one fluoroolefin.

  Centrifugal compressors use rotating elements to accelerate the refrigerant radially, and typically include an impeller and diffuser housed in a housing. Centrifugal compressors typically send fluid to the impeller eye of a rotating impeller, or central inlet, and accelerate it radially outward. Although some static pressure increase occurs in the impeller, most pressure increases occur in the diffuser section of the housing, where the speed is converted to static pressure. Each impeller-diffuser set is a compressor stage. Centrifugal compressors are incorporated in 1 to 12 or more stages, depending on the final pressure desired and the volume of refrigerant being handled.

  The compressor pressure ratio, or compression ratio, is the ratio of absolute discharge pressure to absolute inlet pressure. The pressure provided by the centrifugal compressor is substantially constant over a relatively wide range of volumes.

  A positive displacement compressor draws steam into the chamber and the chamber reduces the volume and compresses the steam. After being compressed, the steam is pushed out of the chamber by reducing the chamber's further volume to zero or nearly zero. Positive displacement compressors can increase pressure, and pressure is limited only by volumetric efficiency and component pressure strength.

  Unlike positive displacement compressors, centrifugal compressors rely entirely on the centrifugal force of the high speed impeller to compress the steam passing through the impeller. There is no volume type, but there is what is called dynamic compression.

  The pressure that the centrifugal compressor can generate depends on the tip speed of the impeller. The tip speed is the speed measured at the tip of the impeller and is related to the diameter of the impeller and the rotational speed per minute. The pressurizing capacity of a centrifugal compressor is determined by the size of the flow path through the impeller. This makes the size of the compressor more dependent on the pressure required than the pressure capacity.

  Due to its high speed operation, centrifugal compressors are inherently large volume, low pressure machines. Centrifugal compressors work best with low pressure refrigerants such as trichlorofluoromethane (CFC-11) or 1,2,2-trichlorotrifluoroethane (CFC-113). Some of the low pressure refrigerant fluids of the present invention may be suitable as alternative droplets for CFC-113 in existing centrifuge instruments.

  Large centrifugal compressors typically operate at 3000 to 7000 revolutions per minute (rpm). Small turbine centrifugal compressors (mini-centrifugal compressors) are designed for high speeds, such as about 40,000 to about 70,000 (rpm) and are typically small impellers of less than 0.15 meters (about 6 inches). Have a size.

  Multi-stage impellers can be used in centrifugal compressors to improve compressor efficiency, thereby reducing the power required in use. For the two-stage system, during operation, the discharge of the first stage impeller is directed to the suction and suction of the second impeller. Both impellers can be operated by the use of a single shaft (or shaft). Each stage can provide a compression ratio of about 4 to 1, that is, the absolute discharge pressure can be four times the absolute suction pressure. Numerous examples of two-stage centrifugal compressor systems, especially for automotive applications, are described in US Pat. Yes.

The present disclosure further relates to a method of heating or effecting in a refrigeration, air conditioning, or heat pump apparatus, the method comprising: (a) a centrifugal compressor; (b) a multi-stage centrifugal compressor; or (c) a single A slab / single pass heat exchanger, wherein the refrigerant or heat transfer fluid composition comprises:
(I) a fluoroolefin of formula E—R ¹ CH═CHR ² or Z—R ¹ CH═CHR ² , wherein R ¹ and R ² are independently C ₁ -C ₆ perfluoro A fluoroolefin which is an alkyl group;
(Ii) a cyclic fluoroolefin of formula cyclo- [CX = CY (CZW) _n- ], wherein X, Y, Z, and W are independently H or F, and n is A cyclic fluoroolefin which is an integer from 2 to 5; or (iii) 1,2,3,3,3-pentafluoro-1-propene (CF ₃ CF═CHF); 1,1,3,3,3-penta fluoro-1-propene _{(CF 3 CH = CF 2)} ; 1,1,2,3,3- pentafluoro-1-propene _{(CHF 2 CF = CF 2)} ; 1,2,3,3- tetrafluoro - 1-propene (CHF ₂ CF═CHF); 2,3,3,3-tetrafluoro-1-propene (CF ₃ CF═CH ₂ ); 1,3,3,3-tetrafluoro-1-propene (CF ₃ CH = CHF); 1,1,2,3- tetrafluoro-1 Ropen _{(CH 2 FCF = CF 2)} ; 1,1,3,3- tetrafluoro-1-propene _{(CHF 2 CH = CF 2)} ; 2,3,3- trifluoro-1-propene (CHF ₂ CF = CH ₂ ); 3,3,3-trifluoro-1-propene (CF ₃ CH═CH ₂ ); 1,1,2-trifluoro-1-propene (CH ₃ CF═CF ₂ ); 1,1, 3-trifluoro-1-propene (CH ₂ FCH═CF ₂ ); 1,2,3-trifluoro-1-propene (CH ₂ FCF═CHF); 1,3,3-trifluoro-1-propene ( CHF ₂ CH = CHF); 1,1,1,2,3,4,4,4- octafluoro-2-butene _{(CF 3 CF = CFCF 3)} ; 1,1,2,3,3,4, 4,4 octafluoro-1-butene _{(CF 3 CF 2 CF = CF} 2); 1,1, , 2,4,4,4-heptafluoro-2-butene _{(CF 3 CF = CHCF 3)} ; 1,2,3,3,4,4,4- heptafluoro-1-butene (CHF = CFCF ₂ CF ₃ ); 1,1,1,2,3,4,4-heptafluoro-2-butene (CHF ₂ CF═CFCF ₃ ); 1,3,3,3-tetrafluoro-2- (trifluoromethyl) -1-propene ((CF ₃ ) ₂ C═CHF); 1,1,3,3,4,4,4-heptafluoro-1-butene (CF ₂ ═CHCF ₂ CF ₃ ); 1,1,2, , 3,4,4,4-heptafluoro-1-butene _{(CF 2 = CFCHFCF 3);} 1,1,2,3,3,4,4- heptafluoro-1-butene (CF ₂ = CFCF ₂ CHF ₂ ); 2,3,3,4,4,4-hexafluoro-1-butene (CF ₃ CF ₂ CF═C H ₂ ); 1,3,3,4,4,4-hexafluoro-1-butene (CHF═CHCF ₂ CF ₃ ); 1,2,3,4,4,4-hexafluoro-1-butene ( CHF = CFCHFCF ₃ ); 1,2,3,3,4,4-hexafluoro-1-butene (CHF═CFCF ₂ CHF ₂ ); 1,1,2,3,4,4-hexafluoro-2- butene _{(CHF 2 CF = CFCHF 2)} ; 1,1,1,2,3,4- hexafluoro-2-butene _{(CH 2 FCF = CFCF 3)} ; 1,1,1,2,4,4- hexa Fluoro-2-butene (CHF ₂ CH═CFCF ₃ ); 1,1,1,3,4,4-hexafluoro-2-butene (CF ₃ CH═CFCHF ₂ ); 1,1,2,3,3 , 4-hexafluoro-1-butene _{(CF 2 = CFCF 2 CH 2} F); 1,1,2, , 4,4-hexafluoro-1-butene _{(CF 2 = CFCHFCHF 2);} 3,3,3- trifluoro-2- (trifluoromethyl) -1-propene _{(CH 2 = C (CF 3} ) 2) 1,1,1,2,4-pentafluoro-2-butene (CH ₂ FCH═CFCF ₃ ); 1,1,1,3,4-pentafluoro-2-butene (CF ₃ CH═CFCH ₂ F) ); 3,3,4,4,4-pentafluoro-1-butene (CF ₃ CF ₂ CH═CH ₂ ); 1,1,1,4,4-pentafluoro-2-butene (CHF ₂ CH═) CHCF ₃ ); 1,1,1,2,3-pentafluoro-2-butene (CH ₃ CF═CFCF ₃ ); 2,3,3,4,4-pentafluoro-1-butene (CH ₂ ═CFCF) ₂ CHF _2); 1,1,2,4,4- pentafluoro-2-butene _{CHF 2 CF = CHCHF 2);} 1,1,2,3,3- pentafluoro-1-butene _{(CH 3 CF 2 CF = CF} 2); 1,1,2,3,4- pentafluoro-2- butene _{(CH 2 FCF = CFCHF 2)} ; 1,1,3,3,3- pentafluoro-2-methyl-1-propene _{(CF 2 = C (CF 3} ) (CH 3)); 2- ( difluoromethyl ) -3,3,3-trifluoro-1-propene _{(CH 2 = C (CHF 2} ) (CF 3)); 2,3,4,4,4- pentafluoro-1-butene (CH ₂ = CFCHFCF _3); 1,2,4,4,4- pentafluoro-1-butene _{(CHF = CFCH 2 CF 3)} ; 1,3,4,4,4- pentafluoro-1-butene (CHF = CHCHFCF ₃₎ 1,3,3,4,4-pentafluoro-1-butene (CHF = CHCF ₂ CHF ₂ ); 1,2,3,4,4-pentafluoro-1-butene (CHF═CFCHFCHF ₂ ); 3,3,4,4-tetrafluoro-1-butene (CH ₂ ═CHCF ₂ CHF) ₂ ); 1,1-difluoro-2- (difluoromethyl) -1-propene (CF ₂ ═C (CHF ₂ ) (CH ₃ )); 1,3,3,3-tetrafluoro-2-methyl-1 - propene _{(CHF = C (CF 3)} (CH 3)); 2- difluoromethyl-3,3-difluoro-1-propene _{(CH 2 = C (CHF 2} ) 2); 1,1,1,2- Tetrafluoro-2-butene (CF ₃ CF═CHCH ₃ ); 1,1,1,3-tetrafluoro-2-butene (CH ₃ CF═CHCF ₃ ); 1,1,1,2,3,4, 4,5,5,5-decafluoro-2-pentene (CF ₃ CF = FCF ₂ CF _3); 1,1,2,3,3,4,4,5,5,5- decafluoro-1-pentene _{(CF 2 = CFCF 2 CF 2} CF 3); 1,1,1, 4,4,4-hexafluoro-2- (trifluoromethyl) -2-butene ((CF ₃ ) ₂ C═CHCF ₃ ); 1,1,1,2,4,4,5,5,5- nonafluoro-2-pentene _{(CF 3 CF = CHCF 2 CF} 3); 1,1,1,3,4,4,5,5,5- nonafluoro-2-pentene _{(CF 3 CH = CFCF 2 CF} 3); 1,2,3,3,4,4,5,5,5- nonafluoro-1-pentene _{(CHF = CFCF 2 CF 2 CF} 3); 1,1,3,3,4,4,5,5, 5-nonafluoro-1-pentene _{(CF 2 = CHCF 2 CF 2} CF 3); 1,1,2,3,3,4,4,5,5- Nonafuruo 1-pentene _{(CF 2 = CFCF 2 CF 2} CHF 2); 1,1,2,3,4,4,5,5,5- nonafluoro-2-pentene _{(CHF 2 CF = CFCF 2 CF} 3); 1,1,1,2,3,4,4,5
, 5-nonafluoro-2-pentene _{(CF 3 CF = CFCF 2 CHF} 2); 1,1,1,2,3,4,5,5,5- nonafluoro-2-pentene (CF ₃ CF = CFCHFCF ₃₎ 1,2,3,4,4,4-hexafluoro-3- (trifluoromethyl) -1-butene (CHF = CFCF (CF ₃ ) ₂ ); 1,1,2,4,4,4- Hexafluoro-3- (trifluoromethyl) -1-butene (CF ₂ = CFCH (CF ₃ ) ₂ ); 1,1,1,4,4,4-hexafluoro-2- (trifluoromethyl) -2 - butene _{(CF 3 CH = C (CF} 3) 2); 1,1,3,4,4,4- hexafluoro-3- (trifluoromethyl) -1-butene _{(CF 2 = CHCF (CF 3} ) _2); 2,3,3,4,4,5,5,5- octafluoro-1-pentene Emissions _{(CH 2 = CFCF 2 CF 2} CF 3); 1,2,3,3,4,4,5,5- octafluoro-1-pentene _{(CHF = CFCF 2 CF 2 CHF} 2); 3,3, 4,4,4-pentafluoro-2- (trifluoromethyl) -1-butene _{(CH 2 = C (CF 3} ) CF 2 CF 3); 1,1,4,4,4- pentafluoro-3- (Trifluoromethyl) -1-butene (CF ₂ ═CHCH (CF ₃ ) ₂ ); 1,3,4,4,4-pentafluoro-3- (trifluoromethyl) -1-butene (CHF═CHCF ( CF ₃ ) ₂ ); 1,1,4,4,4-pentafluoro-2- (trifluoromethyl) -1-butene (CF ₂ ═C (CF ₃ ) CH ₂ CF ₃ ); , 4-tetrafluoro-3- (trifluoromethyl) -1-butene ((CF _{3) 2} CF H = CH _2); 3,3,4,4,5,5,5- heptafluoro-1-pentene _{(CF 3 CF 2 CF 2 CH} = CH 2); 2,3,3,4,4,5 , 5-heptafluoro-1-pentene _{(CH 2 = CFCF 2 CF 2} CHF 2); 1,1,3,3,5,5,5- heptafluoro-1-butene _{(CF 2 = CHCF 2 CH 2} CF _3); 1,1,1,2,4,4,4-heptafluoro-3-methyl-2-butene _{(CF 3 CF = C (CF} 3) (CH 3)); 2,4,4,4 - tetrafluoro-3- (trifluoromethyl) -1-butene _{(CH 2 = CFCH (CF 3} ) 2); 1,4,4,4- tetrafluoro-3- (trifluoromethyl) -1-butene ( CHF = CHCH (CF ₃ ) ₂ ); 1,1,1,4-tetrafluoro-2- (trifluoromethyl) -2 - butene _{(CH 2 FCH = C (CF} 3) 2); 1,1,1,3- tetrafluoro-2- (trifluoromethyl) -2-butene _{(CH 3 CF = C (CF} 3) 2); 1,1,1-trifluoro-2- (trifluoromethyl) -2-butene ((CF ₃ ) ₂ C═CHCH ₃ ); 3,4,4,5,5,5-hexafluoro-2-pentene (CF ₃ CF ₂ CF═CHCH ₃ ); 1,1,1,4,4,4-hexafluoro-2-methyl-2-butene (CF ₃ C (CH ₃ ) ═CHCF ₃ ); 4,5,5,5-hexafluoro-1-pentene (CH ₂ ═CHCF ₂ CHFCF ₃ ); 3- (trifluoromethyl) -4,4,4-trifluoro-1-butene (CH ₂ ═C ( _{CF 3) CH 2 CF 3)} ; 1,1,2,3,3,4,4,5,5,6,6,6- de de Fluoro-1-hexene _{(CF 3 (CF 2) 3} CF = CF 2); 1,1,1,2,2,3,4,5,5,6,6,6- dodecafluoro-3- hexene ( CF ₃ CF ₂ CF═CFCF ₂ CF ₃ ); 1,1,1,4,4,4-hexafluoro-2,3-bis (trifluoromethyl) -2-butene ((CF ₃ ) ₂ C═C (CF ₃ ) ₂ ); 1,1,1,2,3,4,5,5,5-nonafluoro-4- (trifluoromethyl) -2-pentene ((CF ₃ ) ₂ CFCF═CFCF ₃ ); 1,1,1,4,4,5,5,5-octafluoro-2- (trifluoromethyl) -2-pentene ((CF ₃ ) ₂ C═CHC ₂ F ₅ ); 1,1,1, 3,4,5,5,5- octafluoro-4- (trifluoromethyl) -2-pentene _{((CF 3) 2 CFCF =} CHC _3); 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene _{(CF 3 CF 2 CF 2 CF} 2 CH = CH 2); 4,4,4- trifluoro - 3,3-bis (trifluoromethyl) -1-butene (CH ₂ ═CHC (CF ₃ ) ₃ ); 1,1,1,4,4,4-hexafluoro-3-methyl-2- (trifluoro Methyl) -2-butene ((CF ₃ ) ₂ C═C (CH ₃ ) (CF ₃ )); 2,3,3,5,5,5-hexafluoro-4- (trifluoromethyl) -1- pentene _{(CH 2 = CFCF 2 CH (} CF 3) 2); 1,1,1,2,4,4,5,5,5- nonafluoro-3-methyl-2-pentene (CF ₃ CF = C (CH ₃ ) CF ₂ CF ₃ ); 1,1,1,5,5,5-hexafluoro-4- (trifluoromethyl) -2-pentene ( _{CF 3 CH = CHCH (CF 3} ) 2); 3,4,4,5,5,6,6,6- octafluoro-2-hexene _{(CF 3 CF 2 CF 2 CF} = CHCH 3); 3,3 , 4,4,5,5,6,6- octafluoro-1-hexene _{(CH 2 = CHCF 2 CF 2} CF 2 CHF 2); 1,1,1,4,4- pentafluoro-2- (tri Fluoromethyl) -2-pentene ((CF ₃ ) ₂ C═CHCF ₂ CH ₃ ); 4,4,5,5,5-pentafluoro-2- (trifluoromethyl) -1-pentene (CH ₂ ═C (CF ₃ ) CH ₂ C ₂ F ₅ ); 3,3,4,4,5,5,5-heptafluoro-2-methyl-1-pentene (CF ₃ CF ₂ CF ₂ C (CH ₃ ) ═CH _2); 4,4,5,5,6,6,6- heptafluoro-2-hexene _{(CF 3 CF 2 CF 2 CH} = C CH _3); 4,4,5,5,6,6,6- heptafluoro-1-hexene _{(CH 2 = CHCH 2 CF 2} C 2 F 5); 1,1,1,2,2,3, 4 heptafluoro-3- hexene _{(CF 3 CF 2 CF = CFC} 2 H 5); 4,5,5,5- tetrafluoro-4-trifluoromethyl-1-pentene _{(CH 2 = CHCH 2 CF (} CF ₃ ) ₂ ); 1,1,1,2,5,5,5-heptafluoro-4-methyl-2-pentene (CF ₃ CF═CHCH (CF ₃ ) (CH ₃ )); 1,1,1 , 3-Tetrafluoro-2-trifluoromethyl-2-pentene ((CF ₃ ) ₂ C═CFC ₂ H ₅ ); 1,1,1,2,3,4,4,5,5,6,6 , 7,7,7- tetra deca fluoro-2-heptene _{(CF 3 CF = CFCF 2 CF} 2 C 2 F 5); 1,1,1,2 2,3,4,5,5,6,6,7,7,7- tetradecanoyl-fluoro-3- heptene _{(CF 3 CF 2 CF = CFCF} 2 C 2 F 5); 1,1,1,3, 4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene _{(CF 3 CH = CFCF 2 CF} 2 C 2 F 5); 1,1,1,2,4, 4,5,5,6,6,7,7,7- tridecafluoro-2-heptene _{(CF 3 CF = CHCF 2 CF} 2 C 2 F 5); 1,1,1,2,2,4, 5,5,6,6,7,7,7- tridecafluoro-3-heptene _{(CF 3 CF 2 CH = CFCF} 2 C 2 F 5); 1,1,1,2,2,3,5, 5,6,6,7,7,7- tridecafluoro-3-heptene _{(CF 3 CF 2 CF = CHCF} 2 C 2 F 5); CF 2 = CFOCF 2 CF 3 (PEVE); CF 2 = CFOC A fluoroolefin selected from the group consisting of F ₃ (PMVE) and combinations thereof;
At least one fluoroolefin selected from the group consisting of:

  Methods that provide heating or cooling can be used in fixed air conditioning, heat pumps or portable air conditioning and refrigeration systems. Fixed air conditioning and heat pump applications include windows, ductless, duct, terminal type packages, chillers and commercial machines, including rooftop type packages. Refrigeration applications include indoor or household refrigerators and freezers, ice machines, built-in coolers and freezers, walk-in coolers and freezers and transport refrigeration systems.

  The compositions of the present invention can further be used in air conditioning, heating and refrigeration systems using fin and tube heat exchangers, microchannel heat exchangers and vertical or horizontal single pass tube or plate type heat exchangers.

  Conventional microchannel heat exchangers may not be ideal for the low pressure refrigerant composition of the present invention. Low operating pressure and density results in high flow rates and high friction losses in all components. In these cases, the evaporator design can be changed. A single slab / single pass heat exchanger arrangement may be used rather than a number of microchannel slabs connected in sequence (with respect to the refrigerant path). Accordingly, a preferred heat exchanger for the refrigerant or heat transfer fluid composition of the present invention is a single slab / single pass heat exchanger.

  The present invention further relates to a method for effecting cooling comprising the steps of evaporating the fluoroolefin composition of the present invention in the vicinity of the object to be cooled and then condensing said composition.

  The present invention further relates to a method of heating comprising the steps of condensing the fluoroolefin composition of the present invention in the vicinity of the object to be heated and then evaporating the composition.

  The invention comprises compressing a composition comprising at least one fluoroolefin in a centrifugal compressor, condensing the composition, and then evaporating the composition in the vicinity of the object to be cooled. Further relates to the method of bringing in. Furthermore, the centrifugal compressor of the method of the invention can be a multi-stage centrifugal compressor and preferably a two-stage centrifugal compressor.

  The present invention further relates to a method of providing cooling in a refrigeration apparatus, air conditioning apparatus or heat pump apparatus, wherein said apparatus comprises at least one single slab / single pass heat exchanger, said method comprising the composition of the present invention. Condensing the material and then evaporating the composition in the vicinity of the object to be cooled.

  The compositions of the present invention are particularly useful in small turbine centrifugal compressors (mini-centrifugal compressors) that can be used in automatic and window air conditioning, heat pumps, or transport refrigeration, and other applications. These high efficiency mini centrifugal compressors can be driven by an electric motor and can therefore be driven independently of the engine speed. A constant compressor speed allows the system to provide a relatively constant cooling capacity at all engine speeds. This provides an opportunity for increased efficiency at a particularly good high engine speed compared to conventional R-134a automotive air conditioning systems. The advantages of these low pressure systems are greater when considering the cycling of conventional systems at high drive speeds.

  Alternatively, rather than using electric power, the mini centrifugal compressor can be operated by a ratio gear drive assembly comprising an engine exhaust gas driven turbine or a ratio belt drive. While the power available in current automotive designs is about 14 volts, the new mini-centrifugal compressor requires about 50 volts of power. Thus, it may be advantageous to use an alternative power source. A refrigeration system or air conditioning system powered by an engine exhaust gas driven turbine is described in detail in US Patent Publication (Patent Document 7) filed on March 3, 2006. A refrigeration apparatus or air conditioner powered by a ratio gear drive assembly is described in detail in US Pat.

  The present invention includes compressing the composition of the present invention in a mini-centrifugal compressor powered by an engine exhaust gas driven turbine; condensing the composition; and then proximate the object to be cooled Further relates to a method for providing cooling comprising an evaporation step.

  The present invention includes compressing the composition of the present invention in a mini-centrifugal compressor powered by a ratio gear drive assembly having a ratio belt drive; condensing the composition; and then cooling the composition It further relates to a method for providing cooling comprising the step of evaporating in the vicinity of the object.

  The present invention relates to a method for providing cooling in a refrigeration apparatus, air conditioning apparatus or heat pump apparatus, wherein said apparatus comprises at least one single slab / single pass heat exchanger, said method comprising a composition of the present invention. Compressing in a centrifugal compressor, condensing the composition, and then evaporating the composition in the vicinity of the object to be cooled.

  The invention further relates to a method of replacing or replacing a refrigerant composition having a GWP of about 150 or higher, or a high GWP refrigerant with a composition having a lower GWP. One method includes providing an alternative composition comprising at least one fluoroolefin of the present invention. In other embodiments of the present invention, a refrigerant or heat transfer fluid composition of the present invention having a lower GWP than the composition to be replaced or replaced is introduced into a refrigeration, air conditioning or heat pump apparatus. In some cases, the high GWP refrigerant present in the device will need to be removed from the device before introducing the lower GWP composition. In other cases, the fluoroolefin composition of the present invention can be introduced into the apparatus while the high GWP refrigerant is present.

  Global Warming Potential (GWP) is an index for predicting the relative burden of global warming caused by emissions of a particular greenhouse gas into the atmosphere in kilograms compared to the emissions in kilograms of carbon dioxide It is. GWP can be calculated for different time ranges and shows the effect of atmospheric lifetime for a given gas. The GWP for a time range of 100 years is usually the value referenced.

  High GWP refrigerant is any compound capable of functioning as a refrigerant or heat transfer fluid having a GWP of about 1000 or more, or 500 or more, 150 or more, 100 or more, or 50 or more in a time range of 100 years Will. Refrigerants and heat transfer fluids that need to be replaced based on the GWP calculation published by the Intergovernmental Panel on Climate Change (IPCC) are not particularly limited, but include HFC-134a (1,1 1,2-tetrafluoroethane).

  The present invention will provide compositions having zero or low ozone depletion potential and low global warming potential (GWP). The fluoroolefins of the present invention or mixtures of fluoroolefins of the present invention and other refrigerants will have a global warming potential less than many of the currently used hydrofluorocarbon refrigerants. Typically, the fluoroolefins of the present invention are expected to have a GWP of less than about 25. One aspect of the present invention is to provide a refrigerant having a global warming potential of less than 1000, less than 500, less than 150, less than 100, or less than 50. Another aspect of the invention is to reduce the total GWP of the refrigerant mixture by adding a fluoroolefin to the mixture.

  The invention further relates to a method for reducing the GWP of a refrigerant or heat transfer fluid, the method comprising combining the refrigerant or heat transfer fluid with at least one fluoroolefin of the invention. In another embodiment, a method for reducing a global warming potential is suitable for use as a refrigerant or heat transfer fluid in which the first composition is combined with a composition comprising at least one fluoroolefin. Producing a second composition, wherein the second composition has a lower global warming potential than the first composition. It can be seen that the GWP of a mixture or combination of compounds can be calculated as a weight average of GWP for each of the pure compounds.

  The present invention further relates to a method of using the composition of the present invention comprising at least one fluoroolefin to reduce the global warming potential of the original refrigerant or heat transfer fluid composition, said method comprising said original Combining the refrigerant or heat transfer fluid composition with a composition of the invention comprising at least one fluoroolefin to produce a second refrigerant or heat transfer fluid composition, wherein the second The refrigerant or heat transfer fluid composition has a lower global warming potential than the original refrigerant or heat transfer fluid composition.

  The present invention further relates to a method for reducing the GWP of an original refrigerant or heat transfer fluid composition in a refrigeration, air conditioning or heat pump device, wherein the original refrigerant or heat transfer fluid has a GWP of about 150 or more. And said method comprises the step of introducing a second, lower GWP refrigerant or heat transfer fluid composition of the present invention into said refrigeration, air conditioning or heat pump apparatus.

  The present method of reducing the GWP of the original refrigerant removes the original refrigerant or heat transfer fluid composition from the refrigeration, air conditioning or heat pump device before introducing a second, lower GWP refrigerant or heat transfer fluid. The method may further include a step.

  The present invention further relates to a method for exchanging an original refrigerant or heat transfer fluid composition with a second refrigerant or heat transfer fluid composition, wherein the composition of the present invention is used as the second refrigerant or heat transfer fluid composition. Providing a process. The original refrigerant can be any refrigerant used in refrigeration, air conditioning or heat pump devices that need to be replaced.

  The original refrigerant or heat transfer fluid that needs to be replaced can be either a hydrofluorocarbon refrigerant, a chlorofluorocarbon refrigerant, a hydrochlorofluorocarbon, a refrigerant, a fluoroether refrigerant, or a blend of refrigerant compounds.

The hydrofluorocarbon refrigerant of the present invention that may need to be replaced is not particularly limited: CHF ₃ (HFC-23), CH ₂ F ₂ (HFC-32), CH ₃ F (HFC-41), CHF ₂ CF ₃ (HFC-125), CHF ₂ CHF ₂ (HFC-134), CH ₂ FCF ₃ (HFC-134a), CHF ₂ CH ₂ F (HFC 143), CF ₃ CH ₃ (HFC-143a), CHF ₂ CH _{3 (HFC-152a), CH} 2 FCH 3 (HFC-161), CHF 2 CF 2 CF 3 (HFC-227ca), CF 3 CFHCF 3 (HFC-227ea), CHF 2 CF 2 CHF 2 (HFC-236ca) _{, CH 2 FCF 2 CF 3 (} HFC-236cb), CHF 2 CHFCF 3 (HFC-236ea), CF 3 CH 2 CF 3 (HFC-23 _{fa), CH 2 FCF 2 CHF} 2 (HFC-245ca), CH 3 CF 2 CF 3 (HFC-245cb), CHF 2 CHFCHF 2 (HFC-245ea), CH 2 FCHFCF 3 (HFC-245eb), CHF 2 CH ₂ CF ₃ (HFC-245fa), CH ₂ FCF ₂ CH ₂ F (HFC-254ca), CH ₃ CF ₂ CHF ₂ (HFC-254cb), CH ₂ FCHFCHF ₂ (HFC-254ea), CH ₃ CHFCF ₃ (HFC _{-254eb), CHF 2 CH 2 CHF} 2 (HFC-254fa), CH 2 FCH 2 CF 3 (HFC-254fb), CF 3 CH 2 CH 3 (HFC-263fb), CH 3 CF 2 CH 2 F (HFC- _{263ca), CH 3 CF 2 CH} 3 (HFC-272ca), CH 3 CHFCH 2 F (HFC-272e _{), CH 2 FCH 2 CH 2} F (HFC-272fa), CH 3 CH 2 CF 2 H (HFC-272fb), CH 3 CHFCH 3 (HFC-281ea), CH 3 CH 2 CH 2 F (HFC-281fa) _{, CHF 2 CF 2 CF 2 CF} 2 H (HFC-338pcc), CF 3 CH 2 CF 2 CH 3 (HFC-365mfc), CF 3 CHFCHFCF 2 CF 3 (HFC-43-10mee) and the like. These hydrofluorocarbon refrigerants are commercially available or can be prepared by methods known in the art.

  The hydrofluorocarbon refrigerants of the present invention are HFC-125 / HFC-143a / HFC-134a (known by ASHRAE type, R404 or R404A), HFC-32 / HFC-125 / HFC-134a (ASHRAE type, R407 or R407A). , R407B, or R407C), HFC-32 / HFC-125 (R410 or R410A), and HFC-125 / HFC-143a (ASHRAE type: known by R507 or R507A), R413A (R134a / R218) / Isobutane blend), R423A (R134a / R227ea blend), R507A (R125 / R143a blend) and the like may further be included.

The chlorofluorocarbon refrigerants of the present invention that may need to be replaced include R22 (CHF ₂ Cl), R123 (CHCl ₂ CF ₃ ), R124 (CHClFCF ₃ ), R502 (CFC-115 (CClF ₂ CF ₃ ) and R22. And R503 (which is a blend of R23 / R13 (CClF ₃ )).

The hydrochlorofluorocarbons of the present invention that may need to be exchanged include R12 (CF ₂ Cl ₂ ), R11 (CCl ₃ F), R113 (CCl ₂ FCClF ₂ ), R114 (CF ₂ ClCF ₂ Cl), R401A or R401B (A blend of R22 / R152a / R124), R408A (a blend of R22 / R125 / R143a) and the like.

The fluoroether refrigerants of the present invention that may need to be replaced can include compounds similar to hydrofluorocarbons that also contain at least one ether group oxygen atom. Fluoroether refrigerants include, but are not limited to, C ₄ F ₉ OCH ₃ and C ₄ F ₉ OC ₂ H ₅ (both commercially available).

The original refrigerant or heat transfer fluid composition of the present invention that may need to be replaced is optionally 10 weight percent or less of dimethyl ether, or at least one C _{3 to} C ₅ hydrocarbon, such as propane, propylene. And a combination of refrigerants containing cyclopropane, n-butane, isobutane, n-pentane, cyclopentane and neopentane (2,2-dimethylpropane). Examples of refrigerants containing such C ₃ -C ₅ hydrocarbons are HCFC-22 / HFC-125 / propane (known by ASHRAE type, R402 or R402A and R402B), HCFC-22 / octafluoropropane / Propane (known by ASHRAE type, R403 or R403A and R403B), Octafluoropropane / HFC-134a / isobutane (known by ASHRAE type, R413 or R413A), HCFC-22 / HCFC-124 / HCFC-142b / Isobutane (known by ASHRAE classification, R414 or R414A and R414B), HFC-134a / HCFC-124 / n-butane (known by ASHRAE classification, R416 or R416A) HFC-125 / HFC-134a / n-butane (known by ASHRAE type, R417 or R417A), HFC-125 / HFC-134a / dimethyl ether (known by ASHRAE type, R419 or R419A), and HFC-125 / HFC-134a / isobutane (known by ASHRAE classification, R422, R422A, R422B, R422C, R422D).

The present invention further relates to a method for exchanging an original refrigerant or heat transfer fluid composition, wherein the original composition is R134a (HFC-134a, 1, 1, 1, in a refrigeration apparatus, air conditioner, or heat pump apparatus. 2-tetrafluoroethane, CF ₃ CH ₂ F), wherein the method comprises a second step wherein R134a comprises at least one compound selected from the group consisting of trifluoromethyl trifluorovinyl ether (PMVE). Replacing the refrigerant or heat transfer fluid composition.

The present invention further relates to a method for replacing an original refrigerant or heat transfer fluid composition, wherein the original composition is R152a (HFC-152a, 1,1-difluoroethane, CHF ₂ CH ₃ ), wherein the method comprises R152a as E-1,3,3,3-tetrafluoropropene (E-HFC-1234ze), 1,2,3,3,3-penta. Fluoropropene (HFC-1225ye), 2,3,3,3-tetrafluoropropene (HFC-1234yf), 3,3,3-trifluoropropene (HFC-1243zf), and trifluoromethyl trifluorovinyl ether (PMVE) Replacing the second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of No.

The present invention further includes a method for replacing R227ea (HFC-227ea, 1,1,1,2,3,3,3-heptafluoropropane, CF ₃ CHFCF ₃ ) in a refrigeration apparatus, an air conditioner, or a heat pump apparatus. In this regard, in this case, the method includes E-1,3,3,3-tetrafluoropropene (E-HFC-1234ze), 1,2,3,3,3-pentafluoropropene (HFC-1225ye), 2 , 3,3,3-tetrafluoropropene (HFC-1234yf), 3,3,3-trifluoropropene (HFC-1243zf), and at least one selected from the group consisting of trifluoromethyl trifluorovinyl ether (PMVE) Alternatively providing a composition comprising a species of the compound.

The present invention further relates to a method for replacing the original refrigerant or heat transfer fluid composition, wherein the original composition is R113 (CFC-113, 1, 1, 2- Trichloro-1,2,2-trifluoroethane, CFCl ₂ CF ₂ Cl), wherein the method is 1,1,1,3,4,5,5,5-octafluoro-4- ( Trifluoromethyl) -2-butene (HFC-152-11 mmyz); 1,1,1,4,4,5,5,5-octafluoro-2- (trifluoromethyl) -2-pentene (HFC-152) -11 mmtz); 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene (HFC-151-12 mcy); 1,1,1,3- Tetrafluoro-2-butene (HFC-1 1, 1, 1, 4, 4, 4-hexafluoro-2,3-bis (trifluoromethyl) -2-butene (HFC-151-12 mmtt); 1, 2, 3, 3, 4, 4,5,5,6,6-decafluorocyclohexene (FC-C151-10y); 3,3,4,4,5,5,5-heptafluoro-2-methyl-1-pentene (HFC-1567fts) 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene (PFBE); 4,4,5,5,6,6,6-heptafluoro-2-hexene (HFC); -1,567szz); 1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene (F13E); 1,1,1,2,3,4,5,5, 5-Nonafluoro-4- (trifluoromethyl) -2-pentene (HFC- And at least one compound selected from the group consisting of 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (F22E) Replacing the second refrigerant or heat transfer fluid composition.

The invention further relates to a method for exchanging the original refrigerant or heat transfer fluid composition, wherein the original composition is R43-10mee (HFC-43-10mee), 1 , 1,1,2,3,4,4,5,5,5-decafluoropentane, CF ₃ CHFCHFCF ₂ CF ₃ ), wherein the method is 1,1,1,3,4, 5,5,5-octafluoro-4- (trifluoromethyl) -2-butene (HFC-152-11 mmyz); 1,1,1,4,4,5,5,5-octafluoro-2- ( Trifluoromethyl) -2-pentene (HFC-152-11 mmtz); 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene (HFC-151) -12 mcy); 1,1,1,3- Trifluoro-2-butene (HFC-1354mzy); 1,1,1,4,4,4-hexafluoro-2,3-bis (trifluoromethyl) -2-butene (HFC-151-12 mmtt); 1 , 2,3,3,4,4,5,5,6,6-decafluorocyclohexene (FC-C151-10y); 3,3,4,4,5,5,5-heptafluoro-2-methyl -1-pentene (HFC-1567fts); 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene (PFBE); 4,4,5,5,6,6,6 -Heptafluoro-2-hexene (HFC-1567szz); 1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene (F13E); 1,1,1,2 , 3,4,5,5,5-nonafluoro-4- (trif Olomethyl) -2-pentene (HFC-151-12 mmzz); and 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (F22E) Replacing a second refrigerant or heat transfer fluid composition comprising at least one compound.

The present invention further relates to a method for exchanging the original refrigerant or heat transfer fluid composition, wherein the original composition is C ₄ F ₉ OCH ₃ (perfluorobutyl methyl ether) in a refrigeration apparatus, air conditioner, or heat pump apparatus. Wherein the method is 1,1,1,3,4,5,5,5-octafluoro-4- (trifluoromethyl) -2-butene (HFC-152-11 mmyz); 1,1,4,4,5,5,5-octafluoro-2- (trifluoromethyl) -2-pentene (HFC-152-11 mmtz); 1,1,1,2,2,3,4 , 5,5,6,6,6-dodecafluoro-3-hexene (HFC-151-12mcy); 1,1,1,3-tetrafluoro-2-butene (HFC-1354mzy); 1,1,1 , 4,4,4-hexafluo -2,3-bis (trifluoromethyl) -2-butene (HFC-151-12 mmtt); 1,2,3,3,4,4,5,5,6,6-decafluorocyclohexene (FC-C151) -10y); 3,3,4,4,5,5,5-heptafluoro-2-methyl-1-pentene (HFC-1567fts); 3,3,4,4,5,5,6,6 6-nonafluoro-1-hexene (PFBE); 4,4,5,5,6,6,6-heptafluoro-2-hexene (HFC-1567szz); 1,1,1,4,4,5,5 , 6,6,6-decafluoro-2-hexene (F13E); 1,1,1,2,3,4,5,5,5-nonafluoro-4- (trifluoromethyl) -2-pentene (HFC) -151-12 mmzz); and 1,1,1,2,2,5 5,6,6,6- including deca-fluoro-3-hexene at least one second step of replacing the refrigerant or heat transfer fluid composition comprising a compound selected from the group consisting of (F22E).

The present invention further relates to a method for replacing an original refrigerant or heat transfer fluid composition, wherein the original composition is R365mfc (HFC-365mfc, 1,1,1, 3,3-pentafluorobutane, CF ₃ CH ₂ CF ₂ CH ₃ ), wherein the method is 1,1,1,3,4,5,5,5-octafluoro-4- (tri Fluoromethyl) -2-butene (HFC-152-11 mmyz); 1,1,1,4,4,5,5,5-octafluoro-2- (trifluoromethyl) -2-pentene (HFC-152) 11 mmtz); 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene (HFC-151-12mcy); 1,1,1,3-tetra Fluoro-2-butene (HFC- 354 mzy); 1,1,1,4,4,4-hexafluoro-2,3-bis (trifluoromethyl) -2-butene (HFC-151-12 mmtt); 1,2,3,3,4, 4,5,5,6,6-decafluorocyclohexene (FC-C151-10y); 3,3,4,4,5,5,5-heptafluoro-2-methyl-1-pentene (HFC-1567fts) 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene (PFBE); 4,4,5,5,6,6,6-heptafluoro-2-hexene (HFC); -1,567szz); 1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene (F13E); 1,1,1,2,3,4,5,5, 5-Nonafluoro-4- (trifluoromethyl) -2-pentene (HFC 151-12 mmzz); and at least one compound selected from the group consisting of 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (F22E) Replacing the second refrigerant or heat transfer fluid composition.

The present invention further relates to a method for exchanging an original refrigerant or heat transfer fluid composition, wherein the original composition is R11 (CFC-11, trichlorofluoromethane, CFCl _{3 in a} refrigeration apparatus, air conditioner, or heat pump apparatus. Wherein the method is 1,2,3,3,4,4,5,5-octafluorocyclopentene (FC-C1418y); 1,1,1,2,3,4,4, 1,5,5-decafluoro-2-pentene (FC-141-10myy); 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene (HFC-1429myz); 1 , 1,1,3,4,4,5,5,5-nonafluoro-2-pentene (HFC-1429mzy); 3,3,4,4,5,5,5-heptafluoro-1-pentene (HFC) -1447 fz) ,; 1,1 1,1,4,4-hexafluoro-2-butene (F11E); 1,1,1,4,4,4-hexafluoro-2- (trifluoromethyl) -2-butene (HFC-1429mzt); And a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 1,1,1,4,4,5,5,5-octafluoro-2-pentene (F12E) The process of replacing is included.

The present invention further relates to a method for replacing an original refrigerant or heat transfer fluid composition, wherein the original composition is R123 (HCFC-123, 2,2-dichloro-) in a refrigeration apparatus, air conditioner, or heat pump apparatus. 1,1,1-trifluoroethane, CF ₃ CHCl ₂ ), wherein the method is 1,2,3,3,4,4,5,5-octafluorocyclopentene (FC-C1418y); 1,1,1,2,3,4,4,5,5,5-decafluoro-2-pentene (FC-141-10my); 1,1,1,2,4,4,5,5 5-Nonafluoro-2-pentene (HFC-1429myz); 1,1,1,3,4,4,5,5,5-Nonafluoro-2-pentene (HFC-1429mzy); 3,3,4,4 5,5,5-heptafluoro-1-pente (HFC-1447fz) ,; 1,1,1,4,4,4-hexafluoro-2-butene (F11E); 1,1,1,4,4,4-hexafluoro-2- (trifluoromethyl) ) -2-butene (HFC-1429mzt); and at least one compound selected from the group consisting of 1,1,1,4,4,5,5,5-octafluoro-2-pentene (F12E) Replacing the second refrigerant or heat transfer fluid composition.

The present invention further relates to a method for exchanging an original refrigerant or heat transfer fluid composition, wherein the original composition is R245fa (HFC-245fa, 1,1,1,2) in a refrigeration apparatus, air conditioner, or heat pump apparatus. 3,3-pentafluoropropane, CF ₃ CH ₂ CHF ₂ ), wherein the method is 2,3,3-trifluoropropene (HFC-1243yf); 1,1,1,4,4, 4-hexafluoro-2-butene (F11E); 1,3,3,3-tetrafluoropropene (HFC-1234ze); 1,1,1,2,4,4,4-heptafluoro-2-butene ( HFC-1327my); 1,2,3,3-tetrafluoropropene (HFC-1234ye); and pentafluoroethyl trifluorovinyl ether (PEVE) Is the comprising a second step of replacing the refrigerant or heat transfer fluid composition comprising at least one compound.

The present invention further relates to a method for exchanging the original refrigerant or heat transfer fluid composition, wherein the original composition is R114 (CFC-114, 1,2-dichloro-) in a refrigeration apparatus, air conditioner, or heat pump apparatus. 1,1,2,2-tetrafluoroethane, CFCl ₂ CF ₂ Cl), wherein the process is 1,1,1,2,3,4,4,4-octafluoro-2-butene (FC-1318my); 1,2,3,3,4,4-hexafluorocyclobutene (FC-C1316cc); 2,3,3,4,4,4-hexafluoro-1-butene (HFC-1336yf) And a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 3,3,4,4,4-pentafluoro-1-butene (HFC-1345fz) Craft Including the.

The present invention further relates to a method for exchanging an original refrigerant or heat transfer fluid composition, wherein the original composition is R236fa (HFC-236fa, 1,1,1, 3,3,3-hexafluoropropane, CF ₃ CH ₂ CF ₃ ), wherein the method is 1,1,1,2,3,4,4,4-octafluoro-2-butene ( FC-1318my); 1,2,3,3,4,4-hexafluorocyclobutene (FC-C1316cc); 2,3,3,4,4,4-hexafluoro-1-butene (HFC-1336yf) And replacing a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 3,3,4,4,4-pentafluoro-1-butene (HFC-1345fz) Including.

The present invention relates to a method for exchanging an original refrigerant or heat transfer fluid composition, wherein the original composition is R401A in a refrigeration apparatus, an air conditioner, or a heat pump apparatus, wherein the method comprises E-1 1,3,3,3-tetrafluoropropene (E-HFC-1234ze); 1,2,3,3,3-pentafluoropropene (HFC-1225ye); 2,3,3,3-tetrafluoropropene (HFC) -1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and a second refrigerant or heat transfer comprising at least one compound selected from the group consisting of trifluoromethyl trifluorovinyl ether (PMVE) Replacing the fluid composition. R401A is about 53 weight percent HCFC-22 (chlorodifluoromethane, CHF ₂ Cl), about 13 weight percent HFC-152a (1,1-difluoroethane, CHF ₂ CH ₃ ), and about 34 weight percent HCFC-124 ( ASHRAE classification for refrigerant blends containing 2-chloro-1,1,1,2-tetrafluoroethane, CF ₃ CHClF).

The present invention further relates to a method for replacing an original refrigerant or heat transfer fluid composition, wherein the original composition is R401B in a refrigeration apparatus, air conditioner, or heat pump apparatus, wherein the method comprises E 1,3,3,3-tetrafluoropropene (E-HFC-1234ze); 1,2,3,3,3-pentafluoropropene (HFC-1225ye); 2,3,3,3-tetrafluoropropene A second refrigerant comprising at least one compound selected from the group consisting of (HFC-1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyltrifluorovinyl ether (PMVE); Replacing the heat transfer fluid composition. R401B is about 61 weight percent HCFC-22 (chlorodifluoromethane, CHF ₂ Cl), about 11 weight percent HFC-152a (1,1-difluoroethane, CHF ₂ CH ₃ ), and about 28 weight percent HCFC-124 ( ASHRAE classification for refrigerant blends containing 2-chloro-1,1,1,2-tetrafluoroethane, CF ₃ CHClF).

The present invention further relates to a method of replacing the original refrigerant or heat transfer fluid composition, wherein the original composition is R409A in a refrigeration apparatus, air conditioner, or heat pump apparatus, wherein the method comprises E 1,3,3,3-tetrafluoropropene (E-HFC-1234ze); 1,2,3,3,3-pentafluoropropene (HFC-1225ye); 2,3,3,3-tetrafluoropropene A second refrigerant comprising at least one compound selected from the group consisting of (HFC-1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyltrifluorovinyl ether (PMVE); Replacing the heat transfer fluid composition. R409A is about 60 weight percent HCFC-22 (chlorodifluoromethane, CHF ₂ Cl), about 25 weight percent HCFC-124 (2-chloro-1,1,1,2-tetrafluoroethane, CF ₃ CHClF), and ASHRAE classification for refrigerant blends containing about 15 weight percent HCFC-142b (1-chloro-1,1-difluoroethane, CF ₂ ClCH ₃ ).

The present invention further relates to a method for replacing an original refrigerant or heat transfer fluid composition, wherein the original composition is R409B in a refrigeration apparatus, air conditioner, or heat pump apparatus, wherein the method comprises E 1,3,3,3-tetrafluoropropene (E-HFC-1234ze); 1,2,3,3,3-pentafluoropropene (HFC-1225ye); 2,3,3,3-tetrafluoropropene A second refrigerant comprising at least one compound selected from the group consisting of (HFC-1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyltrifluorovinyl ether (PMVE); Replacing the heat transfer fluid composition. R409B is about 65 weight percent HCFC-22 (chlorodifluoromethane, CHF ₂ Cl), about 25 weight percent HCFC-124 (2-chloro-1,1,1,2-tetrafluoroethane, CF ₃ CHClF), and ASHRAE classification for refrigerant blends containing about 10 weight percent HCFC-142b (1-chloro-1,1-difluoroethane, CF ₂ ClCH ₃ ).

The present invention further relates to a method for replacing an original refrigerant or heat transfer fluid composition, wherein the original composition is R414B in a refrigeration apparatus, air conditioner, or heat pump apparatus, wherein the method comprises E -1,3,3,3-tetrafluoropropene (E-HFC-1234ze), 1,2,3,3,3-pentafluoropropene (HFC-1225ye), 2,3,3,3-tetrafluoropropene A second refrigerant comprising at least one compound selected from the group consisting of (HFC-1234yf), 3,3,3-trifluoropropene (HFC-1243zf), and trifluoromethyltrifluorovinyl ether (PMVE) or Replacing the heat transfer fluid composition. R414B is about 50 weight percent HCFC-22 (chlorodifluoromethane, CHF ₂ Cl), about 39 weight percent HCFC-124 (2-chloro-1,1,1,2-tetrafluoroethane, CF ₃ CHClF), about 1.5 percent by weight isobutane _{(R600a, CH 3 CH (CH} 3) CH 3) and about 9.5 weight percent HCFC-142b (1-chloro-1,1-difluoroethane, CF ₂ ClCH ₃₎ refrigerant blends containing Is the ASHRAE type.

The present invention further relates to a method of replacing the original refrigerant or heat transfer fluid composition, wherein the original composition is R416A in a refrigeration apparatus, air conditioner, or heat pump apparatus, wherein the method comprises E 1,3,3,3-tetrafluoropropene (E-HFC-1234ze); 1,2,3,3,3-pentafluoropropene (HFC-1225ye); 2,3,3,3-tetrafluoropropene A second refrigerant comprising at least one compound selected from the group consisting of (HFC-1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyltrifluorovinyl ether (PMVE); Replacing the heat transfer fluid composition. R416A is about 59 weight percent HFC-134a (1,1,1,2-tetrafluoroethane, CF ₃ CH ₂ F)), about 39.5 weight percent HCFC-124 (2-chloro-1,1, ASHRAE classification for refrigerant blends containing 1,2-tetrafluoroethane, CF ₃ CHClF), and about 1.5 weight percent n-butane (CH ₃ CH ₂ CH ₂ CH ₃ ).

The present invention further relates to a method for exchanging an original refrigerant or heat transfer fluid composition, wherein the original composition is R12 (CFC-12, dichlorodifluoromethane, CF _{2 in a} refrigeration unit, air conditioning unit, or heat pump unit. Cl ₂ ), wherein the method is 1,2,3,3,3-pentafluoropropene (HFC-1225ye); 2,3,3,3-tetrafluoropropene (HFC-1234yf); 3 , 3,3-trifluoropropene (HFC-1243zf); and a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of trifluoromethyl trifluorovinyl ether (PMVE) Process.

The present invention further relates to a method for exchanging an original refrigerant or heat transfer fluid composition, wherein the original composition is R500 in a refrigeration apparatus, air conditioner, or heat pump apparatus, wherein the method comprises 1 2,3,3,3-pentafluoropropene (HFC-1225ye); 2,3,3,3-tetrafluoropropene (HFC-1234yf); 3,3,3-trifluoropropene (HFC-1243zf); And replacing a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of trifluoromethyl trifluorovinyl ether (PMVE). R500 is about 73.8 weight percent R12 ((CFC-12, dichlorodifluoromethane, CF ₂ Cl ₂₎ and about 26.2 weight percent R152a (HFC-152a, 1,1- difluoroethane, CHF ₂ CH ₃₎ The ASHRAE classification for the azeotropic refrigerant blend it contains.

  The present invention relates to a method for replacing an original refrigerant or heat transfer fluid composition, wherein the original refrigerant or heat transfer fluid composition is R134a or R12, wherein said R134a or R12 is about 1. Replaced by a second refrigerant or heat transfer fluid composition comprising 0 weight percent to about 37 weight percent HFC-32 and about 99 weight percent to about 63 weight percent HFC-1225ye. In other embodiments, the second refrigerant or heat transfer fluid composition may comprise about 1.0 weight percent to about 10 weight percent HFC-32 and about 99 weight percent to about 90 weight percent HFC-1225ye. .

  The present invention relates to a method for replacing an original refrigerant or heat transfer fluid composition, wherein the original refrigerant or heat transfer fluid composition is R22, R404A, or R410A, where R22, R404A, or R410A. Is replaced by a second refrigerant or heat transfer fluid composition comprising about 1.0 weight percent to about 37 weight percent HFC-32 and about 99 weight percent to about 63 weight percent HFC-1225ye. In other embodiments, the second refrigerant or heat transfer fluid composition may comprise about 20 weight percent to about 37 weight percent HFC-32 and about 80 weight percent to about 63 weight percent HFC-1225ye.

  The present invention further relates to a method for exchanging an original refrigerant or heat transfer fluid composition, wherein the original refrigerant or heat transfer fluid composition is R22, R404A, or R410A, wherein said R22, R404A Or R410A is about 20 weight percent to about 95 weight percent HFC-1225ye, about 1.0 weight percent to about 65 weight percent HFC-32, and about 1.0 weight percent to about 40 weight percent HFC-125; Is replaced by a second refrigerant or heat transfer fluid composition. In other embodiments, the second refrigerant or heat transfer fluid composition comprises about 30 weight percent to about 90 weight percent HFC-1225ye, about 5.0 weight percent to about 55 weight percent HFC-32, and about 1.0 weight percent to about 35 weight percent HFC-125. In yet other embodiments, the second refrigerant or heat transfer fluid composition comprises about 40 weight percent to about 85 weight percent HFC-1225ye, about 10 weight percent to about 45 weight percent HFC-32, and about 1. 0 weight percent to about 28 weight percent HFC-125.

The present invention relates to a method for replacing an original refrigerant or heat transfer fluid composition, wherein the original refrigerant or heat transfer fluid composition is R134a or R12, wherein said R134a or R12 is:
HFC-1243zf and HFC-1225ye;
HFC-1243zf, HFC-1225ye, and HFC-125;
Replaced by a second refrigerant or heat transfer fluid composition comprising HFC-1243zf, HFC-1225ye, and HFC-32; or HFC-1243zf, HFC-1225ye, HFC-125, and HFC-32.

  In all the described methods of replacing the refrigerant, the fluoroolefin can be used to replace the refrigerant in the existing equipment. Furthermore, fluoroolefins can be used to replace the refrigerant in existing equipment designed to use the refrigerant therein. Furthermore, fluoroolefins can be used to replace refrigerant in existing equipment without having to change or replace the lubricant.

  The present invention relates to a method for reducing a fire in a refrigeration apparatus, an air conditioner, or a heat pump apparatus, and the method includes introducing the composition of the present invention into the refrigerant apparatus or the air conditioner.

  When considering flammability, refrigerants that can leak from refrigeration equipment, air conditioning equipment, or heat pump equipment are a major concern. When a leak occurs in a refrigeration or air conditioner, refrigerant and potentially a small amount of lubricant can be released from the system. If this leaked material comes into contact with an ignition source, a fire can occur. A fire means the possibility that a fire may occur in one of the refrigeration apparatus, the air conditioner, or the heat pump apparatus or in the vicinity thereof. Fire reduction in refrigeration equipment, air conditioning equipment, or heat pump equipment can be achieved by using refrigerants or heat transfer fluids that are determined and defined as not flammable by the methods and standards described herein. Can be achieved. Further, the non-flammable fluoroolefin of the present invention can be added to the flammable refrigerant or heat transfer fluid already in the device or prior to adding the flammable refrigerant or heat transfer fluid to the device. The non-flammable fluoroolefins of the present invention reduce the likelihood of fire upon leakage and / or reduce the extent of fire by reducing the temperature or size of any flame formed.

  The present invention further relates to a method of reducing flame hazard in or near a refrigeration apparatus, air conditioner, or heat pump apparatus, the method combining and combining at least one non-combustible fluoroolefin with a combustible refrigerant. A step of introducing the product into a refrigeration apparatus, an air conditioner or a heat pump apparatus.

  The present invention further relates to a method of reducing flame hazard in or near a refrigeration apparatus, air conditioner, or heat pump apparatus, the method combining and combining at least one non-combustible fluoroolefin with a lubricant. Including a step of introducing the product into a refrigeration apparatus, an air conditioner, or a heat pump apparatus including a combustible refrigerant.

  The present invention further relates to a method of reducing flame hazard in or near a refrigeration apparatus, air conditioner or heat pump apparatus, the method comprising introducing at least one fluoroolefin into the apparatus.

  The present invention further relates to a method of using a combustible refrigerant in a refrigeration apparatus, an air conditioner, or a heat pump apparatus, the method comprising combining the combustible refrigerant with at least one fluoroolefin.

  The invention further relates to a method for reducing the flammability of a flammable refrigerant or heat transfer fluid, said method comprising combining the flammable refrigerant with at least one fluoroolefin.

  The present invention further relates to a method of conducting heat from a heat source to a heat sink, wherein the composition of the present invention serves as a heat transfer fluid. The thermal conduction method includes the step of transferring the composition of the present invention from a heat source to a heat sink.

  A heat transfer fluid is used to conduct, move or remove heat from one space, site, object or object to a different space, site, object or object by radiation, conduction or convection. The heat transfer fluid may function as a second coolant by providing a means for conducting cooling (or heating) from the remote refrigeration (or heating) system. In some systems, the heat transfer fluid may be maintained in a constant state throughout the conduction process (ie, not evaporating or condensing). Alternatively, the evaporative cooling process may also use a heat transfer fluid.

  A heat source may be defined as any space, site, object or object that is desired to conduct, move or remove heat. Examples of heat sources may be air gaps that require refrigeration or cooling (open or sealed), such as refrigerated or refrigerated cases in supermarkets, building air gaps that require air conditioning, or automobile passenger compartments that require air conditioning. A heat sink can be defined as any space, part, object or object that can absorb heat. A vapor compression refrigeration system is an example of such a heat sink.

Example 1
(Performance data)
Table 7, CFC-113, HFC-43-10mee , refrigeration performance of the C ₄ F ₉ OCH _3, and compounds of the present invention relative to HFC-365mfc, an evaporator (Evap) and condenser (Cond), discharge temperature Shown as pressure in (Disch T), energy efficiency (COP), and capacity (Cap). The data is based on the following conditions.

Evaporator temperature 40.0 ° F (4.4 ° C)
Capacitor temperature 110.0 ° F (43.3 ° C)
Supercooling temperature 10.0 ° F (5.5 ° C)
Return gas temperature 75.0 ° F (23.8 ° C)
The compressor efficiency is 70%.

(Example 2)
(Performance data)
Table 8 shows the refrigeration performance for the compounds of the invention relative to CFC-11 and HCFC-123, evaporator (Evap) and condenser (Cond), exhaust temperature (Disch T), energy efficiency (COP), and capacity. It is shown as the pressure at (Cap). The data is based on the following conditions.

Evaporator temperature 40.0 ° F (4.4 ° C)
Capacitor temperature 110.0 ° F (43.3 ° C)
Supercooling temperature 10.0 ° F (5.5 ° C)
Return gas temperature 75.0 ° F (23.8 ° C)
The compressor efficiency is 70%.

Example 3
(Performance data)
Table 9 shows the refrigeration performance for the compounds of the present invention relative to HFC-245fa, in evaporator (Evap) and condenser (Cond), exhaust temperature (Dish T), energy efficiency (COP), and capacity (Cap). Shown as pressure. The data is based on the following conditions.

Evaporator temperature 40.0 ° F (4.4 ° C)
Capacitor temperature 110.0 ° F (43.3 ° C)
Supercooling temperature 10.0 ° F (5.5 ° C)
Return gas temperature 75.0 ° F (23.8 ° C)
The compressor efficiency is 70%.

(Example 4)
(Performance data)
Table 10 shows the refrigeration performance for the compounds of the invention relative to CFC-114 and HFC-236fa, evaporator (Evap) and condenser (Cond), exhaust temperature (Disch T), energy efficiency (COP), and capacity. It is shown as the pressure at (Cap). The data is based on the following conditions.

Evaporator temperature 40.0 ° F (4.4 ° C)
Capacitor temperature 110.0 ° F (43.3 ° C)
Supercooling temperature 10.0 ° F (5.5 ° C)
Return gas temperature 75.0 ° F (23.8 ° C)
The compressor efficiency is 70%.

(Example 5)
(Performance data)
Table 11 shows the refrigeration performance for the compounds of the present invention relative to HFC-134a, HFC-152a, and HFC-227ea, evaporator (Evap) and condenser (Cond), exhaust temperature (Dish T), energy efficiency (COP). ) And the pressure in capacity (Cap). The data is based on the following conditions.

Evaporator temperature 40.0 ° F (4.4 ° C)
Capacitor temperature 110.0 ° F (43.3 ° C)
Supercooling temperature 10.0 ° F (5.5 ° C)
Return gas temperature 75.0 ° F (23.8 ° C)
The compressor efficiency is 70%.

(Example 6)
(Flammability)
Flammable compounds can be identified by tests with an electronic ignition source under ASTM (American Society of Testing and Materials) E681-01. Such a test for flammability was determined for 101 kPa (14.7 psia) for the composition of the present disclosure to determine if it was flammable and, if so, to find the lower explosion limit (LFL), Various concentrations were performed in air at 50 percent relative humidity and at the indicated temperatures. The results are shown in Table 12.

  The results indicate that HFC-1234yf and E-HFC-1234ze are flammable, while HFC-1225ye, HFC-1429myz / mzy, and F12E are nonflammable. For a mixture of HFC-1225ye and HFC-32 (which is known to be flammable in the pure state), 37 weight percent HFC-32 may be present to maintain the non-flammable character. It turned out to be the maximum amount possible. These compositions containing fluoroolefins that are non-flammable are candidates that can be more tolerated as refrigerants or heat transfer fluid compositions.

(Example 7)
(Tip speed for generating pressure)
Tip speed can be estimated by forming some basic relationships for refrigeration appliances using centrifugal compressors. The ideal torque that the impeller applies to the gas is defined as follows.

T = m × (v ₂ × r ₂ −v ₁ × r ₁ ) Equation 1
Where
T = torque, Newton meter m = mass rate of flow, kg / sec
v ₂ = swirling speed (tip speed) of refrigerant away from impeller, meter / sec
r ₂ = radius of exit impeller, meter v ₁ = swirl speed of refrigerant entering impeller, meter / sec
r ₁ = inlet impeller radius, meters.

Assuming that the refrigerant effectively enters the impeller in the axial direction, the swirl component of speed v ₁ = 0, and therefore T = m × v ₂ × r ₂ Equation 2
It is.

The output required at the shaft is the product of torque and rotational speed,
P = T × ω Equation 3
And
Where
P = output, W
ω = angular velocity, radians / s
Therefore,
P = T × w = m × v ₂ × r ₂ × ω Equation 4
It is.

At low refrigerant flow rates, the impeller tip speed and refrigerant swirl speed are nearly equal; therefore r ₂ × ω = v ₂ Equation 5
And P = m × v ₂ × v ₂ Formula 6
It is.

  Another equation for the ideal output is the product of the mass fraction of the flow and the isentropic work of compression.

P = m × H _i × (1000 J / kJ) Equation 7
Where
H _i = difference in refrigerant enthalpy from saturated vapor from evaporation conditions to saturated condensation conditions, kJ / kg.

Combining the two formulas 6 and 7,
v ₂ × v ₂ = 1000 × _Hi formula 8
Is obtained.

  Equation 8 is based on several basic assumptions, but provides a good estimate of the impeller tip speed and provides an important way to compare the coolant tip speed.

  Table 13 below shows the theoretical tip speed calculated for 1,2,2-trichlorotrifluoroethane (CFC-113) and the composition of the present invention. The conditions assumed for this comparison are:

Evaporator temperature 40.0 ° F (4.4 ° C)
Capacitor temperature 110.0 ° F (43.3 ° C)
Liquid subcooling temperature 10.0 ° F (5.5 ° C)
Regression gas temperature 75.0 ° F (23.8 ° C)
The compressor efficiency is 70%.

  These are typical conditions for small turbine centrifugal compressors to function.

  This example shows that the compounds of the present invention have tip speeds within about 15 percent of CFC-113 and would be an effective replacement for CFC-113 with minimal compressor design changes. Yes. The most preferred composition has a tip speed within about 10 percent of CFC-113.

(Example 8)
(Refrigeration performance data)
Table 14 shows the performance of various refrigerant compositions of the present invention compared to HFC-134a. In Table 14, Evap Pres is the evaporator pressure, Cond Pres is the condenser pressure, Comp Disc T is the compressor discharge temperature, COP is energy efficiency, and CAP is capacity. The data is based on the following conditions.

Evaporator temperature 40.0 ° F (4.4 ° C)
Capacitor temperature 130.0 ° F (54.4 ° C)
Supercooling amount 10.0 ° F (5.5 ° C)
Return gas temperature 60.0 ° F (15.6 ° C)
The compressor efficiency is 100%.

  Note that overheating is included in the cooling capacity.

  Numerous compositions have even higher energy efficiency (COP) than HFC-134a while maintaining lower or equal discharge pressures and temperatures. The capacities for the compositions listed in Table 14 are also similar to R134a, and these compositions can be alternative refrigerants for R134a in refrigeration and air conditioning, and particularly in portable air conditioning applications. It shows that there is. The results also show that the cooling capacity of HFC-1225ye can be improved with the addition of other compounds such as HFC-32.

Example 9
(Refrigeration performance data)
Table 15 shows the performance of various refrigerant compositions of the present invention compared to R404A and R422A. In Table 15, Evap Pres is the evaporator pressure, Cond Pres is the condenser pressure, Comp Disc T is the compressor discharge temperature, EER is energy efficiency, and CAP is capacity. The data is based on the following conditions.

Evaporator temperature -17.8 ° C
Capacitor temperature 46.1 ° C
Supercooling amount 5.5 ° C
Return gas temperature 15.6 ° C
The compressor efficiency is 70%.

  Note that overheating is included in the cooling capacity.

  A number of compositions have energy efficiency (EER) comparable to the top R404A and R422A. The discharge temperature is also lower than R404A and R507A. The capacity for the compositions listed in Table 15 is also similar to R404A, R507A, and R422A, and these compositions may be alternative refrigerants for R404A, R507A, or R422A in refrigeration and air conditioning. It shows that it is possible.

(Example 10)
(Refrigeration performance data)
Table 16 shows the performance of various refrigerant compositions of the present invention compared to HCFC-22 and R410A. In Table 16, Evap Pres is the evaporator pressure, Cond Pres is the condenser pressure, Comp Disc T is the compressor discharge temperature, EER is energy efficiency, and CAP is capacity. The data is based on the following conditions.

Evaporator temperature 4 ℃
Capacitor temperature 43 ° C
Supercooling amount 6 ℃
Return gas temperature 18 ℃
The compressor efficiency is 70%.

  Note that overheating is included in the cooling capacity.

  The composition has an energy efficiency (EER) comparable to R22 and R410A while maintaining an appropriate exhaust temperature. The capacity for certain compositions listed in Table 16 is also similar to R22, indicating that it can be an alternative refrigerant for R22 in refrigeration and air conditioning. In addition, compositions having capacities approximating or equal to R410A are listed in Table 16, indicating that these compositions can be alternative refrigerants for R410A in refrigeration and air conditioning. .

(Example 11)
(Refrigeration performance data)
Table 17 shows the performance of various refrigerant compositions of the present invention compared to HCFC-22, R410A, R407C, and R417A. In Table 17, Evap Pres is the evaporator pressure, Cond Pres is the condenser pressure, Comp Disc T is the compressor discharge temperature, EER is energy efficiency, and CAP is capacity. The data is based on the following conditions.

Evaporator temperature 4.4 ° C
Capacitor temperature 54.4 ° C
Supercooling amount 5.5 ° C
Return gas temperature 15.6 ° C
The compressor efficiency is 100%.

  Note that overheating is included in the cooling capacity.

  The composition has an energy efficiency (EER) comparable to R22, R407C, R417A, and R410A while maintaining a low exhaust temperature. The capacity for the compositions listed in Table 17 is also similar to R22, R407C and R417A, and these compositions can be alternative refrigerants for R22, R407C or R417A in refrigeration and air conditioning. It shows that there is. The present invention includes the following embodiments.

The present invention includes the following embodiments.

1. A refrigerant or heat transfer fluid composition comprising:
(I) a fluoroolefin of formula E—R ¹ CH═CHR ² or Z—R ¹ CH═CHR ² , wherein R ¹ and R ² are independently C ₁ -C ₆ perfluoro A fluoroolefin which is an alkyl group and wherein the total number of carbons in the compound is at least 5;
(Ii) a cyclic fluoroolefin of formula cyclo- [CX = CY (CZW) _n- ], wherein X, Y, Z, and W are independently H or F, and n is A cyclic fluoroolefin that is an integer from 2 to 5; and (iii) 2,3,3-trifluoro-1-propene (CHF ₂ CF═CH ₂ ); 1,1,2-trifluoro-1-propene (CH ₃ CF = CF ₂ ); 1,2,3-trifluoro-1-propene (CH ₂ FCF═CF ₂ ); 1,1,3-trifluoro-1-propene (CH ₂ FCH═CF ₂ ); 1 , 3,3-trifluoro-1-propene (CHF ₂ CH═CHF); 1,1,1,2,3,4,4,4-octafluoro-2-butene (CF ₃ CF═CFCF ₃ ); 1,1,2,3,3,4,4,4-octafluoro-1-bute (CF ₃ CF ₂ CF═CF ₂ ); 1,1,1,2,4,4,4-heptafluoro-2-butene (CF ₃ CF═CHCF ₃ ); 1, 2, _{3, 3, 4} 1,4,4-heptafluoro-1-butene (CHF═CFCF ₂ CF ₃ ); 1,1,1,2,3,4,4-heptafluoro-2-butene (CHF ₂ CF═CFCF ₃ ); 1 , 3,3,3-tetrafluoro-2- (trifluoromethyl) -1-propene ((CF ₃ ) ₂ C═CHF); 1,1,3,3,4,4,4-heptafluoro-1 - butene _{(CF 2 = CHCF 2 CF 3} ); 1,1,2,3,4,4,4- heptafluoro-1-butene _{(CF 2 = CFCHFCF 3);} 1,1,2,3,3, 4,4 heptafluoro-1-butene _{(CF 2 = CFCF 2 CHF 2} ); 2,3,3,4,4,4- hexa Ruoro-1-butene _{(CF 3 CF 2 CF = CH} 2); 1,3,3,4,4,4- hexafluoro-1-butene _{(CHF = CHCF 2 CF 3)} ; 1,2,3,4 1,4,4-hexafluoro-1-butene (CHF = CFCHFCF ₃ ); 1,2,3,3,4,4-hexafluoro-1-butene (CHF = CFCF ₂ CHF ₂ ); 1,3,4,4-hexafluoro-2-butene (CHF ₂ CF═CFCHF ₂ ); 1,1,1,2,3,4-hexafluoro-2-butene (CH ₂ FCF═CFCF ₃ ); 1 1,1,1,2,4,4-hexafluoro-2-butene (CHF ₂ CH═CFCF ₃ ); 1,1,1,3,4,4-hexafluoro-2-butene (CF ₃ CH═CFCHF) _2); 1,1,2,3,3,4- hexafluoro-1-butene ( _{F 2 = CFCF 2 CH 2 F} ); 1,1,2,3,4,4- hexafluoro-1-butene _{(CF 2 = CFCHFCHF 2);} 3,3,3- trifluoro-2- (trifluoromethyl methyl) -1-propene _{(CH 2 = C (CF 3} ) 2); 1,1,1,2,4- pentafluoro-2-butene _{(CH 2 FCH = CFCF 3)} ; 1,1,1,3 , 4-pentafluoro-2-butene (CF ₃ CH═CFCH ₂ F); 3,3,4,4,4-pentafluoro-1-butene (CF ₃ CF ₂ CH═CH ₂ ); 1,4,4-pentafluoro-2-butene _{(CHF 2 CH = CHCF 3)} ; 1,1,1,2,3- pentafluoro-2-butene _{(CH 3 CF = CFCF 3)} ; 2,3, 3,4,4-pentafluoro-1-butene _{(CH 2 = CFCF 2 CHF 2} ); 1,1 1,2,4,4-pentafluoro-2-butene (CHF ₂ CF═CHCHF ₂ ); 1,1,2,3,3-pentafluoro-1-butene (CH ₃ CF ₂ CF═CF ₂ ); 1 1,1,2,3,4-pentafluoro-2-butene (CH ₂ FCF═CFCHF ₂ ); 1,1,3,3,3-pentafluoro-2-methyl-1-propene (CF ₂ ═C ( _{CF 3) (CH 3))} ; 2- ( difluoromethyl) -3,3,3-trifluoro-1-propene _{(CH 2 = C (CHF 2} ) (CF 3)); 2,3,4,4 , 4-pentafluoro-1-butene (CH ₂ ═CFCHFCF ₃ ); 1,2,4,4,4-pentafluoro-1-butene (CHF═CFCH ₂ CF ₃ ); 1,3,4,4 4-pentafluoro-1-butene (CHF = CHCHFCF _3); 1,3,3,4 4-pentafluoro-1-butene _{(CHF = CHCF 2 CHF 2)} ; 1,2,3,4,4- pentafluoro-1-butene (CHF = CFCHFCHF _2); 3,3,4,4- tetrafluoro 1-butene _{(CH 2 = CHCF 2 CHF 2} ); 1,1- difluoro-2- (difluoromethyl) -1-propene _{(CF 2 = C (CHF 2} ) (CH 3)); 1,3,3 , 3-tetrafluoro-2-methyl-1-propene _{(CHF = C (CF 3)} (CH 3)); 3,3- difluoro-2- (difluoromethyl) -1-propene (CH ₂ = C (CHF ₂ ) ₂ ); 1,1,1,2-tetrafluoro-2-butene (CF ₃ CF═CHCH ₃ ); 1,1,1,3-tetrafluoro-2-butene (CH ₃ CF═CHCF ₃ ) 1,1,1,2,3,4,4,5,5; 5-decafluoro-2-pentene _{(CF 3 CF = CFCF 2 CF} 3); 1,1,2,3,3,4,4,5,5,5- decafluoro-1-pentene (CF ₂ = CFCF ₂ CF ₂ CF ₃ ); 1,1,1,4,4,4-hexafluoro-2- (trifluoromethyl) -2-butene ((CF ₃ ) ₂ C═CHCF ₃ ); 1,1,1 , 2,4,4,5,5,5- nonafluoro-2-pentene _{(CF 3 CF = CHCF 2 CF} 3); 1,1,1,3,4,4,5,5,5- nonafluoro -2 - pentene _{(CF 3 CH = CFCF 2 CF} 3); 1,2,3,3,4,4,5,5,5- nonafluoro-1-pentene _{(CHF = CFCF 2 CF 2 CF} 3); 1,1 , 3,3,4,4,5,5,5-nonafluoro-1-pentene _{(CF 2 = CHCF 2 CF 2} CF 3); 1 , 1,2,3,3,4,4,5,5- nonafluoro-1-pentene _{(CF 2 = CFCF 2 CF 2} CHF 2); 1,1,2,3,4,4,5,5, 5-nonafluoro-2-pentene (CHF ₂ CF═CFCF ₂ CF ₃ ); 1,1,1,2,3,4,4,5,5-nonafluoro-2-pentene (CF ₃ CF═CFCF ₂ CHF ₂₎ ); 1,1,1,2,3,4,5,5,5-nonafluoro-2-pentene (CF ₃ CF═CFCHFCF ₃ ); 1,2,3,4,4,4-hexafluoro-3 -(Trifluoromethyl) -1-butene (CHF = CFCF (CF ₃ ) ₂ ); 1,1,2,4,4,4-hexafluoro-3- (trifluoromethyl) -1-butene (CF _{2 = CFCH (CF 3) 2)} ; 1,1,1,4,4,4- hexafluoro-2- (triphenylmethyl Oromechiru) -2-butene _{(CF 3 CH = C (CF} 3) 2); 1,1,3,4,4,4- hexafluoro-3- (trifluoromethyl) -1-butene (CF ₂ = CHCF (CF _{3) 2);} 2,3,3,4,4,5,5,5- octafluoro-1-pentene _{(CH 2 = CFCF 2 CF 2} CF 3); 1,2,3,3,4 , 4,5,5-octafluoro-1-pentene (CHF = CFCF ₂ CF ₂ CHF ₂ ); 3,3,4,4,4-pentafluoro-2- (trifluoromethyl) -1-butene (CH ₂ = C (CF ₃ ) CF ₂ CF ₃ ); 1,1,4,4,4-pentafluoro-3- (trifluoromethyl) -1-butene (CF ₂ ═CHCH (CF ₃ ) ₂ ); 1 , 3,4,4,4-pentafluoro-3- (trifluoromethyl) -1-butene (CHF) _{CHCF (CF 3) 2);} 1,1,4,4,4- pentafluoro-2- (trifluoromethyl) -1-butene _{(CF 2 = C (CF 3} ) CH 2 CF 3); 3,4 , 4,4-tetrafluoro-3- (trifluoromethyl) -1-butene ((CF ₃ ) ₂ CFCH═CH ₂ ); 3,3,4,4,5,5,5-heptafluoro-1- pentene _{(CF 3 CF 2 CF 2 CH} = CH 2); 2,3,3,4,4,5,5- heptafluoro-1-pentene _{(CH 2 = CFCF 2 CF 2} CHF 2); 1,1, 3,3,5,5,5- heptafluoro-1-butene _{(CF 2 = CHCF 2 CH 2} CF 3); 1,1,1,2,4,4,4- heptafluoro-3-methyl-2 - butene _{(CF 3 CF = C (CF} 3) (CH 3)); 2,4,4,4- tetrafluoro-3- (triphenylmethyl Ruoromechiru) 1-butene _{(CH 2 = CFCH (CF 3} ) 2); 1,4,4,4- tetrafluoro-3- (trifluoromethyl) -1-butene _{(CHF = CHCH (CF 3)} 2) 1,1,1,4-tetrafluoro-2- (trifluoromethyl) -2-butene (CH ₂ FCH═C (CF ₃ ) ₂ ); 1,1,1,3-tetrafluoro-2- ( Trifluoromethyl) -2-butene (CH ₃ CF═C (CF ₃ ) ₂ ); 1,1,1-trifluoro-2- (trifluoromethyl) -2-butene ((CF ₃ ) ₂ C═CHCH _3); 3,4,4,5,5,5- hexafluoro-2-pentene _{(CF 3 CF 2 CF = CHCH} 3); 1,1,1,4,4,4- hexafluoro-2-methyl 2-butene _{(CF 3 C (CH 3)} = CHCF 3); 3,3,4,5, , 5-hexafluoro-1-pentene _{(CH 2 = CHCF 2 CHFCF 3} ); 4,4,4- trifluoro-3- (trifluoromethyl) -1-butene _{(CH 2 = C (CF 3} ) CH 2 CF ₃ ); 1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1-hexene (CF ₃ (CF ₂ ) ₃ CF═CF ₂ ); 1, 1, 2, 2, 3, 4, 5,
5,6,6,6- dodecafluoro-3- hexene _{(CF 3 CF 2 CF = CFCF} 2 CF 3); 1,1,1,4,4,4- hexafluoro-2,3-bis (trifluoromethyl Methyl) -2-butene ((CF ₃ ) ₂ C═C (CF ₃ ) ₂ ); 1,1,1,2,3,4,5,5,5-nonafluoro-4- (trifluoromethyl)- 2-pentene ((CF ₃ ) ₂ CFCF═CFCF ₃ ); 1,1,1,4,4,5,5,5-octafluoro-2- (trifluoromethyl) -2-pentene ((CF ₃ ) ₂ C = CHC ₂ F ₅ ); 1,1,1,3,4,5,5,5-octafluoro-4- (trifluoromethyl) -2-pentene ((CF ₃ ) ₂ CFCF═CHCF ₃ ) ; 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene (CF ₃ CF ₂ CF ₂ C ₂ CH = CH _2); 4,4,4- trifluoro-3,3-bis (tri fluoromethyl) -1-butene _{(CH 2 = CHC (CF 3} ) 3); 1,1,1,4, 4,4-hexafluoro-2- (trifluoromethyl) -3-methyl-2-butene ((CF ₃ ) ₂ C═C (CH ₃ ) (CF ₃ )); 2, _{3, 3,} 5, 5 , 5-hexafluoro-4- (trifluoromethyl) -1-pentene _{(CH 2 = CFCF 2 CH (} CF 3) 2); 1,1,1,2,4,4,5,5,5- nonafluoro 3-methyl-2-pentene _{(CF 3 CF = C (CH} 3) CF 2 CF 3); 1,1,1,5,5,5- hexafluoro-4- (trifluoromethyl) -2-pentene _{(CF 3 CH = CHCH (CF} 3) 2); 3,4,4,5,5,6,6,6- octafluoro-2-f Sen _{(CF 3 CF 2 CF 2 CF} = CHCH 3); 3,3,4,4,5,5,6,6- octafluoro-hexene _{(CH 2 = CHCF 2 CF 2} CF 2 CHF 2); 1 , 1,1,4,4-pentafluoro-2- (trifluoromethyl) -2-pentene ((CF ₃ ) ₂ C═CHCF ₂ CH ₃ ); 4,4,5,5,5-pentafluoro- 2- (trifluoromethyl) -1-pentene _{(CH 2 = C (CF 3} ) CH 2 C 2 F 5); 3,3,4,4,5,5,5- heptafluoro-2-methyl-1 - pentene _{(CF 3 CF 2 CF 2 C} (CH 3) = CH 2); 4,4,5,5,6,6,6- heptafluoro-2-hexene _{(CF 3 CF 2 CF 2 CH} = CHCH 3 ); 4,4,5,5,6,6,6- heptafluoro-1-hexene (CH ₂ = CHCH ₂ CF ₂ C ₂ F _5); 1,1,1,2,2,3,4- heptafluoro-3- hexene _{(CF 3 CF 2 CF = CFC} 2 H 5); 4,5,5,5- tetrafluoro - 4- (trifluoromethyl) -1-pentene _{(CH 2 = CHCH 2 CF (} CF 3) 2); 1,1,1,2,5,5,5- heptafluoro-4-methyl-2-pentene ( CF ₃ CF═CHCH (CF ₃ ) (CH ₃ )); 1,1,1,3-tetrafluoro-2- (trifluoromethyl) -2-pentene ((CF ₃ ) ₂ C═CFC ₂ H ₅ ) 1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene (CF ₃ CF = CFCF ₂ CF ₂ C ₂ F ₅ ); 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoro-3-heptene (CF ₃ CF ₂ CF = CFCF ₂ C ₂ F ₅ ); 1,1,1,3,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene (CF ₃ CH═CFCF ₂ CF ₂ C ₂ F ₅ ); 1,1,1,2,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene (CF ₃ CF═CHCF ₂ CF ₂ C ₂ F ₅ ); 1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF ₃ CF ₂ CH═CFCF ₂ C ₂ F ₅ ); 1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF ₃ CF ₂ CF═CHCF ₂ C ₂ F _{5); CF 2 = CFOCF 2} CF 3 (PEVE) and CF ₂ = CFOCF ₃ (fluoroolefin selected from the group consisting of PMVE);
A refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of:

2. A composition comprising (i) at least one fluoroolefin compound; and (ii) at least one combustible refrigerant;
(A) Formula A fluoroolefins E-R ¹ CH = CHR ² or ^{Z-R 1 CH = CHR 2} , wherein, R ¹ and R ² are independently perfluoro C ₁ -C ₆ A fluoroolefin which is an alkyl group;
(B) a cyclic fluoroolefin of the formula cyclo- [CX = CY (CZW) _n- ], wherein X, Y, Z and W are independently H or F, and n is A cyclic fluoroolefin that is an integer from 2 to 5; and (c) 1,2,3,3,3-pentafluoro-1-propene (CF ₃ CF═CHF); 1,1,3,3,3-penta fluoro-1-propene _{(CF 3 CH = CF 2)} ; 1,1,2,3,3- pentafluoro-1-propene _{(CHF 2 CF = CF 2)} ; 1,1,1,2,3,4 , 4,4-octafluoro-2-butene (CF ₃ CF═CFCF ₃ ); 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF ₃ CF ₂ CF═CF ₂ ); 1,1,1,2,4,4,4-heptafluoro-2-butene (CF ₃ CF═CHC F _3); 1,2,3,3,4,4,4- heptafluoro-1-butene _{(CHF = CFCF 2 CF 3)} ; 1,1,1,2,3,4,4- heptafluoro - 2-butene (CHF ₂ CF═CFCF ₃ ); 1,3,3,3-tetrafluoro-2- (trifluoromethyl) -1-propene ((CF ₃ ) ₂ C═CHF); 1,1,3 , 3,4,4,4-heptafluoro-1-butene _{(CF 2 = CHCF 2 CF 3} ); 1,1,2,3,4,4,4- heptafluoro-1-butene (CF ₂ = CFCHFCF _3); 1,1,2,3,3,4,4- heptafluoro-1-butene _{(CF 2 = CFCF 2 CHF 2} ); 2,3,3,4,4,4- hexafluoro-1- butene _{(CF 3 CF 2 CF = CH} 2); 1,3,3,4,4,4- hexafluoro-1-butene (CH = CHCF ₂ CF _3); 1,2,3,4,4,4- hexafluoro-1-butene (CHF = CFCHFCF _3); 1,2,3,3,4,4- hexafluoro-1-butene _{(CHF = CFCF 2 CHF 2)} ; 1,1,2,3,4,4- hexafluoro-2-butene _{(CHF 2 CF = CFCHF 2)} ; 1,1,1,2,3,4- hexafluoro -2-butene (CH ₂ FCF═CFCF ₃ ); 1,1,1,2,4,4-hexafluoro-2-butene (CHF ₂ CH═CFCF ₃ ); 1,1,1,3,4, 4-hexafluoro-2-butene _{(CF 3 CH = CFCHF 2)} ; 1,1,2,3,3,4- hexafluoro-1-butene _{(CF 2 = CFCF 2 CH 2} F); 1,1, 2,3,4,4-hexafluoro-1-butene (CF ₂ = CFCHFCHF ₂ ); 3,3,3-trifluoro-2- (trifluoromethyl) -1-propene (CH ₂ ═C (CF ₃ ) ₂ ); 1,1,1,2,3,4,4,5, 5,5-decafluoro-2-pentene (CF ₃ CF═CFCF ₂ CF ₃ ); 1,1,2,3,3,4,4,5,5,5-decafluoro-1-pentene (CF ₂₎ = CFCF ₂ CF ₂ CF ₃ ); 1,1,1,4,4,4-hexafluoro-2- (trifluoromethyl) -2-butene ((CF ₃ ) ₂ C═CHCF ₃ ); 1,1 , 1,2,4,4,5,5,5-nonafluoro-2-pentene (CF ₃ CF═CHCF ₂ CF ₃ ); 1,1,1,3,4,4,5,5,5-nonafluoro 2-pentene _{(CF 3 CH = CFCF 2 CF} 3); 1,2,3,3,4,4,5,5,5- nonafluoro-1-pentene ( _{CHF = CFCF 2 CF 2 CF 3} ); 1,1,3,3,4,4,5,5,5- nonafluoro-1-pentene _{(CF 2 = CHCF 2 CF 2} CF 3); 1,1,2 , 3,3,4,4,5,5- nonafluoro-1-pentene _{(CF 2 = CFCF 2 CF 2} CHF 2); 1,1,2,3,4,4,5,5,5- nonafluoro - 2-pentene (CHF ₂ CF═CFCF ₂ CF ₃ ); 1,1,1,2,3,4,4,5,5-nonafluoro-2-pentene (CF ₃ CF═CFCF ₂ CHF ₂ ); 1,1,2,3,4,5,5,5-nonafluoro-2-pentene (CF ₃ CF═CFCHFCF ₃ ); 1,2,3,4,4,4-hexafluoro-3- (trifluoro methyl) -1-butene _{(CHF = CFCF (CF 3)} 2); 1,1,2,4,4,4- hexa Ruoro-3- (trifluoromethyl) -1-butene _{(CF 2 = CFCH (CF 3} ) 2); 1,1,1,4,4,4- hexafluoro-2- (trifluoromethyl) -2 Butene (CF ₃ CH═C (CF ₃ ) ₂ ); 1,1,3,4,4,4-hexafluoro-3- (trifluoromethyl) -1-butene (CF ₂ ═CHCF (CF ₃ ) ₂ ); 2,3,3,4,4,5,5,5- octafluoro-1-pentene _{(CH 2 = CFCF 2 CF 2} CF 3); 1,2,3,3,4,4,5, 5-octafluoro-1-pentene _{(CHF = CFCF 2 CF 2 CHF} 2); 3,3,4,4,4- pentafluoro-2- (trifluoromethyl) -1-butene (CH ₂ = C (CF _{3) CF 2 CF 3);} 1,1,4,4,4- pentafluoro-3- (trifluoromethanesulfonyl Le) -1- butene _{(CF 2 = CHCH (CF 3} ) 2); 1,3,4,4,4- pentafluoro-3- (trifluoromethyl) -1-butene (CHF = CHCF (CF _{3) 2} ); 1,1,4,4,4-pentafluoro-2- (trifluoromethyl) -1-butene (CF ₂ ═C (CF ₃ ) CH ₂ CF ₃ ); Tetrafluoro-3- (trifluoromethyl) -1-butene ((CF ₃ ) ₂ CFCH═CH ₂ ); 3,3,4,4,5,5,5-heptafluoro-1-pentene (CF ₃ CF _{2 CF 2 CH = CH 2)} ; 2,3,3,4,4,5,5- heptafluoro-1-pentene _{(CH 2 = CFCF 2 CF 2} CHF 2); 1,1,3,3,5 5,5 heptafluoro-1-butene _{(CF 2 = CHCF 2 CH 2} CF 3); 1,1,1,2, 4,4,4-heptafluoro-3-methyl-2-butene (CF ₃ CF═C (CF ₃ ) (CH ₃ )); 2,4,4,4-tetrafluoro-3- (trifluoromethyl) 1-butene _{(CH 2 = CFCH (CF 3} ) 2); 1,4,4,4- tetrafluoro-3- (trifluoromethyl) -1-butene _{(CHF = CHCH (CF 3)} 2); 1 , 1,1,4-tetrafluoro-2- (trifluoromethyl) -2-butene (CH ₂ FCH═C (CF ₃ ) ₂ ); 1,1,1,3-tetrafluoro-2- (trifluoro Methyl) -2-butene (CH ₃ CF═C (CF ₃ ) ₂ ); 1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1-hexene ( _{CF 3 (CF 2) 3 CF} = CF 2); 1,1,1,2,2,3,4,5,5,6,6,6- de Kafuruoro 3- hexene _{(CF 3 CF 2 CF = CFCF} 2 CF 3); 1,1,1,4,4,4- hexafluoro-2,3-bis (trifluoromethyl) -2-butene ((CF ₃ ) ₂ C = C (CF ₃ ) ₂ ); 1,1,1,2,3,4,5,5,5-nonafluoro-4- (trifluoromethyl) -2-pentene ((CF ₃ ) ₂ CFCF = CFCF ₃ ); 1,1,1,4,4,5,5,5-octafluoro-2- (trifluoromethyl) -2-pentene ((CF ₃ ) ₂ C═CHC ₂ F ₅ ); 1,1,1,3,4,5,5,5-octafluoro-4- (trifluoromethyl) -2-pentene ((CF ₃ ) ₂ CFCF═CHCF ₃ ); 3,3,4,4 5,5,6,6,6- nonafluoro-1-hexene _{(CF 3 CF 2 CF 2 CF} 2 CH = CH 2) 4,4,4-trifluoro-3,3-bis (trifluoromethyl) -1-butene _{(CH 2 = CHC (CF 3} ) 3); 1,1,1,4,4,4- hexafluoro - 2- (trifluoromethyl) -3-methyl-2-butene ((CF ₃ ) ₂ C═C (CH ₃ ) (CF ₃ )); 2,3,3,5,5,5-hexafluoro-4 - (trifluoromethyl) -1-pentene _{(CH 2 = CFCF 2 CH (} CF 3) 2); 1,1,1,2,4,4,5,5,5- nonafluoro-3-methyl-2- Pentene (CF ₃ CF═C (CH ₃ ) CF ₂ CF ₃ ); 1,1,1,5,5,5-hexafluoro-4- (trifluoromethyl) -2-pentene (CF ₃ CH═CHCH ( CF ₃ ) ₂ ); 1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro 2- heptene _{(CF 3 CF = CFCF 2 CF} 2 C 2 F 5); 1,1,1,2,2,3,4,5,5,6,6,7,7,7- tetradecanoyl fluoro 3- heptene _{(CF 3 CF 2 CF = CFCF} 2 C 2 F 5); 1,1,1,3,4,4,5,5,6,6,7,7,7- tridecafluoro-fluoro-2 - heptene _{(CF 3 CH = CFCF 2 CF} 2 C 2 F 5); 1,1,1,2,4,4,5,5,6,6,7,7,7- tridecafluoro-2-heptene (CF ₃ CF = CHCF ₂ CF ₂ C ₂ F ₅ ); 1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF ₃ CF ₂ CH═CFCF ₂ C ₂ F ₅ ); and 1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF ₃ CF ₂ CF = Fluoroolefin selected from the group consisting of HCF ₂ C ₂ F _5);
A composition selected from the group consisting of:

  3. 3. A cooling method comprising: condensing the composition according to 1 or 2; and then evaporating the composition in the vicinity of an object to be cooled.

  4). 3. A heating method comprising: evaporating the composition according to 1 or 2; and then condensing the composition in the vicinity of an object to be heated.

5. A method for providing heating or cooling in a refrigeration, air conditioning, or heat pump apparatus, wherein the refrigerant or heat transfer fluid composition is (a) a centrifugal compressor; (b) a multi-stage centrifugal compressor, or (c) a single slab / single pass heat exchange. Supplying the device with a vessel; wherein the refrigerant or heat transfer fluid composition comprises:
(I) a fluoroolefin of formula E—R ¹ CH═CHR ² or Z—R ¹ CH═CHR ² , wherein R ¹ and R ² are independently C ₁ -C ₆ perfluoro A fluoroolefin which is an alkyl group;
(Ii) a cyclic fluoroolefin of formula cyclo- [CX = CY (CZW) _n- ], wherein X, Y, Z, and W are independently H or F, and n is A cyclic fluoroolefin which is an integer from 2 to 5; or (iii) 1,2,3,3,3-pentafluoro-1-propene (CF ₃ CF═CHF); 1,1,3,3,3-penta fluoro-1-propene _{(CF 3 CH = CF 2)} ; 1,1,2,3,3- pentafluoro-1-propene _{(CHF 2 CF = CF 2)} ; 1,2,3,3- tetrafluoro - 1-propene (CHF ₂ CF═CHF); 2,3,3,3-tetrafluoro-1-propene (CF ₃ CF═CH ₂ ); 1,3,3,3-tetrafluoro-1-propene (CF ₃ CH = CHF); 1,1,2,3- tetrafluoro-1 Ropen _{(CH 2 FCF = CF 2)} ; 1,1,3,3- tetrafluoro-1-propene _{(CHF 2 CH = CF 2)} ; 2,3,3- trifluoro-1-propene (CHF ₂ CF = CH ₂ ); 3,3,3-trifluoro-1-propene (CF ₃ CH═CH ₂ ); 1,1,2-trifluoro-1-propene (CH ₃ CF═CF ₂ ); 1,1, 3-trifluoro-1-propene (CH ₂ FCH═CF ₂ ); 1,2,3-trifluoro-1-propene (CH ₂ FCF═CHF); 1,3,3-trifluoro-1-propene ( CHF ₂ CH = CHF); 1,1,1,2,3,4,4,4- octafluoro-2-butene _{(CF 3 CF = CFCF 3)} ; 1,1,2,3,3,4, 4,4 octafluoro-1-butene _{(CF 3 CF 2 CF = CF} 2); 1,1, , 2,4,4,4-heptafluoro-2-butene _{(CF 3 CF = CHCF 3)} ; 1,2,3,3,4,4,4- heptafluoro-1-butene (CHF = CFCF ₂ CF ₃ ); 1,1,1,2,3,4,4-heptafluoro-2-butene (CHF ₂ CF═CFCF ₃ ); 1,3,3,3-tetrafluoro-2- (trifluoromethyl) -1-propene ((CF ₃ ) ₂ C═CHF); 1,1,3,3,4,4,4-heptafluoro-1-butene (CF ₂ ═CHCF ₂ CF ₃ ); 1,1,2, , 3,4,4,4-heptafluoro-1-butene _{(CF 2 = CFCHFCF 3);} 1,1,2,3,3,4,4- heptafluoro-1-butene (CF ₂ = CFCF ₂ CHF ₂ ); 2,3,3,4,4,4-hexafluoro-1-butene (CF ₃ CF ₂ CF═C H ₂ ); 1,3,3,4,4,4-hexafluoro-1-butene (CHF═CHCF ₂ CF ₃ ); 1,2,3,4,4,4-hexafluoro-1-butene ( CHF = CFCHFCF ₃ ); 1,2,3,3,4,4-hexafluoro-1-butene (CHF═CFCF ₂ CHF ₂ ); 1,1,2,3,4,4-hexafluoro-2- butene _{(CHF 2 CF = CFCHF 2)} ; 1,1,1,2,3,4- hexafluoro-2-butene _{(CH 2 FCF = CFCF 3)} ; 1,1,1,2,4,4- hexa Fluoro-2-butene (CHF ₂ CH═CFCF ₃ ); 1,1,1,3,4,4-hexafluoro-2-butene (CF ₃ CH═CFCHF ₂ ); 1,1,2,3,3 , 4-hexafluoro-1-butene _{(CF 2 = CFCF 2 CH 2} F); 1,1,2, , 4,4-hexafluoro-1-butene _{(CF 2 = CFCHFCHF 2);} 3,3,3- trifluoro-2- (trifluoromethyl) -1-propene _{(CH 2 = C (CF 3} ) 2) 1,1,1,2,4-pentafluoro-2-butene (CH ₂ FCH═CFCF ₃ ); 1,1,1,3,4-pentafluoro-2-butene (CF ₃ CH═CFCH ₂ F) ); 3,3,4,4,4-pentafluoro-1-butene (CF ₃ CF ₂ CH═CH ₂ ); 1,1,1,4,4-pentafluoro-2-butene (CHF ₂ CH═) CHCF ₃ ); 1,1,1,2,3-pentafluoro-2-butene (CH ₃ CF═CFCF ₃ ); 2,3,3,4,4-pentafluoro-1-butene (CH ₂ ═CFCF) ₂ CHF _2); 1,1,2,4,4- pentafluoro-2-butene _{CHF 2 CF = CHCHF 2);} 1,1,2,3,3- pentafluoro-1-butene _{(CH 3 CF 2 CF = CF} 2); 1,1,2,3,4- pentafluoro-2- butene _{(CH 2 FCF = CFCHF 2)} ; 1,1,3,3,3- pentafluoro-2-methyl-1-propene _{(CF 2 = C (CF 3} ) (CH 3)); 2- ( difluoromethyl ) -3,3,3-trifluoro-1-propene _{(CH 2 = C (CHF 2} ) (CF 3)); 2,3,4,4,4- pentafluoro-1-butene (CH ₂ = CFCHFCF _3); 1,2,4,4,4- pentafluoro-1-butene _{(CHF = CFCH 2 CF 3)} ; 1,3,4,4,4- pentafluoro-1-butene (CHF = CHCHFCF ₃₎ 1,3,3,4,4-pentafluoro-1-butene (CHF = CHCF ₂ CHF ₂ ); 1,2,3,4,4-pentafluoro-1-butene (CHF═CFCHFCHF ₂ ); 3,3,4,4-tetrafluoro-1-butene (CH ₂ ═CHCF ₂ CHF) ₂ ); 1,1-difluoro-2- (difluoromethyl) -1-propene (CF ₂ ═C (CHF ₂ ) (CH ₃ )); 1,3,3,3-tetrafluoro-2-methyl-1 - propene _{(CHF = C (CF 3)} (CH 3)); 2- difluoromethyl-3,3-difluoro-1-propene _{(CH 2 = C (CHF 2} ) 2); 1,1,1,2- Tetrafluoro-2-butene (CF ₃ CF═CHCH ₃ ); 1,1,1,3-tetrafluoro-2-butene (CH ₃ CF═CHCF ₃ ); 1,1,1,2,3,4, 4,5,5,5-decafluoro-2-pentene (CF ₃ CF = FCF ₂ CF _3); 1,1,2,3,3,4,4,5,5,5- decafluoro-1-pentene _{(CF 2 = CFCF 2 CF 2} CF 3); 1,1,1, 4,4,4-hexafluoro-2- (trifluoromethyl) -2-butene ((CF ₃ ) ₂ C═CHCF ₃ ); 1,1,1,2,4,4,5,5,5- nonafluoro-2-pentene _{(CF 3 CF = CHCF 2 CF} 3); 1,1,1,3,4,4,5,5,5- nonafluoro-2-pentene _{(CF 3 CH = CFCF 2 CF} 3); 1,2,3,3,4,4,5,5,5- nonafluoro-1-pentene _{(CHF = CFCF 2 CF 2 CF} 3); 1,1,3,3,4,4,5,5, 5-nonafluoro-1-pentene _{(CF 2 = CHCF 2 CF 2} CF 3); 1,1,2,3,3,4,4,5,5- Nonafuruo 1-pentene _{(CF 2 = CFCF 2 CF 2} CHF 2); 1,1,2,3,4,4,5,5,5- nonafluoro-2-pentene _{(CHF 2 CF = CFCF 2 CF} 3); 1,1,1,2,3,4,4,5,5-nonafluoro-2-pentene (CF ₃ CF═CFCF ₂ CHF ₂ ); 1,1,1,2,3,4,5,5 5-nonafluoro-2-pentene _{(CF 3 CF = CFCHFCF 3)} ; 1,2,3,4,4,4- hexafluoro-3- (trifluoromethyl) -1-butene (CHF = CFCF (CF _{3) 2} ); 1,1,2,4,4,4-hexafluoro-3- (trifluoromethyl) -1-butene (CF ₂ ═CFCH (CF ₃ ) ₂ ); 1,1,1,4,4 , 4-Hexafluoro-2- (trifluoromethyl) -2-butene (CF ₃ CH═C (C F _{3) 2);} 1,1,3,4,4,4- hexafluoro-3- (trifluoromethyl) -1-butene _{(CF 2 = CHCF (CF 3} ) 2); 2,3,3, 4,4,5,5,5-octafluoro-1-pentene _{(CH 2 = CFCF 2 CF 2} CF 3); 1,2,3,3,4,4,5,5- octafluoro-1-pentene _{(CHF = CFCF 2 CF 2 CHF} 2); 3,3,4,4,4- pentafluoro-2- (trifluoromethyl) -1-butene _{(CH 2 = C (CF 3} ) CF 2 CF 3); 1,1,4,4,4- pentafluoro-3- (trifluoromethyl) -1-butene _{(CF 2 = CHCH (CF 3} ) 2); 1,3,4,4,4- pentafluoro -3 - (trifluoromethyl) -1-butene _{(CHF = CHCF (CF 3)} 2); 1,1,4,4,4- Ntafuruoro 2- (trifluoromethyl) -1-butene _{(CF 2 = C (CF 3} ) CH 2 CF 3); 3,4,4,4- tetrafluoro-3- (trifluoromethyl) -1-butene _{((CF 3) 2 CFCH =} CH 2); 3,3,4,4,5,5,5- heptafluoro-1-pentene _{(CF 3 CF 2 CF 2 CH} = CH 2); 2,3,3 , 4,4,5,5-heptafluoro-1-pentene _{(CH 2 = CFCF 2 CF 2} CHF 2); 1,1,3,3,5,5,5- heptafluoro-1-butene (CF _{2 = CHCF 2 CH 2 CF 3)} ; 1,1,1,2,4,4,4- heptafluoro-3-methyl-2-butene _{(CF 3 CF = C (CF} 3) (CH 3)); 2 4,4,4-tetrafluoro-3- (trifluoromethyl) -1-butene (CH ₂ = CFCH CF _{3) 2);} 1,4,4,4- tetrafluoro-3- (trifluoromethyl) -1-butene _{(CHF = CHCH (CF 3)} 2); 1,1,1,4- tetrafluoro - 2- (trifluoromethyl) -2-butene (CH ₂ FCH═C (CF ₃ ) ₂ ); 1,1,1,3-tetrafluoro-2- (trifluoromethyl) -2-butene (CH ₃ CF = C (CF ₃ ) ₂ ); 1,1,1-trifluoro-2- (trifluoromethyl) -2-butene ((C
_{F 3) 2 C = CHCH 3} ); 3,4,4,5,5,5- hexafluoro-2-pentene _{(CF 3 CF 2 CF = CHCH} 3); 1,1,1,4,4,4 - hexafluoro-2-methyl-2-butene _{(CF 3 C (CH 3)} = CHCF 3); 3,3,4,5,5,5- hexafluoro-1-pentene (CH ₂ = CHCF ₂ CHFCF ₃ ); 3- (trifluoromethyl) -4,4,4-trifluoro-1-butene _{(CH 2 = C (CF 3} ) CH 2 CF 3); 1,1,2,3,3,4,4 , 5,5,6,6,6- dodecafluoro-1-hexene _{(CF 3 (CF 2) 3} CF = CF 2); 1,1,1,2,2,3,4,5,5,6 , 6,6-dodecafluoro-3- hexene _{(CF 3 CF 2 CF = CFCF} 2 CF 3); 1,1,1,4,4,4- hexafluoro 2,3-bis (trifluoromethyl) -2-butene _{((CF 3) 2 C =} C (CF 3) 2); 1,1,1,2,3,4,5,5,5- nonafluoro - 4- (trifluoromethyl) -2-pentene ((CF ₃ ) ₂ CFCF═CFCF ₃ ); 1,1,1,4,4,5,5,5-octafluoro-2- (trifluoromethyl)- 2-pentene ((CF ₃ ) ₂ C═CHC ₂ F ₅ ); 1,1,1,3,4,5,5,5-octafluoro-4- (trifluoromethyl) -2-pentene ((CF ₃ ) ₂ CFCF = CHCF ₃ ); 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene (CF ₃ CF ₂ CF ₂ CF ₂ CH═CH ₂ ); , 4-trifluoromethyl-3,3-bis (trifluoromethyl) -1-butene _{(CH 2 = CHC (CF 3} ) 3) 1,1,1,4,4,4-hexafluoro-3-methyl-2- (trifluoromethyl) -2-butene _{((CF 3) 2 C =} C (CH 3) (CF 3)); 2 , 3,3,5,5,5- hexafluoro-4- (trifluoromethyl) -1-pentene _{(CH 2 = CFCF 2 CH (} CF 3) 2); 1,1,1,2,4,4 , 5,5,5-nonafluoro-3-methyl-2-pentene _{(CF 3 CF = C (CH} 3) CF 2 CF 3); 1,1,1,5,5,5- hexafluoro-4- ( trifluoromethyl) -2-pentene _{(CF 3 CH = CHCH (CF} 3) 2); 3,4,4,5,5,6,6,6- octafluoro-2-hexene (CF ₃ CF ₂ CF ₂ CF = CHCH ₃ ); 3,3,4,4,5,5,6,6-octafluoro-1-hexene (CH ₂ ═CHCF ₂ CF ₂ CF ₂ CHF ₂ ); 1,1,1,4,4-pentafluoro-2- (trifluoromethyl) -2-pentene ((CF ₃ ) ₂ C═CHCF ₂ CH ₃ ); , 5,5,5-pentafluoro-2- (trifluoromethyl) -1-pentene _{(CH 2 = C (CF 3} ) CH 2 C 2 F 5); 3,3,4,4,5,5, 5-heptafluoro-2-methyl-1-pentene _{(CF 3 CF 2 CF 2 C} (CH 3) = CH 2); 4,4,5,5,6,6,6- heptafluoro-2-hexenoic ( _{CF 3 CF 2 CF 2 CH =} CHCH 3); 4,4,5,5,6,6,6- heptafluoro-1-hexene _{(CH 2 = CHCH 2 CF 2} C 2 F 5); 1,1, 1,2,2,3,4- heptafluoro-3- hexene _{(CF 3 CF 2 CF = CFC} 2 H 5); 4,5,5,5- Tiger-fluoro-4-trifluoromethyl-1-pentene _{(CH 2 = CHCH 2 CF (} CF 3) 2); 1,1,1,2,5,5,5- heptafluoro-4-methyl-2-pentene (CF ₃ CF═CHCH (CF ₃ ) (CH ₃ )); 1,1,1,3-tetrafluoro-2-trifluoromethyl-2-pentene ((CF ₃ ) ₂ C═CFC ₂ H ₅ ); 1,1,1,2,3,4,4,5,5,6,6,7,7,7- tetradecanoyl-fluoro-2-heptene _{(CF 3 CF = CFCF 2 CF} 2 C 2 F 5); 1,1,1,2,2,3,4,5,5,6,6,7,7,7- tetradecanoyl-fluoro-3- heptene _{(CF 3 CF 2 CF = CFCF} 2 C 2 F 5); 1,1,1,3,4,4,5,5,6,6,7,7,7- tridecafluoro-2-heptene (CF ₃ CH = C _{CF 2 CF 2 C 2 F 5} ); 1,1,1,2,4,4,5,5,6,6,7,7,7- tridecafluoro-2-heptene (CF ₃ CF = CHCF ₂ CF ₂ C ₂ F ₅ ); 1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF ₃ CF ₂ CH═CFCF ₂ C ₁ F ₅ ); 1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF ₃ CF ₂ CF═CHCF ₂ C _{2 F 5); CF 2 = CFOCF} 2 CF 3 (PEVE); CF 2 = CFOCF 3 (PMVE) and fluoro olefin selected from the group consisting of;
A process comprising at least one fluoroolefin selected from the group consisting of:

  6). A method for reducing a flame risk in a refrigeration apparatus, an air conditioner, or a heat pump apparatus using the composition according to 1 or 2, wherein the apparatus includes a combustible refrigerant, and the method includes the composition. Supplying the device, and optionally adding a lubricant to the composition to be added.

  7). A method for reducing the flammability of a flammable refrigerant using the refrigerant or the heat transfer fluid composition according to claim 1, comprising the step of combining the flammable refrigerant with the composition.

  8). A method for replacing the use of a high global warming potential refrigerant, wherein the composition according to 1 or 2 is frozen in place of or in combination with the high global warming potential refrigerant in a refrigeration, air conditioning, or heat pump device. And providing to an air conditioning or heat pump device.

  9. A method for reducing the global warming potential of an original refrigerant or heat transfer fluid composition using the composition described in 1 above, wherein the original refrigerant or heat transfer fluid composition and the composition described in 1 above are used. A second refrigerant or heat transfer fluid composition in combination with an object, wherein the second refrigerant or heat transfer fluid composition is lower than the original refrigerant or heat transfer fluid composition. A method characterized by having a conversion factor.

  10. 3. A method for reducing the GWP of an original refrigerant or heat transfer fluid composition in a refrigeration, air conditioning or heat pump device, wherein the original refrigerant or heat transfer fluid has a GWP of about 150 or more; Supplying a second, lower GWP refrigerant or heat transfer fluid composition to the refrigeration, air conditioning, or heat pump apparatus.

11. A method for replacing an original refrigerant or heat transfer fluid composition with a second refrigerant or heat transfer fluid composition, wherein the composition comprising at least one fluoroolefin is provided as the second refrigerant or heat transfer fluid composition A method comprising the steps of:
The original refrigerant or heat transfer fluid composition is:
(I) R134a substituted with a second refrigerant or heat transfer fluid composition comprising 1,1,1,2-tetrafluoroethane (R134a) comprising trifluoromethyltrifluorovinylether (PMVE);
(Ii) 1,1-difluoroethane (R152a), which is E-1,3,3,3-tetrafluoropropene (E-HFC-1234ze), 1,2,3,3,3-pentafluoropropene ( HFC-1225ye), 2,3,3,3-tetrafluoropropene (HFC-1234yf), 3,3,3-trifluoropropene (HFC-1243zf), and trifluoromethyl trifluorovinyl ether (PMVE) R152a substituted by a second refrigerant or heat transfer fluid composition comprising at least one compound selected from:
(Iii) 1,1,1,2,3,3,3-heptafluoropropane (R227ea), wherein E-1,3,3,3-tetrafluoropropene (E-HFC-1234ze), 2,3,3,3-pentafluoropropene (HFC-1225ye), 2,3,3,3-tetrafluoropropene (HFC-1234yf), 3,3,3-trifluoropropene (HFC-1243zf), and R227ea substituted by a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of trifluoromethyl trifluorovinyl ether (PMVE);
(Iv) 1,1,2-trichloro-1,2,2-trifluoroethane (R113) comprising 1,1,1,3,4,5,5,5-octafluoro-4- (tri Fluoromethyl) -2-butene (HFC-152-11 mmyz); 1,1,1,4,4,5,5,5-octafluoro-2- (trifluoromethyl) -2-pentene (HFC-152) 11 mmtz); 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene (HFC-151-12mcy); 1,1,1,3-tetra Fluoro-2-butene (HFC-1354mzy); 1,1,1,4,4,4-hexafluoro-2,3-bis (trifluoromethyl) -2-butene (HFC-151-12 mmtt); 2,3,3,4,4,5,5,6,6- Cafluorocyclohexene (FC-C151-10y); 3,3,4,4,5,5,5-heptafluoro-2-methyl-1-pentene (HFC-1567fts); 3,3,4,4,5 , 5,6,6,6-nonafluoro-1-hexene (PFBE); 4,4,5,5,6,6,6-heptafluoro-2-hexene (HFC-1567szz); 4,4,5,5,6,6,6-decafluoro-2-hexene (F13E); 1,1,1,2,3,4,5,5,5-nonafluoro-4- (trifluoromethyl) ) -2-pentene (HFC-151-12 mmzz); and 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (F22E) A second refrigerant comprising at least one compound or R113 substituted by thermal fluid composition;
(V) 1,1,1,2,3,4,4,5,5,5-decafluoropentane (R43-10mee), which is 1,1,1,3,4,5,5,5 -Octafluoro-4- (trifluoromethyl) -2-butene (HFC-152-11 mmyz); 1,1,1,4,4,5,5,5-octafluoro-2- (trifluoromethyl)- 2-pentene (HFC-152-11 mmtz); 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene (HFC-151-12 mcy); 1 1,1,1,3-tetrafluoro-2-butene (HFC-1354mzy); 1,1,1,4,4,4-hexafluoro-2,3-bis (trifluoromethyl) -2-butene (HFC) -151-12 mmtt); 1, 2, 3, 3, 4, 4, 5 5,3,6-decafluorocyclohexene (FC-C151-10y); 3,3,4,4,5,5,5-heptafluoro-2-methyl-1-pentene (HFC-1567fts); 3,3 4,4,5,5,6,6,6-nonafluoro-1-hexene (PFBE); 4,4,5,5,6,6,6-heptafluoro-2-hexene (HFC-1567szz); 1,1,1,4,5,5,6,6,6-decafluoro-2-hexene (F13E); 1,1,1,2,3,4,5,5,5-nonafluoro- From 4- (trifluoromethyl) -2-pentene (HFC-151-12 mmzz); and 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (F22E) A first containing at least one compound selected from the group consisting of R43-10mee substituted by the refrigerant or heat transfer fluid composition;
(Vi) C ₄ F ₉ OCH ₃ , 1,1,1,3,4,5,5,5-octafluoro-4- (trifluoromethyl) -2-butene (HFC-152-11 mmyz) 1,1,1,4,4,5,5,5-octafluoro-2- (trifluoromethyl) -2-pentene (HFC-152-11 mmtz); 1,1,1,2,2,3 , 4,5,5,6,6,6-dodecafluoro-3-hexene (HFC-151-12mcy); 1,1,1,3-tetrafluoro-2-butene (HFC-1354mzy); 1,1 , 1,4,4,4-hexafluoro-2,3-bis (trifluoromethyl) -2-butene (HFC-151-12 mmtt); 1,2,3,3,4,4,5,5 6,6-decafluorocyclohexene (FC-C151-10y 3,3,4,4,5,5,5-heptafluoro-2-methyl-1-pentene (HFC-1567fts); 3,3,4,4,5,5,6,6,6-nonafluoro; -1, -hexene (PFBE); 4,4,5,5,6,6,6-heptafluoro-2-hexene (HFC-1567szz); 1,1,1,4,4,5,5,6 6,6-decafluoro-2-hexene (F13E); 1,1,1,2,3,4,5,5,5-nonafluoro-4- (trifluoromethyl) -2-pentene (HFC-151 A second compound comprising at least one compound selected from the group consisting of 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (F22E) C ₄ F ₉ OCH ₃ replaced by a refrigerant or heat transfer fluid composition;
(Vii) 1,1,1,3,3-pentafluorobutane (R365mfc), which is 1,1,1,3,4,5,5,5-octafluoro-4- (trifluoromethyl)- 2-butene (HFC-152-11 mmyz); 1,1,1,4,4,5,5,5-octafluoro-2- (trifluoromethyl) -2-pentene (HFC-152-11 mmtz); 1 1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene (HFC-151-12mcy); 1,1,1,3-tetrafluoro-2- Butene (HFC-1354mzy); 1,1,1,4,4,4-hexafluoro-2,3-bis (trifluoromethyl) -2-butene (HFC-151-12 mmtt); 1,2,3 3,4,4,5,5,6,6-decuff Orocyclohexene (FC-C151-10y); 3,3,4,4,5,5,5-heptafluoro-2-methyl-1-pentene (HFC-1567fts); 3,3,4,4,5 5,6,6,6-nonafluoro-1-hexene (PFBE); 4,4,5,5,6,6,6-heptafluoro-2-hexene (HFC-1567szz); 1,1,1,4 , 4,5,5,6,6,6-decafluoro-2-hexene (F13E); 1,1,1,2,3,4,5,5,5-nonafluoro-4- (trifluoromethyl) 2-pentene (HFC-151-12 mmzz); and at least selected from the group consisting of 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (F22E) Second refrigerant or heat transfer stream containing one compound R365mfc substituted by composition;
(Viii) Fluorotrichloromethane (R11), which is 1,2,3,3,4,4,5,5-octafluorocyclopentene (FC-C1418y); 1,1,1,2,3,4, 4,5,5,5-decafluoro-2-pentene (FC-141-10myy); 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene (HFC-1429myz) 1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene (HFC-1429mzy); 3,3,4,4,5,5,5-heptafluoro-1-pentene (HFC-1447fz) ,; 1,1,1,4,4,4-hexafluoro-2-butene (F11E); 1,1,1,4,4,4-hexafluoro-2- (trifluoromethyl) ) -2-Butene (HFC-1429mzt) And a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 1,1,1,4,4,5,5,5-octafluoro-2-pentene (F12E) R11 substituted by
(Ix) 2,2, -dichloro-1,1,1-trifluoroethane (R123), 1,2,3,3,4,4,5,5-octafluorocyclopentene (FC-C1418y) 1,1,1,2,3,4,4,5,5,5-decafluoro-2-pentene (FC-141-10my); 1,1,1,2,4,4,5,5; , 5-nonafluoro-2-pentene (HFC-1429myz); 1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene (HFC-1429mzy); 3,3,4,4 , 5,5,5-heptafluoro-1-pentene (HFC-1447fz), 1,1,1,4,4,4-hexafluoro-2-butene (F11E); 4,4-Hexafluoro-2- (trifluoromethyl) -2-butene HFC-1429mzt); and a first refrigerant comprising at least one compound selected from the group consisting of 1,1,1,4,4,5,5,5-octafluoro-2-pentene (F12E) or R123 displaced by the heat transfer fluid composition;
(X) 1,1,1,3,3-pentafluoropropane (R245fa), which is 2,3,3-trifluoropropene (HFC-1243yf); 1,1,1,4,4,4- Hexafluoro-2-butene (F11E); 1,3,3,3-tetrafluoropropene (HFC-1234ze); 1,1,1,2,4,4,4-heptafluoro-2-butene (HFC- 1327my); 1,2,3,3-tetrafluoropropene (HFC-1234ye); and a second refrigerant or transfer comprising at least one compound selected from the group consisting of pentafluoroethyl trifluorovinyl ether (PEVE). R245fa displaced by the thermal fluid composition;
(Xi) 1,2-dichloro-1,1,2,2-tetrafluoroethane (R124), which is 1,1,1,2,3,4,4,4-octafluoro-2-butene (R124) FC-1318my); 1,2,3,3,4,4-hexafluorocyclobutene (FC-C1316cc); 2,3,3,4,4,4-hexafluoro-1-butene (HFC-1336yf) And a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 3,3,4,4,4-pentafluoro-1-butene (HFC-1345fz) R124;
(Xii) 1,1,1,3,3,3-hexafluoropropane (R236fa), which is 1,1,1,2,3,4,4,4-octafluoro-2-butene (FC- 1,3,3,3,4,4-hexafluorocyclobutene (FC-C1316cc); 2,3,3,4,4,4-hexafluoro-1-butene (HFC-1336yf); and R236fa substituted by a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 3,3,4,4,4-pentafluoro-1-butene (HFC-1345fz) ;
(Xiii) R401A, E-1,3,3,3-tetrafluoropropene (E-HFC-1234ze); 1,2,3,3,3-pentafluoropropene (HFC-1225ye); At least one selected from the group consisting of 3,3,3-tetrafluoropropene (HFC-1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyltrifluorovinyl ether (PMVE) R401A replaced by a second refrigerant or heat transfer fluid composition comprising a compound of:
(Xiv) R401B, wherein E-1,3,3,3-tetrafluoropropene (E-HFC-1234ze); 1,2,3,3,3-pentafluoropropene (HFC-1225ye); At least one selected from the group consisting of 3,3,3-tetrafluoropropene (HFC-1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyltrifluorovinyl ether (PMVE) R401B replaced by a second refrigerant or heat transfer fluid composition comprising a compound of:
(Xv) R409A, wherein E-1,3,3,3-tetrafluoropropene (E-HFC-1234ze); 1,2,3,3,3-pentafluoropropene (HFC-1225ye); At least one selected from the group consisting of 3,3,3-tetrafluoropropene (HFC-1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyltrifluorovinyl ether (PMVE) R409A replaced by a second refrigerant or heat transfer fluid composition comprising a compound of:
(Xvi) R409B, E-1,3,3,3-tetrafluoropropene (E-HFC-1234ze); 1,2,3,3,3-pentafluoropropene (HFC-1225ye); At least one selected from the group consisting of 3,3,3-tetrafluoropropene (HFC-1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyltrifluorovinyl ether (PMVE) R409B replaced by a second refrigerant or heat transfer fluid composition comprising a compound of:
(Xvii) R414B, E-1,3,3,3-tetrafluoropropene (E-HFC-1234ze); 1,2,3,3,3-pentafluoropropene (HFC-1225ye); At least one selected from the group consisting of 3,3,3-tetrafluoropropene (HFC-1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyltrifluorovinyl ether (PMVE) R414B replaced by a second refrigerant or heat transfer fluid composition comprising a compound of:
(Xviii) R416A, E-1,3,3,3-tetrafluoropropene (E-HFC-1234ze); 1,2,3,3,3-pentafluoropropene (HFC-1225ye); At least one selected from the group consisting of 3,3,3-tetrafluoropropene (HFC-1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyltrifluorovinyl ether (PMVE) R416A substituted by a second refrigerant or heat transfer fluid composition comprising a compound of:
(Xix) dichlorodifluoromethane (R12), 1,2,3,3,3-pentafluoropropene (HFC-1225ye); 2,3,3,3-tetrafluoropropene (HFC-1234yf); 3 , 3,3-trifluoropropene (HFC-1243zf); and a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of trifluoromethyl trifluorovinyl ether (PMVE) And (xx) R500, 1,2,3,3,3-pentafluoropropene (HFC-1225ye); 2,3,3,3-tetrafluoropropene (HFC-1234yf); 3 , 3,3-trifluoropropene (HFC-1243zf); and trifluoromethyltrif Fluorovinyl ether (PMVE) -second refrigerant or heat transfer fluid comprising at least one compound selected from the group consisting of trifluoropropene, 3,3,3-trifluoropropene, and trifluoromethyl trifluorovinyl ether R500 substituted by the composition;
A method characterized in that it is selected from the group consisting of:

  12 A method of using the composition according to 1 or 2 as a heat transfer fluid composition, comprising the step of transferring the composition from a heat source to a heat sink.

  13. (I) recovering a volume of one or more components of the refrigerant composition from at least one refrigerant container; (ii) reusing the one or more recovered components; Fully removing impurities, (iii) and optionally combining all or part of the recovered volume of the component with at least one additional refrigerant composition or component. 3. The method for producing a composition according to 1 or 2 above.

  14 A refrigeration, air conditioning or heat pump device comprising the composition according to 1 or 2 above.

  15. A portable refrigeration or air conditioner comprising the composition according to 1 or 2 above.

Claims (5)

A method for providing heating or cooling in a refrigeration, air conditioning, or heat pump apparatus, wherein the refrigerant or heat transfer fluid is (a) a centrifugal compressor; (b) a multi-stage centrifugal compressor, or (c) a single slab / single pass heat exchanger. wherein the step of introducing into the device with, wherein said refrigerant or heat transfer fluid is a Z-1,1,1,4,4,4-hexafluoro-2-butene, method. To reduce the flammability of flammable refrigerant, a method of using the Z-1,1,1,4,4,4-hexafluoro-2-butene as a refrigerant or heat transfer fluid, said flammable refrigerant A method comprising combining with said refrigerant or heat transfer fluid . A method for reducing the GWP of an original refrigerant or heat transfer fluid in a refrigeration, air conditioning or heat pump apparatus, wherein the original refrigerant or heat transfer fluid has a GWP of 150 or more; a second, lower GWP refrigerant Or a step of introducing a heat transfer fluid into the refrigeration, air conditioning or heat pump device, wherein the original refrigerant or heat transfer fluid is fluorotrichloromethane (R11), 2,2, -dichloro-1,1,1- It is selected from trifluoroethane (R123) or 1,1,1,3,3-pentafluoropropane (R245fa), and the second refrigerant or heat transfer fluid is Z-1,1,1,4,4 , wherein the 4-hexafluoro-2-butene (F11E). A method of using Z-1,1,1,4,4,4-hexafluoro-2-butene as a heat transfer fluid, comprising the step of transferring the heat transfer fluid from a heat source to a heat sink. Method. Frozen containing refrigerant or heat transfer fluid, the air conditioning or heat pump apparatus, said refrigerant or heat transfer fluid is a Z-1,1,1,4,4,4-hexafluoro-2-butene A device characterized .