Compositions comprising fluoroolefins and uses thereof

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

(Mutual reference of related applications) This application is a US provisional patent application No. 60 / 732,581 filed on November 1, 2005 and a US patent application No. 11 / 486,791 filed on July 13, 2006. Claim the benefit of priority based on.

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

Further environmental regulations could ultimately result in the global phasing out of certain HFC refrigerants. Currently, the automobile industry is facing regulations related to the global warming potential for refrigerants used in portable air conditioning. Therefore, there is a great current need to identify new refrigerants with reduced global warming potentials for the portable air conditioning market. In the future, as regulations become more widely applied, there will be an even greater need for refrigerants that can be used in all areas of the refrigeration and air conditioning industry.

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

<p><patcit num="1"><text>U.S. Pat. No. 6,066,768</text></patcit><patcit num="2"><text>U.S. Patent Application No. 11 / 062,044</text></patcit><patcit num="3"><text>U.S. Patent Application No. 10 / 910,495</text></patcit><patcit num="4"><text>US Reissue Patent No. RE36,951</text></patcit><patcit num="5"><text>U.S. Pat. No. 5,065,990</text></patcit><patcit num="6"><text>U.S. Pat. No. 5,363,674</text></patcit><patcit num="7"><text>U.S. Patent Application No. 11 / 367,517</text></patcit><patcit num="8"><text>U.S. Patent Application No. 11 / 378,832</text></patcit></p>

<p><nplcit num="1"><text>Jeanneaux et al., Journal of Fluorine Chemistry, Vol. 4, pp. 261-270 (1974)</text></nplcit><nplcit num="2"><text>1990 ASHRAE Handbook, Refrigeration Systems and Applications, Chapter 8, Title "Lubricants in Refrigeration Systems", pp. 8.1-8.21</text></nplcit><nplcit num="3"><text>"Synthetic Lubricants and High-Performance Fluids", RL Shubkin, Editor, Marcel Dekker, 1993</text></nplcit><nplcit num="4"><text>"Journal of Fluorine Chemistry", Vol. 24, pp. 93-104 (1984)</text></nplcit><nplcit num="5"><text>Journal of Organic Chemistry, Vol. 56, pp. 3187-3189 (1991)</text></nplcit><nplcit num="6"><text>Journal of Fluorine Chemistry, Vol. 125, pp. 99-105 (2004)</text></nplcit></p>

<p> It is an object of the present invention to provide novel refrigerant compositions 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 compared to current refrigerants. To do.</p>

<p> The present invention is: (i) Eq. ER¹CH = CHR²Or ZR¹CH = CHR²Fluoroolefin in the formula, R¹And R²But independently, C₁~ C₆Fluoroolefins, and in the formula, the total number of carbons in the compound is at least 5; (ii) formula cyclo- [CX = CY (CZW)_n-] Cyclic fluoroolefins, in which X, Y, Z, and W are independently H or F, and n is an integer of 2-5; and (iii. ) 2,3,3-Trifluoro-1-propene (CHF)₂CF = CH₂); 1,1,2-Trifluoro-1-propene (CH)₃CF = CF₂); 1,2,3-trifluoro-1-propene (CH)₂FCF = CF₂); 1,1,3-Trifluoro-1-propene (CH)₂FCH = CF₂); 1,3,3-trifluoro-1-propene (CHF)₂CH = CHF); 1,1,1,2,3,4,4,4-octafluoro-2-butene (CF)₃CF = CFCF₃); 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF)₃CF₂CF = CF₂); 1,1,1,2,4,4,4-heptafluoro-2-butene (CF)₃CF = CHCF₃); 1,2,3,3,4,4,4-heptafluoro-1-butene (CHF = CFCF)₂CF₃); 1,1,1,2,3,4,4-heptafluoro-2-butene (CHF)₂CF = CFCF₃); 1,3,3,3-Tetrafluoro-2- (trifluoromethyl) -1-propene ((CF)₃)₂C = CHF); 1,1,3,3,4,4,4-heptafluoro-1-butene (CF)₂= CHCF₂CF₃); 1,1,2,3,4,4,4-heptafluoro-1-butene (CF)₂= CFCHFCF₃); 1,1,2,3,3,4,4-heptafluoro-1-butene (CF)₂= CFCF₂CHF₂); 2,3,3,4,4,4-hexafluoro-1-butene (CF)₃CF₂CF = CH₂); 1,3,3,4,4,4-hexafluoro-1-butene (CHF = CHCF)₂CF₃); 1,2,3,4,4,4-hexafluoro-1-butene (CHF = CFC CHFCF)₃); 1,2,3,3,4,4-hexafluoro-1-butene (CHF = CFCF)₂CHF₂); 1,1,2,3,4,4-hexafluoro-2-butene (CHF)₂CF = CFCHF₂); 1,1,1,2,3,4-hexafluoro-2-butene (CH)₂FCF = CFCF₃); 1,1,1,2,4,4-hexafluoro-2-butene (CHF)₂CH = CFCF₃); 1,1,1,3,4,4-hexafluoro-2-butene (CF)₃CH = CFC CHF₂); 1,1,2,3,3,4-hexafluoro-1-butene (CF)₂= CFCF₂CH₂F); 1,1,2,3,4,4-hexafluoro-1-butene (CF)₂= CFCHFCHF₂); 3,3,3-Trifluoro-2- (trifluoromethyl) -1-propene (CH)₂= C (CF)₃)₂); 1,1,1,2,4-pentafluoro-2-butene (CH)₂FCH = CFCF₃); 1,1,1,3,4-pentafluoro-2-butene (CF)₃CH = CFCH₂F); 3,3,4,4,4-pentafluoro-1-butene (CF)₃CF₂CH = CH₂); 1,1,1,4,4-pentafluoro-2-butene (CHF)₂CH = CHCF₃); 1,1,1,2,3-pentafluoro-2-butene (CH)₃CF = CFCF₃); 2,3,3,4,4-Pentafluoro-1-butene (CH)₂= CFCF₂CHF₂); 1,1,2,4,4-pentafluoro-2-butene (CHF)₂CF = CHCHF₂); 1,1,2,3,3-pentafluoro-1-butene (CH)₃CF₂CF = CF₂); 1,1,2,3,4-pentafluoro-2-butene (CH)₂FCF = CFCHF₂); 1,1,3,3,3-pentafluoro-2-methyl-1-propene (CF)₂= C (CF)₃) (CH₃)); 2- (Difluoromethyl) -3,3,3-trifluoro-1-propene (CH)₂= C (CHF)₂) (CF₃)); 2,3,4,4,4-pentafluoro-1-butene (CH)₂= CFCHFCF₃); 1,2,4,4,4-pentafluoro-1-butene (CHF = CFCH)₂CF₃); 1,3,4,4,4-pentafluoro-1-butene (CHF = CHCHFCF)₃); 1,3,3,4,4-pentafluoro-1-butene (CHF = CHCF)₂CHF₂); 1,2,3,4,4-pentafluoro-1-butene (CHF = CFC CHFCHF)₂); 3,3,4,4-Tetrafluoro-1-butene (CH)₂= CHCF₂CHF₂); 1,1-difluoro-2- (difluoromethyl) -1-propene (CF)₂= C (CHF)₂) (CH₃)); 1,3,3,3-Tetrafluoro-2-methyl-1-propene (CHF = C (CF)₃) (CH₃)); 3,3-Difluoro-2- (difluoromethyl) -1-propene (CH)₂= C (CHF)₂)₂); 1,1,1,2-Tetrafluoro-2-butene (CF)₃CF = CHCH₃); 1,1,1,3-Tetrafluoro-2-butene (CH)₃CF = CHCF₃); 1,1,1,2,3,4,4,5,5,5-decafluoro-2-pentene (CF)₃CF = CFCF₂CF₃); 1,1,2,3,3,4,4,5,5,5-decafluoro-1-pentene (CF)₂= CFCF₂CF₂CF₃); 1,1,1,4,4,4-hexafluoro-2- (trifluoromethyl) -2-butene ((CF)₃)₂C = CHCF₃); 1,1,1,2,4,4,5,5,5-Nonafluoro-2-pentene (CF)₃CF = CHCF₂CF₃); 1,1,1,3,4,4,5,5,5-Nonafluoro-2-pentene (CF)₃CH = CFCF₂CF₃); 1,2,3,3,4,4,5,5,5-Nonafluoro-1-pentene (CHF = CFCF)₂CF₂CF₃); 1,1,3,3,4,4,5,5,5-Nonafluoro-1-pentene (CF)₂= CHCF₂CF₂CF₃); 1,1,2,3,3,4,4,5,5-Nonafluoro-1-pentene (CF)₂= CFCF₂CF₂CHF₂); 1,1,2,3,4,4,5,5,5-Nonafluoro-2-pentene (CHF)₂CF = CFCF₂CF₃); 1,1,1,2,3,4,4,5,5-Nonafluoro-2-pentene (CF)₃CF = CFCF₂CHF₂); 1,1,1,2,3,4,5,5,5-Nonafluoro-2-pentene (CF)₃CF = CFCHFCF₃); 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)₃CH = 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= CFCF₂CF₂CF₃); 1,2,3,3,4,4,5,5-octafluoro-1-pentene (CHF = CFCF)₂CF₂CHF₂); 3,3,4,4,4-Pentafluoro-2- (trifluoromethyl) -1-butene (CH)₂= C (CF)₃) CF₂CF₃); 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) CH₂CF₃); 3,4,4,4-Tetrafluoro-3- (trifluoromethyl) -1-butene ((CF)₃)₂CFCH = CH₂); 3,3,4,4,5,5,5-heptafluoro-1-pentene (CF)₃CF₂CF₂CH = CH₂); 2,3,3,4,4,5,5-heptafluoro-1-pentene (CH)₂= CFCF₂CF₂CHF₂); 1,1,3,3,5,5,5-heptafluoro-1-butene (CF)₂= CHCF₂CH₂CF₃); 1,1,1,2,4,4,4-heptafluoro-3-methyl-2-butene (CF)₃CF = C (CF)₃) (CH₃)); 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)₂FCH = C (CF)₃)₂); 1,1,1,3-Tetrafluoro-2- (trifluoromethyl) -2-butene (CH)₃CF = C (CF)₃)₂); 1,1,1-Trifluoro-2- (trifluoromethyl) -2-butene ((CF)₃)₂C = CHCH₃); 3,4,4,5,5,5-hexafluoro-2-pentene (CF)₃CF₂CF = CHCH₃); 1,1,1,4,4,4-hexafluoro-2-methyl-2-butene (CF)₃C (CH)₃) = CHCF₃); 3,3,4,5,5,5-hexafluoro-1-pentene (CH)₂= CHCF₂CHFCF₃); 4,4,4-Trifluoro-3- (trifluoromethyl) -1-butene (CH)₂= C (CF)₃) CH₂CF₃); 1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1-hexene (CF)₃(CF₂)₃CF = CF₂); 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene (CF)₃CF₂CF = CFCF₂CF₃); 1,1,1,4,4,4-hexafluoro-2,3-bis (trifluoromethyl) -2-butene ((CF)₃)₂C = C (CF)₃)₂); 1,1,1,2,3,4,5,5,5-Nonafluoro-4- (trifluoromethyl) -2-pentene ((CF)₃)₂CFCF = CFCF₃); 1,1,1,4,4,5,5,5-octafluoro-2- (trifluoromethyl) -2-pentene ((CF)₃)₂C = CHC₂F₅); 1,1,1,3,4,5,5,5-octafluoro-4- (trifluoromethyl) -2-pentene ((CF)₃)₂CFCF = CHCF₃); 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene (CF)₃CF₂CF₂CF₂CH = CH₂); 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)₂C = C (CH)₃) (CF₃)); 2,3,3,5,5,5-hexafluoro-4- (trifluoromethyl) -1-pentene (CH)₂= CFCF₂CH (CF)₃)₂); 1,1,1,2,4,4,5,5,5-Nonafluoro-3-methyl-2-pentene (CF)₃CF = C (CH)₃) CF₂CF₃); 1,1,1,5,5,5-hexafluoro-4- (trifluoromethyl) -2-pentene (CF)₃CH = CHCH (CF)₃)₂); 3,4,4,5,5,6,6,6-octafluoro-2-hexene (CF)₃CF₂CF₂CF = CHCH₃); 3,3,4,4,5,5,6,6-octafluoro1-hexene (CH)₂= CHCF₂CF₂CF₂CHF₂); 1,1,1,4,4-pentafluoro-2- (trifluoromethyl) -2-pentene ((CF)₃)₂C = CHCF₂CH₃); 4,4,5,5,5-pentafluoro-2- (trifluoromethyl) -1-pentene (CH)₂= C (CF)₃) CH₂C₂F₅); 3,3,4,4,5,5,5-heptafluoro-2-methyl-1-pentene (CF)₃CF₂CF₂C (CH)₃) = CH₂); 4,4,5,5,6,6,6-heptafluoro-2-hexene (CF)₃CF₂CF₂CH = CHCH₃); 4,4,5,5,6,6,6-heptafluoro-1-hexene (CH)₂= CHCH₂CF₂C₂F₅); 1,1,1,2,2,3,4-heptafluoro-3-hexene (CF)₃CF₂CF = CFC₂H₅); 4,5,5,5-Tetrafluoro-4- (trifluoromethyl) -1-pentene (CH)₂= CHCH₂CF (CF)₃)₂); 1,1,1,2,5,5,5-heptafluoro-4-methyl-2-pentene (CF)₃CF = CHCH (CF)₃) (CH₃)); 1,1,1,3-Tetrafluoro-2- (trifluoromethyl) -2-pentene ((CF)₃)₂C = CFC₂H₅); 1,1,1,2,3,4,4,5,5,6,6,7,7,7-Tetradecafluoro-2-heptene (CF)₃CF = CFCF₂CF₂C₂F₅); 1,1,1,2,2,3,4,5,5,6,6,7,7,7-Tetradecafluoro-3-heptene (CF)₃CF₂CF = CFCF₂C₂F₅); 1,1,1,3,4,4,5,5,6,6,7,7,7-Tridecafluoro-2-heptene (CF)₃CH = CFCF₂CF₂C₂F₅); 1,1,1,2,4,4,5,5,6,6,7,7,7-Tridecafluoro-2-heptene (CF)₃CF = CHCF₂CF₂C₂F₅); 1,1,1,2,2,4,5,5,6,6,7,7,7-Tridecafluoro-3-heptene (CF)₃CF₂CH = CFCF₂C₂F₅); 1,1,1,2,2,3,5,5,6,6,7,7,7-Tridecafluoro-3-heptene (CF)₃CF₂CF = CHCF₂C₂F₅); CF₂= CFOCF₂CF₃(PEVE) and CF₂= CFOCF₃Fluoroolefins selected from the group consisting of (PMVE); relating to a refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of.</p><p> The present invention is: (i) a composition comprising at least one fluoroolefin compound; and (ii) at least one flammable refrigerant; said fluoroolefin is: formula (a) ER.¹CH = CHR²Or ZR¹CH = CHR²Fluoroolefin in the formula, R¹And R²But independently, C₁~ C₆Fluoroolefin, which is a perfluoroalkyl group of_n-] Cyclic fluoroolefins, in which X, Y, Z, and W are independently H or F, and n is an integer of 2-5; and (c. ) 1,2,3,3,3-Pentafluoro-1-propene (CF)₃CF = CHF); 1,1,3,3,3-pentafluoro-1-propene (CF)₃CH = CF₂); 1,1,2,3,3-pentafluoro-1-propene (CHF)₂CF = CF₂); 1,1,1,2,3,4,4,4-octafluoro-2-butene (CF)₃CF = CFCF₃); 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF)₃CF₂CF = CF₂); 1,1,1,2,4,4,4-heptafluoro-2-butene (CF)₃CF = CHCF₃); 1,2,3,3,4,4,4-heptafluoro-1-butene (CHF = CFCF)₂CF₃); 1,1,1,2,3,4,4-heptafluoro-2-butene (CHF)₂CF = CFCF₃); 1,3,3,3-Tetrafluoro-2- (trifluoromethyl) -1-propene ((CF)₃)₂C = CHF); 1,1,3,3,4,4,4-heptafluoro-1-butene (CF)₂= CHCF₂CF₃); 1,1,2,3,4,4,4-heptafluoro-1-butene (CF)₂= CFCHFCF₃); 1,1,2,3,3,4,4-heptafluoro-1-butene (CF)₂= CFCF₂CHF₂); 2,3,3,4,4,4-hexafluoro-1-butene (CF)₃CF₂CF = CH₂); 1,3,3,4,4,4-hexafluoro-1-butene (CHF = CHCF)₂CF₃); 1,2,3,4,4,4-hexafluoro-1-butene (CHF = CFC CHFCF)₃); 1,2,3,3,4,4-hexafluoro-1-butene (CHF = CFCF)₂CHF₂); 1,1,2,3,4,4-hexafluoro-2-butene (CHF)₂CF = CFCHF₂); 1,1,1,2,3,4-hexafluoro-2-butene (CH)₂FCF = CFCF₃); 1,1,1,2,4,4-hexafluoro-2-butene (CHF)₂CH = CFCF₃); 1,1,1,3,4,4-hexafluoro-2-butene (CF)₃CH = CFC CHF₂); 1,1,2,3,3,4-hexafluoro-1-butene (CF)₂= CFCF₂CH₂F); 1,1,2,3,4,4-hexafluoro-1-butene (CF)₂= CFCHFCHF₂); 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)₃CF = CFCF₂CF₃); 1,1,2,3,3,4,4,5,5,5-decafluoro-1-pentene (CF)₂= CFCF₂CF₂CF₃); 1,1,1,4,4,4-hexafluoro-2- (trifluoromethyl) -2-butene ((CF)₃)₂C = CHCF₃); 1,1,1,2,4,4,5,5,5-Nonafluoro-2-pentene (CF)₃CF = CHCF₂CF₃); 1,1,1,3,4,4,5,5,5-Nonafluoro-2-pentene (CF)₃CH = CFCF₂CF₃); 1,2,3,3,4,4,5,5,5-Nonafluoro-1-pentene (CHF = CFCF)₂CF₂CF₃); 1,1,3,3,4,4,5,5,5-Nonafluoro-1-pentene (CF)₂= CHCF₂CF₂CF₃); 1,1,2,3,3,4,4,5,5-Nonafluoro-1-pentene (CF)₂= CFCF₂CF₂CHF₂); 1,1,2,3,4,4,5,5,5-Nonafluoro-2-pentene (CHF)₂CF = CFCF₂CF₃); 1,1,1,2,3,4,4,5,5-Nonafluoro-2-pentene (CF)₃CF = CFCF₂CHF₂); 1,1,1,2,3,4,5,5,5-Nonafluoro-2-pentene (CF)₃CF = CFCHFCF₃); 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)₃CH = 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= CFCF₂CF₂CF₃); 1,2,3,3,4,4,5,5-octafluoro-1-pentene (CHF = CFCF)₂CF₂CHF₂); 3,3,4,4,4-Pentafluoro-2- (trifluoromethyl) -1-butene (CH)₂= C (CF)₃) CF₂CF₃); 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) CH₂CF₃); 3,4,4,4-Tetrafluoro-3- (trifluoromethyl) -1-butene ((CF)₃)₂CFCH = CH₂); 3,3,4,4,5,5,5-heptafluoro-1-pentene (CF)₃CF₂CF₂CH = CH₂); 2,3,3,4,4,5,5-heptafluoro-1-pentene (CH)₂= CFCF₂CF₂CHF₂); 1,1,3,3,5,5,5-heptafluoro-1-butene (CF)₂= CHCF₂CH₂CF₃); 1,1,1,2,4,4,4-heptafluoro-3-methyl-2-butene (CF)₃CF = C (CF)₃) (CH₃)); 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)₂FCH = C (CF)₃)₂); 1,1,1,3-Tetrafluoro-2- (trifluoromethyl) -2-butene (CH)₃CF = C (CF)₃)₂); 1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1-hexene (CF)₃(CF₂)₃CF = CF₂); 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene (CF)₃CF₂CF = CFCF₂CF₃); 1,1,1,4,4,4-hexafluoro-2,3-bis (trifluoromethyl) -2-butene ((CF)₃)₂C = C (CF)₃)₂); 1,1,1,2,3,4,5,5,5-Nonafluoro-4- (trifluoromethyl) -2-pentene ((CF)₃)₂CFCF = CFCF₃); 1,1,1,4,4,5,5,5-octafluoro-2- (trifluoromethyl) -2-pentene ((CF)₃)₂C = CHC₂F₅); 1,1,1,3,4,5,5,5-octafluoro-4- (trifluoromethyl) -2-pentene ((CF)₃)₂CFCF = CHCF₃); 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene (CF)₃CF₂CF₂CF₂CH = CH₂); 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)₂C = C (CH)₃) (CF₃)); 2,3,3,5,5,5-hexafluoro-4- (trifluoromethyl) -1-pentene (CH)₂= CFCF₂CH (CF)₃)₂); 1,1,1,2,4,4,5,5,5-Nonafluoro-3-methyl-2-pentene (CF)₃CF = C (CH)₃) CF₂CF₃); 1,1,1,5,5,5-hexafluoro-4- (trifluoromethyl) -2-pentene (CF)₃CH = CHCH (CF)₃)₂); 1,1,1,2,3,4,4,5,5,6,6,7,7,7-Tetradecafluoro-2-heptene (CF)₃CF = CFCF₂CF₂C₂F₅); 1,1,1,2,2,3,4,5,5,6,6,7,7,7-Tetradecafluoro-3-heptene (CF)₃CF₂CF = CFCF₂C₂F₅); 1,1,1,3,4,4,5,5,6,6,7,7,7-Tridecafluoro-2-heptene (CF)₃CH = CFCF₂CF₂C₂F₅); 1,1,1,2,4,4,5,5,6,6,7,7,7-Tridecafluoro-2-heptene (CF)₃CF = CHCF₂CF₂C₂F₅); 1,1,1,2,2,4,5,5,6,6,7,7,7-Tridecafluoro-3-heptene (CF)₃CF₂CH = CFCF₂C₂F₅); And 1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF)₃CF₂CF = CHCF₂C₂F₅) Fluoroolefins selected from the group; further relates to compositions selected from the group consisting of.</p><p> The present invention further relates to methods of using a refrigerant or heat transfer fluid composition in a refrigeration, air conditioning, or heat pump apparatus, wherein the composition is (a) a centrifugal compressor; (b) a multistage centrifugal compressor, or (c). ) Includes the step of feeding the device having a single slab / single pass heat exchanger; where the refrigerating composition or heat transfer composition is used to provide heating or cooling in the device; and said. The frozen composition or heat transfer composition is: (i) Eq. ER¹CH = CHR²Or ZR¹CH = CHR²Fluoroolefin in the formula, R¹And R²But independently, C₁~ C₆Fluoroolefin, which is a perfluoroalkyl group of_n-] Cyclic fluoroolefins, in which X, Y, Z, and W are independently H or F, and n is an integer of 2-5; or (iii). ) 1,2,3,3,3-Pentafluoro-1-propene (CF)₃CF = CHF); 1,1,3,3,3-pentafluoro-1-propene (CF)₃CH = CF₂); 1,1,2,3,3-pentafluoro-1-propene (CHF)₂CF = CF₂); 1,2,3,3-Tetrafluoro-1-propene (CHF)₂CF = CHF); 2,3,3,3-tetrafluoro-1-propen (CF)₃CF = CH₂); 1,3,3,3-Tetrafluoro-1-propene (CF)₃CH = CHF); 1,1,2,3-tetrafluoro-1-propene (CH)₂FCF = CF₂); 1,1,3,3-tetrafluoro-1-propene (CHF)₂CH = CF₂); 2,3,3-Trifluoro-1-propene (CHF)₂CF = CH₂); 3,3,3-Trifluoro-1-propene (CF)₃CH = CH₂); 1,1,2-Trifluoro-1-propene (CH)₃CF = CF₂); 1,1,3-Trifluoro-1-propene (CH)₂FCH = CF₂); 1,2,3-trifluoro-1-propene (CH)₂FCF = CHF); 1,3,3-trifluoro-1-propene (CHF)₂CH = CHF); 1,1,1,2,3,4,4,4-octafluoro-2-butene (CF)₃CF = CFCF₃); 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF)₃CF₂CF = CF₂); 1,1,1,2,4,4,4-heptafluoro-2-butene (CF)₃CF = CHCF₃); 1,2,3,3,4,4,4-heptafluoro-1-butene (CHF = CFCF)₂CF₃); 1,1,1,2,3,4,4-heptafluoro-2-butene (CHF)₂CF = CFCF₃); 1,3,3,3-Tetrafluoro-2- (trifluoromethyl) -1-propene ((CF)₃)₂C = CHF); 1,1,3,3,4,4,4-heptafluoro-1-butene (CF)₂= CHCF₂CF₃); 1,1,2,3,4,4,4-heptafluoro-1-butene (CF)₂= CFCHFCF₃); 1,1,2,3,3,4,4-heptafluoro-1-butene (CF)₂= CFCF₂CHF₂); 2,3,3,4,4,4-hexafluoro-1-butene (CF)₃CF₂CF = CH₂); 1,3,3,4,4,4-hexafluoro-1-butene (CHF = CHCF)₂CF₃); 1,2,3,4,4,4-hexafluoro-1-butene (CHF = CFC CHFCF)₃); 1,2,3,3,4,4-hexafluoro-1-butene (CHF = CFCF)₂CHF₂); 1,1,2,3,4,4-hexafluoro-2-butene (CHF)₂CF = CFCHF₂); 1,1,1,2,3,4-hexafluoro-2-butene (CH)₂FCF = CFCF₃); 1,1,1,2,4,4-hexafluoro-2-butene (CHF)₂CH = CFCF₃); 1,1,1,3,4,4-hexafluoro-2-butene (CF)₃CH = CFC CHF₂); 1,1,2,3,3,4-hexafluoro-1-butene (CF)₂= CFCF₂CH₂F); 1,1,2,3,4,4-hexafluoro-1-butene (CF)₂= CFCHFCHF₂); 3,3,3-Trifluoro-2- (trifluoromethyl) -1-propene (CH)₂= C (CF)₃)₂); 1,1,1,2,4-pentafluoro-2-butene (CH)₂FCH = CFCF₃); 1,1,1,3,4-pentafluoro-2-butene (CF)₃CH = CFCH₂F); 3,3,4,4,4-pentafluoro-1-butene (CF)₃CF₂CH = CH₂); 1,1,1,4,4-pentafluoro-2-butene (CHF)₂CH = CHCF₃); 1,1,1,2,3-pentafluoro-2-butene (CH)₃CF = CFCF₃); 2,3,3,4,4-Pentafluoro-1-butene (CH)₂= CFCF₂CHF₂); 1,1,2,4,4-pentafluoro-2-butene (CHF)₂CF = CHCHF₂); 1,1,2,3,3-pentafluoro-1-butene (CH)₃CF₂CF = CF₂); 1,1,2,3,4-pentafluoro-2-butene (CH)₂FCF = CFCHF₂); 1,1,3,3,3-pentafluoro-2-methyl-1-propene (CF)₂= C (CF)₃) (CH₃)); 2- (Difluoromethyl) -3,3,3-trifluoro-1-propene (CH)₂= C (CHF)₂) (CF₃)); 2,3,4,4,4-pentafluoro-1-butene (CH)₂= CFCHFCF₃); 1,2,4,4,4-pentafluoro-1-butene (CHF = CFCH)₂CF₃); 1,3,4,4,4-pentafluoro-1-butene (CHF = CHCHFCF)₃); 1,3,3,4,4-pentafluoro-1-butene (CHF = CHCF)₂CHF₂); 1,2,3,4,4-pentafluoro-1-butene (CHF = CFC CHFCHF)₂); 3,3,4,4-Tetrafluoro-1-butene (CH)₂= CHCF₂CHF₂); 1,1-difluoro-2- (difluoromethyl) -1-propene (CF)₂= C (CHF)₂) (CH₃)); 1,3,3,3-Tetrafluoro-2-methyl-1-propene (CHF = C (CF)₃) (CH₃)); 2-Difluoromethyl-3,3-difluoro-1-propene (CH)₂= C (CHF)₂)₂); 1,1,1,2-Tetrafluoro-2-butene (CF)₃CF = CHCH₃); 1,1,1,3-Tetrafluoro-2-butene (CH)₃CF = CHCF₃); 1,1,1,2,3,4,4,5,5,5-decafluoro-2-pentene (CF)₃CF = CFCF₂CF₃); 1,1,2,3,3,4,4,5,5,5-decafluoro-1-pentene (CF)₂= CFCF₂CF₂CF₃); 1,1,1,4,4,4-hexafluoro-2- (trifluoromethyl) -2-butene ((CF)₃)₂C = CHCF₃); 1,1,1,2,4,4,5,5,5-Nonafluoro-2-pentene (CF)₃CF = CHCF₂CF₃); 1,1,1,3,4,4,5,5,5-Nonafluoro-2-pentene (CF)₃CH = CFCF₂CF₃); 1,2,3,3,4,4,5,5,5-Nonafluoro-1-pentene (CHF = CFCF)₂CF₂CF₃); 1,1,3,3,4,4,5,5,5-Nonafluoro-1-pentene (CF)₂= CHCF₂CF₂CF₃); 1,1,2,3,3,4,4,5,5-Nonafluoro-1-pentene (CF)₂= CFCF₂CF₂CHF₂); 1,1,2,3,4,4,5,5,5-Nonafluoro-2-pentene (CHF)₂CF = CFCF₂CF₃); 1,1,1,2,3,4,4,5,5-Nonafluoro-2-pentene (CF)₃CF = CFCF₂CHF₂); 1,1,1,2,3,4,5,5,5-Nonafluoro-2-pentene (CF)₃CF = CFCHFCF₃); 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)₃CH = 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= CFCF₂CF₂CF₃); 1,2,3,3,4,4,5,5-octafluoro-1-pentene (CHF = CFCF)₂CF₂CHF₂); 3,3,4,4,4-Pentafluoro-2- (trifluoromethyl) -1-butene (CH)₂= C (CF)₃) CF₂CF₃); 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) CH₂CF₃); 3,4,4,4-Tetrafluoro-3- (trifluoromethyl) -1-butene ((CF)₃)₂CFCH = CH₂); 3,3,4,4,5,5,5-heptafluoro-1-pentene (CF)₃CF₂CF₂CH = CH₂); 2,3,3,4,4,5,5-heptafluoro-1-pentene (CH)₂= CFCF₂CF₂CHF₂); 1,1,3,3,5,5,5-heptafluoro-1-butene (CF)₂= CHCF₂CH₂CF₃); 1,1,1,2,4,4,4-heptafluoro-3-methyl-2-butene (CF)₃CF = C (CF)₃) (CH₃)); 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)₂FCH = C (CF)₃)₂); 1,1,1,3-Tetrafluoro-2- (trifluoromethyl) -2-butene (CH)₃CF = C (CF)₃)₂); 1,1,1-Trifluoro-2- (trifluoromethyl) -2-butene ((CF)₃)₂C = CHCH₃); 3,4,4,5,5,5-hexafluoro-2-pentene (CF)₃CF₂CF = CHCH₃); 1,1,1,4,4,4-hexafluoro-2-methyl-2-butene (CF)₃C (CH)₃) = CHCF₃); 3,3,4,5,5,5-hexafluoro-1-pentene (CH)₂= CHCF₂CHFCF₃); 3- (Trifluoromethyl) -4,4,4-trifluoro-1-butene (CH)₂= C (CF)₃) CH₂CF₃); 1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1-hexene (CF)₃(CF₂)₃CF = CF₂); 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene (CF)₃CF₂CF = CFCF₂CF₃); 1,1,1,4,4,4-hexafluoro-2,3-bis (trifluoromethyl) -2-butene ((CF)₃)₂C = C (CF)₃)₂); 1,1,1,2,3,4,5,5,5-Nonafluoro-4- (trifluoromethyl) -2-pentene ((CF)₃)₂CFCF = CFCF₃); 1,1,1,4,4,5,5,5-octafluoro-2- (trifluoromethyl) -2-pentene ((CF)₃)₂C = CHC₂F₅); 1,1,1,3,4,5,5,5-octafluoro-4- (trifluoromethyl) -2-pentene ((CF)₃)₂CFCF = CHCF₃); 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene (CF)₃CF₂CF₂CF₂CH = CH₂); 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- (trifluoromethyl) -2-butene ((CF)₃)₂C = C (CH)₃) (CF₃)); 2,3,3,5,5,5-hexafluoro-4- (trifluoromethyl) -1-pentene (CH)₂= CFCF₂CH (CF)₃)₂); 1,1,1,2,4,4,5,5,5- Nonafuru Oro-3-methyl-2-pentene (CF₃CF = C (CH)₃) CF₂CF₃); 1,1,1,5,5,5-hexafluoro-4- (trifluoromethyl) -2-pentene (CF)₃CH = CHCH (CF)₃)₂); 3,4,4,5,5,6,6,6-octafluoro-2-hexene (CF)₃CF₂CF₂CF = CHCH₃); 3,3,4,4,5,5,6,6-octafluoro-1-hexene (CH)₂= CHCF₂CF₂CF₂CHF₂); 1,1,1,4,4-pentafluoro-2- (trifluoromethyl) -2-pentene ((CF)₃)₂C = CHCF₂CH₃); 4,4,5,5,5-pentafluoro-2- (trifluoromethyl) -1-pentene (CH)₂= C (CF)₃) CH₂C₂F₅); 3,3,4,4,5,5,5-heptafluoro-2-methyl-1-pentene (CF)₃CF₂CF₂C (CH)₃) = CH₂); 4,4,5,5,6,6,6-heptafluoro-2-hexene (CF)₃CF₂CF₂CH = CHCH₃); 4,4,5,5,6,6,6-heptafluoro-1-hexene (CH)₂= CHCH₂CF₂C₂F₅); 1,1,1,2,2,3,4-heptafluoro-3-hexene (CF)₃CF₂CF = CFC₂H₅); 4,5,5,5-Tetrafluoro-4-trifluoromethyl-1-pentene (CH)₂= CHCH₂CF (CF)₃)₂); 1,1,1,2,5,5,5-heptafluoro-4-methyl-2-pentene (CF)₃CF = CHCH (CF)₃) (CH₃)); 1,1,1,3-Tetrafluoro-2-trifluoromethyl-2-pentene ((CF)₃)₂C = CFC₂H₅); 1,1,1,2,3,4,4,5,5,6,6,7,7,7-Tetradecafluoro-2-heptene (CF)₃CF = CFCF₂CF₂C₂F₅); 1,1,1,2,2,3,4,5,5,6,6,7,7,7-Tetradecafluoro-3-heptene (CF)₃CF₂CF = CFCF₂C₂F₅); 1,1,1,3,4,4,5,5,6,6,7,7,7-Tridecafluoro-2-heptene (CF)₃CH = CFCF₂CF₂C₂F₅); 1,1,1,2,4,4,5,5,6,6,7,7,7-Tridecafluoro-2-heptene (CF)₃CF = CHCF₂CF₂C₂F₅); 1,1,1,2,2,4,5,5,6,6,7,7,7-Tridecafluoro-3-heptene (CF)₃CF₂CH = CFCF₂C₂F₅); 1,1,1,2,2,3,5,5,6,6,7,7,7-Tridecafluoro-3-heptene (CF)₃CF₂CF = CHCF₂C₂F₅); CF₂= CFOCF₂CF₃(PEVE); CF₂= CFOCF₃Includes at least one fluoroolefin selected from the group consisting of (PMVE) and fluoroolefins selected from the group consisting of combinations thereof;</p>

The present invention relates to compositions containing at least one fluoroolefin. Fluoroolefin means 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, including foaming agents, swelling agents, fire extinguishing agents, heat transfer media (refrigerators, refrigerators, air conditioning systems, heat pumps, coolers, to name a few). Includes use as (such as heat transfer fluids and refrigerants) for use in etc.

A heat transfer fluid (also referred to herein as a heat transfer composition or heat transfer fluid composition) is a working fluid used to transfer 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 reverse.

In the present invention, the formula ER¹CH = CHR²Or ZR¹CH = CHR²To provide a fluoroolefin having (formula I), in the formula, R¹And R²Independently, C₁~ C₆Perfluoroalkyl group of. R¹And R²The example of the group is not particularly limited, but CF₃, C₂F_5、CF₂CF₂CF₃, CF (CF)₃)₂, CF₂CF₂CF₂CF₃, CF (CF)₃) CF₂CF₃, CF₂CF (CF)₃)₂, C (CF)₃)₃, CF₂CF₂CF₂CF₂CF₃, CF₂CF₂CF (CF)₃)₂, C (CF)₃)₂C₂F₅, CF₂CF₂CF₂CF₂CF₂CF₃, CF (CF)₃) CF₂CF₂C₂F₅, And C (CF)₃)₂CF₂C₂F₅Can be mentioned. 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 another embodiment, the fluoroolefin of formula I has at least about 5 carbon atoms in the molecule. An exemplary, non-limiting compound of formula I is shown in Table 1.

<tables num="1"><img file="JP6442011B2_D0001.tif" /></tables>

<tables num="2"><img file="JP6442011B2_D0002.tif" /></tables>

<tables num="3"><img file="JP6442011B2_D0003.tif" /></tables>

The compound of formula I is of formula R¹The perfluoroalkyl iodide of I is given by the formula R²CH = CH₂In contact with the perfluoroalkyltrihydroolefin of¹CH₂CHIR²It can be prepared by the step of forming a trihydroiolated perfluoroalkane. This trihydroiodinated perfluoroalkane is then dehydroiodinated and R¹CH = CHR²Is possible to form. Alternatively, Olefin R¹CH = CHR²Then formula R²The perfluoroalkyl iodide of I is given by the formula R¹CH = CH₂Formulated by reacting with the perfluoroalkyltrihydroolefin of¹CHICH₂R²Can be prepared by dehydroiodination of trihydroiodinated perfluoroalkanes.

The step of contacting the perfluoroalkyl iodide with the perfluoroalkyl trihydroolefin is to combine the reactants in a suitable reaction vessel capable of operating the reactants at reaction temperature and under self-pressure of the product. Can be done in batch mode. Suitable reaction vessels are those made of stainless steel, especially those of the austenite type, and Monel® nickel-copper alloys, Hastelloy® nickel-based alloys and Inconel ( Examples include well-known high nickel alloys such as nickel-chromium alloys.

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

The ratio of perfluoroalkyl iodide to perfluoroalkyl trihydroolefin should be between about 1: 1 and about 4: 1, preferably about 1.5: 1 to 2.5: 1. Ratios less than 1.5: 1 tend to result in large amounts of 2: 1 adducts as reported by (Non-Patent Document 1).

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

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

The trihydroiodinated perfluoroalkane prepared by reacting the perfluoroalkyl iodide with a perfluoroalkyl trihydroolefin can be used directly in the dehydroiodination step, or preferably by distillation prior to the dehydroiodination step. Can be recovered and purified.

The dehydroiodination step is carried out by contacting the trihydroiodinated perfluoroalkane with a basic material. Suitable basic substances include alkali metal hydroxides (eg sodium hydroxide or potassium hydroxide), alkali metal oxides (eg sodium oxide), alkaline earth metals hydroxide (eg calcium hydroxide), alkalis. Examples include mixtures of basic substances such as earth metal oxides (eg calcium oxide), alkali metal alkoxides (eg sodium methoxydo or sodium ethoxydo), aqueous ammonia, sodium amides, or soda lime. Preferred basic substances are sodium hydroxide and potassium hydroxide.

The step of contacting the trihydroiodide perfluoroalkane with a basic material 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 dehydroiodization step include alcohols (eg, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and tertiary butanol), nitriles (eg, acetonitrile, propionitrile, butyronitrile). , Benzonitrile, or adiponitrile), dimethylsulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, or sulfolane and one or more polar organic solvents. The choice of solvent can depend on the boiling point product and the ease of separation of the trace amount of solvent from the product during purification. Typically, ethanol or isopropanol is a good solvent for the reaction.

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

The preferred temperature for the dehydroiodination reaction is 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 pressure or under pressure. Of note is the dehydroiodination reaction that distills out of the reaction vessel as the compound of formula I is formed.

Alternatively, the dehydroiodization reaction uses an aqueous solution of the basic substance in an alkane (eg, hexane, heptane, or octane), aromatic hydrocarbon (eg, eg, hexane, heptane, or octane) of one or more of the trihydroiodated perfluoroalkanes. (Toluene), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride, or perchloroethylene), or ethers (eg, diethyl ether, methyl t-butyl ether, tetrahydrofuran, 2-methyl tetrahydrofuran, dioxane, dimethoxyethane, It can be carried out by contacting a solution in a low polar organic solvent such as (diglyme, or tetraglyme) in the presence of an interphase transfer catalyst. Suitable phase transfer catalysts include quaternary ammonium halides (eg, tetrabutylammonium bromide, tetrabutylammonium hydrosulfate, triethylbenzylammonium chloride, dodecyltrimethylammonium chloride, and tricaprylyl methylammonium chloride), fourth. Primary 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). Examples include compounds.

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

The preferred reaction time for the dehydroiodination reaction is from about 15 minutes to about 6 hours or more, depending on the solubility of the reactants. The dehydroiodination reaction is typically rapid and requires about 30 minutes to about 3 hours to complete.

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

In another embodiment of the invention, the fluoroolefin is a cyclic fluoroolefin (cyclo-[CX = CY (CZW))._n-] (Equation II), in which X, Y, Z, and W are selected independently of H and F, and n is an integer of 2-5). Typical cyclic fluoroolefins of formula II are listed in Table 2.

<tables num="4"><img file="JP6442011B2_D0004.tif" /></tables>

In other embodiments, fluoroolefins may include these compounds listed in Table 3.

<tables num="5"><img file="JP6442011B2_D0005.tif" /></tables>

<tables num="6"><img file="JP6442011B2_D0006.tif" /></tables>

<tables num="7"><img file="JP6442011B2_D0007.tif" /></tables>

<tables num="8"><img file="JP6442011B2_D0008.tif" /></tables>

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

1,1,1,4,4-pentafluoro-2-butane is 1,1,1,2,4,4-hexafluorobutane (CHF)₂CH₂CHFCF₃), Can be prepared in the gas phase at room temperature by dehydrofluorination on solid KOH. The synthesis of 1,1,1,2,4,4-hexafluorobutane is described in US Patent Publication (Patent Document 1), which is incorporated herein by reference.

1,1,1,4,4,4-hexafluoro-2-butene is 1,1,1,4,4,4-hexafluoro-2-iodobutane (CF)₃CHICH₂CF₃), The phase transfer catalyst can be prepared at about 60 ° C by reaction with KOH. The synthesis of 1,1,1,4,4,4-hexafluoro-2-iodobutane is performed by methyl perfluoroiodate (CF).₃I) and 3,3,3-trifluoropropene (CF)₃CH = CH₂), At about 200 ° C., under self-pressure, can be carried out by reaction for about 8 hours.

3,4,4,5,5,5-hexafluoro-2-pentene is 1,1,1,2,2,3,3-heptafluoropentane (CF)₃CF₂CF₂CH₂CH₃), Can be prepared by dehydrofluorination at 200-300 ° C. using solid KOH or on a carbon catalyst. 1,1,1,2,2,3,3-heptafluoropentane is 3,3,4,4,5,5,5-heptafluoro-1-pentene (CF)₃CF₂CF₂CH = CH₂) Can be prepared by hydrogenation.

1,1,1,2,3,4-hexafluoro-2-butane uses solid KOH 1,1,1,2,3,3,4-heptafluorobutane (CH)₂FCF₂CHFCF₃) Can be prepared by dehydrofluorination.

1,1,1,2,4,4-hexafluoro-2-butane uses solid KOH 1,1,1,2,2,4,4-heptafluorobutane (CHF)₂CH₂CF₂CF₃) Can be prepared by dehydrofluorination.

1,1,1,3,4,4-hexafluoro2-butane uses solid KOH 1,1,1,3,3,4,4-heptafluorobutane (CF)₃CH₂CF₂CHF₂) Can be prepared by dehydrofluorination.

1,1,1,2,4-pentafluoro-2-butene uses solid KOH 1,1,1,2,2,3-hexafluorobutane (CH)₂FCH₂CF₂CF₃) Can be prepared by dehydrofluorination.

1,1,1,3,4-pentafluoro-2-butane uses solid KOH 1,1,1,3,3,4-hexafluorobutane (CF)₃CH₂CF₂CH₂Can be prepared by dehydrofluorination of F).

1,1,1,3-tetrafluoro-2-butane is 1,1,1,3,3-pentafluorobutane (CF)₃CH₂CF₂CH₃) Can be prepared by reacting with aqueous KOH at 120 ° C.

1,1,1,4,4,5,5,5-octafluoro-2-pentene is (CF)₃CHICH₂CF₂CF₃), Can be prepared by reaction with KOH at about 60 ° C using a phase transfer catalyst. The synthesis of 4-iodo-1,1,1,2,2,5,5,5-octafluoropentane is performed by perfluoromethyl iodide (CF).₃CF₂It can be carried out by the reaction of I) and 3,3,3-trifluoropropene at about 200 ° C. under self-pressure for about 8 hours.

1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexane is 1,1,1,2,2,5,5,6,6,6-decafluoro -3-Iodine hexane (CF)₃CF₂CHICH₂CF₂CF₃), Can be prepared 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 is performed by perfluoromethyl iodide (CF).₃CF₂I) and 3,3,4,4,4-pentafluoro-1-butene (CF)₃CF₂CH = CH₂), At about 200 ° C., under self-pressure, can be carried out by reaction 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-iodoine. -2- (Trifluoromethyl) -pentane (CF)₃CHICH₂CF (CF)₃)₂), Can be prepared by dehydrofluorination in isopropanol with KOH. CF₃CHICH₂CF (CF)₃)₂Is (CF₃)₂CF of CFI₃CH = CH₂It is formed from the reaction 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)₃CH = CHCF₃), Tetrafluoroethylene (CF)₂= CF₂) And Antimony pentafluoride (SbF)₅) Can be prepared.

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

2,3,3,4,4,5,5,5-octafluoro-1-pentene in solid KOH of 2,2,3,3,4,4,5,5,5-nonafluoropentane 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. Can be prepared by dehydrofluorination at elevated temperature in.

The compositions of the present invention may comprise a single compound of Formula I, Formula II, or Table 3, or may comprise a combination of said compounds. In addition, many of the compounds of formulas I, II, and Table 3 can exist as different conformational isomers or steric isomers. The present invention is intended to include all single conformational isomers, single stereoisomers or combinations thereof. For example, 1,3,3,3-tetrafluoropropene (HFC-1234ze) represents an E-isomer, a Z-isomer, or a mixture of either combination or both isomers in any ratio. Means that. Another example is F12E, which represents an E-isomer, a Z-isomer, or a mixture of either combination or both isomers in any ratio.

The compositions of the present invention have zero or low ozone depletion potential and low global warming potential (GWP). The fluoroolefins of the invention or mixtures of fluoroolefins of the invention with other refrigerants will have a lower global warming potential than many currently used hydrofluorocarbon refrigerants. One aspect of the 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 present invention is to reduce the total GWP of the refrigerant mixture by adding a fluoroolefin to the mixture.

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

Alternative means of forming the compositions of the present invention are: (i) recovering a volume of one or more components of the refrigerant composition from at least one refrigerant container, (ii) one or more of the above. A step of sufficiently removing impurities, (iii) and optionally, all or part of the recovered volume of the constituents, so that the plurality of recovered constituents can be reused, at least one of the same. Includes steps to combine with additional refrigerant compositions or ingredients.

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

Residual Refrigerant means any amount of Refrigerant Blend or Refrigerant Blend Component that can be removed from the Refrigerant Container by any method known for transferring Refrigerant Blend or Refrigerant Blend Components.

The impurity can be any component in the refrigerant blend or refrigerant blend component for its use in refrigerating equipment, air conditioning equipment or heat pumping equipment. Such impurities are not particularly limited, but are the particles such as metal or elastomer that can flow out from the refrigerating lubricant, the refrigerating device, the air conditioner or the heat pump device, and the refrigerant blend composition described in the present specification. Included are any other contaminants that can adversely affect performance.

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

It may be necessary to provide an additional refrigerant blend or refrigerant blend component to the residual refrigerant blend or refrigerant blend component in order to produce a composition that meets the required specifications for a given product. For example, if the refrigerant blend has three components within a certain weight percent range, then one or more of the components are given in order to regenerate the composition within specification limits. It may be necessary to add in quantity.

The compositions of the present invention that are useful as refrigerants or heat transfer fluids are: (i) Eq. ER¹CH = CHR²Or ZR¹CH = CHR²Fluoroolefin in the formula, R¹And R²But independently, C₁~ C₆Fluoroolefins, and in the formula, the total number of carbons in the compound is at least 5; (ii) formula cyclo- [CX = CY (CZW)_n-] Cyclic fluoroolefins, in which X, Y, Z, and W are independently H or F, and n is an integer of 2-5; and (iii. ) 1,2,3,3,3-Pentafluoro-1-propene (CF)₃CF = CHF); 1,1,3,3,3-pentafluoro-1-propene (CF)₃CH = CF₂); 1,1,2,3,3-pentafluoro-1-propene (CHF)₂CF = CF₂); 1,2,3,3-Tetrafluoro-1-propene (CHF)₂CF = CHF); 2,3,3,3-tetrafluoro-1-propen (CF)₃CF = CH₂); 1,1,2,3-tetrafluoro-1-propene (CH)₂FCF = CF₂); 1,1,3,3-tetrafluoro-1-propene (CHF)₂CH = CF₂); 2,3,3-Trifluoro-1-propene (CHF)₂CF = CH₂); 3,3,3-Trifluoro-1-propene (CF)₃CH = CH₂); 1,1,2-Trifluoro-1-propene (CH)₃CF = CF₂); 1,2,3-trifluoro-1-propene (CH)₂FCF = CF₂); 1,1,3-Trifluoro-1-propene (CH)₂FCH = CF₂); 1,3,3-trifluoro-1-propene (CHF)₂CH = CHF); 1,1,1,2,3,4,4,4-octafluoro-2-butene (CF)₃CF = CFCF₃); 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF)₃CF₂CF = CF₂); 1,1,1,2,4,4,4-heptafluoro-2-butene (CF)₃CF = CHCF₃); 1,2,3,3,4,4,4-heptafluoro-1-butene (CHF = CFCF)₂CF₃); 1,1,1,2,3,4,4-heptafluoro-2-butene (CHF)₂CF = CFCF₃); 1,3,3,3-Tetrafluoro-2- (trifluoromethyl) -1-propene ((CF)₃)₂C = CHF); 1,1,3,3,4,4,4-heptafluoro-1-butene (CF)₂= CHCF₂CF₃); 1,1,2,3,4,4,4-heptafluoro-1-butene (CF)₂= CFCHFCF₃); 1,1,2,3,3,4,4-heptafluoro-1-butene (CF)₂= CFCF₂CHF₂); 2,3,3,4,4,4-hexafluoro-1-butene (CF)₃CF₂CF = CH₂); 1,3,3,4,4,4-hexafluoro-1-butene (CHF = CHCF)₂CF₃); 1,2,3,4,4,4-hexafluoro-1-butene (CHF = CFC CHFCF)₃); 1,2,3,3,4,4-hexafluoro-1-butene (CHF = CFCF)₂CHF₂); 1,1,2,3,4,4-hexafluoro-2-butene (CHF)₂CF = CFCHF₂); 1,1,1,2,3,4-hexafluoro-2-butene (CH)₂FCF = CFCF₃); 1,1,1,2,4,4-hexafluoro-2-butene (CHF)₂CH = CFCF₃); 1,1,1,3,4,4-hexafluoro-2-butene (CF)₃CH = CFC CHF₂); 1,1,2,3,3,4-hexafluoro-1-butene (CF)₂= CFCF₂CH₂F); 1,1,2,3,4,4-hexafluoro-1-butene (CF)₂= CFCHFCHF₂); 3,3,3-Trifluoro-2- (trifluoromethyl) -1-propene (CH)₂= C (CF)₃)₂); 1,1,1,2,4-pentafluoro-2-butene (CH)₂FCH = CFCF₃); 1,1,1,3,4-pentafluoro-2-butene (CF)₃CH = CFCH₂F); 3,3,4,4,4-pentafluoro-1-butene (CF)₃CF₂CH = CH₂); 1,1,1,4,4-pentafluoro-2-butene (CHF)₂CH = CHCF₃); 1,1,1,2,3-pentafluoro-2-butene (CH)₃CF = CFCF₃); 2,3,3,4,4-Pentafluoro-1-butene (CH)₂= CFCF₂CHF₂); 1,1,2,4,4-pentafluoro-2-butene (CHF)₂CF = CHCHF₂); 1,1,2,3,3-pentafluoro-1-butene (CH)₃CF₂CF = CF₂); 1,1,2,3,4-pentafluoro-2-butene (CH)₂FCF = CFCHF₂); 1,1,3,3,3-pentafluoro-2-methyl-1-propene (CF)₂= C (CF)₃) (CH₃)); 2- (Difluoromethyl) -3,3,3-trifluoro-1-propene (CH)₂= C (CHF)₂) (CF₃)); 2,3,4,4,4-pentafluoro-1-butene (CH)₂= CFCHFCF₃); 1,2,4,4,4-pentafluoro-1-butene (CHF = CFCH)₂CF₃); 1,3,4,4,4-pentafluoro-1-butene (CHF = CHCHFCF)₃); 1,3,3,4,4-pentafluoro-1-butene (CHF = CHCF)₂CHF₂); 1,2,3,4,4-pentafluoro-1-butene (CHF = CFC CHFCHF)₂); 3,3,4,4-Tetrafluoro-1-butene (CH)₂= CHCF₂CHF₂); 1,1-difluoro-2- (difluoromethyl) -1-propene (CF)₂= C (CHF)₂) (CH₃)); 1,3,3,3-Tetrafluoro-2-methyl-1-propene (CHF = C (CF)₃) (CH₃)); 3,3-Difluoro-2- (difluoromethyl) -1-propene (CH)₂= C (CHF)₂)₂); 1,1,1,2-Tetrafluoro-2-butene (CF)₃CF = CHCH₃); 1,1,1,3-Tetrafluoro-2-butene (CH)₃CF = CHCF₃); 1,1,1,2,3,4,4,5,5,5-decafluoro-2-pentene (CF)₃CF = CFCF₂CF₃); 1,1,2,3,3,4,4,5,5,5-decafluoro-1-pentene (CF)₂= CFCF₂CF₂CF₃); 1,1,1,4,4,4-hexafluoro-2- (trifluoromethyl) -2-butene ((CF)₃)₂C = CHCF₃); 1,1,1,2,4,4,5,5,5-Nonafluoro-2-pentene (CF)₃CF = CHCF₂CF₃); 1,1,1,3,4,4,5,5,5-Nonafluoro-2-pentene (CF)₃CH = CFCF₂CF₃); 1,2,3,3,4,4,5,5,5-Nonafluoro-1-pentene (CHF = CFCF)₂CF₂CF₃); 1,1,3,3,4,4,5,5,5-Nonafluoro-1-pentene (CF)₂= CHCF₂CF₂CF₃); 1,1,2,3,3,4,4,5,5-Nonafluoro-1-pentene (CF)₂= CFCF₂CF₂CHF₂); 1,1,2,3,4,4,5,5,5-Nonafluoro-2-pentene (CHF)₂CF = CFCF₂CF₃); 1,1,1,2,3,4,4,5,5-Nonafluoro-2-pentene (CF)₃CF = CFCF₂CHF₂); 1,1,1,2,3,4,5,5,5-Nonafluoro-2-pentene (CF)₃CF = CFCHFCF₃); 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)₃CH = 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= CFCF₂CF₂CF₃); 1,2,3,3,4,4,5,5-octafluoro-1-pentene (CHF = CFCF)₂CF₂CHF₂); 3,3,4,4,4-Pentafluoro-2- (trifluoromethyl) -1-butene (CH)₂= C (CF)₃) CF₂CF₃); 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) CH₂CF₃); 3,4,4,4-Tetrafluoro-3- (trifluoromethyl) -1-butene ((CF)₃)₂CFCH = CH₂); 3,3,4,4,5,5,5-heptafluoro-1-pentene (CF)₃CF₂CF₂CH = CH₂); 2,3,3,4,4,5,5-heptafluoro-1-pentene (CH)₂= CFCF₂CF₂CHF₂); 1,1,3,3,5,5,5-heptafluoro-1-butene (CF)₂= CHCF₂CH₂CF₃); 1,1,1,2,4,4,4-heptafluoro-3-methyl-2-butene (CF)₃CF = C (CF)₃) (CH₃)); 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)₂FCH = C (CF)₃)₂); 1,1,1,3-Tetrafluoro-2- (trifluoromethyl) -2-butene (CH)₃CF = C (CF)₃)₂); 1,1,1-Trifluoro-2- (trifluoromethyl) -2-butene ((CF)₃)₂C = CHCH₃); 3,4,4,5,5,5-hexafluoro-2-pentene (CF)₃CF₂CF = CHCH₃); 1,1,1,4,4,4-hexafluoro-2-methyl-2-butene (CF)₃C (CH)₃) = CHCF₃); 3,3,4,5,5,5-hexafluoro-1-pentene (CH)₂= CHCF₂CHFCF₃); 4,4,4-Trifluoro-3- (trifluoromethyl) -1-butene (CH)₂= C (CF)₃) CH₂CF₃); 1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1-hexene (CF)₃(CF₂)₃CF = CF₂); 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene (CF)₃CF₂CF = CFCF₂CF₃); 1,1,1,4,4,4-hexafluoro-2,3-bis (trifluoromethyl) -2-butene ((CF)₃)₂C = C (CF)₃)₂); 1,1,1,2,3,4,5,5,5-Nonafluoro-4- (trifluoromethyl) -2-pentene ((CF)₃)₂CFCF = CFCF₃); 1,1,1,4,4,5,5,5-octafluoro-2- (trifluoromethyl) -2-pentene ((CF)₃)₂C = CHC₂F₅); 1,1,1,3,4,5,5,5-octafluoro-4- (trifluoromethyl) -2-pentene ((CF)₃)₂CFCF = CHCF₃); 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene (CF)₃CF₂CF₂CF₂CH = CH₂); 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)₂C = C (CH)₃) (CF₃)); 2,3,3,5,5,5-hexafluoro-4- (trifluoromethyl) -1-pentene (CH)₂= CFCF₂CH (CF)₃)₂); 1,1,1,2,4,4,5,5,5-Nonafluoro-3-methyl-2-pentene (CF)₃CF = C (CH)₃) CF₂CF₃); 1,1,1,5,5,5-hexafluoro-4- (trifluoromethyl) -2-pentene (CF)₃CH = CHCH (CF)₃)₂); 3,4,4,5,5,6,6,6-octafluoro-2-hexene (CF)₃CF₂CF₂CF = CHCH₃); 3,3,4,4,5,5,6,6-octafluoro1-hexene (CH)₂= CHCF₂CF₂CF₂CHF₂); 1,1,1,4,4-pentafluoro-2- (trifluoromethyl) -2-pentene ((CF)₃)₂C = CHCF₂CH₃); 4,4,5,5,5-pentafluoro-2- (trifluoromethyl) -1-pentene (CH)₂= C (CF)₃) CH₂C₂F₅); 3,3,4,4,5,5,5-heptafluoro-2-methyl-1-pentene (CF)₃CF₂CF₂C (CH)₃) = CH₂); 4,4,5,5,6,6,6-heptafluoro-2-hexene (CF)₃CF₂CF₂CH = CHCH₃); 4,4,5,5,6,6,6-heptafluoro-1-hexene (CH)₂= CHCH₂CF₂C₂F₅); 1,1,1,2,2,3,4-heptafluoro-3-hexene (CF)₃CF₂CF = CFC₂H₅); 4,5,5,5-Tetrafluoro-4- (trifluoromethyl) -1-pentene (CH)₂= CHCH₂CF (CF)₃)₂); 1,1,1,2,5,5,5-heptafluoro-4-methyl-2-pentene (CF)₃CF = CHCH (CF)₃) (CH₃)); 1,1,1,3-Tetrafluoro-2- (trifluoromethyl) -2-pentene ((CF)₃)₂C = CFC₂H₅); 1,1,1,2,3,4,4,5,5,6,6,7,7,7-Tetradecafluoro-2-heptene (CF)₃CF = CFCF₂CF₂C₂F₅); 1,1,1,2,2,3,4,5,5,6,6,7,7,7-Tetradecafluoro-3-heptene (CF)₃CF₂CF = CFCF₂C₂F₅); 1,1,1,3,4,4,5,5,6,6,7,7,7-Tridecafluoro-2-heptene (CF)₃CH = CFCF₂CF₂C₂F₅); 1,1,1,2,4,4,5,5,6,6,7,7,7-Tridecafluoro-2-heptene (CF)₃CF = CHCF₂CF₂C₂F₅); 1,1,1,2,2,4,5,5,6,6,7,7,7-Tridecafluoro-3-heptene (CF)₃CF₂CH = CFCF₂C₂F₅); 1,1,1,2,2,3,5,5,6,6,7,7,7-Tridecafluoro-3-heptene (CF)₃CF₂CF = CHCF₂C₂F₅); CF₂= CFOCF₂CF₃(PEVE) and CF₂= CFOCF₃Fluoroolefins selected from the group consisting of (PMVE); Containing at least one fluoroolefin selected from the group consisting of.

The present invention further relates to compositions comprising at least one fluoroolefin and at least one flammable refrigerant or heat transfer fluid, wherein the fluoroolefin is: (i) ER.¹CH = CHR²Or ZR¹CH = CHR²Fluoroolefin in the formula, R¹And R²But independently, C₁~ C₆Fluoroolefins, and in the formula, the total number of carbons in the compound is at least 5; (ii) formula cyclo- [CX = CY (CZW)_n-] Cyclic fluoroolefins, in which X, Y, Z, and W are independently H or F, and n is an integer of 2-5; and (iii. ) 1,2,3,3,3-Pentafluoro-1-propene (CF)₃CF = CHF); 1,1,3,3,3-pentafluoro-1-propene (CF)₃CH = CF₂); 1,1,2,3,3-pentafluoro-1-propene (CHF)₂CF = CF₂); 1,2,3,3-Tetrafluoro-1-propene (CHF)₂CF = CHF); 2,3,3,3-tetrafluoro-1-propen (CF)₃CF = CH₂); 1,1,2,3-tetrafluoro-1-propene (CH)₂FCF = CF₂); 1,1,3,3-tetrafluoro-1-propene (CHF)₂CH = CF₂); 2,3,3-Trifluoro-1-propene (CHF)₂CF = CH₂); 3,3,3-Trifluoro-1-propene (CF)₃CH = CH₂); 1,1,2-Trifluoro-1-propene (CH)₃CF = CF₂); 1,2,3-trifluoro-1-propene (CH)₂FCF = CF₂); 1,1,3-Trifluoro-1-propene (CH)₂FCH = CF₂); 1,3,3-trifluoro-1-propene (CHF)₂CH = CHF); 1,1,1,2,3,4,4,4-octafluoro-2-butene (CF)₃CF = CFCF₃); 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF)₃CF₂CF = CF₂); 1,1,1,2,4,4,4-heptafluoro-2-butene (CF)₃CF = CHCF₃); 1,2,3,3,4,4,4-heptafluoro-1-butene (CHF = CFCF)₂CF₃); 1,1,1,2,3,4,4-heptafluoro-2-butene (CHF)₂CF = CFCF₃); 1,3,3,3-Tetrafluoro-2- (trifluoromethyl) -1-propene ((CF)₃)₂C = CHF); 1,1,3,3,4,4,4-heptafluoro-1-butene (CF)₂= CHCF₂CF₃); 1,1,2,3,4,4,4-heptafluoro-1-butene (CF)₂= CFCHFCF₃); 1,1,2,3,3,4,4-heptafluoro-1-butene (CF)₂= CFCF₂CHF₂); 2,3,3,4,4,4-hexafluoro-1-butene (CF)₃CF₂CF = CH₂); 1,3,3,4,4,4-hexafluoro-1-butene (CHF = CHCF)₂CF₃); 1,2,3,4,4,4-hexafluoro-1-butene (CHF = CFC CHFCF)₃); 1,2,3,3,4,4-hexafluoro-1-butene (CHF = CFCF)₂CHF₂); 1,1,2,3,4,4-hexafluoro-2-butene (CHF)₂CF = CFCHF₂); 1,1,1,2,3,4-hexafluoro-2-butene (CH)₂FCF = CFCF₃); 1,1,1,2,4,4-hexafluoro-2-butene (CHF)₂CH = CFCF₃); 1,1,1,3,4,4-hexafluoro-2-butene (CF)₃CH = CFC CHF₂); 1,1,2,3,3,4-hexafluoro-1-butene (CF)₂= CFCF₂CH₂F); 1,1,2,3,4,4-hexafluoro-1-butene (CF)₂= CFCHFCHF₂); 3,3,3-Trifluoro-2- (trifluoromethyl) -1-propene (CH)₂= C (CF)₃)₂); 1,1,1,2,4-pentafluoro-2-butene (CH)₂FCH = CFCF₃); 1,1,1,3,4-pentafluoro-2-butene (CF)₃CH = CFCH₂F); 3,3,4,4,4-pentafluoro-1-butene (CF)₃CF₂CH = CH₂); 1,1,1,4,4-pentafluoro-2-butene (CHF)₂CH = CHCF₃); 1,1,1,2,3-pentafluoro-2-butene (CH)₃CF = CFCF₃); 2,3,3,4,4-Pentafluoro-1-butene (CH)₂= CFCF₂CHF₂); 1,1,2,4,4-pentafluoro-2-butene (CHF)₂CF = CHCHF₂); 1,1,2,3,3-pentafluoro-1-butene (CH)₃CF₂CF = CF₂); 1,1,2,3,4-pentafluoro-2-butene (CH)₂FCF = CFCHF₂); 1,1,3,3,3-pentafluoro-2-methyl-1-propene (CF)₂= C (CF)₃) (CH₃)); 2- (Difluoromethyl) -3,3,3-trifluoro-1-propene (CH)₂= C (CHF)₂) (CF₃)); 2,3,4,4,4-pentafluoro-1-butene (CH)₂= CFCHFCF₃); 1,2,4,4,4-pentafluoro-1-butene (CHF = CFCH)₂CF₃); 1,3,4,4,4-pentafluoro-1-butene (CHF = CHCHFCF)₃); 1,3,3,4,4-pentafluoro-1-butene (CHF = CHCF)₂CHF₂); 1,2,3,4,4-pentafluoro-1-butene (CHF = CFC CHFCHF)₂); 3,3,4,4-Tetrafluoro-1-butene (CH)₂= CHCF₂CHF₂); 1,1-difluoro-2- (difluoromethyl) -1-propene (CF)₂= C (CHF)₂) (CH₃)); 1,3,3,3-Tetrafluoro-2-methyl-1-propene (CHF = C (CF)₃) (CH₃)); 3,3-Difluoro-2- (difluoromethyl) -1-propene (CH)₂= C (CHF)₂)₂); 1,1,1,2-Tetrafluoro-2-butene (CF)₃CF = CHCH₃); 1,1,1,3-Tetrafluoro-2-butene (CH)₃CF = CHCF₃); 1,1,1,2,3,4,4,5,5,5-decafluoro-2-pentene (CF)₃CF = CFCF₂CF₃); 1,1,2,3,3,4,4,5,5,5-decafluoro-1-pentene (CF)₂= CFCF₂CF₂CF₃); 1,1,1,4,4,4-hexafluoro-2- (trifluoromethyl) -2-butene ((CF)₃)₂C = CHCF₃); 1,1,1,2,4,4,5,5,5-Nonafluoro-2-pentene (CF)₃CF = CHCF₂CF₃); 1,1,1,3,4,4,5,5,5-Nonafluoro-2-pentene (CF)₃CH = CFCF₂CF₃); 1,2,3,3,4,4,5,5,5-Nonafluoro-1-pentene (CHF = CFCF)₂CF₂CF₃); 1,1,3,3,4,4,5,5,5-Nonafluoro-1-pentene (CF)₂= CHCF₂CF₂CF₃); 1,1,2,3,3,4,4,5,5-Nonafluoro-1-pentene (CF)₂= CFCF₂CF₂CHF₂); 1,1,2,3,4,4,5,5,5-Nonafluoro-2-pentene (CHF)₂CF = CFCF₂CF₃); 1,1,1,2,3,4,4,5,5-Nonafluoro-2-pentene (CF)₃CF = CFCF₂CHF₂); 1,1,1,2,3,4,5,5,5-Nonafluoro-2-pentene (CF)₃CF = CFCHFCF₃); 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)₃CH = 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= CFCF₂CF₂CF₃); 1,2,3,3,4,4,5,5-octafluoro-1-pentene (CHF = CFCF)₂CF₂CHF₂); 3,3,4,4,4-Pentafluoro-2- (trifluoromethyl) -1-butene (CH)₂= C (CF)₃) CF₂CF₃); 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) CH₂CF₃); 3,4,4,4-Tetrafluoro-3- (trifluoromethyl) -1-butene ((CF)₃)₂CFCH = CH₂); 3,3,4,4,5,5,5-heptafluoro-1-pentene (CF)₃CF₂CF₂CH = CH₂); 2,3,3,4,4,5,5-heptafluoro-1-pentene (CH)₂= CFCF₂CF₂CHF₂); 1,1,3,3,5,5,5-heptafluoro-1-butene (CF)₂= CHCF₂CH₂CF₃); 1,1,1,2,4,4,4-heptafluoro-3-methyl-2-butene (CF)₃CF = C (CF)₃) (CH₃)); 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)₂FCH = C (CF)₃)₂); 1,1,1,3-Tetrafluoro-2- (trifluoromethyl) -2-butene (CH)₃CF = C (CF)₃)₂); 1,1,1-Trifluoro-2- (trifluoromethyl) -2-butene ((CF)₃)₂C = CHCH₃); 3,4,4,5,5,5-hexafluoro-2-pentene (CF)₃CF₂CF = CHCH₃); 1,1,1,4,4,4-hexafluoro-2-methyl-2-butene (CF)₃C (CH)₃) = CHCF₃); 3,3,4,5,5,5-hexafluoro-1-pentene (CH)₂= CHCF₂CHFCF₃); 4,4,4-Trifluoro-3- (trifluoromethyl) -1-butene (CH)₂= C (CF)₃) CH₂CF₃); 1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1-hexene (CF)₃(CF₂)₃CF = CF₂); 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene (CF)₃CF₂CF = CFCF₂CF₃); 1,1,1,4,4,4-hexafluoro-2,3-bis (trifluoromethyl) -2-butene ((CF)₃)₂C = C (CF)₃)₂); 1,1,1,2,3,4,5,5,5-Nonafluoro-4- (trifluoromethyl) -2-pentene ((CF)₃)₂CFCF = CFCF₃); 1,1,1,4,4,5,5,5-octafluoro-2- (trifluoromethyl) -2-pentene ((CF)₃)₂C = CHC₂F₅); 1,1,1,3,4,5,5,5-octafluoro-4- (trifluoromethyl) -2-pentene ((CF)₃)₂CFCF = CHCF₃); 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene (CF)₃CF₂CF₂CF₂CH = CH₂); 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)₂C = C (CH)₃) (CF₃)); 2,3,3,5,5,5-hexafluoro-4- (trifluoromethyl) -1-pentene (CH)₂= CFCF₂CH (CF)₃)₂); 1,1,1,2,4,4,5,5,5-Nonafluoro-3-methyl-2-pentene (CF)₃CF = C (CH)₃) CF₂CF₃); 1,1,1,5,5,5-hexafluoro-4- (trifluoromethyl) -2-pentene (CF)₃CH = CHCH (CF)₃)₂); 3,4,4,5,5,6,6,6-octafluoro-2-hexene (CF)₃CF₂CF₂CF = CHCH₃); 3,3,4,4,5,5,6,6-octafluoro1-hexene (CH)₂= CHCF₂CF₂CF₂CHF₂); 1,1,1,4,4-pentafluoro-2- (trifluoromethyl) -2-pentene ((CF)₃)₂C = CHCF₂CH₃); 4,4,5,5,5-pentafluoro-2- (trifluoromethyl) -1-pentene (CH)₂= C (CF)₃) CH₂C₂F₅); 3,3,4,4,5,5,5-heptafluoro-2-methyl-1-pentene (CF)₃CF₂CF₂C (CH)₃) = CH₂); 4,4,5,5,6,6,6-heptafluoro-2-hexene (CF)₃CF₂CF₂CH = CHCH₃); 4,4,5,5,6,6,6-heptafluoro-1-hexene (CH)₂= CHCH₂CF₂C₂F₅); 1,1,1,2,2,3,4-heptafluoro-3-hexene (CF)₃CF₂CF = CFC₂H₅); 4,5,5,5-Tetrafluoro-4- (trifluoromethyl) -1-pentene (CH)₂= CHCH₂CF (CF)₃)₂); 1,1,1,2,5,5,5-heptafluoro-4-methyl-2-pentene (CF)₃CF = CHCH (CF)₃) (CH₃)); 1,1,1,3-Tetrafluoro-2- (trifluoromethyl) -2-pentene ((CF)₃)₂C = CFC₂H₅); 1,1,1,2,3,4,4,5,5,6,6,7,7,7-Tetradecafluoro-2-heptene (CF)₃CF = CFCF₂CF₂C₂F₅); 1,1,1,2,2,3,4,5,5,6,6,7,7,7-Tetradecafluoro-3-heptene (CF)₃CF₂CF = CFCF₂C₂F₅); 1,1,1,3,4,4,5,5,6,6,7,7,7-Tridecafluoro-2-heptene (CF)₃CH = CFCF₂CF₂C₂F₅); 1,1,1,2,4,4,5,5,6,6,7,7,7-Tridecafluoro-2-heptene (CF)₃CF = CHCF₂CF₂C₂F₅); 1,1,1,2,2,4,5,5,6,6,7,7,7-Tridecafluoro-3-heptene (CF)₃CF₂CH = CFCF₂C₂F₅); 1,1,1,2,2,3,5,5,6,6,7,7,7-Tridecafluoro-3-heptene (CF)₃CF₂CF = CHCF₂C₂F₅); CF₂= CFOCF₂CF₃(PEVE) and CF₂= CFOCF₃Fluoroolefins selected from the group consisting of (PMVE); selected from the group consisting of.

Of particular importance in compositions containing at least one flammable refrigerant and at least one fluoroolefin are these fluoroolefins, which are themselves nonflammable. The flammability of fluoroolefins is considered to be 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 expected flammability:

<maths num="1"><img file="JP6442011B2_D0009.tif" /></maths>

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 cutoff for the nonflammable fluoroolefin flammability factor was determined. Fluoroolefins are ASTMs equipped with an electronic ignition source under the conditions specified by ASHRAE (American Society of Heating, Refrigerating and Air-Conditioning Engineers, Inc.) Standard 34-2001. (American Society of Testing and Materials) Testing under E681-01 can determine whether it is flammable or nonflammable. Such flammability tests, along with the compound of interest, at 101 kPa (14.7 psia) and specific temperatures to determine the lower explosive limit (LFL) and / or upper explosive limit (UFL) of the test compound in air. Performed in air at various concentrations (often 100 ° C (212 ° F)).

The flammability coefficients for a number of fluoroolefins are listed in Table 4, along with experimental determinations of flammability or nonflammability. Therefore, it is possible to predict with respect to the other fluoroolefins of the present disclosure whether they will actually be most useful as nonflammable fluoroolefins in combination with the flammable refrigerants of the present disclosure.

<tables num="9"><img file="JP6442011B2_D0010.tif" /></tables>

<tables num="10"><img file="JP6442011B2_D0011.tif" /></tables>

<tables num="11"><img file="JP6442011B2_D0012.tif" /></tables>

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

In another embodiment of the invention, the fluoroolefins used in the composition with the flammable refrigerant are: Formula (a) ER.¹CH = CHR²Or ZR¹CH = CHR²Fluoroolefin in the formula, R¹And R²But independently, C₁~ C₆Fluoroolefin, which is a perfluoroalkyl group of_n-] Cyclic fluoroolefins, where X, Y, Z, and W are independently H or F, and n is an integer of 2-5, and the flammability coefficient is greater than or equal to 0.70. Cyclic fluoroolefins; and (c) 1,2,3,3,3-pentafluoro-1-propene (CF)₃CF = CHF); 1,1,3,3,3-pentafluoro-1-propene (CF)₃CH = CF₂); 1,1,2,3,3-pentafluoro-1-propene (CHF)₂CF = CF₂); 1,1,1,2,3,4,4,4-octafluoro-2-butene (CF)₃CF = CFCF₃); 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF)₃CF₂CF = CF₂); 1,1,1,2,4,4,4-heptafluoro-2-butene (CF)₃CF = CHCF₃); 1,2,3,3,4,4,4-heptafluoro-1-butene (CHF = CFCF)₂CF₃); 1,1,1,2,3,4,4-heptafluoro-2-butene (CHF)₂CF = CFCF₃); 1,3,3,3-Tetrafluoro-2- (trifluoromethyl) -1-propene ((CF)₃)₂C = CHF); 1,1,3,3,4,4,4-heptafluoro-1-butene (CF)₂= CHCF₂CF₃); 1,1,2,3,4,4,4-heptafluoro-1-butene (CF)₂= CFCHFCF₃); 1,1,2,3,3,4,4-heptafluoro-1-butene (CF)₂= CFCF₂CHF₂); 2,3,3,4,4,4-hexafluoro-1-butene (CF)₃CF₂CF = CH₂); 1,3,3,4,4,4-hexafluoro-1-butene (CHF = CHCF)₂CF₃); 1,2,3,4,4,4-hexafluoro-1-butene (CHF = CFC CHFCF)₃); 1,2,3,3,4,4-hexafluoro-1-butene (CHF = CFCF)₂CHF₂); 1,1,2,3,4,4-hexafluoro-2-butene (CHF)₂CF = CFCHF₂); 1,1,1,2,3,4-hexafluoro-2-butene (CH)₂FCF = CFCF₃); 1,1,1,2,4,4-hexafluoro-2-butene (CHF)₂CH = CFCF₃); 1,1,1,3,4,4-hexafluoro-2-butene (CF)₃CH = CFC CHF₂); 1,1,2,3,3,4-hexafluoro-1-butene (CF)₂= CFCF₂CH₂F); 1,1,2,3,4,4-hexafluoro-1-butene (CF)₂= CFCHFCHF₂); 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)₃CF = CFCF₂CF₃); 1,1,2,3,3,4,4,5,5,5-decafluoro-1-pentene (CF)₂= CFCF₂CF₂CF₃); 1,1,1,4,4,4-hexafluoro-2- (trifluoromethyl) -2-butene ((CF)₃)₂C = CHCF₃); 1,1,1,2,4,4,5,5,5-Nonafluoro-2-pentene (CF)₃CF = CHCF₂CF₃); 1,1,1,3,4,4,5,5,5-Nonafluoro-2-pentene (CF)₃CH = CFCF₂CF₃); 1,2,3,3,4,4,5,5,5-Nonafluoro-1-pentene (CHF = CFCF)₂CF₂CF₃); 1,1,3,3,4,4,5,5,5-Nonafluoro-1-pentene (CF)₂= CHCF₂CF₂CF₃); 1,1,2,3,3,4,4,5,5-Nonafluoro-1-pentene (CF)₂= CFCF₂CF₂CHF₂); 1,1,2,3,4,4,5,5,5-Nonafluoro-2-pentene (CHF)₂CF = CFCF₂CF₃); 1,1,1,2,3,4,4,5,5-Nonafluoro-2-pentene (CF)₃CF = CFCF₂CHF₂); 1,1,1,2,3,4,5,5,5-Nonafluoro-2-pentene (CF)₃CF = CFCHFCF₃); 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)₃CH = 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= CFCF₂CF₂CF₃); 1,2,3,3,4,4,5,5-octafluoro-1-pentene (CHF = CFCF)₂CF₂CHF₂); 3,3,4,4,4-Pentafluoro-2- (trifluoromethyl) -1-butene (CH)₂= C (CF)₃) CF₂CF₃); 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) CH₂CF₃); 3,4,4,4-Tetrafluoro-3- (trifluoromethyl) -1-butene ((CF)₃)₂CFCH = CH₂); 3,3,4,4,5,5,5-heptafluoro-1-pentene (CF)₃CF₂CF₂CH = CH₂); 2,3,3,4,4,5,5-heptafluoro-1-pentene (CH)₂= CFCF₂CF₂CHF₂); 1,1,3,3,5,5,5-heptafluoro-1-butene (CF)₂= CHCF₂CH₂CF₃); 1,1,1,2,4,4,4-heptafluoro-3-methyl-2-butene (CF)₃CF = C (CF)₃) (CH₃)); 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)₂FCH = C (CF)₃)₂); 1,1,1,3-Tetrafluoro-2- (trifluoromethyl) -2-butene (CH)₃CF = C (CF)₃)₂); 1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1-hexene (CF)₃(CF₂)₃CF = CF₂); 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene (CF)₃CF₂CF = CFCF₂CF₃); 1,1,1,4,4,4-hexafluoro-2,3-bis (trifluoromethyl) -2-butene ((CF)₃)₂C = C (CF)₃)₂); 1,1,1,2,3,4,5,5,5-Nonafluoro-4- (trifluoromethyl) -2-pentene ((CF)₃)₂CFCF = CFCF₃); 1,1,1,4,4,5,5,5-octafluoro-2- (trifluoromethyl) -2-pentene ((CF)₃)₂C = CHC₂F₅); 1,1,1,3,4,5,5,5-octafluoro-4- (trifluoromethyl) -2-pentene ((CF)₃)₂CFCF = CHCF₃); 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene (CF)₃CF₂CF₂CF₂CH = CH₂); 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)₂C = C (CH)₃) (CF₃)); 2,3,3,5,5,5-hexafluoro-4- (trifluoromethyl) -1-pentene (CH)₂= CFCF₂CH (CF)₃)₂); 1,1,1,2,4,4,5,5,5-Nonafluoro-3-methyl-2-pentene (CF)₃CF = C (CH)₃) CF₂CF₃); 1,1,1,5,5,5-hexafluoro-4- (trifluoromethyl) -2-pentene (CF)₃CH = CHCH (CF)₃)₂); 1,1,1,2,3,4,4,5,5,6,6,7,7,7-Tetradecafluoro-2-heptene (CF)₃CF = CFCF₂CF₂C₂F₅); 1,1,1,2,2,3,4,5,5,6,6,7,7,7-Tetradecafluoro-3-heptene (CF)₃CF₂CF = CFCF₂C₂F₅); 1,1,1,3,4,4,5,5,6,6,7,7,7-Tridecafluoro-2-heptene (CF)₃CH = CFCF₂CF₂C₂F₅); 1,1,1,2,4,4,5,5,6,6,7,7,7-Tridecafluoro-2-heptene (CF)₃CF = CHCF₂CF₂C₂F₅); 1,1,1,2,2,4,5,5,6,6,7,7,7-Tridecafluoro-3-heptene (CF)₃CF₂CH = CFCF₂C₂F₅); And 1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF)₃CF₂CF = CHCF₂C₂F₅) Is 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 flammable refrigerants are: Eq. (a) ER.¹CH = CHR²Or ZR¹CH = CHR²Fluoroolefin in the formula, R¹And R²But independently, C₁~ C₆A fluoroolefin having a flammability coefficient of 0.70 or more; and a cyclo- [CX = CY (CZW) of formula (b)._n-] Cyclic fluoroolefins, in which X, Y, Z, and W are independently H or F, and n is an integer of 2-5, and the flammability coefficient is 0.70. It can be at least one fluoroolefin selected from the group consisting of the above cyclic fluoroolefins.

The flammability coefficient provides a criterion for predicting the flammability of a given fluoroolefin compound, while certain isomers with a given molecular equation are flammable while others are nonflammable. There can be certain variable factors such as the position of the hydrogen atom on the molecule that may cause this. Therefore, the flammability factor can only be used as a tool for predicting flammability characteristics.

The flammable refrigerants of the present invention include any compound that can be shown to propagate a flame when mixed with air under certain conditions of temperature, pressure and composition. Flammable refrigerants are equipped with an electronic ignition source under the conditions specified by ASHRAE (American Society of Heating, Refrigerating 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 flammability tests include the Lower Explosion Limit (LFL) of the test compound in air and 101 kPa (14.7 psia) and a specific temperature (typically 100 ° C (212 ° F), or about 23 ° C (73 ° F)) with refrigerant to determine the upper explosion limit (UFL). Performed in air at various concentrations (at room temperature).

As a practical matter, a refrigerant can be distinguished as flammable when it leaks from a refrigerating or air conditioner and when it can ignite in contact with an ignition source. The compositions of the present invention are unlikely to ignite even during such a leak.

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

The flammable HFC refrigerant is not particularly limited: difluoromethane (HFC-32), fluoromethane (HFC-41), 1,1,1-trifluoroethane (HFC-143a), 1,1,2-tri Fluoroethane (HFC-143), 1,1-difluoroethane (HFC-152a), Fluoroethane (HFC-161), 1,1,1-Trifluoropropane (HFC-263fb), 1,1,1,3, Examples include 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-propen (HFC-1234yf); 1,1,2,3-tetrafluoro-1-propen (HFC-1234yc); 1,1,3,3 -Tetrafluoro-1-propen (HFC-1234zc); 2,3,3-trifluoro-1-propen (HFC-1243yf); 3,3,3-trifluoro-1-propen (HFC-1243zf); 1 , 1,2-Trifluoro-1-propen (HFC-1243yc); 1,1,3-trifluoro-1-propen (HFC-1243zc); 1,2,3-trifluoro-1-propen (HFC-) Includes further fluoroolefins containing 1243ye); and 1,3,3-trifluoro-1-propene (HFC-1243ze).

The flammable refrigerants of the present invention further include fluoroethers, which are compounds similar to hydrofluorocarbons and also contain at least one ether group oxygen atom. The typical fluoroether refrigerant is not particularly limited, but is commercially available C.₄F₉OC₂H₅Can be mentioned.

The flammable refrigerant of the present invention further includes a hydrocarbon refrigerant. Typical hydrocarbon refrigerants are not particularly limited, but are 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- Includes heptane, methylcyclopentane, and n-hexane. Flammable hydrocarbon refrigerants are available from multiple commercial suppliers.

The flammable refrigerants of the present invention are both available from multiple commercial suppliers, dimethyl ether (DME, CH).₃OCH₃) And methyl t-butyl ether (MTBE, (CH)₃)₃COCH₃) And other hydrocarbon ethers.

The flammable refrigerant of the present invention is a commercially available compound, ammonia (NH).₃) Is further included.

The flammable refrigerants of the present invention are two or more flammable refrigerants (eg, such that the entire mixture is still considered a flammable refrigerant when identified under the ASTM conditions described herein, or as a practical matter. It may further contain a mixture of two or more refrigerants, such as a mixture of two HFCs or one HFC and a hydrocarbon) or a mixture containing a flammable refrigerant and a non-flammable refrigerant.

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

Examples of mixtures of two or more flammable refrigerants are propane / isobutane; HFC-152a / isobutane, R32 / propane; R32 / isobutane; and HFC-152a / CO.₂Examples include HFC / carbon dioxide mixtures.

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 present invention is to reduce the flammability of a flammable frozen mixture by adding a nonflammable fluoroolefin to the mixture.

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

The compositions of the invention that are useful as refrigerants or heat transfer fluids, including at least one fluoroolefin and at least one flammable refrigerant, contain an effective amount of fluoroolefin in the results of ASTM E681-01. Based on this, a nonflammable composition can be produced.

The compositions of the 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 compositions of the 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 another embodiment, the compositions of the 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 the 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 of HFC-32 were found to be nonflammable, and compositions containing 38 weight percent or more of HFC-32 were found to be flammable. The present disclosure provides nonflammable compositions comprising from about 1.0 weight percent to about 37.0 weight percent HFC-32 and from about 99.0 weight percent to about 63 weight percent HFC-1225ye.

Also of particular interest are the 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 HFC-125. including. 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 HFC. Includes -125. In yet another embodiment, 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 HFC. Includes -125. These compositions containing less than about 40 weight percent HFC-32 are expected to be nonflammable compositions. This explosive 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 another particularly interesting embodiment, the flammable refrigerant comprises HFC-1243zf and a nonflammable fluoroolefin intended to reduce the flammability of the entire composition. The composition may 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 may 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 compositions are 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. Including HFC-125. Alternatively, the composition is 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. including.

In other embodiments of particular interest, the compositions are 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. Including HFC-32. Alternatively, the composition is 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-32. including.

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; from about 1.0 weight percent to about 50 weight percent. HFC-125; and HFC-32 from about 1.0 weight percent to about 50 weight percent. Alternatively, the composition is 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 contains about 1.0 weight percent to about 10 weight percent HFC-32.

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

The compositions of the present invention can be used in combination with desiccants 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. Typical molecular sieves include MOLSIV XH-7, XH-6, XH-9 and XH-11 (UOP LLC of Des Plaines, IL). HFC-32, XH-11 desiccant and the like are preferable as the refrigerant having a small molecular size.

The compositions of the present invention may further comprise at least one lubricant. The lubricants of the present invention include those preferred for use in refrigeration or air conditioning equipment. Of these, lubricants are conveniently used in compression refrigeration equipment that uses chlorofluorocarbon refrigerants. Such lubricants and their properties are studied herein by reference (Non-Patent Document 2). The lubricant of the present invention may include those commonly known as "mineral oils" in the field of compression refrigeration lubrication. Mineral oils are paraffins (ie, linear and branched-carbon-chains, saturated hydrocarbons), naphthenes (ie, cyclic paraffins) and aromatic compounds (ie, one or more characterized by alternating double bonds). Contains ring-containing unsaturated, cyclic hydrocarbons). 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 polys (alpha-olefins). A typical ordinary lubricant of the present invention is commercially available BVM100N (BVA oil (BVA)). Paraffinic mineral oil purchased from Oils), Suniso® 3GS and Suniso® 5GS (naphthenic mineral oil purchased from Crompton Co.), Suntex ( Sontex (registered trademark) 372LT (naphthenic mineral oil purchased from Pennzoil), Calumet (registered trademark) RO-30 (naphthenic mineral oil purchased from Calumet Lubricants), Zerol (Zerol) (registered trademark) 75, Zerol (registered trademark) 150 and Zerol (registered trademark) 500 (linear alkylbenzene purchased from Shrieve Chemicals) and HAB22 (Shin Nihon Oil (New Japan Oil) Branched alkylbenzene) purchased from Nippon Oil).

Lubricants of the present invention further include those designed for use with hydrofluorocarbon refrigerants and those that are miscible with the refrigerants of the present invention under the operating conditions of compression refrigeration and air conditioners. Such lubricants and their properties are discussed in (Non-Patent Document 3). Such lubricants are not particularly limited, but are polyol esters (POE) such as Castrol® 100 (Castrol of the United Kingdom), Dow (Midland, Michigan). Examples thereof include polyalkylene glycols (PAG) such as RL-488A manufactured by Dow Chemical of Midland, Michigan), and polyvinyl ether (PVE).

The lubricants of the present invention are selected by taking into account 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 invention to enhance lubricity and system stability, if desired. These additives are generally known in the field of refrigeration compressor lubrication and are wear resistant agents, superpressure lubricants, corrosion and oxidation inhibitors, metal surface deactivators, foaming and anti-foaming controls. Agents, leak detection agents and the like can be mentioned. In general, these additives are present only in small amounts relative to the overall lubricant composition. These are typically used in concentrations ranging from less than about 0.1% to about 3% of each additive. These additives are selected based on the individual system requirements. Some typical examples of such additives may include, but are not limited to, lubrication-enhancing additives such as alkyl or aryl esters of phosphoric acid and alkyl or aryl esters of thiophosphate. In addition, metal dialkyl dithiophosphates (eg zinc dialkyl dithiophosphate or ZDDP, Lubrizol 1375) and other components of this family of chemicals can be used in the compositions of the invention. Other wear resistant additives include natural product oils and asymmetric polyhydroxyl lubricants 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 phenol (such as butylated hydroxytoluene, or BHT), hydroxylamine, thiol, phosphite, epoxide, or lactone. The water scavenger is not particularly limited, and examples thereof include orthoesters such as trimethyl orthoformate, -triethyl, and -tripropyl. A single additive or a combination thereof may be used.

In one embodiment, the invention relates to thiophosphates, butylated triphenylphosphorothionates, organic phosphates, dialkylthiophosphates, terpenes, terpenoids, fullerenes, functionalized perfluoropolyethers, polyoxyalkylated aromatics. Group consisting of group compounds, epoxides, fluorinated epoxides, oxetane, ascorbic acid, thiols, lactones, thioethers, nitromethanes, alkylsilanes, benzophenone derivatives, aryl sulfides, divinyl terephthalates, diphenyl terephthalates, alkylamines, hindered amine antioxidants, and phenols. A composition comprising at least one fluoroolefin selected from and at least one stabilizer is provided. Alkylamines include triethylamine, tributylamine, diisopropylamine, triisopropylamine, triisobutylamine, and other components of this family of alkylamine compounds.

In other embodiments, the stabilizers of the invention may comprise a particular combination of stabilizers. One combination of stabilizers of particular interest 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 oxetane.

Terpenes are hydrocarbon compounds characterized by a structure containing two or more isoprene (2-methyl-1,3-butadiene) repeating units. The terpene may be acyclic or cyclic. Typical terpenes are not particularly limited, but myrcene (2-methyl-6-methyl-enocta-1,7-diene), aloosimene, β-ocimene, teleben, limonene (or d-limonene), retinal, pinene ( Or α-pinene), menthol, geraniol, farnesol, phytol, vitamin A, terpinene, δ-3-calene, terpinolene, ferlandren, fenken and mixtures thereof. Terpene stabilizers can be commercially available, prepared by methods known in the art, or isolated from natural sources.

Terpenoids are natural products and related compounds that are characterized by a structure that contains two or more isoprene repeat units and optionally oxygen. Typical terpenoids are lycopene (CAS Registry Number [502-65-8]), β-carotene (CAS Registry Number [7235-40-7]), and xanthophile, ie, zeaxanthin (CAS Registry Number [144-68]). Carotinoids such as -3]); retinoids such as hepaxanthin (CAS Registry Number [512-39-0]) and isotretinoin (CAS Registry Number [4759-48-2]); Avietan (CAS Registry Number] [640-43-7]); Ambrosan (CAS Registry Number [24749-18-6]); Aristolan (CAS Registry Number [29788-49-6]); Achisan (CAS Registry Number [24379-83-7]) ]); Bay Elan (CAS Registry Number [2359-83-3]), Visabolan (CAS Registry Number [29799-19-7]); Bornan (CAS Registry Number [464-15-3]); [20479-00-9]); Sedran (CAS Registry Number [13567-54-9]); Damaran (CAS Registry Number [545-22-2]); Driman (CAS Registry Number [5951-58-6]) Eremophilan (CAS Registry Number [3242-05-5]); Eudesman (CAS Registry Number [473-11-0]); Fenkan (CAS Registry Number [6248-88-0]); Gamma Seran (CAS Registry Number [CAS] 559-65-9]); Germacran (CAS Registry Number [645-10-3]); Ziban (CAS Registry Number [6902-95-0]); Glayanotoxan (CAS Registry Number [39907-73-8]) Guiron (CAS Registry Number [489-80-5]); Himakaran (CAS Registry Number [20479-45-2]); Hopan (CAS Registry Number [471-62-5]); Humran (CAS Registry Number [430]) -19-3]); Kaulan (CAS Registry Number [1573-40-6]); Rabdan (CAS Registry Number [561-90-0]); Ranostan (CAS Registry Number [474-20-4]); Lupine (CAS Registry Number [464-]) 99-3]); p-Mentan (CAS Registry Number [99-82-1]); Oleanan (CAS Registry Number [471-67-0]); Offioboran (CAS Registry Number [20098-65-1]); Piclasan (CAS Registry Number [35732-97-9]); Pimaran (CAS Registry Number [30257-03-5]); Pinan (CAS Registry Number [473-55-2]); Podkarpan (CAS Registry Number [471-]) 78-3]); Protostan (CAS Registry Number [70050-78-1]); Rosan (CAS Registry Number [6812-82-4]); Taxan (CAS Registry Number [1605-68-1]); Tujan (CAS Registry Number [471-12-5]); Tricotecan (CAS Registry Number [24706-08-9]); and Ursan (CAS Registry Number [464-93-7]). The terpenoids of the invention can be commercially available, prepared by methods known in the art, or isolated from natural sources. Thujone (CAS Registry Number [471-12-5]); Tricotecan (CAS Registry Number [24706-08-9]); and Ulsan (CAS Registry Number [464-93-7]). The terpenoids of the invention can be commercially available, prepared by methods known in the art, or isolated from natural sources. Thujone (CAS Registry Number [471-12-5]); Tricotecan (CAS Registry Number [24706-08-9]); and Ulsan (CAS Registry Number [464-93-7]). The terpenoids of the invention can be commercially available, prepared by methods known in the art, or isolated from natural sources.

In one embodiment, the terpene or terpenoid stabilizer can be combined with at least one epoxide. Typical 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 invention can be combined with at least one fluorinated epoxide. The fluorinated epoxide of the present invention can be represented by Equation 3, in which R²~ R⁵Each of is H, an alkyl of 1 to 6 carbon atoms or a fluoroalkyl of 1 to 6 carbon atoms, but R²~ R⁵At least one of them is a fluoroalkyl group.

<chemistry num="1"><img file="JP6442011B2_D0013.tif" /></chemistry>

Typical fluorinated epoxide stabilizers include, but are not limited to, trifluoromethyloxylane and 1,1-bis (trifluoromethyl) oxylane. 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 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, in the formula, R.₁~ R₆Can be the same or different and can be selected from hydrogen, alkyl or substituted alkyl, aryl or substituted aryl.

<chemistry num="2"><img file="JP6442011B2_D0014.tif" /></chemistry>

The typical oxetane stabilizer is not particularly limited, but is 3-ethyl-3-hydroxymethyl-oxetane such as OXT-101 (Toagosei Co., Ltd); OXT-211 (Toagosei Co., Ltd.). 3-Ethyl-3-((phenoxy) methyl) -oxetane; and OXT-212 (Toagosei Co., Ltd), etc. 3-ethyl-3-((phenoxy) methyl)- 3-((2-Ethyl-hexyloxy) methyl) -oxetane can be mentioned.

Another particularly interesting embodiment is a combination of stabilizers containing fullerenes. Fullerene stabilizers can be combined with at least one compound selected from the group consisting of epoxides, fluorinated epoxides, and oxetane. Epoxides, fluorinated epoxides, and oxetane for combination with fullerenes have already been described herein as for combinations with terpenes or terpenoids.

Another particularly interesting embodiment is a combination of stabilizers, including phenol. Fullerene stabilizers can be combined with at least one compound selected from the group consisting of epoxides, fluorinated epoxides, and oxetane. Epoxides, fluorinated epoxides, and oxetane for combination with phenol have already been described herein as for combinations with terpenes or terpenoids.

As the phenol stabilizer, 2,6-di-tert-butyl-4-methylphenol; 2,6-di-tert-butyl-4-ethylphenol; 2,4-dimethyl-6-tetrabutylphenol; tocopherol, etc. Hydroquinone and alkylated hydroquinone, including alkylated monophenols, t-butylhydroquinone, other derivatives of hydroquinone, etc., 4,4'-thio-bis (2-methyl-6-tert-butylphenol); 4,4'- Thiobis (3-methyl-6-tetrabutylphenol); hydroxylated thiodiphenyl ether containing 2,2'-thiobis (4 methyl-6-tert-butylphenol), etc., 4,4'-methylenebis (2,6-di-tert) -Butylphenol); 4,4'-bis (2,6-di-tert-butylphenol); 2,2'-or derivative of 4,4-biphenoldiol; 2,2'-methylenebis (4-ethyl-6- tert Butylphenol); 2,2'-methylenebis (4-methyl-6-tertbutylphenol); 4,4-butylidenebis (3-methyl-6-tert-butylphenol); 4,4-isopropyridenebis (2,6- Di-tert-butylphenol); 2,2'-methylenebis (4-methyl-6-nonylphenol); 2,2'-isobutylidenebis (4,6-dimethylphenol; 2,2'-methylenebis (4-methyl) Alkylidene-bisphenol containing -6-cyclohexylphenol, 2,2'-methylenebis (4-ethyl-6-tert-butylphenol); 2,2- or 4,4-biphenyldiol containing butylated hydroxyltolutyl (BHT), Bisphenol containing heteroatoms including 2,6-di-tert-α-dimethylamino-p-cresol, 4,4-thiobis (6-tert-butyl-m-cresol), etc .; Acylaminophenol; 2,6- Di-tert-butyl-4 (N, N'-dimethylaminomethylphenol);Bis (3-methyl-4-hydroxy-5-tert-butylbenzyl) sulfides; one or more substitutions such as sulfides containing bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfides, etc. Includes any substituted or unsubstituted phenolic compound containing phenol containing an unsubstituted cyclic, linear, or branched aliphatic substituent.

In one embodiment of the invention, these combinations of terpenes or terpenoids, or stabilizers containing fullerene or phenol, with at least one compound selected from the group consisting of epoxides, fluorinated epoxides, and oxetane: Areoxalyl bis (benzylidene) hydrazine (CAS registration number 6629-10-3); N, N'-bis (3,5-di-tert-butyl-4-hydroxyhydrosinamoyl hydrazine) (CAS registration number) 32687-78-8); 2,2'-oxamidebis-ethyl- (3,5-d-tert-butyl-4-hydroxyhydrocinnamete) (CAS registration number 70331-94-1); N, N'- (Disalicyclidene) -1,2-propanediamine (CAS registration number 94-91-1); and ethylenediaminetetraacetic acid (CAS registration number 60-00-4) and additions selected from the group consisting of salts thereof. Stabilizer compounds may further be included.

In other embodiments of the invention, these combinations of stabilizers containing terpen or terpenoids, or fullerene or phenol, with at least one compound selected from the group consisting of epoxides, fluorinated epoxides, and oxetane , Triethylamine; tributylamine; triisopropylamine; diisobutylamine; triisopropylamine; triisobutylamine; and hindered amines may further comprise at least one alkylamine selected from the group consisting of antioxidants.

The compositions of the present invention may further comprise a compound or composition that is a tracer, such as hydrofluorocarbons (HFCs), hydrocarbon hydrocarbons, hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodides compounds. , Aldehydes, Aldehydes, Ketones, Nitrocarbon Hydrocarbons (N)₂It is selected from the group consisting of O) and combinations thereof. The tracer used in the present invention has a composition different from that used as a refrigerant or a heat transfer fluid, and is described in the US Patent Publication (Patent Document 2) filed on February 18, 2005, as described in the refrigerant and the heat transfer fluid. The heat transfer composition is added in a predetermined amount in which either dilution, contamination or other denaturation of the composition is detectable.

Typical tracer compounds for use in this composition are listed in Table 5.

<tables num="12"><img file="JP6442011B2_D0015.tif" /></tables>

<tables num="13"><img file="JP6442011B2_D0016.tif" /></tables>

<tables num="14"><img file="JP6442011B2_D0017.tif" /></tables>

<tables num="15"><img file="JP6442011B2_D0018.tif" /></tables>

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 the frozen / heated fluid in the compositions of the invention, or multiple tracer compounds can be combined in any proportion to serve as a tracer blend. A tracer blend may 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 are present as multiple isomers, such as structural or optical. A single isomer or multiple isomers of the same compound can be used in any proportion that prepares the tracer compound. In addition, a 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.

Tracer compounds or tracer blends 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 compositions 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, heat pump device. It is a useful component for detecting the leakage of water. The fluorescence of the dye may be observed under ultraviolet light. Solubilizers may be needed 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 regions of the electromagnetic spectrum. The fluorescence produced by the UV fluorescent dye can be detected under irradiation with UV light that emits radiation having a wavelength of any of 10 nanometers to 750 nanometers. Thus, if such a UV fluorescent dye-containing refrigerant or heat transfer fluid leaks from a given location in a refrigeration, air conditioning, or heat pump device, fluorescence will be detected at or near the leak point. It is possible. Such UV fluorescent dyes include, but are not limited to, naphthalimide, perylene, coumarin, anthracene, phenanthracene, xanthene, thioxanthene, naphthoxanthene, fluororecein, and derivatives of the dyes or combinations thereof. Be done. The solubilizer of the present invention consists of hydrocarbons, hydrocarbon ethers, polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and 1,1,1-trifluoroalkanes. Contains at least one compound selected from the group.

The hydrocarbon solubilizer of the present invention contains linear, branched or cyclic alkanes or alkene-containing hydrocarbons containing 16 or less carbon atoms and containing only hydrogen without containing other functional groups. Including. Representative hydrocarbon solubilizers include propane, propylene, cyclopropane, n-butane, isobutane, n-pentane, octane, decane, and hexadecane. It should be noted that if the refrigerant is a hydrocarbon, the solubilizer cannot be the same hydrocarbon.

Hydrocarbon ether solubilizers of the present invention include ethers such as dimethyl ether (DME), which contain only carbon, hydrogen and oxygen.

The polyoxyalkylene glycol ether solubilizer of the present invention has the formula R.¹[(OR²)_xOR³]_y(In the formula: x is an integer from 1 to 3; y is an integer from 1 to 4; R¹Is selected from hydrogen, and aliphatic hydrocarbon radicals with 1-6 carbon atoms and y-binding sites; R²Is selected from aliphatic hydrocarbylene radicals with 2-4 carbon atoms; R³Is selected from hydrogen, and aliphatic and alicyclic hydrocarbon radicals with 1-6 carbon atoms; R¹And R³At least one of the hydrocarbon radicals); where the polyoxyalkylene glycol ether has a molecular weight of about 100 to about 300 atomic weights. As used herein, a binding site means a radical site that can be used to form a covalent bond with another radical. The hydrocarbylene radical means a divalent hydrocarbon radical. In the present invention, the preferred polyoxyalkylene glycol ether solubilizer is R.¹[(OR²)_xOR³]_yRepresented by: x is preferably 1-2; y is preferably 1; R¹~ R³Is preferably selected independently of hydrogen and aliphatic hydrocarbon radicals with 1 to 4 carbon atoms; R²Is preferably selected from aliphatic hydrocarbylene radicals having 2 or 3 carbon atoms, most preferably 3 carbon atoms; the polyoxyalkylene glycol ether molecular weight is preferably from about 100 to about 250 atomic weights. The unit, most preferably about 125 to about 250 atomic mass units. R with 1 to 6 carbon atoms¹~ R³Hydrocarbon radicals can be straight, branched or cyclic. Typical R¹~ R³Examples of the hydrocarbon radical include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, and cyclohexyl. If the free hydroxyl radicals on the polyoxyalkylene glycol ether solubilizer may be incompatible with certain compression refrigeration equipment materials of structure (eg, Mylar®), then R¹~ R³Is preferably an aliphatic hydrocarbon radical having 1 to 4 carbon atoms, most preferably 1 carbon atom. R with 2-4 carbon atoms²Aliphatic hydrocarbylene radicals are repetitive oxyalkylene radicals-(OR²)_x-Forms, which contains oxyethylene radicals, oxypropylene radicals, and oxybutylene radicals. R in one polyoxyalkylene glycol ether solubilizer molecule²The oxyalkylene radicals containing may be the same, or one molecule is different R²It may contain an oxyalkylene group. The polyoxyalkylene glycol ether solubilizer preferably contains at least one oxypropylene group. R¹If is an aliphatic or alicyclic hydrocarbon radical with 1-6 carbon atoms and a y-binding site, the group can be straight, branched or cyclic. Typical R with two binding sites¹Examples of the aliphatic hydrocarbon radical include an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a cyclopentylene group and a cyclohexylene group. Typical R with 3 or 4 binding sites¹Aliphatic hydrocarbon radicals include polyalcohols such as trimethylolpropane, glycerin, and pentaerythritol, their hydroxyl groups derived from 1,2,3-trihydroxycyclohexane and 1,3,5-trihydroxycyclohexane. Residues from removal can be mentioned.

Typical polyoxyalkylene glycol ether solubilizers include, but are not limited to, CH.₃OCH₂CH (CH)₃) O (H or CH₃) (Propylene glycol methyl (or dimethyl) ether), CH₃O [CH₂CH (CH)₃) O]₂(H or CH₃) (Dipropylene glycol methyl (or dimethyl) ether), CH₃O [CH₂CH (CH)₃) O]₃(H or CH₃) (Tripropylene glycol methyl (or dimethyl) ether), C₂H₅OCH₂CH (CH)₃) O (H or C₂H₅) (Propylene glycol ethyl (or diethyl) ether), C₂H₅O [CH₂CH (CH)₃) O]₂(H or C₂H₅) (Dipropylene glycol ethyl (or diethyl) ether), C₂H₅O [CH₂CH (CH)₃) O]₃(H or C₂H₅) (Tripropylene glycol ethyl (or diethyl) ether), C₃H₇OCH₂CH (CH)₃) O (H or C₃H₇) (Propylene glycol n-propyl (or di-n-propyl) ether), C₃H₇O [CH₂CH (CH)₃) O]₂(H or C₃H₇) (Dipropylene glycol n-propyl (or di-n-propyl) ether), C₃H₇O [CH₂CH (CH)₃) O]₃(H or C₃H₇) (Tripropylene glycol n-propyl (or di-n-propyl) ether), C₄H₉OCH₂CH (CH)₃) OH (Propylene Glycol n-Butyl Ether), C₄H₉O [CH₂CH (CH)₃) O]₂(H or C₄H₉) (Dipropylene glycol n-butyl (or di-n-butyl) ether), C₄H₉O [CH₂CH (CH)₃) O]₃(H or C₄H₉) (Tripropylene glycol n-butyl (or di-n-butyl) ether), (CH₃)₃COCH₂CH (CH)₃) OH (Propylene Glycol t-Butyl Ether), (CH₃)₃CO [CH₂CH (CH)₃) O]₂(H or (CH₃)₃) (Dipropylene glycol t-butyl (or di-t-butyl) ether), (CH₃)₃CO [CH₂CH (CH)₃) O]₃(H or (CH₃)₃) (Tripropylene glycol t-butyl (or di-t-butyl) ether), C₅H₁₁OCH₂CH (CH)₃) OH (Propylene Glycol n-Pentyl Ether), C₄H₉OCH₂CH (C₂H₅) OH (butylene glycol n-butyl ether), C₄H₉O [CH₂CH (C₂H₅) O]₂H (dibutylene glycol n-butyl ether), trimethylolpropane tri-n-butyl ether (C)₂H₅C (CH)₂O (CH₂)₃CH₃)₃) And trimethylolpropane di-n-butyl ether (C)₂H₅C (CH)₂OC (CH)₂)₃CH₃)₂CH₂OH).

The amide solubilizer of the present invention has the formula R.¹C (O) NR²R³And cyclo- [R⁴C (O) N (R)⁵)-] (In the formula, R¹, R², R³And R⁵Are independently selected from aliphatic and alicyclic hydrocarbon radicals with 1-12 carbon atoms; R⁴Is represented by an aliphatic hydrocarbylene group having 3-12 carbon atoms), wherein the amide has a molecular weight of about 100-about 300 atomic weights. The molecular weight of the amide is preferably about 160 to about 250 atomic mass units. R¹, R², R³And R⁵Can optionally include substituted hydrocarbon radicals, i.e. groups containing non-hydrocarbon substituents selected from halogens (eg, fluorine, chlorine) and alkoxides (eg, methoxy). R¹, R², R³And R⁵Optionally contains heteroatom-substituted hydrocarbon radicals, ie atomic nitrogen (aza-), oxygen (oxa-) or sulfur (thia) in the radical chain, otherwise from carbon atoms. It may contain radicals to be composed. Usually, 3 or less non-hydrocarbon substituents and heteroatoms, and preferably 1 or less, are R.^1~3It will be present for every 10 carbon atoms in, and the presence of any of such non-hydrocarbon substituents and heteroatoms must be considered for the application of the molecular weight limits described above. Preferred amide solubilizers are composed of carbon, hydrogen, nitrogen and oxygen. Typical R¹, R², R³And R⁵Hydrocarbon 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 configuration isomers can be mentioned. A preferred embodiment of the amide solubilizer is the formula cyclo- [R] described above.⁴C (O) N (R)⁵)-] R⁴Is a hydrocarbylene radical (CR)⁶R⁷)_nCan be expressed by, in other words, the formula cyclo-[(CR⁶R⁷)_nC (O) N (R)⁵)-] (In the formula, the above-mentioned values for molecular weight are applied, n is an integer of 3 to 5, and R⁵Is a saturated hydrocarbon radical containing 1 to 12 carbon atoms, R⁶And R⁷Independently, the R presented above^1~3(Selected (for each n) by the rules that define). Formula: Cyclo-[(CR⁶R⁷)_nC (O) N (R)⁵)-] In the lactam represented by], all R⁶And R⁷Is preferably hydrogen, or contains a single saturated hydrocarbon radical in n methylene units, and R⁵Is a saturated hydrocarbon radical containing 3 to 12 carbon atoms. For example, 1- (saturated hydrocarbon radical) -5-methylpyrrolidine-2-one.

Representative 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-methylpiperid-2-one, 1-pentyl-5-methylpiperid-2-one, 1-hexylcaprolactam, 1-hexyl-5-methylpyrrolidine-2-one , 5-Methyl-1-pentylpiperid-2-one, 1,3-dimethylpiperid-2-one, 1-methylcaprolactam, 1-butyl-pyrrolidin-2-one, 1,5-dimethylpiperid-2-one, 1- Includes decyl-5-methylpyrrolidine-2-one, 1-dodecylpyrrolidi-2-one, N, N-dibutylformamide and N, N-diisopropylacetamide.

The ketone solubilizer of the present invention has the formula R.¹C (O) R²(In the formula, R¹And R²Independently comprises a ketone represented by an aliphatic, alicyclic and aryl hydrocarbon radical having 1-12 carbon atoms), wherein the ketone is about 70-about 300 atoms. It has a molecular weight in units of mass. R in the ketone¹And R²Is preferably independently selected from aliphatic and alicyclic hydrocarbon radicals having 1-9 carbon atoms. The molecular weight of the ketone is preferably about 100 to 200 atomic mass units. R¹And R²Can together form linked hydrocarbylene radicals and form five, six, or seven-membered cyclic ketones such as cyclopentanone, cyclohexanone, and cycloheptanone. R¹And R²Can optionally include substituted hydrocarbon radicals, i.e. radicals containing non-hydrocarbon substituents selected from halogens (eg, fluorine, chlorine) and alkoxides (eg, methoxy). R¹And R²Optionally contains heteroatom-substituted hydrocarbon radicals, ie atomic nitrogen (aza-), oxygen (keto-, oxa-) or sulfur (thia-) in the radical chain, otherwise. It may contain radicals composed of carbon atoms. Usually, 3 or less non-hydrocarbon substituents and heteroatoms, and preferably 1 or less, are R.¹And R²It will be present for every 10 carbon atoms in, and the presence of any of such non-hydrocarbon substituents and heteroatoms must be considered for the application of the molecular weight limits described above. General formula R¹C (O) R²Typical R in¹And R²As aliphatic, alicyclic and aryl hydrocarbon radicals, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, Includes octyl, nonyl, decyl, undecyl, dodecyl and their configuration isomers, as well as phenyl, benzyl, cumenyl, mesityl, trill, xsilyl and phenethyl.

Typical 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-nonanonone, 2-decanone, 4-decanone, 2-decalon, 2-tridecanone, dihexyl ketone and dicyclohexyl ketone. ..

The nitrile solubilizer of the present invention has the formula R.¹CN (in formula, R¹Contains a nitrile represented by an aliphatic, alicyclic or aryl hydrocarbon radical having 5 to 12 carbon atoms, wherein the nitrile is of about 90 to about 200 atomic weight units. Has a molecular weight. R in the nitrile solubilizer¹Is preferably selected from aliphatic and alicyclic hydrocarbon radicals having 8-10 carbon atoms. The molecular weight of the nitrile solubilizer is preferably about 120 to about 140 atomic mass units. R¹Can optionally include substituted hydrocarbon radicals, i.e. radicals containing non-hydrocarbon substituents selected from halogens (eg, fluorine, chlorine) and alkoxides (eg, methoxy). R¹Optionally contains heteroatom-substituted hydrocarbon radicals, ie atomic nitrogen (aza-), oxygen (keto-, oxa-) or sulfur (thia-) in the radical chain, otherwise. It may contain radicals composed of carbon atoms. Usually, 3 or less non-hydrocarbon substituents and heteroatoms, and preferably 1 or less, are R.¹It will be present for every 10 carbon atoms in, and the presence of any of such non-hydrocarbon substituents and heteroatoms must be considered for the application of the molecular weight limits described above. General formula R¹Typical R in CN¹The aliphatic, alicyclic and aryl hydrocarbon radicals include pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their conformational isomers, and phenyl. Included are benzyl, cumenyl, mesityl, trill, xylyl and phenethyl.

Typical nitrile solubilizers include, but are not limited to, 1-cyanopentane, 2,2-dimethyl-4-cyanopentane, 1-cyanohexane, 1-cyanoheptan, 1-cyanooctane, 2-cyanooctane, Included are 1-cyanononane, 1-cyanodecane, 2-cyanodecane, 1-cyanoundecane and 1-cyanododecane.

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

Typical 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 solubilizer of the present invention has the general formula R.¹CO₂R²(In the formula, R¹And R²Independently comprises esters represented by linear and cyclic, saturated and unsaturated, alkyl and aryl radicals). Preferred esters, which are essentially composed of the elements C, H, and O, have a molecular weight of about 80 to about 550 atomic mass units.

Typical esters are, but not limited to, (CH₃)₂CHCH₂OOC (CH)₂)_2-4OCOCH₂CH (CH)₃)₂(Diisobutyl dibasic ester), ethyl hexanoate, ethyl heptanoate, n-butyl propionate, n-propyl propionate, ethyl benzoate, di-n-propylphthalate, benzoic acid ethoxyethyl ester, Dipropyl carbonate, "Exxate 700" (commercially available C)₇Alkyl acetate), "Exxate 800" (commercially available C)₈Alkyl acetate), dibutyl phthalate, and tert-butyl acetate.

The lactone solubilizers of the present invention include lactones represented by the structures [A], [B], and [C].

<chemistry num="3"><img file="JP6442011B2_D0019.tif" /></chemistry>

These lactones are functional group-CO₂-Contains in the ring of 6 (A), or preferably 5 atoms (B), where R for structures [A] and [B].₁From R₈Are independently selected from hydrogen or linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals. Each R₁From R₈Is another R₁From R₈Can be connected to form a ring. Lactone has a structure [C] (in the formula, R₁From R₆Can independently have an extracyclic alkylidene group, as in hydrogen or linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals). Each R₁From R₆Is another R₁From R₆Can be connected to form a ring. The lactone solubilizer has a molecular weight range of about 80 to about 300 atomic weights, preferably about 80 to about 200 atomic weights.

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

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<tables num="17"><img file="JP6442011B2_D0021.tif" /></tables>

<tables num="18"><img file="JP6442011B2_D0022.tif" /></tables>

Lactone solubilizers generally have a kinematic viscosity of less than about 7 centimeters at 40 ° C. 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 may be commercially available or prepared by the methods described in the US Patent Gazette (Patent Document 3) filed August 3, 2004, which is incorporated herein by reference. obtain.

The aryl ether solubilizer of the present invention has the formula R.¹OR²(In the formula, R¹Is selected from aryl hydrocarbon radicals with 6-12 carbon atoms; R²Further comprises an aryl ether (selected from aliphatic hydrocarbon radicals having 1 to 4 carbon atoms), wherein the aryl ether has a molecular weight of about 100 to about 150 atomic mass units. .. General formula R¹OR²Typical R inside¹Aryl radicals include phenyl, biphenyl, cumenyl, mesityl, tolyl, xylyl, naphthyl and pyridyl. General formula R¹OR²Typical R in²Aliphatic hydrocarbon radicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl. Typical aromatic ether solubilizers include, but are not limited to, methylphenyl ether (anisole), 1,3-dimethoxybenzene, ethylphenyl ether and butyl phenyl ether.

The fluoroether solubilizer of the present invention has the general formula R.¹OCF₂CF₂H (in the formula, R¹Is selected from aliphatic, alicyclic, and aromatic hydrocarbon radicals having about 5 to about 15 carbon atoms, preferably primary, linear, saturated, alkyl radicals). Including things. Typical fluoroether solubilizers include, but are not limited to, C.₈H₁₇OCF₂CF₂H and C₆H₁₃OCF₂CF₂H is mentioned. It should be noted that if the refrigerant is a fluoroether, the solubilizer cannot be the same fluoroether.

Fluoroether solubilizers may further include ethers derived from fluoroolefins and polyols. Fluoroolefins are of type CF₂= CXY (in the formula, X is hydrogen, chlorine or fluorine, and Y is chlorine, fluorine, CF₃Or OR_f(In the formula, R_fIs CF₃, C₂F₅, Or C₃F₇It can be)). Typical fluoroolefins are tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, and perfluoromethyl vinyl ether. The polyol can be straight or branched. Linear polyols are of type HOCH₂(CHOH)_x(CRR')_yCH₂OH (in the formula, R and R'are hydrogen, or CH₃, Or C₂H₅And in the formula, x is an integer from 0 to 4 and y is an integer from 0 to 4). Branched polyols are of type C (OH)_t(R)_u(CH₂OH)_v[(CH₂)_mCH₂OH]_w(In the formula, R is hydrogen, CH₃Or C₂H₅Can be an integer from 0 to 3, t and u can be 0 or 1, v and w can be integers from 0 to 4, and in the equation, t + u + v + w = 4 It can also be). Representative polyols are trimethylolpropane, pentaerythritol, butanediol, and ethylene glycol.

The 1,1,1-trifluoroalkane solubilizer of the present invention has the general formula CF.₃R¹(In the formula, R¹Is selected from aliphatic and alicyclic hydrocarbon radicals having about 5 to about 15 carbon atoms, preferably primary, linear, saturated alkyl radicals) 1,1,1 -Includes trifluoroalkanes. Typical 1,1,1-trifluoroalkane solubilizers include, but are not limited to, 1,1,1-trifluorohexane and 1,1,1-trifluorododecane.

The solubilizer of the present invention may exist as a single compound or as a mixture of two or more solubilizers. Mixtures of solubilizers can contain two solubilizers from the same class of compounds, so to speak, two lactones, or two different classes such as lactones and polyoxyalkylene glycol ethers. May contain seed solubilizers.

In the composition comprising a refrigerant and a UV fluorescent dye, or a heat transfer fluid and a UV fluorescent dye, a composition of about 0.001 weight percent to about 1.0 weight percent, preferably 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 the UV dye.

The solubility of these UV fluorescent dyes in the refrigerant and heat transfer composition may be inferior. Therefore, methods of introducing these dyes into refrigeration, air conditioning, or heat pump equipment have been cumbersome, costly, and time consuming. The US Patent Gazette (Patent Document 4), incorporated herein by reference, describes methods using dye powders, solid pellets or slurries of dyes that can be inserted into components of refrigeration or air conditioners. As the refrigerant and lubricant circulate through the device, the dye is dissolved or dispersed and transported throughout the device. Numerous other methods of introducing dyes into refrigeration or air conditioners are described in this document.

Ideally, the UV fluorescent dye can be dissolved in the refrigerant itself, which does not require any special method for introduction into refrigeration, air conditioning, or heat pump equipment. The present invention relates to a composition comprising a UV fluorescent dye that can be dissolved and introduced into a system in combination with a solubilizer. The compositions of the present invention will allow storage and transport of dye-containing refrigerants and heat transfer fluids while maintaining the dye in solution, even at low temperatures.

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

Solubilizers such as ketones can have an unfavorable odor, which can be masked by the addition of odor masking agents or fragrances. Typical examples of odor masking agents or air fresheners are Evergreen, Fresh Lemon, Cherry, Cinnamon, Peppermint, Floral or Orange Peel. Orange Peel) (all of which are commercially available), as well as d-limonene and pinene can be mentioned. Such odor masking agents can be used in concentrations as high as about 0.001% to about 15% by weight, based on the combined weight of the odor masking agent and the solubilizing agent.

The present invention further relates to a method of using a refrigerant or heat transfer fluid composition containing an ultraviolet fluorescent dye to detect a leak in a refrigerating device, an air conditioner, or a heat pump device. The presence of the dye in the composition allows the detection of refrigerant leaks in refrigeration, air conditioning, or heat pump equipment. Leak detection assists in resolving and / or preventing inefficient operation of equipment or system or instrument destruction. Leak detection also aids in the inclusion of chemicals used in the operation of the device.

The method comprises, as described herein, a refrigerant, a composition containing an ultraviolet fluorescent dye or a composition containing a heat transfer fluid and a UV fluorescent dye, and optionally the solubilizer described herein. , Freezing, air conditioning, or providing to heat pump equipment, and utilizing suitable means for detecting UV fluorescent dye-containing refrigerants. Suitable means for detecting the dye include, but are not limited to, ultraviolet lamps often referred to as "black light" or "blue light". Such UV lamps are designed for the purpose of detecting UV fluorescent dyes and are commercially available from a number of suppliers. Once the UV fluorescent dye-containing composition has been introduced into a refrigeration, air conditioning, or heat pump device and circulated throughout the system, the UV lamp illuminates the device and observes the fluorescence of the dye near any of the leak points. This makes it possible to identify the leak point or the position near the leak point.

Mechanical refrigeration is essentially a thermodynamic application, where cooling media such as refrigerants go through the cycle so that they can be recovered for reuse. Commonly used cycles include vapor compression, absorption, vapor jets or ejectors, and air.

Vapor-compression refrigeration systems include evaporators, compressors, capacitors, and expansion devices. The steam compression cycle reuses the refrigerant in a multi-stage step that provides a cooling effect in one step and heat in the other step. The cycle can simply be described as follows. The liquid refrigerant enters the evaporator through the expansion device, and the liquid refrigerant boils in the evaporator at a low temperature to form a gas to bring about cooling. The low pressure gas enters the compressor, where the gas is compressed to increase its pressure and temperature. The high pressure (compressed) gaseous refrigerant then enters the capacitor, in which the refrigerant condenses and releases its heat to the environment. The refrigerant returns to the expansion device through which the liquid expands from the high pressure level in the capacitor to the low pressure level in the evaporator, which repeats the cycle.

There are various types of compressors that can be used in refrigeration applications. Compressors generally depend on the mechanical means of compressing the fluid, as a reciprocating, rotary, jet, centrifuge, scroll, screw or axial flow, or depending on how the mechanical element acts on the compressed fluid. Can be classified as positive (eg, reciprocating, scroll or screw) or dynamic (eg, centrifugal or jet).

The compositions of the invention comprising fluoroolefins 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 a positive displacement compressor or a dynamic compressor can be used in the process of the present invention. Centrifugal compressors are one preferred type of appliance for certain refrigerant compositions containing 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 deliver fluid to the impeller eye of a rotating impeller, or the central inlet, and accelerate it radially outward. Some static pressure rise occurs in the impeller, but most pressure rises occur in the diffuser section of the enclosure, where the velocity is converted to static pressure. Each impeller-diffuser set is the stage of the compressor. Centrifugal compressors are incorporated in 1-12 or more stages, depending on the desired final pressure and the volume of refrigerant treated.

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

In the positive displacement compressor, the steam is drawn into the chamber, and the chamber reduces the volume to compress the steam. After being compressed, the steam is pushed out of the chamber by reducing the volume of the chamber to zero or almost zero. Positive displacement compressors can increase pressure, which is limited only by volumetric efficiency and withstand strength of the component.

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 positive displacement type, but rather there is what is called dynamic compression.

The pressure that a centrifugal compressor can generate depends on the tip speed of the impeller. Tip velocity is the velocity of the impeller measured at its tip and is related to the diameter of the impeller and its rotational speed per minute. The pressurizing capacity of the 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 required pressure than the pressurizing capacity.

Due to its high speed operation, the centrifugal compressor is essentially a large volume, low pressure machine. 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 appliances.

Large centrifugal compressors typically operate at 3000-7000 rpm. Small turbine centrifugal compressors (mini-centrifugal compressors) are designed for high speeds ranging from about 40,000 to about 70,000 (rpm) and typically have a small impeller size of less than 0.15 meters (about 6 inches).

Multistage impellers can be used in centrifugal compressors to improve compressor efficiency, thereby reducing the power required for use. For the two-stage system, during operation, the discharge of the first stage impeller goes to the suction 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: 1, that is, the absolute discharge pressure can be four times the absolute suction pressure. A number of examples of two-stage centrifugal compressor systems, especially for automotive applications, are described in US Patent Gazette (Patent Document 5) and US Patent Gazette (Patent Document 6), both incorporated herein by reference. There is.

The present disclosure further relates to methods of heating or bringing in refrigeration, air conditioning, or heat pump equipment, wherein the refrigerant or heat transfer fluid composition is (a) centrifugal compressor; (b) multistage centrifugal compressor, or (c) single. Including the step of introducing into the device having a slab / single pass heat exchanger; where the refrigerant or heat transfer fluid composition is: (i) ER.¹CH = CHR²Or ZR¹CH = CHR²Fluoroolefin in the formula, R¹And R²But independently, C₁~ C₆Fluoroolefin, which is a perfluoroalkyl group of_n-] Cyclic fluoroolefins, in which X, Y, Z, and W are independently H or F, and n is an integer of 2-5; or (iii). ) 1,2,3,3,3-Pentafluoro-1-propene (CF)₃CF = CHF); 1,1,3,3,3-pentafluoro-1-propene (CF)₃CH = CF₂); 1,1,2,3,3-pentafluoro-1-propene (CHF)₂CF = CF₂); 1,2,3,3-Tetrafluoro-1-propene (CHF)₂CF = CHF); 2,3,3,3-tetrafluoro-1-propen (CF)₃CF = CH₂); 1,3,3,3-Tetrafluoro-1-propene (CF)₃CH = CHF); 1,1,2,3-tetrafluoro-1-propene (CH)₂FCF = CF₂); 1,1,3,3-tetrafluoro-1-propene (CHF)₂CH = CF₂); 2,3,3-Trifluoro-1-propene (CHF)₂CF = CH₂); 3,3,3-Trifluoro-1-propene (CF)₃CH = CH₂); 1,1,2-Trifluoro-1-propene (CH)₃CF = CF₂); 1,1,3-Trifluoro-1-propene (CH)₂FCH = CF₂); 1,2,3-trifluoro-1-propene (CH)₂FCF = CHF); 1,3,3-trifluoro-1-propene (CHF)₂CH = CHF); 1,1,1,2,3,4,4,4-octafluoro-2-butene (CF)₃CF = CFCF₃); 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF)₃CF₂CF = CF₂); 1,1,1,2,4,4,4-heptafluoro-2-butene (CF)₃CF = CHCF₃); 1,2,3,3,4,4,4-heptafluoro-1-butene (CHF = CFCF)₂CF₃); 1,1,1,2,3,4,4-heptafluoro-2-butene (CHF)₂CF = CFCF₃); 1,3,3,3-Tetrafluoro-2- (trifluoromethyl) -1-propene ((CF)₃)₂C = CHF); 1,1,3,3,4,4,4-heptafluoro-1-butene (CF)₂= CHCF₂CF₃); 1,1,2,3,4,4,4-heptafluoro-1-butene (CF)₂= CFCHFCF₃); 1,1,2,3,3,4,4-heptafluoro-1-butene (CF)₂= CFCF₂CHF₂); 2,3,3,4,4,4-hexafluoro-1-butene (CF)₃CF₂CF = CH₂); 1,3,3,4,4,4-hexafluoro-1-butene (CHF = CHCF)₂CF₃); 1,2,3,4,4,4-hexafluoro-1-butene (CHF = CFC CHFCF)₃); 1,2,3,3,4,4-hexafluoro-1-butene (CHF = CFCF)₂CHF₂); 1,1,2,3,4,4-hexafluoro-2-butene (CHF)₂CF = CFCHF₂); 1,1,1,2,3,4-hexafluoro-2-butene (CH)₂FCF = CFCF₃); 1,1,1,2,4,4-hexafluoro-2-butene (CHF)₂CH = CFCF₃); 1,1,1,3,4,4-hexafluoro-2-butene (CF)₃CH = CFC CHF₂); 1,1,2,3,3,4-hexafluoro-1-butene (CF)₂= CFCF₂CH₂F); 1,1,2,3,4,4-hexafluoro-1-butene (CF)₂= CFCHFCHF₂); 3,3,3-Trifluoro-2- (trifluoromethyl) -1-propene (CH)₂= C (CF)₃)₂); 1,1,1,2,4-pentafluoro-2-butene (CH)₂FCH = CFCF₃); 1,1,1,3,4-pentafluoro-2-butene (CF)₃CH = CFCH₂F); 3,3,4,4,4-pentafluoro-1-butene (CF)₃CF₂CH = CH₂); 1,1,1,4,4-pentafluoro-2-butene (CHF)₂CH = CHCF₃); 1,1,1,2,3-pentafluoro-2-butene (CH)₃CF = CFCF₃); 2,3,3,4,4-Pentafluoro-1-butene (CH)₂= CFCF₂CHF₂); 1,1,2,4,4-pentafluoro-2-butene (CHF)₂CF = CHCHF₂); 1,1,2,3,3-pentafluoro-1-butene (CH)₃CF₂CF = CF₂); 1,1,2,3,4-pentafluoro-2-butene (CH)₂FCF = CFCHF₂); 1,1,3,3,3-pentafluoro-2-methyl-1-propene (CF)₂= C (CF)₃) (CH₃)); 2- (Difluoromethyl) -3,3,3-trifluoro-1-propene (CH)₂= C (CHF)₂) (CF₃)); 2,3,4,4,4-pentafluoro-1-butene (CH)₂= CFCHFCF₃); 1,2,4,4,4-pentafluoro-1-butene (CHF = CFCH)₂CF₃); 1,3,4,4,4-pentafluoro-1-butene (CHF = CHCHFCF)₃); 1,3,3,4,4-pentafluoro-1-butene (CHF = CHCF)₂CHF₂); 1,2,3,4,4-pentafluoro-1-butene (CHF = CFC CHFCHF)₂); 3,3,4,4-Tetrafluoro-1-butene (CH)₂= CHCF₂CHF₂); 1,1-difluoro-2- (difluoromethyl) -1-propene (CF)₂= C (CHF)₂) (CH₃)); 1,3,3,3-Tetrafluoro-2-methyl-1-propene (CHF = C (CF)₃) (CH₃)); 2-Difluoromethyl-3,3-difluoro-1-propene (CH)₂= C (CHF)₂)₂); 1,1,1,2-Tetrafluoro-2-butene (CF)₃CF = CHCH₃); 1,1,1,3-Tetrafluoro-2-butene (CH)₃CF = CHCF₃); 1,1,1,2,3,4,4,5,5,5-decafluoro-2-pentene (CF)₃CF = CFCF₂CF₃); 1,1,2,3,3,4,4,5,5,5-decafluoro-1-pentene (CF)₂= CFCF₂CF₂CF₃); 1,1,1,4,4,4-hexafluoro-2- (trifluoromethyl) -2-butene ((CF)₃)₂C = CHCF₃); 1,1,1,2,4,4,5,5,5-Nonafluoro-2-pentene (CF)₃CF = CHCF₂CF₃); 1,1,1,3,4,4,5,5,5-Nonafluoro-2-pentene (CF)₃CH = CFCF₂CF₃); 1,2,3,3,4,4,5,5,5-Nonafluoro-1-pentene (CHF = CFCF)₂CF₂CF₃); 1,1,3,3,4,4,5,5,5-Nonafluoro-1-pentene (CF)₂= CHCF₂CF₂CF₃); 1,1,2,3,3,4,4,5,5-Nonafluoro-1-pentene (CF)₂= CFCF₂CF₂CHF₂); 1,1,2,3,4,4,5,5,5-Nonafluoro-2-pentene (CHF)₂CF = CFCF₂CF₃); 1,1,1,2,3,4,4,5,5-Nonafluoro-2-pentene (CF)₃CF = CFCF₂CHF₂); 1,1,1,2,3,4,5,5,5-Nonafluoro-2-pentene (CF)₃CF = CFCHFCF₃); 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)₃CH = 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= CFCF₂CF₂CF₃); 1,2,3,3,4,4,5,5-octafluoro-1-pentene (CHF = CFCF)₂CF₂CHF₂); 3,3,4,4,4-Pentafluoro-2- (trifluoromethyl) -1-butene (CH)₂= C (CF)₃) CF₂CF₃); 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) CH₂CF₃); 3,4,4,4-Tetrafluoro-3- (trifluoromethyl) -1-butene ((CF)₃)₂CFCH = CH₂); 3,3,4,4,5,5,5-heptafluoro-1-pentene (CF)₃CF₂CF₂CH = CH₂); 2,3,3,4,4,5,5-heptafluoro-1-pentene (CH)₂= CFCF₂CF₂CHF₂); 1,1,3,3,5,5,5-heptafluoro-1-butene (CF)₂= CHCF₂CH₂CF₃); 1,1,1,2,4,4,4-heptafluoro-3-methyl-2-butene (CF)₃CF = C (CF)₃) (CH₃)); 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)₂FCH = C (CF)₃)₂); 1,1,1,3-Tetrafluoro-2- (trifluoromethyl) -2-butene (CH)₃CF = C (CF)₃)₂); 1,1,1-Trifluoro-2- (trifluoromethyl) -2-butene ((CF)₃)₂C = CHCH₃); 3,4,4,5,5,5-hexafluoro-2-pentene (CF)₃CF₂CF = CHCH₃); 1,1,1,4,4,4-hexafluoro-2-methyl-2-butene (CF)₃C (CH)₃) = CHCF₃); 3,3,4,5,5,5-hexafluoro-1-pentene (CH)₂= CHCF₂CHFCF₃); 3- (Trifluoromethyl) -4,4,4-trifluoro-1-butene (CH)₂= C (CF)₃) CH₂CF₃); 1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1-hexene (CF)₃(CF₂)₃CF = CF₂); 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene (CF)₃CF₂CF = CFCF₂CF₃); 1,1,1,4,4,4-hexafluoro-2,3-bis (trifluoromethyl) -2-butene ((CF)₃)₂C = C (CF)₃)₂); 1,1,1,2,3,4,5,5,5-Nonafluoro-4- (trifluoromethyl) -2-pentene ((CF)₃)₂CFCF = CFCF₃); 1,1,1,4,4,5,5,5-octafluoro-2- (trifluoromethyl) -2-pentene ((CF)₃)₂C = CHC₂F₅); 1,1,1,3,4,5,5,5-octafluoro-4- (trifluoromethyl) -2-pentene ((CF)₃)₂CFCF = CHCF₃); 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene (CF)₃CF₂CF₂CF₂CH = CH₂); 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- (trifluoromethyl) -2-butene ((CF)₃)₂C = C (CH)₃) (CF₃)); 2,3,3,5,5,5-hexafluoro-4- (trifluoromethyl) -1-pentene (CH)₂= CFCF₂CH (CF)₃)₂); 1,1,1,2,4,4,5,5,5-Nonafluoro-3-methyl-2-pentene (CF)₃CF = C (CH)₃) CF₂CF₃); 1,1,1,5,5,5-hexafluoro-4- (trifluoromethyl) -2-pentene (CF)₃CH = CHCH (CF)₃)₂); 3,4,4,5,5,6,6,6-octafluoro-2-hexene (CF)₃CF₂CF₂CF = CHCH₃); 3,3,4,4,5,5,6,6-octafluoro-1-hexene (CH)₂= CHCF₂CF₂CF₂CHF₂); 1,1,1,4,4-pentafluoro-2- (trifluoromethyl) -2-pentene ((CF)₃)₂C = CHCF₂CH₃); 4,4,5,5,5-pentafluoro-2- (trifluoromethyl) -1-pentene (CH)₂= C (CF)₃) CH₂C₂F₅); 3,3,4,4,5,5,5-heptafluoro-2-methyl-1-pentene (CF)₃CF₂CF₂C (CH)₃) = CH₂); 4,4,5,5,6,6,6-heptafluoro-2-hexene (CF)₃CF₂CF₂CH = CHCH₃); 4,4,5,5,6,6,6-heptafluoro-1-hexene (CH)₂= CHCH₂CF₂C₂F₅); 1,1,1,2,2,3,4-heptafluoro-3-hexene (CF)₃CF₂CF = CFC₂H₅); 4,5,5,5-Tetrafluoro-4-trifluoromethyl-1-pentene (CH)₂= CHCH₂CF (CF)₃)₂); 1,1,1,2,5,5,5-heptafluoro-4-methyl-2-pentene (CF)₃CF = CHCH (CF)₃) (CH₃)); 1,1,1,3-Tetrafluoro-2-trifluoromethyl-2-pentene ((CF)₃)₂C = CFC₂H₅); 1,1,1,2,3,4,4,5,5,6,6,7,7,7-Tetradecafluoro-2-heptene (CF)₃CF = CFCF₂CF₂C₂F₅); 1,1,1,2,2,3,4,5,5,6,6,7,7,7-Tetradecafluoro-3-heptene (CF)₃CF₂CF = CFCF₂C₂F₅); 1,1,1,3,4,4,5,5,6,6,7,7,7-Tridecafluoro-2-heptene (CF)₃CH = CFCF₂CF₂C₂F₅); 1,1,1,2,4,4,5,5,6,6,7,7,7-Tridecafluoro-2-heptene (CF)₃CF = CHCF₂CF₂C₂F₅); 1,1,1,2,2,4,5,5,6,6,7,7,7-Tridecafluoro-3-heptene (CF)₃CF₂CH = CFCF₂C₂F₅); 1,1,1,2,2,3,5,5,6,6,7,7,7-Tridecafluoro-3-heptene (CF)₃CF₂CF = CHCF₂C₂F₅); CF₂= CFOCF₂CF₃(PEVE); CF₂= CFOCF₃Includes at least one fluoroolefin selected from the group consisting of (PMVE) and fluoroolefins selected from the group consisting of combinations thereof;

Methods that result in 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 window, ductless, duct, terminal type packages, coolers and commercial machines, including rooftop type packages. Refrigerating applications include indoor or household refrigerators and freezers, ice makers, built-in coolers and freezers, walk-in coolers and freezers and transport refrigeration systems.

The compositions of the present invention can also 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 compositions of the present invention. Low operating pressure and density result in high flow velocity and high friction loss in all components. In these cases, the evaporator design can be changed. A single slab / single pass heat exchanger arrangement can be used rather than a number of sequentially connected microchannel slabs (with respect to the refrigerant path). Therefore, the 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 methods that result in cooling, including the step of evaporating the fluoroolefin composition of the invention in the vicinity of an object to be cooled, followed by the step of condensing the composition.

The present invention further relates to a heating method comprising a step of condensing the fluoroolefin composition of the present invention in the vicinity of an object to be heated, followed by a step of evaporating the composition.

The present invention comprises compressing a composition containing at least one fluoroolefin in a centrifugal compressor, condensing the composition, and then evaporating the composition in the vicinity of an object to be cooled. Further on how to bring, including. Further, the centrifugal compressor of the method of the present 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 refrigerator, air conditioner, or heat pump device, wherein the device comprises at least one single slab / single pass heat exchanger, wherein the method comprises the composition of the invention. It comprises the steps of 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, as well as other applications. These high efficiency mini centrifugal compressors can be driven by a motor and, therefore, can be driven independently of engine speed. The constant compressor speed allows the system to provide a relatively constant cooling capacity at all engine speeds. This offers an opportunity for increased efficiency, especially at high speed engine speeds, compared to traditional R-134a automotive air conditioning systems. The advantages of these low voltage systems are even greater when considering the cycle operation of conventional systems at high drive speeds.

Alternatively, rather than using electric power, the mini-centrifugal compressor can be operated by an engine exhaust driven turbine or a ratio gear drive assembly with 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. Therefore, the use of alternative power sources would be advantageous. A refrigerating device or an air conditioner powered by an engine exhaust gas driven turbine is described in detail in a US Patent Gazette (Patent Document 7) filed on March 3, 2006. A refrigeration or air conditioner powered by a ratio gear drive assembly is described in detail in a US Patent Gazette (Patent Document 8) filed on March 17, 2006.

The present invention compresses the composition of the invention in a mini-centrifugal compressor powered by an engine exhaust gas driven turbine; the step of condensing the composition; then the composition in the vicinity of an object to be cooled. Further relates to methods that result in cooling, including the step of evaporating in.

The present invention is a step of compressing the composition of the present invention in a mini-centrifugal compressor powered by a ratio gear drive assembly having a ratio belt drive; a step of condensing the composition; then the composition should be cooled. Further relates to methods that result in cooling, including the step of evaporating in the vicinity of an object.

The present invention relates to a method of providing cooling in a refrigerator, air conditioner, or heat pump device, wherein the device comprises at least one single slab / single pass heat exchanger, the method comprising the composition of the invention. It includes a step of compressing in a centrifugal compressor, a step of condensing the composition, and then a step of evaporating the composition in the vicinity of an object to be cooled.

The present invention further relates to a method of replacing or replacing a refrigerant composition having a GWP of about 150 or more, or a high GWP refrigerant, with a composition having a lower GWP. One method comprises providing a composition comprising at least one fluoroolefin of the present invention as an alternative. In another embodiment of the invention, the refrigerant or heat transfer fluid composition of the invention having a lower GWP than the composition to be replaced or replaced is introduced into a refrigeration, air conditioning or heat pump device. 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 compositions of the present invention can be introduced into the device in the presence of a high GWP refrigerant.

The Global Warming Potential (GWP) is an index for predicting the relative burden of global warming due to the emission of specific greenhouse gases into the atmosphere in kilograms compared to the emission of carbon dioxide in kilograms. Is. GWP can be calculated for different time ranges and indicates the effect of atmospheric lifetime on a given gas. The GWP for a 100-year time range is usually the value referenced.

A 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 over a time range of 100 years. Will. Refrigerants and heat transfer fluids that need to be replaced based on GWP calculations published by the Intergovernmental Panel on Climate Change (IPCC) are not particularly limited, but HFC-134a (1,1). , 1,2-Tetrafluoroethane).

The present invention will provide compositions with zero or low ozone depletion potential and low global warming potential (GWP). The fluoroolefins of the invention or mixtures of fluoroolefins of the invention with other refrigerants will have a global warming potential that is less than many of the hydrofluorocarbon refrigerants currently in use. Typically, the fluoroolefins of the invention are expected to have a GWP of less than about 25. One aspect of the 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 fluoroolefins to the mixture.

The present invention further relates to a method of lowering 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 present invention. In another embodiment, the method of reducing the global warming potential is suitable for use as a refrigerant or a heat transfer fluid in combination with the first composition in combination with a composition containing at least one fluoroolefin. It comprises the step of producing the second composition, wherein the second composition has a lower global warming potential than the first composition. It can be confirmed that the GWP of a mixture or combination of compounds can be calculated as the 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 containing at least one fluoroolefin in order to reduce the global warming potential of the original refrigerant or heat transfer fluid composition. The second refrigerant or heat transfer fluid composition of the above is combined with the composition of the present invention containing at least one fluoroolefin to produce a second refrigerant or heat transfer fluid composition, wherein the second Refrigerant or heat transfer fluid composition of the above has a lower global warming potential than the original refrigerant or heat transfer fluid composition.

The present invention further relates to a method of reducing the GWP of the 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 about 150 or more GWP. The method comprises the second step of introducing the lower GWP refrigerant or heat transfer fluid composition of the present invention into the refrigeration, air conditioning or heat pump apparatus.

This 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. Further steps may be included.

The present invention further relates to a method of exchanging the 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. Including the process of providing. The original refrigerant can be any of the refrigerants used in refrigeration, air conditioning or heat pump equipment that needs 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), CH₂F₂(HFC-32), CH₃F (HFC-41), CHF₂CF₃(HFC-125), CHF₂CHF₂(HFC-134), CH₂FCF₃(HFC-134a), CHF₂CH₂F (HFC143), CF₃CH₃(HFC-143a), CHF₂CH₃(HFC-152a), CH₂FCH₃(HFC-161), CHF₂CF₂CF₃(HFC-227ca), CF₃CFHCF₃(HFC-227ea), CHF₂CF₂CHF₂(HFC-236ca), CH₂FCF₂CF₃(HFC-236cb), CHF₂CHFCF₃(HFC-236ea), CF₃CH₂CF₃(HFC-236fa), CH₂FCF₂CHF₂(HFC-245ca), CH₃CF₂CF₃(HFC-245cb), CHF₂CHFCHF₂(HFC-245ea), CH₂FCHFCF₃(HFC-245eb), CHF₂CH₂CF₃(HFC-245fa), CH₂FCF₂CH₂F (HFC-254ca), CH₃CF₂CHF₂(HFC-254cb), CH₂FCHFCHF₂(HFC-254ea), CH₃CHFCF₃(HFC-254eb), CHF₂CH₂CHF₂(HFC-254fa), CH₂FCH₂CF₃(HFC-254fb), CF₃CH₂CH₃(HFC-263fb), CH₃CF₂CH₂F (HFC-263ca), CH₃CF₂CH₃(HFC-272ca), CH₃CHFCH₂F (HFC-272ea), CH₂FCH₂CH₂F (HFC-272fa), CH₃CH₂CF₂H (HFC-272fb), CH₃CHFCH₃(HFC-281ea), CH₃CH₂CH₂F (HFC-281fa), CHF₂CF₂CF₂CF₂H (HFC-338pcc), CF₃CH₂CF₂CH₃(HFC-365mfc), CF₃CHFCHFCF₂CF₃(HFC-43-10mee) can be mentioned. These hydrofluorocarbon refrigerants can be commercially available or 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 blends), R423A (R134a / R227ea blends), R507A (R125 / R143a blends), etc. may further include co-boiling, co-boiling-like and non-co-boiling compositions.

The chlorofluorocarbon refrigerant of the present invention that may need to be replaced is R22 (CHF).₂Cl), R123 (CHCl)₂CF₃), R124 (CHClFCF)₃), R502 (CFC-115 (CClF)₂CF₃) And R22), R503 (R23 / R13 (CClF)₃) Is a blend of) and the like.

As the hydrochlorofluorocarbon of the present invention that may need to be replaced, R12 (CF)₂Cl₂), R11 (CCl₃F), R113 (CCl₂FCClF₂), R114 (CF)₂ClCF₂Cl), 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 may contain compounds similar to hydrofluorocarbons that also contain at least one ether group oxygen atom. The fluoroether refrigerant is not particularly limited, but C.₄F₉OCH₃, And C₄F₉OC₂H₅(Both are commercially available).

The original refrigerant or heat transfer fluid composition of the invention that may need to be replaced is optionally no more than 10 weight percent dimethyl ether, or at least one C.₃~ C₅It further comprises a combination of refrigerants containing hydrocarbons such as propane, propylene, cyclopropane, n-butane, isobutane, n-pentane, cyclopentane and neopentane (2,2-dimethylpropane). C like this₃~ C₅Examples of hydrocarbon-containing refrigerants are HCFC-22 / HFC-125 / propane (known by ASHRAE type, R402 or R402A and R402B), HCFC-22 / octafluoropropane / propane (ASHRAE type, R403 or R403A). And R403B), octafluoropropane / HFC-134a / isobutane (ASHRAE type, known by R413 or R413A), HCFC-22 / HCFC-124 / HCFC-142b / isobutane (ASHRAE type, R414 or R414A) And R414B), HFC-134a / HCFC-124 / n-butane (ASHRAE type, known by R416 or R416A), HFC-125 / HFC-134a / n-butane (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 type, R422, R422A, R422B, R422C, It is an isobutane-like composition (known by R422D).

The present invention further relates to a method of replacing the original refrigerant or heat transfer fluid composition, wherein the original composition is R134a (HFC-134a, 1,1,1, in a refrigerating device, air conditioner, or heat pump device. 2-Tetrafluoroethane, CF₃CH₂F), where the method replaces R134a with a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of trifluoromethyltrifluorovinyl ether (PMVE). Includes steps.

The present invention further relates to a method of exchanging the original refrigerant or heat transfer fluid composition, wherein the original composition is R152a (HFC-152a, 1,1-difluoroethane, in a refrigerating device, an air conditioner, or a heat pump device. CHF₂CH₃), Where the method describes R152a as 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 trifluoromethyltrifluorovinyl ether (PMVE) It comprises a step of replacing with a second refrigerant or heat transfer fluid composition containing at least one compound selected.

The present invention relates to R227ea (HFC-227ea, 1,1,1,2,3,3,3-heptafluoropropane, CF) in refrigerating equipment, air conditioning equipment, or heat pumping equipment.₃CHFCF₃), Here, the method is E-1,3,3,3-tetrafluoropropene (E-HFC-1234ze), 1,2,3,3,3-pentafluoropropene. Consists of (HFC-1225ye), 2,3,3,3-tetrafluoropropene (HFC-1234yf), 3,3,3-trifluoropropene (HFC-1243zf), and trifluoromethyltrifluorovinyl ether (PMVE) It comprises the step of providing an alternative composition comprising at least one compound selected from the group.

The present invention further relates to a method of exchanging the original refrigerant or heat transfer fluid composition, wherein the original composition is R113 (CFC-113, 1,1,2-) in a refrigerating device, an air conditioner, or a heat pump device. Trichloro-1,2,2-trifluoroethane, CFCl₂CF₂Cl), where the method is 1,1,1,3,4,5,5,5-octafluoro-4- (trifluoromethyl) -2-butene (HFC-152-11 mmyyz); 1,1,1,4,4,5,5,5-octafluoro-2- (trifluoromethyl) -2-pentene (HFC-152-11mmtz); 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-151-12mmtt); 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- ( From the group consisting of trifluoromethyl) -2-pentene (HFC-151-12mmzz); and 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (F22E) It comprises replacing a second refrigerant or heat transfer fluid composition containing at least one compound selected.

The present invention further relates to a method of replacing the original refrigerant or heat transfer fluid composition, wherein the original composition is R43-10mee (HFC-43-10mee), 1 in a refrigerating device, air conditioner, or heat pump device. , 1,1,2,3,4,4,5,5,5-decafluoropentane, CF₃CHFCHFCF₂CF₃), Where the method is 1,1,1,3,4,5,5,5-octafluoro-4- (trifluoromethyl) -2-butene (HFC-152-11 mmyyz); 1 , 1,1,4,4,5,5,5-octafluoro-2- (trifluoromethyl) -2-pentene (HFC-152-11mmtz); 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-151-12mmtt); 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- (tri) Select from the group consisting of fluoromethyl) -2-pentene (HFC-151-12mmzz); and 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (F22E). It comprises the step of replacing a second refrigerant or heat transfer fluid composition containing at least one compound.

The present invention further relates to a method of exchanging the original refrigerant or heat transfer fluid composition, wherein the original composition is C in a refrigerating device, an air conditioner, or a heat pump device.₄F₉OCH₃(Perfluorobutylmethyl ether), wherein the method is 1,1,1,3,4,5,5,5-octafluoro-4- (trifluoromethyl) -2-butene (HFC-). 152-11mmyyz); 1,1,1,4,4,5,5,5-octafluoro-2- (trifluoromethyl) -2-pentene (HFC-152-11mmtz); 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-151-12mmtt); 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-151-12mmzz); and 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (F22E) ) Includes a step of replacing a second refrigerant or heat transfer fluid composition containing at least one compound selected from the group consisting of).

The present invention further relates to a method of exchanging the original refrigerant or heat transfer fluid composition, wherein the original composition is R365mfc (HFC-365mfc, 1,1,1, in a refrigerating device, an air conditioner, or a heat pump device. 3,3-Pentafluorobutane, CF₃CH₂CF₂CH₃), Where the method is 1,1,1,3,4,5,5,5-octafluoro-4- (trifluoromethyl) -2-butene (HFC-152-11 mmyyz); 1 , 1,1,4,4,5,5,5-octafluoro-2- (trifluoromethyl) -2-pentene (HFC-152-11mmtz); 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-151-12mmtt); 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- (tri) Select from the group consisting of fluoromethyl) -2-pentene (HFC-151-12mmzz); and 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (F22E). It comprises the step of replacing a second refrigerant or heat transfer fluid composition containing at least one compound.

The present invention further relates to a method of exchanging the original refrigerant or heat transfer fluid composition, wherein the original composition is R11 (CFC-11, trichlorofluoromethane, CFCl) in a refrigerating device, an air conditioner, or a heat pump device.₃), Where 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-141-10myy); 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)- A first containing at least one compound selected from the group consisting of 2-butene (HFC-1429mzt); and 1,1,1,4,4,5,5,5-octafluoro-2-pentene (F12E). Includes the step of replacing the refrigerant or heat transfer fluid composition of 2.

The present invention further relates to a method of exchanging the original refrigerant or heat transfer fluid composition, wherein the original composition is R123 (HCFC-123, 2,2-dichloro-) in a refrigerating device, an air conditioner, or a heat pump device. 1,1,1-trifluoroethane, CF₃CHCl₂), Where 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-141-10myy); 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)- A first containing at least one compound selected from the group consisting of 2-butene (HFC-1429mzt); and 1,1,1,4,4,5,5,5-octafluoro-2-pentene (F12E). Includes the step of replacing the refrigerant or heat transfer fluid composition of 2.

The present invention further relates to a method of exchanging the original refrigerant or heat transfer fluid composition, wherein the original composition is R245fa (HFC-245fa, 1,1,1, in a refrigerating device, an air conditioner, or a heat pump device. 3,3-Pentafluoropropane, CF₃CH₂CHF₂), Where 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-Tetra It comprises replacing a second refrigerant or heat transfer fluid composition containing at least one compound selected from the group consisting of fluoropropene (HFC-1234ye); and pentafluoroethyl trifluorovinyl ether (PEVE).

The present invention further relates to a method of exchanging the original refrigerant or heat transfer fluid composition, wherein the original composition is R114 (CFC-114, 1,2-dichloro-) in a refrigerating device, an air conditioner, or a heat pump device. 1,1,2,2-tetrafluoroethane, CFCl₂CF₂Cl), where 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 3,3,4,4,4-pentafluoro- It comprises replacing a second refrigerant or heat transfer fluid composition containing at least one compound selected from the group consisting of 1-butene (HFC-1345fz).

The present invention further relates to a method of exchanging the original refrigerant or heat transfer fluid composition, wherein the original composition is R236fa (HFC-236fa, 1,1,1, in a refrigerating device, an air conditioner, or a heat pump device. 3,3,3-Hexafluoropropane, CF₃CH₂CF₃), Where 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 3,3,4,4,4-pentafluoro-1 -Contains a step of replacing a second refrigerant or heat transfer fluid composition containing at least one compound selected from the group consisting of butene (HFC-1345fz).

The present invention relates to a method of exchanging an original refrigerant or heat transfer fluid composition, wherein the original composition is R401A in a refrigeration system, an air conditioner, or a heat pump device, wherein the method is E-1. , 3,3,3-Tetrafluoropropene (E-HFC-1234ze); 1,2,3,3,3-Pentafluoropropene (HFC-1225ye); 2,3,3,3-Tetrafluoropropene (HFC) A second refrigerant or heat transfer containing at least one compound selected from the group consisting of -1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyltrifluorovinyl ether (PMVE). Includes the step of replacing the fluid composition. R401A is about 53 weight percent HCFC-22 (chlorodifluoromethane, CHF)₂Cl), about 13 weight percent HFC-152a (1,1-difluoroethane, CHF)₂CH₃), And about 34 weight percent HCFC-124 (2-chloro-1,1,1,2-tetrafluoroethane, CF₃This is the ASHRAE type for refrigerant blends containing CHClF).

The present invention further relates to a method of exchanging an original refrigerant or heat transfer fluid composition, wherein the original composition is R401B in a refrigeration system, an air conditioner, or a heat pump device, wherein the method is 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 or a second refrigerant containing at least one compound selected from the group consisting of (HFC-1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyltrifluorovinyl ether (PMVE). Includes the step of replacing the heat transfer fluid composition. R401B is about 61 weight percent HCFC-22 (chlorodifluoromethane, CHF)₂Cl), about 11 weight percent HFC-152a (1,1-difluoroethane, CHF)₂CH₃), And about 28 weight percent HCFC-124 (2-chloro-1,1,1,2-tetrafluoroethane, CF₃This is the ASHRAE type for refrigerant blends containing CHClF).

The present invention further relates to a method of exchanging an original refrigerant or heat transfer fluid composition, wherein the original composition is R409A in a refrigeration system, an air conditioner, or a heat pump device, wherein the method is 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 or a second refrigerant containing at least one compound selected from the group consisting of (HFC-1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyltrifluorovinyl ether (PMVE). Includes the step of replacing the heat transfer fluid composition. R409A is about 60 weight percent HCFC-22 (chlorodifluoromethane, CHF)₂Cl), about 25 weight percent HCFC-124 (2-chloro-1,1,1,2-tetrafluoroethane, CF₃CHClF), and about 15 weight percent HCFC-142b (1-chloro-1,1-difluoroethane, CF)₂ClCH₃) Is an ASHRAE type for a refrigerant blend containing.

The present invention further relates to a method of exchanging an original refrigerant or heat transfer fluid composition, wherein the original composition is R409B in a refrigeration system, an air conditioner, or a heat pump device, wherein the method is 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 or a second refrigerant containing at least one compound selected from the group consisting of (HFC-1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyltrifluorovinyl ether (PMVE). Includes the step of replacing the heat transfer fluid composition. R409B is about 65 weight percent HCFC-22 (chlorodifluoromethane, CHF)₂Cl), about 25 weight percent HCFC-124 (2-chloro-1,1,1,2-tetrafluoroethane, CF₃CHClF), and about 10 weight percent HCFC-142b (1-chloro-1,1-difluoroethane, CF)₂ClCH₃) Is an ASHRAE type for a refrigerant blend containing.

The present invention further relates to a method of exchanging an original refrigerant or heat transfer fluid composition, wherein the original composition is R414B in a refrigeration system, an air conditioner, or a heat pump device, wherein the method is 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 or a second refrigerant containing at least one compound selected from the group consisting of (HFC-1234yf), 3,3,3-trifluoropropene (HFC-1243zf), and trifluoromethyltrifluorovinyl ether (PMVE). Includes the step of replacing the heat transfer fluid composition. R414B is about 50 weight percent HCFC-22 (chlorodifluoromethane, CHF)₂Cl), about 39 weight percent HCFC-124 (2-chloro-1,1,1,2-tetrafluoroethane, CF₃CHClF), about 1.5 weight percent isobutane (R600a, CH)₃CH (CH)₃) CH₃) And about 9.5 weight percent HCFC-142b (1-chloro-1,1-difluoroethane, CF₂ClCH₃) Is an ASHRAE type for a refrigerant blend containing.

The present invention further relates to a method of exchanging an original refrigerant or heat transfer fluid composition, wherein the original composition is R416A in a refrigeration system, an air conditioner, or a heat pump device, wherein the method is 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 or a second refrigerant containing at least one compound selected from the group consisting of (HFC-1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyltrifluorovinyl ether (PMVE). Includes the step of replacing the heat transfer fluid composition. R416A is about 59 weight percent HFC-134a (1,1,1,2-tetrafluoroethane, CF)₃CH₂F))), about 39.5 weight percent HCFC-124 (2-chloro-1,1,1,2-tetrafluoroethane, CF₃CHClF), and about 1.5 weight percent n-butane (CH)₃CH₂CH₂CH₃) Is an ASHRAE type for a refrigerant blend containing.

The present invention further relates to a method of exchanging the original refrigerant or heat transfer fluid composition, wherein the original composition is R12 (CFC-12, dichlorodifluoromethane, CF) in a refrigerating device, an air conditioner, or a heat pump device.₂Cl₂), Where 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 step of replacing a second refrigerant or heat transfer fluid composition containing at least one compound selected from the group consisting of trifluoromethyltrifluorovinyl ether (PMVE). Including.

The present invention further relates to a method of exchanging an original refrigerant or heat transfer fluid composition, wherein the original composition is R500 in a refrigerating apparatus, an air conditioner, or a heat pump apparatus, 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); It comprises replacing a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of and trifluoromethyltrifluorovinyl ether (PMVE). R500 is about 73.8 weight percent R12 ((CFC-12, dichlorodifluoromethane, CF)₂Cl₂) And about 26.2 weight percent R152a (HFC-152a, 1,1-difluoroethane, CHF)₂CH₃) Is an ASHRAE type for azeotropic refrigerant blends.

The present invention relates to a method of replacing the original refrigerant or heat transfer fluid composition, wherein the original refrigerant or heat transfer fluid composition is R134a or R12, wherein the R134a or R12 is about 1.0 weight. It is replaced by a second refrigerant or heat transfer fluid composition containing from percent to about 37 weight percent HFC-32 and from about 99 weight percent to about 63 weight percent HFC-1225ye. In other embodiments, the second refrigerant or heat transfer fluid composition may comprise from about 1.0 weight percent to about 10 weight percent HFC-32 and from about 99 weight percent to about 90 weight percent HFC-1225ye.

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

The present invention further relates to a method of exchanging the original refrigerant or heat transfer fluid composition, wherein the original refrigerant or heat transfer fluid composition is R22, R404A, or R410A, wherein the R22, R404A. Or R410A is a second containing 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 refrigerant or heat transfer fluid composition. In other embodiments, the second refrigerant or heat transfer fluid composition is 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. Includes percent to about 35 weight percent HFC-125. In yet another embodiment, the second refrigerant or heat transfer fluid composition is 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. Includes percent to about 28 weight percent HFC-125.

The present invention relates to a method of exchanging an original refrigerant or heat transfer fluid composition, wherein the original refrigerant or heat transfer fluid composition is R134a or R12, wherein the R134a or R12 is: HFC-1243zf. And HFC-1225ye; HFC-1243zf, HFC-1225ye, and HFC-125; HFC-1243zf, HFC-1225ye, and HFC-32; or HFC-1243zf, HFC-1225ye, HFC-125, and HFC-32. It is replaced by a second refrigerant or heat transfer fluid composition.

In all of the aforementioned methods of replacing the refrigerant, fluoroolefins can be used to replace the refrigerant in existing appliances. In addition, fluoroolefins can be used to replace said refrigerants in existing appliances designed to use the refrigerants therein. In addition, fluoroolefins can be used to replace refrigerants in existing appliances without the need to change or replace lubricants.

The present invention relates to a method for reducing fire in a refrigerating device, an air conditioner, or a heat pump device, the method comprising introducing the composition of the present invention into the refrigerant device or air conditioner.

When considering flammability, the refrigerant that can leak from refrigeration equipment, air conditioners, or heat pump equipment is a major concern. Refrigerants and potentially small amounts of lubricant can be released from the system in the event of a leak in a refrigerator or air conditioner. A fire can occur if this leaked material comes into contact with the ignition source. A fire means the possibility of a fire occurring in or near a refrigerating device, an air conditioner, or a heat pump device. Fire reduction in refrigeration, air conditioning, or heat pump equipment is achieved by using refrigerants or heat transfer fluids that are determined and defined as not considered flammable by the methods and criteria described herein. Can be achieved. Further, the nonflammable fluoroolefins of the present invention can be added to the flammable refrigerant or heat transfer fluid already in the apparatus, or before the flammable refrigerant or heat transfer fluid is added to the apparatus. The nonflammable fluoroolefins of the present invention reduce the extent of fire by reducing the likelihood of fire in the event of a leak and / or reducing the temperature or size of any flame formed.

The present invention further relates to a method of reducing flame risk in or near a refrigerating device, an air conditioner, or a heat pump device, wherein the method combines at least one nonflammable fluoroolefin with a flammable refrigerant, and a combination thereof. Includes the step of introducing flammers into a refrigeration system, air conditioner, or heat pump system.

The present invention further relates to a method of reducing flame risk in or near a refrigerating device, an air conditioner, or a heat pump device, wherein the method combines at least one nonflammable fluoroolefin with a lubricant. It comprises the step of introducing the thing into a refrigerating device containing a flammable refrigerant, an air conditioner, or a heat pump device.

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

The present invention further relates to a method of using a flammable refrigerant in a refrigerating device, an air conditioner, or a heat pump device, and the method includes a step of combining the flammable refrigerant with at least one fluoroolefin.

The present invention further relates to a method of reducing the flammability of a flammable refrigerant or heat transfer fluid, the method comprising combining a 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 heat conduction method includes a step of transferring the composition of the present invention from a heat source to a heat sink.

Heat transfer fluids are used to conduct, transfer or remove heat from one space, part, object or object to another space, part, object or object by radiation, conduction, or convection. The heat transfer fluid can function as a second coolant by providing a means of conducting cooling (or heating) from the remote refrigeration (or heating) system. In some systems, the heat transfer fluid can be kept constant throughout the conduction process (ie, does not evaporate or condense). Alternatively, the evaporative cooling process may also use a heat transfer fluid.

A heat source can be defined as any space, site, object or object for which heat is desired to be conducted, transferred or removed. Examples of heat sources can be voids (open or closed) that require freezing or cooling, such as refrigeration or freezing cases in supermarkets, building voids that require air conditioning, or automobile passenger compartments that require air conditioning. A heat sink can be defined as any endothermic space, site, object or object. The vapor compression refrigeration system is an example of such a heat sink.

<p> (Example 1) (Performance data) Table 7 shows CFC-113, HFC-43-10mee, and C.₄F₉OCH₃, And the refrigeration performance of the compounds of the invention compared to HFC-365mfc as pressures in evaporator (Evap) and capacitors (Cond), discharge temperature (Disch T), energy efficiency (COP), and capacity (Cap). Shown. The data is based on the following conditions:</p><p> 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) Compressor efficiency is 70%.</p><p><tables num="19"><img file="JP6442011B2_D0023.tif" /></tables></p><p> (Example 2) (Performance data) Table 8 shows the refrigerating performance of the compounds of the present invention compared to CFC-11 and HCFC-123, with evaporator (Evap) and condenser (Cond), discharge temperature (Disch T), and Shown as pressure in energy efficiency (COP) and capacity (Cap). The data is based on the following conditions:</p><p> 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) Compressor efficiency is 70%.</p><p><tables num="20"><img file="JP6442011B2_D0024.tif" /></tables></p><p> (Example 3) (Performance data) Table 9 shows the refrigerating performance of the compound of the present invention compared to HFC-245fa, evaporator (Evap) and capacitor (Cond), discharge temperature (Disch T), and energy efficiency (COP). ), And the pressure at capacity (Cap). The data is based on the following conditions:</p><p> 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) Compressor efficiency is 70%.</p><p><tables num="21"><img file="JP6442011B2_D0025.tif" /></tables></p><p> (Example 4) (Performance data) Table 10 shows the refrigerating performance of the compounds of the present invention compared to CFC-114 and HFC-236fa, evaporator (Evap) and condenser (Cond), discharge temperature (Disch T), and Shown as pressure in energy efficiency (COP) and capacity (Cap). The data is based on the following conditions:</p><p> 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) Compressor efficiency is 70%.</p><p><tables num="22"><img file="JP6442011B2_D0026.tif" /></tables></p><p> (Example 5) (Performance data) Table 11 shows the refrigerating performance of the compounds of the present invention compared to HFC-134a, HFC-152a, and HFC-227ea, evaporator (Evap) and condenser (Cond), and discharge temperature. Shown as pressure in (Disch T), energy efficiency (COP), and capacity (Cap). The data is based on the following conditions:</p><p> 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) Compressor efficiency is 70%.</p><p><tables num="23"><img file="JP6442011B2_D0027.tif" /></tables></p><p> (Example 6) (Flammable) Flammable compounds can be identified by testing with an electronic ignition source under ASTM (American Society of Testing and Materials) E681-01. Such tests of flammability, 101 kPa (14.7 psia), 50 for the compositions of the present disclosure, to determine if they are flammable and, if so, to find the downward flammability limit (LFL). Performed at various concentrations in air at percent relative humidity, and the temperature indicated. The results are shown in Table 12.</p><p><tables num="24"><img file="JP6442011B2_D0028.tif" /></tables></p><p> The results show that HFC-1234yf and E-HFC-1234ze are flammable, while HFC-1225ye, HFC-1429myz / mzy, and F12E are nonflammable. For mixtures of HFC-1225ye and HFC-32 (known to be flammable in the pure state), 37 weight percent HFC-32 may be present to maintain the nonflammable characteristics. It turned out to be the maximum amount possible. These compositions, which include nonflammable fluoroolefins, are candidates that are more acceptable as refrigerant or heat transfer fluid compositions.</p><p> (Example 7) (tip speed for generating pressure) The tip speed can be estimated by forming some basic relationships for refrigeration equipment using a centrifugal compressor. The ideal torque that the impeller applies to the gas is defined as follows.</p><p> T = m × (v₂× r₂-v₁× r₁) In Equation 1, T = torque, Newton meter m = mass ratio of flow, kg / sec v₂= Refrigerant swirl speed (tip speed) away from the impeller, metric / sec r₂= Exit impeller radius, meters v₁= Swirling speed of refrigerant entering the impeller, metric / sec r₁= The radius of the entrance impeller, meters.</p><p> Assuming that the refrigerant effectively enters the impeller in the axial direction, the swirling component of velocity v₁= 0, so T = m × v₂× r₂ Equation 2.</p><p> The output required by the shaft is the product of torque and rotational speed, P = T × ω Equation 3, in which P = output, W ω = angular velocity, radians / s and therefore P = T × w = m × v₂× r₂× ω Equation 4.</p><p> At low refrigerant flow rates, the tip speed of the impeller and the swirling speed of the refrigerant are almost equal;₂× ω = v₂ Equation 5 and P = m × v₂× v₂ Equation 6</p><p> Another equation for ideal output is the product of the mass ratio of the flow and the isentropic work of compression.</p><p> P = m × H_i× (1000J / kJ) Of the 7 formulas, H_i= Difference in enthalpy of refrigerant from saturated vapor under saturated condensation conditions from evaporation conditions, kJ / kg.</p><p> Combining the two expressions in equations 6 and 7, v₂× v₂= 1000 × H_i Equation 8 is obtained.</p><p> Equation 8 is based on some basic assumptions, but provides a good estimate of impeller tip velocities and an important way to compare refrigerant tip velocities.</p><p> Table 13 below shows the theoretical tip velocities calculated for 1,2,2-trichlorotrifluoroethane (CFC-113) and the compositions of the present invention. The conditions assumed for this comparison are:</p><p> Evaporator temperature 40.0 ° F (4.4 ° C) Capacitor temperature 110.0 ° F (43.3 ° C) Liquid subcool temperature 10.0 ° F (5.5 ° C) Return gas temperature 75.0 ° F (23.8 ° C) Compressor efficiency is 70%.</p><p> These are typical conditions for a small turbine centrifugal compressor to work.</p><p><tables num="25"><img file="JP6442011B2_D0029.tif" /></tables></p><p> This example shows that the compounds of the invention have tip velocities within about 15 percent of CFC-113 and would be an effective alternative to CFC-113 with minimal compressor design changes. There is. The most preferred composition has a tip velocity within about 10 percent of CFC-113.</p><p> (Example 8) (Refrigerating performance data) Table 14 shows the performance of various refrigerant compositions of the present invention as compared with HFC-134a. In Table 14, Evap Pres is the evaporator pressure, Cond Pres is the capacitor pressure, Comp Disch T is the compressor discharge temperature, COP is energy efficiency, and CAP is capacity. The data is based on the following conditions:</p><p> 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) Compressor efficiency is 100%.</p><p> Note that overheating is included in the cooling capacity.</p><p><tables num="26"><img file="JP6442011B2_D0030.tif" /></tables></p><p><tables num="27"><img file="JP6442011B2_D0031.tif" /></tables></p><p> Numerous compositions have even higher energy efficiencies (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, which can be an alternative refrigerant for R134a in refrigeration and air conditioning, and especially in portable air conditioning applications. It shows that there is. The results also show that the cooling capacity of HFC-1225ye can be improved by the addition of other compounds such as HFC-32.</p><p> (Example 9) (Refrigerating performance data) Table 15 shows the performance of various refrigerant compositions of the present invention as compared with R404A and R422A. In Table 15, Evap Pres is the evaporator pressure, Cond Pres is the capacitor pressure, Comp Disch T is the compressor discharge temperature, EER is energy efficiency, and CAP is capacity. The data is based on the following conditions:</p><p> Evaporator temperature -17.8 ° C Capacitor temperature 46.1 ° C Supercooling 5.5 ° C Return gas temperature 15.6 ° C Compressor efficiency is 70%.</p><p> Note that overheating is included in the cooling capacity.</p><p><tables num="28"><img file="JP6442011B2_D0032.tif" /></tables></p><p><tables num="29"><img file="JP6442011B2_D0033.tif" /></tables></p><p> Numerous compositions have energy efficiency (EER) comparable to the top R404A and R422A. The discharge temperature is also lower than R404A and R507A. The capacities for the compositions listed in Table 15 are also similar to R404A, R507A, and R422A, and these compositions can be alternative refrigerants for R404A, R507A, or R422A in refrigeration and air conditioning. It shows that it is possible.</p><p> (Example 10) (Refrigerating performance data) Table 16 shows the performance of various refrigerant compositions of the present invention as compared with HCFC-22 and R410A. In Table 16, Evap Pres is the evaporator pressure, Cond Pres is the capacitor pressure, Comp Disch T is the compressor discharge temperature, EER is energy efficiency, and CAP is capacity. The data is based on the following conditions:</p><p> Evaporator temperature 4 ° C Capacitor temperature 43 ° C Supercooling amount 6 ° C Return gas temperature 18 ° C Compressor efficiency is 70%.</p><p> Note that overheating is included in the cooling capacity.</p><p><tables num="30"><img file="JP6442011B2_D0034.tif" /></tables></p><p><tables num="31"><img file="JP6442011B2_D0035.tif" /></tables></p><p> The composition has energy efficiency (EER) comparable to R22 and R410A while maintaining a suitable emission 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 with capacities similar to or equal to R410A are listed in Table 16 indicating that these compositions can be alternative refrigerants for R410A in refrigeration and air conditioning. ..</p><p> (Example 11) (Refrigerating performance data) Table 17 shows the performance of various refrigerant compositions of the present invention as compared with HCFC-22, R410A, R407C, and R417A. In Table 17, Evap Pres is the evaporator pressure, Cond Pres is the capacitor pressure, Comp Disch T is the compressor discharge temperature, EER is energy efficiency, and CAP is capacity. The data is based on the following conditions:</p><p> Evaporator temperature 4.4 ° C Capacitor temperature 54.4 ° C Supercooling amount 5.5 ° C Return gas temperature 15.6 ° C Compressor efficiency is 100%.</p><p> Note that overheating is included in the cooling capacity.</p><p><tables num="32"><img file="JP6442011B2_D0036.tif" /></tables></p><p> The composition has energy efficiency (EER) comparable to R22, R407C, R417A, and R410A while maintaining a low emission temperature. The capacities for the compositions listed in Table 17 are also similar to R22, R407C and R417A, which 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.</p><p>The present invention includes the following embodiments.</p><p> 1. Refrigerant or heat transfer fluid composition: Equation (i) ER¹CH = CHR²Or ZR¹CH = CHR²Fluoroolefin in the formula, R¹And R²But independently, C₁~ C₆Fluoroolefins, and in the formula, the total number of carbons in the compound is at least 5; (ii) formula cyclo- [CX = CY (CZW)_n-] Cyclic fluoroolefins, in which X, Y, Z, and W are independently H or F, and n is an integer of 2-5; and (iii. ) 2,3,3-Trifluoro-1-propene (CHF)₂CF = CH₂); 1,1,2-Trifluoro-1-propene (CH)₃CF = CF₂); 1,2,3-trifluoro-1-propene (CH)₂FCF = CF₂); 1,1,3-Trifluoro-1-propene (CH)₂FCH = CF₂); 1,3,3-trifluoro-1-propene (CHF)₂CH = CHF); 1,1,1,2,3,4,4,4-octafluoro-2-butene (CF)₃CF = CFCF₃); 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF)₃CF₂CF = CF₂); 1,1,1,2,4,4,4-heptafluoro-2-butene (CF)₃CF = CHCF₃); 1,2,3,3,4,4,4-heptafluoro-1-butene (CHF = CFCF)₂CF₃); 1,1,1,2,3,4,4-heptafluoro-2-butene (CHF)₂CF = CFCF₃); 1,3,3,3-Tetrafluoro-2- (trifluoromethyl) -1-propene ((CF)₃)₂C = CHF); 1,1,3,3,4,4,4-heptafluoro-1-butene (CF)₂= CHCF₂CF₃); 1,1,2,3,4,4,4-heptafluoro-1-butene (CF)₂= CFCHFCF₃); 1,1,2,3,3,4,4-heptafluoro-1-butene (CF)₂= CFCF₂CHF₂); 2,3,3,4,4,4-hexafluoro-1-butene (CF)₃CF₂CF = CH₂); 1,3,3,4,4,4-hexafluoro-1-butene (CHF = CHCF)₂CF₃); 1,2,3,4,4,4-hexafluoro-1-butene (CHF = CFC CHFCF)₃); 1,2,3,3,4,4-hexafluoro-1-butene (CHF = CFCF)₂CHF₂); 1,1,2,3,4,4-hexafluoro-2-butene (CHF)₂CF = CFCHF₂); 1,1,1,2,3,4-hexafluoro-2-butene (CH)₂FCF = CFCF₃); 1,1,1,2,4,4-hexafluoro-2-butene (CHF)₂CH = CFCF₃); 1,1,1,3,4,4-hexafluoro-2-butene (CF)₃CH = CFC CHF₂); 1,1,2,3,3,4-hexafluoro-1-butene (CF)₂= CFCF₂CH₂F); 1,1,2,3,4,4-hexafluoro-1-butene (CF)₂= CFCHFCHF₂); 3,3,3-Trifluoro-2- (trifluoromethyl) -1-propene (CH)₂= C (CF)₃)₂); 1,1,1,2,4-pentafluoro-2-butene (CH)₂FCH = CFCF₃); 1,1,1,3,4-pentafluoro-2-butene (CF)₃CH = CFCH₂F); 3,3,4,4,4-pentafluoro-1-butene (CF)₃CF₂CH = CH₂); 1,1,1,4,4-pentafluoro-2-butene (CHF)₂CH = CHCF₃); 1,1,1,2,3-pentafluoro-2-butene (CH)₃CF = CFCF₃); 2,3,3,4,4-Pentafluoro-1-butene (CH)₂= CFCF₂CHF₂); 1,1,2,4,4-pentafluoro-2-butene (CHF)₂CF = CHCHF₂); 1,1,2,3,3-pentafluoro-1-butene (CH)₃CF₂CF = CF₂); 1,1,2,3,4-pentafluoro-2-butene (CH)₂FCF = CFCHF₂); 1,1,3,3,3-pentafluoro-2-methyl-1-propene (CF)₂= C (CF)₃) (CH₃)); 2- (Difluoromethyl) -3,3,3-trifluoro-1-propene (CH)₂= C (CHF)₂) (CF₃)); 2,3,4,4,4-pentafluoro-1-butene (CH)₂= CFCHFCF₃); 1,2,4,4,4-pentafluoro-1-butene (CHF = CFCH)₂CF₃); 1,3,4,4,4-pentafluoro-1-butene (CHF = CHCHFCF)₃); 1,3,3,4,4-pentafluoro-1-butene (CHF = CHCF)₂CHF₂); 1,2,3,4,4-pentafluoro-1-butene (CHF = CFC CHFCHF)₂); 3,3,4,4-Tetrafluoro-1-butene (CH)₂= CHCF₂CHF₂); 1,1-difluoro-2- (difluoromethyl) -1-propene (CF)₂= C (CHF)₂) (CH₃)); 1,3,3,3-Tetrafluoro-2-methyl-1-propene (CHF = C (CF)₃) (CH₃)); 3,3-Difluoro-2- (difluoromethyl) -1-propene (CH)₂= C (CHF)₂)₂); 1,1,1,2-Tetrafluoro-2-butene (CF)₃CF = CHCH₃); 1,1,1,3-Tetrafluoro-2-butene (CH)₃CF = CHCF₃); 1,1,1,2,3,4,4,5,5,5-decafluoro-2-pentene (CF)₃CF = CFCF₂CF₃); 1,1,2,3,3,4,4,5,5,5-decafluoro-1-pentene (CF)₂= CFCF₂CF₂CF₃); 1,1,1,4,4,4-hexafluoro-2- (trifluoromethyl) -2-butene ((CF)₃)₂C = CHCF₃); 1,1,1,2,4,4,5,5,5-Nonafluoro-2-pentene (CF)₃CF = CHCF₂CF₃); 1,1,1,3,4,4,5,5,5-Nonafluoro-2-pentene (CF)₃CH = CFCF₂CF₃); 1,2,3,3,4,4,5,5,5-Nonafluoro-1-pentene (CHF = CFCF)₂CF₂CF₃); 1,1,3,3,4,4,5,5,5-Nonafluoro-1-pentene (CF)₂= CHCF₂CF₂CF₃); 1,1,2,3,3,4,4,5,5-Nonafluoro-1-pentene (CF)₂= CFCF₂CF₂CHF₂); 1,1,2,3,4,4,5,5,5-Nonafluoro-2-pentene (CHF)₂CF = CFCF₂CF₃); 1,1,1,2,3,4,4,5,5-Nonafluoro-2-pentene (CF)₃CF = CFCF₂CHF₂); 1,1,1,2,3,4,5,5,5-Nonafluoro-2-pentene (CF)₃CF = CFCHFCF₃); 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)₃CH = 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= CFCF₂CF₂CF₃); 1,2,3,3,4,4,5,5-octafluoro-1-pentene (CHF = CFCF)₂CF₂CHF₂); 3,3,4,4,4-Pentafluoro-2- (trifluoromethyl) -1-butene (CH)₂= C (CF)₃) CF₂CF₃); 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) CH₂CF₃); 3,4,4,4-Tetrafluoro-3- (trifluoromethyl) -1-butene ((CF)₃)₂CFCH = CH₂); 3,3,4,4,5,5,5-heptafluoro-1-pentene (CF)₃CF₂CF₂CH = CH₂); 2,3,3,4,4,5,5-heptafluoro-1-pentene (CH)₂= CFCF₂CF₂CHF₂); 1,1,3,3,5,5,5-heptafluoro-1-butene (CF)₂= CHCF₂CH₂CF₃); 1,1,1,2,4,4,4-heptafluoro-3-methyl-2-butene (CF)₃CF = C (CF)₃) (CH₃)); 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)₂FCH = C (CF)₃)₂); 1,1,1,3-Tetrafluoro-2- (trifluoromethyl) -2-butene (CH)₃CF = C (CF)₃)₂); 1,1,1-Trifluoro-2- (trifluoromethyl) -2-butene ((CF)₃)₂C = CHCH₃); 3,4,4,5,5,5-hexafluoro-2-pentene (CF)₃CF₂CF = CHCH₃); 1,1,1,4,4,4-hexafluoro-2-methyl-2-butene (CF)₃C (CH)₃) = CHCF₃); 3,3,4,5,5,5-hexafluoro-1-pentene (CH)₂= CHCF₂CHFCF₃); 4,4,4-Trifluoro-3- (trifluoromethyl) -1-butene (CH)₂= C (CF)₃) CH₂CF₃); 1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1-hexene (CF)₃(CF₂)₃CF = CF₂); 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene (CF)₃CF₂CF = CFCF₂CF₃); 1,1,1,4,4,4-hexafluoro-2,3-bis (trifluoromethyl) -2-butene ((CF)₃)₂C = C (CF)₃)₂); 1,1,1,2,3,4,5,5,5-Nonafluoro-4- (trifluoromethyl) -2-pentene ((CF)₃)₂CFCF = CFCF₃); 1,1,1,4,4,5,5,5-octafluoro-2- (trifluoromethyl) -2-pentene ((CF)₃)₂C = CHC₂F₅); 1,1,1,3,4,5,5,5-octafluoro-4- (trifluoromethyl) -2-pentene ((CF)₃)₂CFCF = CHCF₃); 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene (CF)₃CF₂CF₂CF₂CH = CH₂); 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)₂C = C (CH)₃) (CF₃)); 2,3,3,5,5,5-hexafluoro-4- (trifluoromethyl) -1-pentene (CH)₂= CFCF₂CH (CF)₃)₂); 1,1,1,2,4,4,5,5,5-Nonafluoro-3-methyl-2-pentene (CF)₃CF = C (CH)₃) CF₂CF₃); 1,1,1,5,5,5-hexafluoro-4- (trifluoromethyl) -2-pentene (CF)₃CH = CHCH (CF)₃)₂); 3,4,4,5,5,6,6,6-octafluoro-2-hexene (CF)₃CF₂CF₂CF = CHCH₃); 3,3,4,4,5,5,6,6-octafluoro1-hexene (CH)₂= CHCF₂CF₂CF₂CHF₂); 1,1,1,4,4-pentafluoro-2- (trifluoromethyl) -2-pentene ((CF)₃)₂C = CHCF₂CH₃); 4,4,5,5,5-pentafluoro-2- (trifluoromethyl) -1-pentene (CH)₂= C (CF)₃) CH₂C₂F₅); 3,3,4,4,5,5,5-heptafluoro-2-methyl-1-pentene (CF)₃CF₂CF₂C (CH)₃) = CH₂); 4,4,5,5,6,6,6-heptafluoro-2-hexene (CF)₃CF₂CF₂CH = CHCH₃); 4,4,5,5,6,6,6-heptafluoro-1-hexene (CH)₂= CHCH₂CF₂C₂F₅); 1,1,1,2,2,3,4-heptafluoro-3-hexene (CF)₃CF₂CF = CFC₂H₅); 4,5,5,5-Tetrafluoro-4- (trifluoromethyl) -1-pentene (CH)₂= CHCH₂CF (CF)₃)₂); 1,1,1,2,5,5,5-heptafluoro-4-methyl-2-pentene (CF)₃CF = CHCH (CF)₃) (CH₃)); 1,1,1,3-Tetrafluoro-2- (trifluoromethyl) -2-pentene ((CF)₃)₂C = CFC₂H₅); 1,1,1,2,3,4,4,5,5,6,6,7,7,7-Tetradecafluoro-2-heptene (CF)₃CF = CFCF₂CF₂C₂F₅); 1,1,1,2,2,3,4,5,5,6,6,7,7,7-Tetradecafluoro-3-heptene (CF)₃CF₂CF = CFCF₂C₂F₅); 1,1,1,3,4,4,5,5,6,6,7,7,7-Tridecafluoro-2-heptene (CF)₃CH = CFCF₂CF₂C₂F₅); 1,1,1,2,4,4,5,5,6,6,7,7,7-Tridecafluoro-2-heptene (CF)₃CF = CHCF₂CF₂C₂F₅); 1,1,1,2,2,4,5,5,6,6,7,7,7-Tridecafluoro-3-heptene (CF)₃CF₂CH = CFCF₂C₂F₅); 1,1,1,2,2,3,5,5,6,6,7,7,7-Tridecafluoro-3-heptene (CF)₃CF₂CF = CHCF₂C₂F₅); CF₂= CFOCF₂CF₃(PEVE) and CF₂= CFOCF₃A refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of fluoroolefins selected from the group consisting of (PMVE).</p><p> 2. A composition comprising (i) at least one fluoroolefin compound; and (ii) at least one flammable refrigerant; said fluoroolefin: (a) formula ER.¹CH = CHR²Or ZR¹CH = CHR²Fluoroolefin in the formula, R¹And R²But independently, C₁~ C₆Fluoroolefin, which is a perfluoroalkyl group of_n-] Cyclic fluoroolefins, in which X, Y, Z, and W are independently H or F, and n is an integer of 2-5; and (c. ) 1,2,3,3,3-Pentafluoro-1-propene (CF)₃CF = CHF); 1,1,3,3,3-pentafluoro-1-propene (CF)₃CH = CF₂); 1,1,2,3,3-pentafluoro-1-propene (CHF)₂CF = CF₂); 1,1,1,2,3,4,4,4-octafluoro-2-butene (CF)₃CF = CFCF₃); 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF)₃CF₂CF = CF₂); 1,1,1,2,4,4,4-heptafluoro-2-butene (CF)₃CF = CHCF₃); 1,2,3,3,4,4,4-heptafluoro-1-butene (CHF = CFCF)₂CF₃); 1,1,1,2,3,4,4-heptafluoro-2-butene (CHF)₂CF = CFCF₃); 1,3,3,3-Tetrafluoro-2- (trifluoromethyl) -1-propene ((CF)₃)₂C = CHF); 1,1,3,3,4,4,4-heptafluoro-1-butene (CF)₂= CHCF₂CF₃); 1,1,2,3,4,4,4-heptafluoro-1-butene (CF)₂= CFCHFCF₃); 1,1,2,3,3,4,4-heptafluoro-1-butene (CF)₂= CFCF₂CHF₂); 2,3,3,4,4,4-hexafluoro-1-butene (CF)₃CF₂CF = CH₂); 1,3,3,4,4,4-hexafluoro-1-butene (CHF = CHCF)₂CF₃); 1,2,3,4,4,4-hexafluoro-1-butene (CHF = CFC CHFCF)₃); 1,2,3,3,4,4-hexafluoro-1-butene (CHF = CFCF)₂CHF₂); 1,1,2,3,4,4-hexafluoro-2-butene (CHF)₂CF = CFCHF₂); 1,1,1,2,3,4-hexafluoro-2-butene (CH)₂FCF = CFCF₃); 1,1,1,2,4,4-hexafluoro-2-butene (CHF)₂CH = CFCF₃); 1,1,1,3,4,4-hexafluoro-2-butene (CF)₃CH = CFC CHF₂); 1,1,2,3,3,4-hexafluoro-1-butene (CF)₂= CFCF₂CH₂F); 1,1,2,3,4,4-hexafluoro-1-butene (CF)₂= CFCHFCHF₂); 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)₃CF = CFCF₂CF₃); 1,1,2,3,3,4,4,5,5,5-decafluoro-1-pentene (CF)₂= CFCF₂CF₂CF₃); 1,1,1,4,4,4-hexafluoro-2- (trifluoromethyl) -2-butene ((CF)₃)₂C = CHCF₃); 1,1,1,2,4,4,5,5,5-Nonafluoro-2-pentene (CF)₃CF = CHCF₂CF₃); 1,1,1,3,4,4,5,5,5-Nonafluoro-2-pentene (CF)₃CH = CFCF₂CF₃); 1,2,3,3,4,4,5,5,5-Nonafluoro-1-pentene (CHF = CFCF)₂CF₂CF₃); 1,1,3,3,4,4,5,5,5-Nonafluoro-1-pentene (CF)₂= CHCF₂CF₂CF₃); 1,1,2,3,3,4,4,5,5-Nonafluoro-1-pentene (CF)₂= CFCF₂CF₂CHF₂); 1,1,2,3,4,4,5,5,5-Nonafluoro-2-pentene (CHF)₂CF = CFCF₂CF₃); 1,1,1,2,3,4,4,5,5-Nonafluoro-2-pentene (CF)₃CF = CFCF₂CHF₂); 1,1,1,2,3,4,5,5,5-Nonafluoro-2-pentene (CF)₃CF = CFCHFCF₃); 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)₃CH = 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= CFCF₂CF₂CF₃); 1,2,3,3,4,4,5,5-octafluoro-1-pentene (CHF = CFCF)₂CF₂CHF₂); 3,3,4,4,4-Pentafluoro-2- (trifluoromethyl) -1-butene (CH)₂= C (CF)₃) CF₂CF₃); 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) CH₂CF₃); 3,4,4,4-Tetrafluoro-3- (trifluoromethyl) -1-butene ((CF)₃)₂CFCH = CH₂); 3,3,4,4,5,5,5-heptafluoro-1-pentene (CF)₃CF₂CF₂CH = CH₂); 2,3,3,4,4,5,5-heptafluoro-1-pentene (CH)₂= CFCF₂CF₂CHF₂); 1,1,3,3,5,5,5-heptafluoro-1-butene (CF)₂= CHCF₂CH₂CF₃); 1,1,1,2,4,4,4-heptafluoro-3-methyl-2-butene (CF)₃CF = C (CF)₃) (CH₃)); 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)₂FCH = C (CF)₃)₂); 1,1,1,3-Tetrafluoro-2- (trifluoromethyl) -2-butene (CH)₃CF = C (CF)₃)₂); 1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1-hexene (CF)₃(CF₂)₃CF = CF₂); 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene (CF)₃CF₂CF = CFCF₂CF₃); 1,1,1,4,4,4-hexafluoro-2,3-bis (trifluoromethyl) -2-butene ((CF)₃)₂C = C (CF)₃)₂); 1,1,1,2,3,4,5,5,5-Nonafluoro-4- (trifluoromethyl) -2-pentene ((CF)₃)₂CFCF = CFCF₃); 1,1,1,4,4,5,5,5-octafluoro-2- (trifluoromethyl) -2-pentene ((CF)₃)₂C = CHC₂F₅); 1,1,1,3,4,5,5,5-octafluoro-4- (trifluoromethyl) -2-pentene ((CF)₃)₂CFCF = CHCF₃); 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene (CF)₃CF₂CF₂CF₂CH = CH₂); 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)₂C = C (CH)₃) (CF₃)); 2,3,3,5,5,5-hexafluoro-4- (trifluoromethyl) -1-pentene (CH)₂= CFCF₂CH (CF)₃)₂); 1,1,1,2,4,4,5,5,5-Nonafluoro-3-methyl-2-pentene (CF)₃CF = C (CH)₃) CF₂CF₃); 1,1,1,5,5,5-hexafluoro-4- (trifluoromethyl) -2-pentene (CF)₃CH = CHCH (CF)₃)₂); 1,1,1,2,3,4,4,5,5,6,6,7,7,7-Tetradecafluoro-2-heptene (CF)₃CF = CFCF₂CF₂C₂F₅); 1,1,1,2,2,3,4,5,5,6,6,7,7,7-Tetradecafluoro-3-heptene (CF)₃CF₂CF = CFCF₂C₂F₅); 1,1,1,3,4,4,5,5,6,6,7,7,7-Tridecafluoro-2-heptene (CF)₃CH = CFCF₂CF₂C₂F₅); 1,1,1,2,4,4,5,5,6,6,7,7,7-Tridecafluoro-2-heptene (CF)₃CF = CHCF₂CF₂C₂F₅); 1,1,1,2,2,4,5,5,6,6,7,7,7-Tridecafluoro-3-heptene (CF)₃CF₂CH = CFCF₂C₂F₅); And 1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF)₃CF₂CF = CHCF₂C₂F₅) A fluoroolefin selected from the group consisting of; a composition characterized by being selected from the group consisting of.</p><p> 3. A cooling method comprising a step of condensing the composition according to 1 or 2 above, and then evaporating the composition in the vicinity of an object to be cooled.</p><p> 4. A heating method comprising a step of evaporating the composition according to 1 or 2 above, and then condensing the composition in the vicinity of an object to be heated.</p><p> 5. A method of providing heating or cooling in refrigeration, air conditioning, or heat pump equipment, in which the refrigerant or heat transfer fluid composition is (a) centrifugal compressor; (b) multistage centrifugal compressor, or (c) single slab / single pass Including the step of supplying to the device having a heat exchanger; where the refrigerant or heat transfer fluid composition is: Eq. (I) ER.¹CH = CHR²Or ZR¹CH = CHR²Fluoroolefin in the formula, R¹And R²But independently, C₁~ C₆Fluoroolefin, which is a perfluoroalkyl group of_n-] Cyclic fluoroolefins, in which X, Y, Z, and W are independently H or F, and n is an integer of 2-5; or (iii). ) 1,2,3,3,3-Pentafluoro-1-propene (CF)₃CF = CHF); 1,1,3,3,3-pentafluoro-1-propene (CF)₃CH = CF₂); 1,1,2,3,3-pentafluoro-1-propene (CHF)₂CF = CF₂); 1,2,3,3-Tetrafluoro-1-propene (CHF)₂CF = CHF); 2,3,3,3-tetrafluoro-1-propen (CF)₃CF = CH₂); 1,3,3,3-Tetrafluoro-1-propene (CF)₃CH = CHF); 1,1,2,3-tetrafluoro-1-propene (CH)₂FCF = CF₂); 1,1,3,3-tetrafluoro-1-propene (CHF)₂CH = CF₂); 2,3,3-Trifluoro-1-propene (CHF)₂CF = CH₂); 3,3,3-Trifluoro-1-propene (CF)₃CH = CH₂); 1,1,2-Trifluoro-1-propene (CH)₃CF = CF₂); 1,1,3-Trifluoro-1-propene (CH)₂FCH = CF₂); 1,2,3-trifluoro-1-propene (CH)₂FCF = CHF); 1,3,3-trifluoro-1-propene (CHF)₂CH = CHF); 1,1,1,2,3,4,4,4-octafluoro-2-butene (CF)₃CF = CFCF₃); 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF)₃CF₂CF = CF₂); 1,1,1,2,4,4,4-heptafluoro-2-butene (CF)₃CF = CHCF₃); 1,2,3,3,4,4,4-heptafluoro-1-butene (CHF = CFCF)₂CF₃); 1,1,1,2,3,4,4-heptafluoro-2-butene (CHF)₂CF = CFCF₃); 1,3,3,3-Tetrafluoro-2- (trifluoromethyl) -1-propene ((CF)₃)₂C = CHF); 1,1,3,3,4,4,4-heptafluoro-1-butene (CF)₂= CHCF₂CF₃); 1,1,2,3,4,4,4-heptafluoro-1-butene (CF)₂= CFCHFCF₃); 1,1,2,3,3,4,4-heptafluoro-1-butene (CF)₂= CFCF₂CHF₂); 2,3,3,4,4,4-hexafluoro-1-butene (CF)₃CF₂CF = CH₂); 1,3,3,4,4,4-hexafluoro-1-butene (CHF = CHCF)₂CF₃); 1,2,3,4,4,4-hexafluoro-1-butene (CHF = CFC CHFCF)₃); 1,2,3,3,4,4-hexafluoro-1-butene (CHF = CFCF)₂CHF₂); 1,1,2,3,4,4-hexafluoro-2-butene (CHF)₂CF = CFCHF₂); 1,1,1,2,3,4-hexafluoro-2-butene (CH)₂FCF = CFCF₃); 1,1,1,2,4,4-hexafluoro-2-butene (CHF)₂CH = CFCF₃); 1,1,1,3,4,4-hexafluoro-2-butene (CF)₃CH = CFC CHF₂); 1,1,2,3,3,4-hexafluoro-1-butene (CF)₂= CFCF₂CH₂F); 1,1,2,3,4,4-hexafluoro-1-butene (CF)₂= CFCHFCHF₂); 3,3,3-Trifluoro-2- (trifluoromethyl) -1-propene (CH)₂= C (CF)₃)₂); 1,1,1,2,4-pentafluoro-2-butene (CH)₂FCH = CFCF₃); 1,1,1,3,4-pentafluoro-2-butene (CF)₃CH = CFCH₂F); 3,3,4,4,4-pentafluoro-1-butene (CF)₃CF₂CH = CH₂); 1,1,1,4,4-pentafluoro-2-butene (CHF)₂CH = CHCF₃); 1,1,1,2,3-pentafluoro-2-butene (CH)₃CF = CFCF₃); 2,3,3,4,4-Pentafluoro-1-butene (CH)₂= CFCF₂CHF₂); 1,1,2,4,4-pentafluoro-2-butene (CHF)₂CF = CHCHF₂); 1,1,2,3,3-pentafluoro-1-butene (CH)₃CF₂CF = CF₂); 1,1,2,3,4-pentafluoro-2-butene (CH)₂FCF = CFCHF₂); 1,1,3,3,3-pentafluoro-2-methyl-1-propene (CF)₂= C (CF)₃) (CH₃)); 2- (Difluoromethyl) -3,3,3-trifluoro-1-propene (CH)₂= C (CHF)₂) (CF₃)); 2,3,4,4,4-pentafluoro-1-butene (CH)₂= CFCHFCF₃); 1,2,4,4,4-pentafluoro-1-butene (CHF = CFCH)₂CF₃); 1,3,4,4,4-pentafluoro-1-butene (CHF = CHCHFCF)₃); 1,3,3,4,4-pentafluoro-1-butene (CHF = CHCF)₂CHF₂); 1,2,3,4,4-pentafluoro-1-butene (CHF = CFC CHFCHF)₂); 3,3,4,4-Tetrafluoro-1-butene (CH)₂= CHCF₂CHF₂); 1,1-difluoro-2- (difluoromethyl) -1-propene (CF)₂= C (CHF)₂) (CH₃)); 1,3,3,3-Tetrafluoro-2-methyl-1-propene (CHF = C (CF)₃) (CH₃)); 2-Difluoromethyl-3,3-difluoro-1-propene (CH)₂= C (CHF)₂)₂); 1,1,1,2-Tetrafluoro-2-butene (CF)₃CF = CHCH₃); 1,1,1,3-Tetrafluoro-2-butene (CH)₃CF = CHCF₃); 1,1,1,2,3,4,4,5,5,5-decafluoro-2-pentene (CF)₃CF = CFCF₂CF₃); 1,1,2,3,3,4,4,5,5,5-decafluoro-1-pentene (CF)₂= CFCF₂CF₂CF₃); 1,1,1,4,4,4-hexafluoro-2- (trifluoromethyl) -2-butene ((CF)₃)₂C = CHCF₃); 1,1,1,2,4,4,5,5,5-Nonafluoro-2-pentene (CF)₃CF = CHCF₂CF₃); 1,1,1,3,4,4,5,5,5-Nonafluoro-2-pentene (CF)₃CH = CFCF₂CF₃); 1,2,3,3,4,4,5,5,5-Nonafluoro-1-pentene (CHF = CFCF)₂CF₂CF₃); 1,1,3,3,4,4,5,5,5-Nonafluoro-1-pentene (CF)₂= CHCF₂CF₂CF₃); 1,1,2,3,3,4,4,5,5-Nonafluoro-1-pentene (CF)₂= CFCF₂CF₂CHF₂); 1,1,2,3,4,4,5,5,5-Nonafluoro-2-pentene (CHF)₂CF = CFCF₂CF₃); 1,1,1,2,3,4,4,5,5-Nonafluoro-2-pentene (CF)₃CF = CFCF₂CHF₂); 1,1,1,2,3,4,5,5,5-Nonafluoro-2-pentene (CF)₃CF = CFCHFCF₃); 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)₃CH = 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= CFCF₂CF₂CF₃); 1,2,3,3,4,4,5,5-octafluoro-1-pentene (CHF = CFCF)₂CF₂CHF₂); 3,3,4,4,4-Pentafluoro-2- (trifluoromethyl) -1-butene (CH)₂= C (CF)₃) CF₂CF₃); 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) CH₂CF₃); 3,4,4,4-Tetrafluoro-3- (trifluoromethyl) -1-butene ((CF)₃)₂CFCH = CH₂); 3,3,4,4,5,5,5-heptafluoro-1-pentene (CF)₃CF₂CF₂CH = CH₂); 2,3,3,4,4,5,5-heptafluoro-1-pentene (CH)₂= CFCF₂CF₂CHF₂); 1,1,3,3,5,5,5-heptafluoro-1-butene (CF)₂= CHCF₂CH₂CF₃); 1,1,1,2,4,4,4-heptafluoro-3-methyl-2-butene (CF)₃CF = C (CF)₃) (CH₃)); 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)₂FCH = C (CF)₃)₂); 1,1,1,3-Tetrafluoro-2- (trifluoromethyl) -2-butene (CH)₃CF = C (CF)₃)₂); 1,1,1-Trifluoro-2- (trifluoromethyl) -2-butene ((CF)₃)₂C = CHCH₃); 3,4,4,5,5,5-hexafluoro-2-pentene (CF)₃CF₂CF = CHCH₃); 1,1,1,4,4,4-hexafluoro-2-methyl-2-butene (CF)₃C (CH)₃) = CHCF₃); 3,3,4,5,5,5-hexafluoro-1-pentene (CH)₂= CHCF₂CHFCF₃); 3- (Trifluoromethyl) -4,4,4-trifluoro-1-butene (CH)₂= C (CF)₃) CH₂CF₃); 1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1-hexene (CF)₃(CF₂)₃CF = CF₂); 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene (CF)₃CF₂CF = CFCF₂CF₃); 1,1,1,4,4,4-hexafluoro-2,3-bis (trifluoromethyl) -2-butene ((CF)₃)₂C = C (CF)₃)₂); 1,1,1,2,3,4,5,5,5-Nonafluoro-4- (trifluoromethyl) -2-pentene ((CF)₃)₂CFCF = CFCF₃); 1,1,1,4,4,5,5,5-octafluoro-2- (trifluoromethyl) -2-pentene ((CF)₃)₂C = CHC₂F₅); 1,1,1,3,4,5,5,5-octafluoro-4- (trifluoromethyl) -2-pentene ((CF)₃)₂CFCF = CHCF₃); 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene (CF)₃CF₂CF₂CF₂CH = CH₂); 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- (trifluoromethyl) -2-butene ((CF)₃)₂C = C (CH)₃) (CF₃)); 2,3,3,5,5,5-hexafluoro-4- (trifluoromethyl) -1-pentene (CH)₂= CFCF₂CH (CF)₃)₂); 1,1,1,2,4,4,5,5,5-Nonafluoro-3-methyl-2-pentene (CF)₃CF = C (CH)₃) CF₂CF₃); 1,1,1,5,5,5-hexafluoro-4- (trifluoromethyl) -2-pentene (CF)₃CH = CHCH (CF)₃)₂); 3,4,4,5,5,6,6,6-octafluoro-2-hexene (CF)₃CF₂CF₂CF = CHCH₃); 3,3,4,4,5,5,6,6-octafluoro-1-hexene (CH)₂= CHCF₂CF₂CF₂CHF₂); 1,1,1,4,4-pentafluoro-2- (trifluoromethyl) -2-pentene ((CF)₃)₂C = CHCF₂CH₃); 4,4,5,5,5-pentafluoro-2- (trifluoromethyl) -1-pentene (CH)₂= C (CF)₃) CH₂C₂F₅); 3,3,4,4,5,5,5-heptafluoro-2-methyl-1-pentene (CF)₃CF₂CF₂C (CH)₃) = CH₂); 4,4,5,5,6,6,6-heptafluoro-2-hexene (CF)₃CF₂CF₂CH = CHCH₃); 4,4,5,5,6,6,6-heptafluoro-1-hexene (CH)₂= CHCH₂CF₂C₂F₅); 1,1,1,2,2,3,4-heptafluoro-3-hexene (CF)₃CF₂CF = CFC₂H₅); 4,5,5,5-Tetrafluoro-4-trifluoromethyl-1-pentene (CH)₂= CHCH₂CF (CF)₃)₂); 1,1,1,2,5,5,5-heptafluoro-4-methyl-2-pentene (CF)₃CF = CHCH (CF)₃) (CH₃)); 1,1,1,3-Tetrafluoro-2-trifluoromethyl-2-pentene ((CF)₃)₂C = CFC₂H₅); 1,1,1,2,3,4,4,5,5,6,6,7,7,7-Tetradecafluoro-2-heptene (CF)₃CF = CFCF₂CF₂C₂F₅); 1,1,1,2,2,3,4,5,5,6,6,7,7,7-Tetradecafluoro-3-heptene (CF)₃CF₂CF = CFCF₂C₂F₅); 1,1,1,3,4,4,5,5,6,6,7,7,7-Tridecafluoro-2-heptene (CF)₃CH = CFCF₂CF₂C₂F₅); 1,1,1,2,4,4,5,5,6,6,7,7,7-Tridecafluoro-2-heptene (CF)₃CF = CHCF₂CF₂C₂F₅); 1,1,1,2,2,4,5,5,6,6,7,7,7-Tridecafluoro-3-heptene (CF)₃CF₂CH = CFCF₂C₂F₅); 1,1,1,2,2,3,5,5,6,6,7,7,7-Tridecafluoro-3-heptene (CF)₃CF₂CF = CHCF₂C₂F₅); CF₂= CFOCF₂CF₃(PEVE); CF₂= CFOCF₃(PMVE) and fluoroolefins selected from the group consisting of combinations thereof; a method comprising at least one fluoroolefin selected from the group consisting of.</p><p> 6. A method of reducing the risk of flames in a refrigerating device, an air conditioner, or a heat pump device using the composition according to 1 or 2 above, wherein the device contains a flammable refrigerant, and the method is the composition. A method comprising feeding the material to the device and optionally adding a lubricant to the composition to be added.</p><p> 7. A method for reducing the flammability of a flammable refrigerant by using the refrigerant or heat transfer fluid composition according to 1 above, which comprises a step of combining the flammable refrigerant with the composition. ..</p><p> 8. The composition according to 1 or 2 above, which is a method of replacing the use of a high global warming potential refrigerant, in place of or in combination with the high global warming potential refrigerant in refrigeration, air conditioning, or heat pump equipment. A method comprising the steps of providing a refrigeration, air conditioning, or heat pump device.</p><p> 9. A method for reducing the global warming coefficient of the original refrigerant or heat transfer fluid composition using the composition according to 1 above, which is described in 1 above with the original refrigerant or heat transfer fluid composition. In the step of producing a second refrigerant or heat transfer fluid composition in combination with the composition of the above, 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 global warming coefficient.</p><p> 10. A method of reducing the GWP of the original refrigerant or heat transfer fluid composition in a refrigeration, air conditioning or heat pump system, wherein the original refrigerant or heat transfer fluid has about 150 or more GWP; said 1 or 2 A method comprising supplying the second, lower GWP refrigerant or heat transfer fluid composition according to the above to the refrigeration, air conditioning or heat pump apparatus.</p><p> 11. A method of replacing the original refrigerant or heat transfer fluid composition with a second refrigerant or heat transfer fluid composition, wherein the composition containing at least one fluoroolefin is replaced with the second refrigerant or heat transfer fluid composition. The original refrigerant or heat transfer fluid composition is: (i) 1,1,1,2-tetrafluoroethane (R134a), trifluoromethyltrifluorovinyl ether. R134a; (ii) 1,1-difluoroethane (R152a) substituted with a second refrigerant or heat transfer fluid composition containing (PMVE), 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-tri R152a replaced by a second refrigerant or heat transfer fluid composition containing at least one compound selected from the group consisting of fluoropropene (HFC-1243zf) and trifluoromethyltrifluorovinyl ether (PMVE); (iii) 1,1,1,2,3,3,3-heptafluoropropane (R227ea), 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 R227ea substituted with a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of trifluoromethyltrifluorovinyl ether (PMVE); (iv) 1,1,2-Trichloro-1,2,2-trifluoroethane (R113), 1,1,1,3,4,5,5,5-octafluoro-4- (tri) Fluoromethyl) -2-butene (HFC-152-11mmyyz); 1,1,1,4,4,5,5,5-octafluoro-2- (trifluoromethyl) -2-pentene (HFC-152-) 11mmtz); 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-151-12mmtt); 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-Penten (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-151-12mmzz); and 1,1,1,2,2,5,5,6,6, Replaced by a second refrigerant or heat transfer fluid composition containing at least one compound selected from the group consisting of 6-decafluoro-3-hexene (F22E) R113; (v) 1,1,1, 2,3,4,4,5,5,5-decafluoropentane (R43-10mee), 1,1,1,3,4,5,5,5-octafluoro-4- (trifluoro) Methyl) -2-butene (HFC-152-11mmyyz); 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-151-12mmtt); 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-151-12mmzz) ); And a second refrigerant containing at least one compound selected from the group consisting of 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (F22E). Or replaced by a heat transfer fluid composition R43-10mee; (vi) C6-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 contains at least one compound selected from the group consisting of 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (F22E). R43-10mee replaced by a second refrigerant or heat transfer fluid composition; (vi) C6-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 contains at least one compound selected from the group consisting of 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (F22E). R43-10mee replaced by a second refrigerant or heat transfer fluid composition; (vi) C₄F₉OCH₃And 1,1,1,3,4,5,5,5-octafluoro-4- (trifluoromethyl) -2-butene (HFC-152-11mmyyz); 1,1,1,4, 4,5,5,5-octafluoro-2- (trifluoromethyl) -2-pentene (HFC-152-11mmtz); 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-151-12mmtt); 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-151-12mmzz); 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). C replaced by a second refrigerant or heat transfer fluid composition containing₄F₉OCH₃; (vii) 1,1,1,3,3-pentafluorobutane (R365mfc), 1,1,1,3,4,5,5,5-octafluoro-4- (trifluoromethyl)- 2-Buten (HFC-152-11mmyyz); 1,1,1,4,4,5,5,5-octafluoro-2- (trifluoromethyl) -2-pentene (HFC-152-11mmtz); 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-151-12mmtt); 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-151-12mmzz); and 1,1,1,2,2,5,5,6,6,6-decafluoro -3-R365mfc; (viii) fluorotrichloromethane (R11) substituted with a second refrigerant or heat transfer fluid composition containing at least one compound selected from the group consisting of hexene (F22E). 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 A second refrigerant containing at least one compound selected from the group consisting of (HFC-1429mzt); and 1,1,1,4,4,5,5,5-octafluoro-2-pentene (F12E). Alternatively, R11; (ix) 2,2,-dichloro-1,1,1-trifluoroethane (R123) substituted by the heat transfer fluid composition, 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 1,1,1,4,4,5,5 R123; (x) 1,1,1 substituted with a second refrigerant or heat transfer fluid composition containing at least one compound selected from the group consisting of 5-octafluoro-2-pentene (F12E). , 3,3-Pentafluoropropane (R245fa), 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,At least one selected from the group consisting of 4-heptafluoro-2-butene (HFC-1327my); 1,2,3,3-tetrafluoropropene (HFC-1234ye); and pentafluoroethyltrifluorovinyl ether (PEVE). R245fa; (xi) 1,2-dichloro-1,1,2,2-tetrafluoroethane (R124) substituted with a second CFC or heat transfer fluid composition comprising a species compound, 1, 1,1,2,3,4,4,4-octafluoro-2-butene (FC-1318my); 1,2,3,3,4,4-hexafluorocyclobutene (FC-C1316cc); 2, Selected from the group consisting of 3,3,4,4,4-hexafluoro-1-butene (HFC-1336yf); and 3,3,4,4,4-pentafluoro-1-butene (HFC-1345fz) R124; (xii) 1,1,1,3,3,3-hexafluoropropane (R236fa) substituted with a second CFC or heat transfer fluid composition comprising at least one compound. , 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 3,3,4,4,4-pentafluoro-1-butene (HFC-1345fz) R236fa; (xiii) R401A substituted with a second CFC or heat transfer fluid composition comprising at least one compound to be 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-1225ye) HFC-1243zf);R401A; (xiv) R401B substituted with a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of trifluoromethyltrifluorovinyl ether (PMVE) and 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 or carrier containing at least one compound selected from the group consisting of HFC-1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyltrifluorovinyl ether (PMVE). R401B; (xv) R409A substituted by thermofluid composition, 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 trifluoromethyltrifluorovinyl ether (PMVE) R409A; (xvi) R409B substituted with a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of E-1,3,3,3-tetrafluoro. Propen (E-HFC-1234ze); 1,2,3,3,3-pentafluoropropen (HFC-1225ye); 2,3,3,3-tetrafluoropropen (HFC-1234yf); 3,3,3 -R409B substituted with a second refrigerant or heat transfer fluid composition containing at least one compound selected from the group consisting of trifluoropropene (HFC-1243zf); and trifluoromethyltrifluorovinyl ether (PMVE); (xvii) R414B, 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 trifluoromethyltri R414B; (xviii) R416A substituted with a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of fluorovinyl ether (PMVE), E-1,3,3. , 3-Tetrafluoropropen (E-HFC-1234ze); 1,2,3,3,3-Pentafluoropropen (HFC-1225ye); 2,3,3,3-Tetrafluoropropen (HFC-1234yf); By a second refrigerant or heat transfer fluid composition containing at least one compound selected from the group consisting of 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyltrifluorovinyl ether (PMVE). Substituted R416A; (xix) dichlorodifluoromethane (R12), 1,2,3,3,3-pentafluoropropene (HFC-1225ye); 2,3,3,3-tetrafluoropropene (HFC) A second refrigerant or heat transfer containing at least one compound selected from the group consisting of -1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyltrifluorovinyl ether (PMVE). R12; and (xx) R500 substituted by the fluid composition, 1,2,3,3,3-pentafluoropropene (HFC-1225ye); 2,3,3,3-tetrafluoropropene (HFC) -1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyltrifluorovinyl ether (PMVE) -trifluoropropene, 3,3,3-Selected from the group consisting of trifluoropropene and R500; substituted with a second refrigerant or heat transfer fluid composition containing at least one compound selected from the group consisting of trifluoromethyltrifluorovinyl ether. A method characterized by that.</p><p> 12. A method of using the composition according to 1 or 2 as a heat transfer fluid composition, which comprises a step of transferring the composition from a heat source to a heat sink.</p><p> 13. (i) The step of recovering a volume of one or more components of the refrigerant composition from at least one refrigerant container, (ii) the one or more recovered components can be reused. As such, it comprises the steps of sufficiently removing impurities, (iii) and optionally combining all or part of the recovered volume of the constituent with at least one additional refrigerant composition or constituent. The method for producing a composition according to 1 or 2 above.</p><p> 14. A refrigeration, air conditioning or heat pump device comprising the composition according to 1 or 2 above.</p><p> 15. A portable refrigeration or air conditioner comprising the composition according to 1 or 2 above.</p>