AU2020220053A1 - Compositions comprising fluoroolefins and uses thereof - Google Patents

Compositions comprising fluoroolefins and uses thereof Download PDF

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AU2020220053A1
AU2020220053A1 AU2020220053A AU2020220053A AU2020220053A1 AU 2020220053 A1 AU2020220053 A1 AU 2020220053A1 AU 2020220053 A AU2020220053 A AU 2020220053A AU 2020220053 A AU2020220053 A AU 2020220053A AU 2020220053 A1 AU2020220053 A1 AU 2020220053A1
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hfc
butene
trifluoromethyl
pentene
weight percent
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AU2020220053A
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Thomas J. Leck
Barbara Haviland Minor
Nandini Mouli
Mario Joseph Nappa
Deepak Perti
Velliyur Nott Mallikarjuna Rao
Corneille Schmitz
Allen Capron Sievert
Ekaterina N. Swearingen
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Chemours Co FC LLC
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Chemours Co FC LLC
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Priority claimed from AU2012229664A external-priority patent/AU2012229664B2/en
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Priority to AU2020220053A priority Critical patent/AU2020220053A1/en
Publication of AU2020220053A1 publication Critical patent/AU2020220053A1/en
Abandoned legal-status Critical Current

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Abstract

The present invention relates to fluoroolefin compositions. The fluoroolefin compositions of the present invention are useful as refrigerants or heat transfer fluids and in processes for producing cooling or heat. Additionally, the fluoroolefin compositions of the present invention may be used to replace currently used refrigerant or heat transfer fluid compositions that have higher global warming potential.

Description

P/00/011 Regulation 3.2
AUSTRALIA
Patents Act 1990
COMPLETE SPECIFICATION FOR A DIVISIONAL PATENT ORIGINAL
Name of Applicant: THE CHEMOURS COMPANY FC, LLC
Actual Inventors: SIEVERT, Allen Capron NAPPA, Mario Joseph MINOR, Barbara Haviland LECK, Thomas J. RAO, Velliyur Nott Mallikarjuna SWEARINGEN, Ekaterina N. SCHMITZ, Corneille MOULI, Nandini PERTI, Deepak
Address for Service: Houlihan2, Level 1, 70 Doncaster Road, Balwyn North, Victoria 3104, Australia
Invention Title: COMPOSITIONS COMPRISING FLUOROOLEFINS ANDUSESTHEREOF
The following statement is a full description of this invention, including the best method of performing it known to the Applicant:
COMPOSITIONS COMPRISING FLUOROOLEFINS AND USES THEREOF
The present Application is a Divisional Application from Australian Patent Application No. 2020213451, which is a Divisional of Application No. 2018282475, which is a Divisional of Application No. 2017201286, which is a Divisional of Application No. 2015202652, which is a Divisional of Application No. 2012229664 and in turn is a Divisional of Application No. 2006308717. The entire disclosures of Australian Patent Application No.s 2020213451, 2018282475, 2017201286, 2015202652, 2012229664, 2006308717 and their corresponding International Application No. PCT/US2006/042686, are incorporated herein by reference.
FIELD OF THE INVENTION The present invention relates to compositions for use in refrigeration, air-conditioning or heat pump systems wherein the composition comprises at least one fluoroolefin. The compositions of the present invention are useful in processes for producing refrigeration or heat, as heat transfer fluids and many other uses.
BACKGROUND OF THE INVENTION The refrigeration industry has been working for the past few decades to find replacement refrigerants for the ozone depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) being phased out as a result of the Montreal Protocol. The solution for most refrigerant producers has been the commercialization of hydrofluorocarbon (HFC) refrigerants. The new HFC refrigerants, HFC-134a being the most widely used at this time, have zero ozone depletion potential and thus are not affected by the current regulatory phase out as a result of the Montreal Protocol. Further environmental regulations may ultimately cause global phase out of certain HFC refrigerants. Currently, the automobile industry is facing regulations relating to global warming potential for refrigerants used in mobile air-conditioning. Therefore, there is a great current need to identify new refrigerants with reduced global warming potential for the mobile air conditioning market. Should the regulations be more broadly applied in the future, an even greater need will be felt for refrigerants that can be used in all areas of the refrigeration and air-conditioning industry. Currently proposed replacement refrigerants for HFC-134a include HFC-152a, pure hydrocarbons such as butane or propane, or
1A
"natural" refrigerants such as C02. Many of these suggested replacements are toxic, flammable, and/or have low energy efficiency. Therefore, new alternative refrigerants are being sought. The object of the present invention is to provide novel 5 refrigerant compositions and heat transfer fluid compositions that provide unique characteristics to meet the demands of low or zero ozone depletion potential and lower global warming potential as compared to current refrigerants.
10 BRIEF SUMMARY OF THE INVENTION The present invention relates to a refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of: (i) fluoroolefins of the formula E- or Z-RCH=CHR 2 , wherein 15 R 1 and R 2 are, independently, C1 to C perfluoroalkyl groups, and wherein the total number of carbons in the compound is at least 5; (ii) cyclic fluoroolefins of the formulacyclo-[CX=CY(CZW)n-], wherein X, Y, Z, and W, independently, are H or F, and n is an integer from 2 to 5; and (iii) fluoroolefins selected from the group consisting of: 2,3,3-trifluoro-1-propene (CHF 2CF=CH 2); 1,1,2-trifluoro 1-propene (CH 3CF=CF 2); 1,2,3-trifluoro-1-propene (CH 2FCF=CF 2); 1,1,3-trifluoro-1-propene (CH FCH=CF ); 2 2 1,3,3-trifluoro-1-propene (CHF 2CH=CHF); 1,1,1,2,3,4,4,4 octafluoro-2-butene (CF 3CF=CFCF 3); 1,1,2,3,3,4,4,4 octafluoro-1-butene (CF 3CF2CF=CF 2); 1,1,1,2,4,4,4 heptafluoro-2-butene (CF 3CF=CHCF 3); 1,2,3,3,4,4,4 heptafluoro-1-butene (CHF=CFCF 2CF 3); 1,1,1,2,3,4,4 heptafluoro-2-butene (CHF 2CF=CFCF 3); 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=CHCF 2CF 3); 1,1,2,3,4,4,4 heptafluoro-1-butene (CF 2=CFCHFCF 3); 1,1,2,3,3,4,4 heptafluoro-1-butene (CF 2=CFCF 2CHF 2); 2,3,3,4,4,4 hexafluoro-1-butene (CF 3CF 2CF=CH 2); 1,3,3,4,4,4 hexafluoro-1-butene (CHF=CHCF 2CF 3); 1,2,3,4,4,4 hexafluoro-1-butene (CHF=CFCHFCF3); 1,2,3,3,4,4 hexafluoro-1-butene (CHF=CFCF2CHF2); 1,1,2,3,4,4 hexafluoro-2-butene (CHF2CF=CFCHF 2); 1,1,1,2,3,4 hexafluoro-2-butene (CH 2FCF=CFCF 3); 1,1,1,2,4,4 5 hexafluoro-2-butene (CHF 2CH=CFCF3); 1,1,1,3,4,4 hexafluoro-2-butene (CF3CH=CFCHF2); 1,1,2,3,3,4 hexafluoro-1-butene (CF2=CFCF2 CH 2F); 1,1,2,3,4,4 hexafluoro-1-butene (CF2=CFCHFCHF 2); 3,3,3-trifluoro-2 (trifluoromethyl)-1-propene (CH 2=C(CF 3)2); 1,1,1,2,4 10 pentafluoro-2-butene (CH 2FCH=CFCF 3); 1,1,1,3,4 pentafluoro-2-butene (CF3CH=CFCH 2F); 3,3,4,4,4 pentafluoro-1-butene (CF3CF2CH=CH 2); 1,1,1,4,4 pentafluoro-2-butene (CHF 2CH=CHCF 3); 1,1,1,2,3 pentafluoro-2-butene (CH 3CF=CFCF 3); 2,3,3,4,4 15 pentafluoro-1-butene (CH 2=CFCF 2CHF 2); 1,1,2,4,4 pentafluoro-2-butene (CHF 2CF=CHCHF 2); 1,1,2,3,3 pentafluoro-1-butene (CH 3CF2 CF=CF 2); 1,1,2,3,4 pentafluoro-2-butene (CH 2FCF=CFCHF 2); 1,1,3,3,3 pentafluoro-2-methyl-1-propene (CF2=C(CF 3)(CH 3)); 2 (difluoromethyl)-3,3,3-trifluoro-1-propene (CH 2=C(CHF 2)(CF 3)); 2,3,4,4,4-pentafluoro-1-butene (CH 2=CFCHFCF 3); 1, 2 ,4,4,4-pentafluoro-1-butene (CHF=CFCH 2CF3); 1, 3 ,4,4,4-pentafluoro-1-butene (CHF=CHCHFCF3); 1,3,3,4,4-pentafluoro-1-butene (CHF=CHCF 2CHF 2); 1,2,3,4,4-pentafluoro-1-butene (CHF=CFCHFCHF2); 3,3,4,4-tetrafluoro-1-butene (CH 2=CHCF 2CHF 2); 1,1-difluoro-2-(difluoromethyl)-1 propene (CF 2=C(CHF 2 )(CH 3)); 1,3,3,3-tetrafluoro-2-methyl-1 propene (CHF=C(CF 3)(CH 3)); 3,3-difluoro-2-(difluoromethyl) 1-propene (CH 2=C(CHF 2)2); 1,1,1,2-tetrafluoro-2-butene (CF3CF=CHCH 3); 1,1,1,3-tetrafluoro-2-butene (CH 3CF=CHCF 3); 1,1,1,2,3,4 ,4 ,5,5,5-decafluoro-2-pentene (CF 3CF=CFCF 2CF 3); 1,1, 2 ,3 ,3 ,4,4,5,5,5-decafluoro-1 pentene (CF2=CFCF 2CF2CF 3); 1,1,1,4,4,4-hexafluoro-2 (trifluoromethyl)-2-butene ((CF 3 ) C=CHCF ); 2 3 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene(CF CF=CHCF 3 2CF3);
1,1,1, 3 ,4,4, 5 ,5,5-nonafluoro-2-pentene (CF CH=CFCF CF ); 3 2 3 1,2,3,3,4,4,5,5,5-nonafluoro-1-pentene (CHF=CFCF 2CF 2CF 3); 1,1,3,3,4,4,5,5,5-nonafluoro-1 pentene (CF 2=CHCF 2CF 2CF 3); 1,1,2,3,3,4,4,5,5-nonafluoro 5 1-pentene (CF 2=CFCF 2CF 2CHF 2); 1,1,2,3,4,4,5,5,5 nonafluoro-2-pentene (CHF 2CF=CFCF 2CF 3); 1,1,1,2,3,4,4,5 ,5-nonafluoro-2-pentene (CF 3CF=CFCF 2CHF 2); 1,1,1,2,3,4,5,5,5-nonafluoro-2 pentene (CF 3CF=CFCHFCF 3); 1,2,3,4,4,4-hexafluoro-3 (trifluoromethyl)-1-butene (CHF=CFCF(CF 3)2); 1,1,2,4,4,4 hexafluoro-3-(trifluoromethyl)-1-butene (CF 2=CFCH(CF ) 2); 3 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=CFCF2CF 2CF 3); 1,2,3,3,4,4,5,5-octafluoro-1 pentene (CHF=CFCF 2CF 2CHF 2); 3,3,4,4,4-pentafluoro-2 (trifluoromethyl)-1-butene (CH 2=C(CF 3)CF 2CF 3); 1,1,4,4,4 pentafluoro-3-(trifluoromethyl)-1-butene (CF 2 =CHCH(CF ) ); 3 2 1, 3 ,4 ,4 ,4 -pentafluoro-3-(trifluoromethyl)-1-butene (CHF=CHCF(CF 3)2); 1,1,4,4,4-pentafluoro-2 (trifluoromethyl)-1-butene (CF 2=C(CF 3)CH 2CF 3); 3,4,4,4 tetrafluoro-3-(trifluoromethyl)-1-butene ((CF 3)2CFCH=CH ); 2 3,3,4,4,5,5,5-heptafluoro-1-pentene (CF 3CF 2CF 2CH=CH 2); 2,3,3,4,4,5,5-heptafluoro-1-pentene (CH 2=CFCF CF CHF ); 2 2 2 1,1,3,3,5,5,5-heptafluoro-1-butene(CF 2=CHCF 2CH 2CF 3); 1,1,1,2,4,4,4-heptafluoro-3-methyl-2-butene (CF 3CF=C(CF 3)(CH 3)); 2,4,4,4-tetrafluoro-3-(trifluoromethyl) I-butene (CH 2=CFCH(CF 3)2); 1,4,4,4-tetrafluoro-3 (trifluoromethyl)-1-butene (CHF=CHCH(CF 3)2); 1,1,1,4 tetrafluoro-2-(trifluoromethyl)-2-butene (CH 2 FCH=C(CF 3 ) ); 2 1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-butene (CH 3 CF=C(CF 3 )2); 1,1,1-trifluoro-2-(trifluoromethyl)-2-butene ((CF 3) 2 C=CHCH 3 ); 3,4,4,5,5,5-hexafluoro-2-pentene (CF 3CF 2CF=CHCH3); 1,1,1,4,4,4-hexafluoro-2-methyl-2 butene (CF 3C(CH 3)=CHCF 3); 3 ,3,4,5,5,5-hexafluoro-1 pentene (CH 2=CHCF 2CHFCF 3); 4,4,4-trifluoro-3
(trifluoromethyl)-1-butene (CH 2=C(CF 3)CH CF ); 2 3 1,1, 2 ,3 ,3 ,4 ,4 ,5,5,6,6,6-dodecafluoro-1-hexene (CF 3(CF 2)3CF=CF 2); 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3 hexene (CF 3CF 2CF=CFCF 2CF 3); 1,1,1,4,4,4-hexafluoro-2,3 5 bis(trifluoromethyl)-2-butene ((CF 3) 2 C=C(CF 3) ); 2 1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)-2-pentene ((CF 3)2CFCF=CFCF 3); 1,1,1,4,4,5,5,5-octafluoro-2 (trifluoromethyl)-2-pentene ((CF 3)2C=CHC 2F5 ); 1,1,1,3,4 ,5,5,5-octafluoro-4-(trifluoromethyl)-2-pentene 10 ((CF3) 2CFCF=CHCF 3); 3,3,4,4,5,5,6,6,6-nonafluoro-1 hexene (CF 3 CF 2CF 2CF 2CH=CH 2); 4,4,4-trifluoro-3,3 bis(trifluoromethyl)-1-butene (CH 2=CHC(CF 3)3); 1,1,1,4,4,4 hexafluoro-2-(trifluoromethyl)-3-methyl-2-butene ((CF 3) 2 C=C(CH 3 )(CF 3)); 2,3,3,5,5,5-hexafluoro-4 (trifluoromethyl)-1-pentene (CH 2 =CFCF 2 CH(CF ) ); 3 2 1,1,1,2,4,4,5,5,5-nonafluoro-3-methyl-2-pentene (CF 3CF=C(CH 3)CF 2CF 3); 1,1,1,5,5,5-hexafluoro-4 (trifluoromethyl)-2-pentene (CF 3CH=CHCH(CF ) ); 32 3,4,4,5,5,6,6,6-octafluoro-2-hexene (CF 3CF 2CF 2CF=CHCH 3); 3,3,4,4,5,5,6,6-octafluorol-hexene (CH 2 =CHCF 2 CF 2 CF 2 CHF 2); 1,1,1,4,4-pentafluoro-2 (trifluoromethyl)-2-pentene ((CF 3)2C=CHCF2CH 3); 4,4,5,5,5 pentafluoro-2-(trifluoromethyl)-1-pentene (CH 2=C(CF 3)CH 2C 2F); 3,3,4,4,5,5,5-heptafluoro-2-methyl-1 pentene (CF 3 CF 2 CF 2 C(CH 3 )=CH 2 ); 4,4,5,5,6,6,6-heptafluoro 2-hexene (CF 3CF 2CF 2CH=CHCH 3); 4,4,5,5,6,6,6 heptafluoro-1-hexene (CH 2=CHCH 2CF 2C 2 F 5); 1,1,1,2,2,3,4 heptafluoro-3-hexene (CF 3CF 2CF=CFC 2H5 ); 4,5,5,5 tetrafluoro-4-(trifluoromethyl)-1-pentene (CH 2=CHCH 2CF(CF 3)2); 1,1,1,2,5,5,5-heptafluoro-4-methyl 2-pentene (CF 3CF=CHCH(CF 3)(CH 3)); 1,1,1,3-tetrafluoro-2 (trifluoromethyl)-2-pentene ((CF3) 2C=CFC H ); 2 5 1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene (CF 3CF=CFCF 2CF 2C 2F); 1,1,1,2,2,3,4,5,5,6,6,7,7,7 tetradecafluoro-3-heptene (CF3CF 2CF=CFCF C F); 2 2 1,1,1,3,4,4,5,5,6,6, 7 ,7 ,7 -tridecafluoro-2-heptene
(CF 3CH=CFCF 2CF2C2F); 1,1,1,2,4,4,5,5,6,6,7,7,7 tridecafluoro-2-heptene (CF 3CF=CHCF2CF 2C 2F); 1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF 3CF2CH=CFCF2C2F); 1,1,1,2,2,3,5,5,6,6,7,7,7 5 tridecafluoro-3-heptene (CF3CF2CF=CHCF C F); 2 2 CF2=CFOCF 2CF3 (PEVE) and CF2=CFOCF 3 (PMVE). The present invention further relates to a composition comprising: (i) at least one fluoroolefin compound; and (ii) at least one flammable refrigerant; wherein said fluoroolefin is selected from the group 10 consisting of: (a) fluoroolefins of the formula E- or Z-RCH=CHR2 , wherein R 1 and R 2 are, independently, C1 to C perfluoroalkyl groups; (b) cyclic fluoroolefins of the formula cyclo-[CX=CY(CZW)n-], wherein X, Y, Z, and W, independently, are H or F, and n is an 15 integer from 2 to 5; and (c) fluoroolefins selected from the group consisting of: 1, 2 ,3 ,3,3-pentafluoro-1-propene (CF3CF=CHF); 1,1,3,3,3 pentafluoro-1-propene (CF3CH=CF 2); 1,1,2,3,3-pentafluoro-1 propene (CHF 2CF=CF 2); 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=CHCF 3); 1,2,3,3,4,4,4-heptafluoro-1-butene (CHF=CFCF2 CF3); 1,1,1,2,3,4,4-heptafluoro-2-butene (CHF2CF=CFCF 3); 1,3,3,3-tetrafluoro-2-(trifluoromethyl)-1-propene ((CF 3)2C=CHF); 1,1,3,3,4,4,4-heptafluoro-1-butene (CF2=CHCF 2CF 3); 1,1,2,3,4,4,4-heptafluoro-1-butene (CF2=CFCHFCF 3); 1,1,2,3,3,4,4-heptafluoro-1-butene (CF2=CFCF2CHF 2); 2,3,3,4,4,4-hexafluoro-1-butene (CF 3CF 2CF=CH2); 1,3,3,4,4,4-hexafluoro-1-butene (CHF=CHCF 2CF3); 1,2,3,4,4,4-hexafluoro-1-butene (CHF=CFCHFCF3); 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=CFCF 3); 1,1,1,2,4,4-hexafluoro-2-butene (CHF 2CH=CFCF3); 1,1,1,3,4,4-hexafluoro-2-butene (CF3CH=CFCHF2); 1,1,2,3,3,4-hexafluoro-1-butene
(CF 2=CFCF 2CH 2F); 1,1,2,3,4,4-hexafluoro-1-butene (CF 2=CFCHFCHF 2); 3,3,3-trifluoro-2-(trifluoromethyl)-1-propene (CH 2=C(CF 3) 2 ); 1,1,1, 2 ,3 ,4 ,4 ,5,5,5-decafluoro-2-pentene (CF 3CF=CFCF 2CF 3); 1,1, 2 ,3 ,3 ,4 ,4,5,5,5-decafluoro-1-pentene 5 (CF 2=CFCF 2 CF 2 CF 3 ); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2 butene ((CF 3)2C=CHCF 3); 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene (CF 3CF=CHCF 2CF 3); 1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene (CF 3CH=CFCF 2CF 3); 1, 2 ,3,3,4,4,5,5,5-nonafluoro-1-pentene (CHF=CFCF 2CF 2CF 3); 1,1,3,3,4,4,5,5,5-nonafluoro-1-pentene 10 (CF 2=CHCF 2CF 2CF 3); 1 ,1 ,2,3,3,4,4,5,5-nonafluoro-1-pentene (CF 2=CFCF 2CF 2CHF 2); 1,1, 2 ,3 ,4 ,4 ,5,5,5-nonafluoro-2-pentene (CHF 2CF=CFCF 2CF 3); 1,1,1,2,3,4 ,4 ,5 ,5-nonafluoro-2-pentene (CF 3CF=CFCF 2CHF 2); 1,1,1, 2 ,3 ,4 ,5,5,5-nonafluoro-2-pentene (CF 3CF=CFCHFCF 3); 1, 2 ,3 ,4 ,4,4-hexafluoro-3-(trifluoromethyl)-1 15 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 CH=C(CF ) ); 3 32 1,1, 3 ,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene (CF 2 =CHCF(CF 3) 2); 2 ,3 ,3, 4 ,4,5,5,5-octafluoro-1-pentene (CH 2=CFCF 2CF 2CF 3); 1, 2 ,3 ,3 ,4 ,4,5,5-octafluoro-1-pentene (CHF=CFCF 2CF 2CHF 2); 3, 3 ,4 ,4 ,4 -pentafluoro-2-(trifluoromethyl)-1 butene (CH 2=C(CF 3)CF 2CF 3); 1,1,4,4,4-pentafluoro-3 (trifluoromethyl)-1-butene (CF 2=CHCH(CF 3)2); 1,3,4,4,4 pentafluoro-3-(trifluoromethyl)-l-butene (CHF=CHCF(CF ) ); 32 1,1, 4 ,4 ,4 -pentafluoro-2-(trifluoromethyl)-1-butene (CF2=C(CF 3)CH 2CF 3); 3 ,4 ,4,4-tetrafluoro-3-(trifluoromethyl)-1 butene ((CF 3)2CFCH=CH 2); 3 ,3 ,4 ,4 ,5,5,5-heptafluoro-1-pentene (CF 3CF 2CF 2CH=CH 2); 2,3,3,4,4,5,5-heptafluoro-1-pentene (CH 2=CFCF2CF 2CHF 2); 1,1,3,3,5,5,5-heptafluoro-1-butene (CF 2 =CHCF 2 CH 2 CF 3 ); 1,1,1, 2 ,4 ,4 ,4-heptafluoro-3-methyl-2-butene (CF 3CF=C(CF 3)(CH 3)); 2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1 butene (CH 2=CFCH(CF 3)2); 1, 4 ,4 ,4-tetrafluoro-3-(trifluoromethyl)-1 butene (CHF=CHCH(CF 3)2); 1,1,1,4-tetrafluoro-2-(trifluoromethyl) 2-butene (CH 2FCH=C(CF 3)2); 1,1,1,3-tetrafluoro-2-(trifluoromethy) 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(CF 2)3CF=CF 2); 1,1,1,2,2,3,4,5,5,,6,6-dodecafluoro-3 hexene (CF 3CF 2 CF=CFCF 2CF 3); 1,1,1,4,4,4-hexafluoro-2,3 bis(trifluoromethyl)-2-butene ((CF 3 )2 C=C(CF 3 ) 2); 1,1,1,2,3,4,5,5,5 nonafluoro-4-(trifluoromethyl)-2-pentene ((CF ) CFCF=CFCF 32 3); 1, 11,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-pentene 5 ((CF 3)2C=CHC 2F); 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2 pentene ((CF 3)2CFClF=CHCF 3); 3 ,3 ,4,4,5,5,6,6,6-nonafluoro-1 hexene (CF 3CF 2CF 2CF 2CH=CH 2); 4,4,4-trifluoro-3,3 bis(trifluoromethyl)-1-butene (CH 2=CHC(CF 3 ) 3); 1,1,1,4,4,4 hexafluoro-2-(trifluoromethyl)-3-methyl-2-butene 10 ((CF 3) 2 C=C(CH 3 )(CF 3)); 2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1 pentene (CH 2=CFCF 2CH(CF 3)2); 1,1,1, 2 ,4,4,5,5,5-nonafluoro-3 methyl-2-pentene (CF 3CF=C(CH 3)CF 2CF 3); 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=CFCF 2CF 2C 2F); 1,1,1,2,2,3,4,5,5,6,6,7,7,7 tetradecafluoro-3-heptene (CF 3CF 2CF=CFCF C F ); 2 25 1,1,1,3,4 ,4 ,5,5, 6 ,6,7,7,7-tridecafluoro-2-heptene (CF 3CH=CFCF 2CF 2C 2F 5); 1,1,1, 2 ,4 ,4 ,5,5,6,6,7,7,7-tridecafluoro-2 heptene (CF 3CF=CHCF 2CF 2C 2F); 1,1,1,2,2,4,5,5,6,6,7,7,7 tridecafluoro-3-heptene (CF 3CF 2CH=CFCF 2C 2F5); and 1,1,1,2,2 ,3 ,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF 3CF 2CF=CHCF 2C 2F5 ). The present invention further relates to a method of using a refrigerant or heat transfer fluid composition in refrigeration, air conditioning, or heat pump apparatus, said method comprising introducing said composition into said apparatus having (a) centrifugal compressor; (b) multi-stage centrifugal compressor, or (c) single slab/single pass heat exchanger; wherein said refrigerant or heat transfer composition is employed in said apparatus to result in heating or cooling; and wherein said refrigerant or heat transfer composition comprises at least one fluoroolefin selected from the group consisting of: (i) fluoroolefins of the formula E- or Z-R'CH=CHR 2 , wherein R1 and R2 are, independently, C1 to C6 perfluoroalkyl groups,; (ii) cyclic fluoroolefins of the formula cyclo-[CX=CY(CZW)n-], wherein X, Y, Z, and W, independently, are H or F, and n is an integer from 2 to 5; or
(iii) fluoroolefins selected from the group consisting of: 1, 2 ,3, 3 ,3-pentafluoro-1-propene (CF 3CF=CHF); 1,1, 3 ,3, 3 -pentafluoro-1 propene (CF 3CH=CF 2); 1,1,2,3,3-pentafluoro-1-propene (CHF CF=CF 2 2); 1,2,3,3-tetrafluoro-1-propene (CHF 2CF=CHF); 2,3,3,3-tetrafluoro-1 5 propene (CF 3CF=CH 2); 1,3,3,3-tetrafluoro-1-propene (CF 3CH=CHF); 1,1,2,3-tetrafluoro-1-propene (CH 2FCF=CF 2); 1,1,3,3-tetrafluoro-1 propene (CHF2CH=CF 2); 2,3,3-trifluoro-1-propene (CHF 2 CF=CH ); 3,3,3 2 trifluoro-1-propene (CF 3CH=CH 2); 1,1,2-trifluoro-1-propene (CH 3CF=CF 2
) 1,1,3-trifluoro-1-propene (CH 2FCH=CF 2); 1,2,3-trifluoro-1-propene 10 (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=CFCF 3); 1,1,2,3,3,4,4,4 octafluoro-1-butene (CF 3CF 2CF=CF 2); 1,1,1, 2 ,4,4,4-heptafluoro-2-butene (CF 3CF=CHCF 3); 1, 2 ,3 ,3,4,4,4-heptafluoro-1-butene (CHF=CFCF 2CF 3); 1,1,1,2,3,4,4-heptafluoro-2-butene (CHF 2CF=CFCF ); 1,3,3,3-tetrafluoro 3 2-(trifluoromethyl)-1-propene ((CF 3)2C=CHF); 1,1,3,3,4,4,4-heptafluoro-1 butene (CF 2=CHCF 2CF 3); 1,1,2,3,4,4,4-heptafluoro-1-butene (CF 2=CFCHFCF 3); 1,1,2,3,3,4,4-heptafluoro-1-butene (CF =CFCF 2 2CHF 2
) 2,3,3,4,4,4-hexafluoro-1-butene (CF 3CF 2CF=CH 2); 1,3,3,4,4,4-hexafluoro 1-butene (CHF=CHCF 2CF 3); 1,2,3,4,4,4-hexafluoro-1-butene (CHF=CFCHFCF 3); 1,2,3,3,4,4-hexafluoro-1-butene (CHF=CFCF CHF 2 2); 1,1,2,3,4,4-hexafluoro-2-butene (CHF 2CF=CFCHF 2); 1,1,1,2,3,4 hexafluoro-2-butene (CH 2 FCF=CFCF 3); 1,1,1,2,4,4-hexafluoro-2-butene (CHF 2CH=CFCF 3); 1,1,1,3,4,4-hexafluoro-2-butene (CF CH=CFCHF 3 2); 1,1,2,3,3,4-hexafluoro-1-butene (CF 2=CFCF2CH 2F); 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=CFCF 3); 1,1,1,3,4-pentafluoro-2-butene (CF CH=CFCH F); 3 2 3,3,4,4,4-pentafluoro-1-butene (CF 3CF 2CH=CH 2); 1,1,1,4,4-pentafluoro-2 butene (CHF 2CH=CHCF 3); 1,1,1,2,3-pentafluoro-2-butene (CH 3CF=CFCF 3); 2, 3 ,3,4,4-pentafluoro-1-butene (CH =CFCF 2 2CHF 2 )
1,1, 2 ,4,4-pentafluoro-2-butene (CHF 2CF=CHCHF 2); 1,1,2,3,3-pentafluoro 1-butene (CH 3CF 2CF=CF 2); 1,1,2,3 ,4-pentafluoro-2-butene (CH 2 FCF=CFCHF 2); 1,1,3,3,3-pentafluoro-2-methyl-l-propene (CF 2 =C(CF 3)(CH 3)); 2-(difluoromethyl)-3,3,3-trifluoro-1-propene (CH 2=C(CHF2)(CF 3)); 2,3,4,4,4-pentafluoro-1-butene (CH =CFCHFCF 2 3); 1,2,4,4,4-pentafluoro-1-butene (CHF=CFCH 2CF 3); 1,3,4,4,4-pentafluoro-1 butene (CHF=CHCHFCF 3); 1,3,3,4,4-pentafluoro-1-butene (CHF=CHCF 2CHF 2); 1,2,3,4,4-pentafluoro-1-butene (CHF=CFCHFCHF 2); 3,3,4,4-tetrafluoro-1-butene (CH 2=CHCF 2CHF 2); 1,1-difluoro-2 (difluoromethyl)-1-propene (CF 2=C(CHF 2)(CH 3)); 1,3,3,3-tetrafluoro-2 5 methyl-I-propene (CHF=C(CF 3)(CH 3)); 2-difluoromethyl-3,3-difluoro-1 propene (CH 2=C(CHF 2) 2 ); 1,1,1,2-tetrafluoro-2-butene (CF CF=CHCH 3 3); 1,1,1,3-tetrafluoro-2-butene (CH 3CF=CHCF 3); 1,1,1,2,3,4,4,5,5,5 decafluoro-2-pentene (CF 3CF=CFCF 2CF 3); 1,1,2,3,3,4,4,5,5,5-decafluoro I-pentene (CF 2=CFCF 2CF 2CF 3); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl) 10 2-butene ((CF 3)2C=CHCF 3); 1,1,1, 2 ,4 ,4 ,5,5,5-nonafluoro-2-pentene (CF 3CF=CHCF 2CF 3); 1,1,1, 3 ,4 ,4 ,5,5,5-nonafluoro-2-pentene (CF 3CH=CFCF 2CF 3); 1, 2 ,3 ,3, 4 ,4,5,5,5-nonafluoro-1-pentene (CHF=CFCF 2CF 2CF 3); 1,1,3,3 ,4 ,4 ,5,5,5-nonafluoro-1-pentene (CF 2=CHCF 2CF 2CF 3); 1,1, 2 ,3,3,4,4,5,5-nonafluoro-1-pentene (CF 2=CFCF2 CF 2CHF 2); 1,1, 2 ,3 ,4 ,4 ,5,5,5-nonafluoro-2-pentene (CHF 2CF=CFCF 2CF 3); 1,1,1, 2 ,3 ,4 ,4 ,5,5-nonafluoro-2-pentene (CF 3CF=CFCF 2CHF 2); 1,1,1, 2 ,3 ,4 ,5,5,5-nonafluoro-2-pentene (CF 3CF=CFCHFCF 3); 1, 2 ,3 ,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene (CHF=CFCF(CF3)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 =CFCF 2 CF 2 CF 3 ); 1,2,3,3,4,4 ,5 ,5-octafluoro-1-pentene (CHF=CFCF 2CF 2CHF2); 3 ,3 ,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene (CH 2=C(CF 3)CF 2CF 3); 1,1, 4 ,4,4-pentafluoro-3-(trifluoromethyl)-l-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 (CF2=C(CF 3)CH 2CF 3); 3 ,4 ,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene ((CF 3)2CFCH=CH 2); 3,3,4,4,5,5,5-heptafluoro-1-pentene (CF 3CF 2CF 2CH=CH 2); 2,3,3,4,4,5,5-heptafluoro-1-pentene (CH 2 =CFCF 2 CF 2 CHF 2); 1,1,3,3,5,5,5-heptafluoro-1-butene (CF 2=CHCF 2CH 2CF 3); 1,1,1, 2 ,4 ,4,4-heptafluoro-3-methyl-2-butene (CF 3CF=C(CF 3)(CH 3)); 2 ,4 ,4 ,4-tetrafluoro-3-(trifluoromethyl)-1-butene (CH 2=CFCH(CF3)2); 1,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene (CHF=CHCH(CF 3)2); 1,1,1, 4 -tetrafluoro-2-(trifluoromethyl)-2-butene (CH 2 FCH=C(CF 3)2); 1,1,1, 3 -tetrafluoro-2-(trifluoromethyl)-2-butene
(CH 3CF=C(CF 3)2); 1,1,1-trifluoro-2-(trifluoromethyl)-2-butene ((CF 3)2C=CHCH 3); 3,4,4,5,5,5-hexafluoro-2-pentene (CF 3CF 2CF=CHCH ); 3 1,1,1, 4 ,4 ,4 -hexafluoro-2-methyl-2-butene (CF C(CH )=CHCF 3 3 3); 3 ,3,4,5,5,5-hexafluoro-1-pentene (CH 2=CHCF 2CHFCF ); 3 3 5 (trifluoromethyl)-4,4,4-trifluoro-1-butene (CH =C(CF )CH 2 3 2 CF 3); 1,1, 2 ,3 ,3 ,4 ,4 ,5,5,6,6,6-dodecafluoro-1-hexene (CF (CF ) CF=CF 3 23 2); 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene(CF CF CF=CFCF 3 2 2CF 3); 1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)-2-butene ((CF ) C=C(CF 3 ) 2); 3 2 1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)-2-pentene 10 ((CF 3)2CFCF=CFCF 3); 1,1,1, 4 ,4 ,5,5,5-octafluoro-2-(trifluoromethyl)-2 pentene ((CF 3)2C=CHC 2F); 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl) 2-pentene ((CF 3)2CFCF=CHCF 3); 3 ,3 ,4 ,4 ,5,5,6,6,6-nonafluoro-1-hexene (CF 3CF 2CF 2CF 2CH=CH 2); 4,4,4-trifluoro-3,3-bis(trifluoromethyl)-1-butene (CH 2=CHC(CF 3)3); 1,1,1, 4 ,4 ,4-hexafluoro-3-methyl-2-(trifluoromethyl)-2 butene ((CF 3)2C=C(CH 3)(CF 3)); 2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl) I-pentene (CH 2=CFCF 2CH(CF 3)2); 1,1,1,2,4,4,5,5,5-nonafluoro-3-methyl 2-pentene (CF 3CF=C(CH 3)CF 2CF 3); 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 3CF 2CF 2CF=CHCH 3); 3 ,3, 4 ,4,5,5,6,6-octafluoro-1 hexene (CH 2=CHCF 2CF 2CF 2CHF 2); 1,1,1,4,4-pentafluoro-2 (trifluoromethyl)-2-pentene ((CF 3)2C=CHCF 2CH 3); 4,4,5,5,5-pentafluoro-2 (trifluoromethyl)-1-pentene (CH 2 =C(CF 3 )CH 2 C 2 F); 3,3,4,4,5,5,5 heptafluoro-2-methyl-1-pentene (CF 3CF 2CF 2C(CH 3)=CH 2); 4,4,5,5,6,6,6 heptafluoro-2-hexene (CF 3CF 2CF 2CH=CHCH 3); 4,4,5,5,6,6,6-heptafluoro 1-hexene (CH 2=CHCH2CF 2C 2F5); 1,1,1, 2 ,2 ,3,4-heptafluoro-3-hexene (CF 3CF 2CF=CFC 2 H 5); 4,5,5,5-tetrafluoro-4-trifluoromethyl-l-pentene (CH 2=CHCH 2CF(CF 3)2); 1,1,1,2,5,5,5-heptafluoro-4-methyl-2-pentene (CF 3CF=CHCH(CF 3)(CH 3)); 1,1,1, 3 -tetrafluoro-2-trifluoromethyl-2-pentene ((CF 3)2C=CFC 2H); 1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene (CF 3CF=CFCF 2CF 2C 2F 5); 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoro-3 heptene (CF 3CF 2CF=CFCF 2C 2F); 1,1,1, 3 ,4 ,4 ,5,5,6,6,7,7,7-tridecafluoro 2-heptene (CF 3CH=CFCF 2CF 2C 2F); 1,1,1,2,4,4,5,5,6,6,7,7,7 tridecafluoro-2-heptene (CF3CF=CHCF 2CF C F); 2 2 1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene(CF CF CH=CFCF 3 2 2C 2F); 1,1,1,2,2,3,5,5,6 ,6 ,7 ,7 ,7 -tridecafluoro-3-heptene (CF CF CF=CHCF 3 2 2C 2F);
CF 2=CFOCF 2CF 3 (PEVE); CF 2=CFOCF 3 (PMVE) and combinations thereof.
DETAILED DESCRIPTION OF THE INVENTION 5 The present invention relates to compositions comprising at least one fluoroolefin. By fluoroolefin is meant any compound containing carbon, fluorine and optionally, hydrogen or oxygen that also contains at least one double bond. These fluoroolefins may be linear, branched or cyclic. 10 These compositions have a variety of utilities in working fluids, which include use as foaming agents, blowing agents,fire extinguishing agents, heat transfer mediums (such as heat transfer fluids and refrigerants for use in refrigeration systems, refrigerators, air-conditioning systems, heat pumps, chillers, and the like), to name a few. 15 A heat transfer fluid (also referred to herein as a heat transfer composition or heat transfer fluid composition) is a working fluid used to carry heat from a heat source to a heat sink. A refrigerant is a compound or mixture of compounds that function as a heat transfer fluid in a cycle wherein the fluid undergoes a phase change from a liquid to a gas and back. The present invention provides fluoroolefins having the formula E- or Z-R'CH=CHR2 (Formula 1), wherein R 1 and R2 are, independently, C 1 to C6perfluoroalkyl groups. Examples of R 1 and R2 groups include, but are not limited to, CF 3 , C 2F, CF 2CF 2CF 3, CF(CF ) , CF CF CF 32 2 2 2CF 3 ,
CF(CF 3)CF 2CF 3, CF 2CF(CF 3)2, C(CF ) , CF CF CF CF 3 3 2 2 2 2CF 3 ,
CF 2 CF 2 CF(CF 3) 2 , C(CF 3) 2 C 2 F 5 , CF 2CF CF CF CF CF 2 2 2 2 3, CF(CF 3 )
CF 2CF 2C 2F, and C(CF 3)2CF 2C 2 F. In one embodiment the fluoroolefins of Formula I, have at least about 3 carbon atoms in the molecule. In another embodiment, the fluoroolefins of Formula I have at least about 4 carbon atoms in the molecule. In yet another embodiment, the fluoroolefins of Formula I have at least about 5 carbon atoms in the molecule. Exemplary, non-limiting Formula I compounds are presented in Table 1.
TABLEI
Code StructureChmclN e MlE CF 3CH=CHCF 3 1,1, 4 4, ,4-hexafluoro-2-butene F12E CF 3CH=CHC 2F5 1, 1 1I, 4 ,4 ,5,5,-octafluoro..2-pentene F13E CF 3CH=CHCF 2C 2F5, 1,1,I1, 4 ,4 ,5,5,6 6, ,6 -decafluoro-2-hexene F1 NE CF 3CH=CHCF(CF 3)2 1, 1, 4S,S,-heptaluoro-4-(trifluoromethy)2pentene F22E C 2F 5CH=CHC 2F5, 1, 1,I1, 2 ,2 ,5,5,6 ,6 ,6-decafluoro-3-hexene F14E CF 3CH=CH(CF 2)3CF 3 1 ,5,,,, ,1oealor--etn F14iE CF3C=CHC2CF(F3)21, 1, 1, 4 ,4 ,, 6, 6 6 -nonafluoro-5..(trifluoromethyl)-2 FI~i CFCH=HCF 2 F~c 3 )2 hexene 14sE CF 3CH=CHCF(CF 3)C 2F 5 1,1,1,4,5,, 6 ,6 ,6-nonfiuoro-4-(trifluoromethyl)2hexene F14tE C3CH=CH(CF3)31, 1,1,5,5,5-hexafluoro-4,4-bis(trifluoromethyj)-2 F14t CFCH=CC~c 3)3 pentene F23E C 2Ff)CH=CHCF 2C 2F 5 1,1,1,2,2,5,5,6,6,7,7,7-dodecafluoro-3-heptene F23iE C2F5CH=CHCF(CF 3)2 1, 1, 1,2 ,2 ,5 ,6 ,6 ,6-nonafiuoro-5-(trifluoromethy )-3 hexene F15E CF 3CH=CH(CF 2)4CF3 1,1, 1, 4 ,4 ,5,5, 6 ,6 ,7 ,7,8,8,8-tetradecafluoro-2-octene FI'5iE CF 3CH=CH-CF 2CF 2CF(CF 3)2 1, 1, 1,4,4,5,5,6,7 ,7 , 7-undecafluoro-6-(trifluoromethyi)-2 heptene F5E CF 3CH=CH-C(CF 3)2C2Fr, 1,1,1,5,5,6 ,6 ,6 -octafluoro-4,4-bis(trifluoromethyl)-2 Fl~tEhexene F24E C 2F 5CH=CH(CF 2)3CF 3 1,1,1, 2,2,S,5,6,6 ,7,7,8,8,8-tetradecafluoro-3-octene C 2F 5H=CCF2 F(C 3)2 1, 1,1,2,2,5,5,6 ,7 ,7 ,7-undecafluoro-6-(trifluoromethy).3 F24iE C25HCC2FC32heptene
F24sE C2F5H=CHC(CF3C2F51,1,1, 2 ,2,5, 6 6 7 ,7,7-undecafluoro-5-(trifluoromethy;)-3 F24s 2FCH=CCFCFC C 2F 5 heptene F24tE C2F5C=CHC(F3)31, 1, 1, 2 , 2 6,6,6-octafluoro-5,5-bis(trifluoromethyj)-3 F24t 2FCH=HC~c C 3)3 hexene F3-3E C2F5CF 2CH=CHCF 2C 2F5 1,1,1, 2,2 ,3 ,3 ,6 ,6 , 7 7,8,8,8-tetradecafluoro-4-octene F3i0E (CF 3)2CFCH=CHCF(CF 3)2 1,1,1, 2,, 6 ,6,6-octafluoro-2,5-bis(trifluoromethyl)-3 hexene F33iE C2FSCF 2CH=CHCF(CF 3)2 1, 1, 1,2,5,5,6,6,7,7,7 -undecafluoro-2-(trifluoromethyl)-3
F16E CF 3CH=CH(CF 2)f5CF 3 1,l,l1,4 ,4 ,5,5,6,6,7,7,8,8,,9,9,9-exadecafuro-2. nonene Fl6sE CF 3CH=CHCF(CF 3)(CF 2)2C 2Fs 1, 1,1, 4 ,5,5,6,6,7,7,8,8,8-tridecafluoro-4 (trifiuoromethyl)-2-heptene Fl6tE CF 3CH=CHC(CF 3)2CF 2C 2F 5 1,1,1, 6 6 ,6 -octafluoro-4,4-bis(trifluoromethy)2 heptene F25E 2F5CHCH(CF)4CF31, 1,1, 2, 2,S,5, 6,6,7,7,8,8,9,9,9-hexadecafluoro-3 F25E 2F 5 H=CHCF C 2)CF 3 nonene F25iE C2F5CH=CH-CF 2CF 2CF(CF 3)2 1, 1, 1, 2 ,2 5,5,6,6,7,8,8,8-tridecaflujoro-7 _________________________(trifluoromethyl)-3octene
F25t C2FCH=H-C(~s)22F51, 1,1,2,2,6,6,7,7,7-decafluoro-5,5-bis(trifluoromethyi)-3 C 2 5CHC-C(F F25t 3)2 2Fsheptene
F34E C 2FsCF 2CH=CH-(CF 2)3CF3 1,AA,2,2,3,3,6,6,7,7,8,8,9,9,9-hexadecafluoro-4
F34iE 1,1,1,2,2,3,3,6,6,7,8,8,8-tridecafluoro-7 C 2FgCF 2CH=CH- CF2CF(CF 3)2 (trifluoromethyl)-4-octene 2 5 ~FCCC(F) F34sE ~ ~ ~ 2~ ~ 11,2,2,3,3,6,7,7,8,8,8-tridecafuoro-6 1 1 F34s C25CFCH=CCF(F3)2F5 (trifluoromethyl)-4-octene F4E C 2F 5CF2CH=CHC(CF 3)3 1, 1,1,5,5,6,6,7,7,7decafuoro-2,2-bis(trifluoromethyI)-3 F34tEheptene 'F~4E (CF 3)2CFCH=CH(CF 2)3CF 3 1,1,1,2,5,5,6,6,7,7,8,8,8-tridecafluoro-2(trifuoromethyt) F~i4E3-octene
F314E (CF 3)2CFCH=CHCF 2CF(CF 3)2 1,1 1,2,5,5,6,7,7,7-decafluoro-2,6-bis(trifluoromethYl)-3 heptene F~isE (CF 3)2CFCH=CHCF(CF 3)C 2F 5 1, 1,1,2,5,6,6,7,7,7decafuoro-2,5-bis(tfluoromethyi)-3 F~i~sEheptene 3 3)2 FCH=HC(C F~i~E 1,,1,2,6,6,6-heptafluoro-2,5,5-tris(trifluoromethyI)- (C (C3)2FCH=HC(C3)3hexene 3 3 F~i~E C2Ff5CH=CH(CF 2)5qCF3 0-octadecaftuoro-3 1,1, 1,2,2,5,5,6,6,7,7,8,8,9,9,10,10,1 F6' F26E decene F26sE C7FfCH=CHCF(CF 3)(CF 2)2C2F5 111 ,,, ,, ,,8,9,9,9-pentadecafiuoro-5 (trifluoromethyl)-3-nolefle
F26tE C 2F5CH=CHC(CFa) 2- CF 2C2F5 1,1,1,2,2,6,6,7,7,8,8,8-dodecafluoro-5,5 bis(trifluoromethyl)-3-octefle F35E C2F5CF 2CH=CH-(CF 2)4CF 3 1,1, 1, 2 ,2,3,3,6,6,7,7,8,8,9,9,10,10,10-octadecafluoro-,4 F35E decene
F5E35E C 2F.5 CF)2CH=CHCF 2CF2 m 1,1,1,2,2,3,3,6,6,7,7,8,9,9,9-pentadecafluoro-8 CF(CF 32 (trifluoromethyl)-4-nolefle
F35tE C2F5CF2CH=CH-C(CF 3)2C 2F5, 1,1,1,2,2,3,3,7,7,8,8,8-dodecafluoro-6,6 bis(trifluoromethyl)-4-octefle F~5E (CF 3)2 GFCH=CH-(CF 2)4CF 3 1,1,1,2,5,5,6,6,7,7,8,8,9,9,9-pentadecafuoro-2 F~i5E (irifluoromethyl)-3-flofefle 5E (CF 3)2CFCH=CHCF 2CF 2- 1,1,1,2,5,5,6,6,7,8,8,8-dodecafluoro-2,7 F~i CF(CF 3)2 bis(trifluoromethyl -3-octene
F~itE CF32CFH=CC(C3)22F5 1,1,1,2,6,6,7,7,7nonafuoro-2,5,5-Stris~~fluoromTethyI) (F 3)2 FCHHC(C F~i~E 3)2 2F 6 3-heptene F4E CF 3(CF 2)3CH=CH(CF 2)30F3 1, 1,1,2,2,3,3,4,4,7,7,8,8,9,9,10,10,1 0-octadecafluoro-5 F44E decene
F44iE CF3(0F 2)3CH=CH-CF 2CF(CF 3)2 1,1,1,2,3,3,6,6,7,7,8,8,9,9,9-pentadecafluoro-2 (trifluoromethyD-4-flofefle F4E CF3(CF 2)3CH=CHCF(CF 3)C 2F5 1 , 1, ,,,, ,,8,9,9,9-pentadecafiuoro-3 (trifluoromethyD-4-flofefle F4E CF 3(CF 2)3CH=CHC(CF 3)3 1,1,1,5,5,6,6,7,7,8,8,8-dodecafluoro-2,2, F44tE bis(trifluoromethyl)-3octefle
F44iE (CF 3) 2CFCF 2CH=CHCF 2CF- 1,1,1,2,3,3,6,6,7,8,8,8-dodecafluoro-2,7 (CF 3 ) 2 bis(trifluoromethyl)-4-octene
F~i4sE (CF 3)2CFCF 2CH=CHCF(CF 3 )- 1,1,1,2,3,3,6,7,7,8,8,8-dodecafluoro-2,6 C 2 F5 bis(trifiuoromethyl)-4-octene
Fi4tE (CF 3)2CFCF 2CH=CHC(CF 3 )3 1,1,15,5,6,7,7,7-nonafluoro-2,2,6-tris(trifluoromethyl) 3-heptene
F4s4sE C 2F 5CF(CF)CH=CH- 1,1,1,2,2,3,6,7,7,8,8,8-dodecafluoro-3,6 CF(CF 3 )C 2 F5 bis(trifluoromethyl)-4-octene
F4s4tE 2F 5CF(CF 3)CH=CH- C(CF3 )3 CF~s~tE3-heptene 1,1,1,5,6,6,7,7,7-nonafluoro-2,2,5-tris(trifluoromethyl)
F4t4tE (CF3)aCCH=CH- C(CF3)) '11,1,6,6,6-hexafluoro-2,2,5,5-tetrakis(trifluoromethyl) 3)3 CH=C-C(C F~t~E (C 33 3-hexene
Compounds of Formula I may be prepared by contacting a perfluoroalkyl iodide of the formula R1l with a perfluoroalkyltrihydroolefin of the formula R2CH=CH 2 to form a trihydroiodoperfluoroalkane of the formula R 1 CH 2CHIR 2 . This trihydroiodoperfluoroalkane can then be dehydroiodinated to form RCH=CHR 2. Alternatively, the olefin RCH=CHR 2 may be prepared by dehydroiodination of a trihydroiodoperfluoroalkane of the formula R'CHICH 2R 2 formed in turn by reacting a perfluoroalkyl iodide of the formula R21with a perfluoroalkyltrihydroolefin of the formula R'CH=CH 2 .
Said contacting of a perfluoroalkyl iodide with a perfluoroalkyltrihydroolefin may take place in batch mode by combining the reactants in a suitable reaction vessel capable of operating under the autogenous pressure of the reactants and products at reaction temperature. Suitable reaction vessels include fabricated from stainless steels, in particular of the austenitic type, and the well-known high nickel alloys such as Monel@ nickel-copper alloys, Hastelloy@ nickel based alloys and Inconel@ nickel-chromium alloys. Alternatively, the reaction may take be conducted in semi-batch mode in which the perfluoroalkyltrihydroolefin reactant is added to the perfluoroakyl iodide reactant by means of a suitable addition apparatus such as a pump at the reaction temperature. The ratio of perfluoroalkyl iodide to perfluoroalkyltrihydroolefin should be between about 1:1 to about 4:1, preferably from about 1.5:1 to 2.5:1. Ratios less than 1.5:1 tend to result in large amounts of the 2:1 adduct as reported by Jeanneaux, et. al. in Journal of Fluorine Chemistry, Vol. 4, pages 261-270 (1974).
Preferred temperatures for contacting of said perfluoroalkyl iodide with said perfluoroalkyltrihydroolefin are preferably within the range of about 1500C to 300°C, preferably from about 1700C to about 2500C, and most preferably from about 1800C to about 2300C. 5 Suitable contact times for the reaction of the perfluoroalkyl iodide with the perfluoroalkyltrihydroolefin are from about 0.5 hour to 18 hours, preferably from about 4 to about 12 hours. The trihydroiodoperfluoroalkane prepared by reaction of the perfluoroalkyl iodide with the perfluoroalkyltrihydroolefin may be used 10 directly in the dehydroiodination step or may preferably be recovered and purified by distillation prior to the dehydroiodination step. The dehydroiodination step is carried out by contacting the trihydroiodoperfluoroalkane with a basic substance. Suitable basic substances include alkali metal hydroxides (e.g., sodium hydroxide or 15 potassium hydroxide), alkali metal oxide (for example, sodium oxide), alkaline earth metal hydroxides (e.g., calcium hydroxide), alkaline earth metal oxides (e.g., calcium oxide), alkali metal alkoxides (e.g., sodium methoxide or sodium ethoxide), aqueous ammonia, sodium amide, or mixtures of basic substances such as soda lime. Preferred basic substances are sodium hydroxide and potassium hydroxide. Said contacting of the trihydroiodoperfluoroalkane with a basic substance may take place in the liquid phase preferably in the presence of a solvent capable of dissolving at least a portion of both reactants. Solvents suitable for the dehydroiodination step include one or more polar organic solvents such as alcohols (e.g., methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and tertiary butanol), nitriles (e.g., acetonitrile, propionitrile, butyronitrile, benzonitrile, or adiponitrile), dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, or sulfolane. The choice of solvent may depend on the boiling point product and the ease of separation of traces of the solvent from the product during purification. Typically, ethanol or isopropanol are good solvents for the reaction. Typically, the dehydroiodination reaction may be carried out by addition of one of the reactants (either the basic substance or the trihydroiodoperfluoroalkane) to the other reactant in a suitable reaction vessel. Said reaction may be fabricated from glass, ceramic, or metal and is preferably agitated with an impeller or stirring mechanism. Temperatures suitable for the dehydroiodination reaction are from about 10°C to about 100°C, preferably from about 200C to about 5 700C. The dehydroiodination reaction may be carried out at ambient pressure or at reduced or elevated pressure. Of note are dehydroiodination reactions in which the compound of Formula I is distilled out of the reaction vessel as it is formed. Alternatively, the dehydroiodination reaction may be conducted 10 by contacting an aqueous solution of said basic substance with a solution of the trihydroiodoperfluoroalkane in one or more organic solvents of lower polarity such as an alkane (e.g., hexane, heptane, or octane), aromatic hydrocarbon (e.g., toluene), halogenated hydrocarbon (e.g., methylene chloride, chloroform, carbon tetrachloride, or perchloroethylene), or ether 15 (e.g., diethyl ether, methyl tert-butyl ether, tetrahydrofuran, 2-methyl tetrahydrofuran, dioxane, dimethoxyethane, diglyme, or tetraglyme) in the presence of a phase transfer catalyst. Suitable phase transfer catalysts include quaternary ammonium halides (e.g., tetrabutylammonium bromide, tetrabutylammonium hydrosulfate, triethylbenzylammonium chloride, dodecyltrimethylammonium chloride, and tricaprylymethylammonium chloride), quaternary phosphonium halides (e.g., triphenylmethylphosphonium bromide and tetraphenylphosphonium chloride), or cyclic polyether compounds known in the art as crown ethers (e.g., 18-crown-6 and 15-crown-5). Alternatively, the dehydroiodination reaction may be conducted in the absence of solvent by adding the trihydroiodoperfluoroalkane to a solid or liquid basic substance. Suitable reaction times for the dehydroiodination reactions are from about 15 minutes to about six hours or more depending on the solubility of the reactants. Typically the dehydroiodination reaction is rapid and requires about 30 minutes to about three hours for completion. The compound of formula I may 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 present invention, fluoroolefins comprise cyclic fluoroolefins (cyclo-[CX=CY(CZW)n-] (Formula 11), wherein
X, Y, Z, and W are independently selected from H and F, and n is an integer from 2 to 5). Representative cyclic fluoroolefins of Formula 11 are listed in Table 2.
TABLE2 Cyclic Structure Chemical name fluoroolefins FC-C1316cc cyclo-CF2CF 2CF=CF- 1,2,3,3,4,4-hexafluorocyclobutene HFC-C1334cc cyclo-CF2CF 2CH=CH- 3 ,3,4,4-tetrafluorocyclobutene HFC-C1436 cyclo-CF2CF 2CF 2CH=CH- 3,3,4,4,5,5, hexafluorocyclopentene FC-C1418y cyclo-CF2CF=CFCF 2CF 2- 1,2,3,3,4,4,5,5 octafluorocyclopentene FC-C151-10y cyco-CF 2CF=CFCF 2CF 2CF 2 - 1,2,3,3,4,4,5,5,6,6 decafluorocyclohexene
In another embodiment, fluoroolefins may comprise those compounds listed in Table 3. TABLE 3 Name Structure Chemical name HFC-1225ye CF 3CF=CHF 1,2,3,3,3-pentafluoro-1-propene HFC-1225zc CF3CH=CF 2 1,1,3,3,3-pentafluoro-1-propene HFC-1225yc CHF 2CF=CF 2 1,1,2,3,3-pentafluoro-1-propene HFC-1234ye CHF 2CF=CHF 1,2,3,3-tetrafluoro-1-propene HFC-1234yf CF 3CF=CH 2 2,3,3,3-tetrafluoro-1-propene HFC-1234ze CF 3CH=CHF 1,3,3,3-tetrafluoro-1-propene HFC-1234yc CH 2FCF=CF 2 1,1,2,3-tetrafluoro-1-propene HFC-1234zc CHF 2CH=CF 2 1,1,3,3-tetrafluoro-1-propene HFC-1243yf CHF 2 CF=CH 2 2,3,3-trifluoro-1-propene HFC-1243zf CF 3CH=CH 2 3,3,3-trifluoro-1-propene HFC-1243yc CH 3CF=CF 2 1,1,2-trifluoro-1-propene HFC-1243zc CH 2FCH=CF 2 1,1,3-trifluoro-I-propene HFC-1243e CH 2FCF=CHF 1,2,3-trifluoro-1-propene HFC-1243ze CHF 2CH=CHF 1,3,3-trifluoro-1-propene FC-1318my CF 3CF=CFCF 3 1,1,1,2,3,4,4,4-octafluoro-2-butene FC-1318cy CF 3CF 2CF=CF 2 1,1, 2 ,3,3,4,4,4-octafluoro-1-butene HFC-1327my CF3CF=CHCF 3 1,1,1,2,4,4,4-heptafluoro-2-butene HFC-1327ye CHF=CFCF 2CF 3 1,2,3,3,4,4,4-heptafluoro--butene HFc-1327py CHF 2CF=CFCF 3 1,1,1,2,3,4,4-heptafluoro-2-butene HFC-1327et (CF 3)2C=CHF 1,3,3,3-tetrafluoro-2 (trifluoromethyl)-1-propene HFC-1327cz CF 2=CHCF 2CF 3 1,1,3,3,4,4,4-heptafluoro-1-butene HFC-1327cye CF 2 = CFCHFCF3 1,1,2,3,4,4,4-heptafluoro-1-butene HFC-1327cyc CF 2=CFCF 2 CHF 2 1,1,2,3,3,4,4-heptafluoro-1-butene HFC-1336yf CF3CF 2CF=CH 2 2,3,3,4,4,4-hexafluoro-1-butene HFC-1336ze CHF=CHCF 2CF 3 1,3,3,4,4,4-hexafluoro-1-butene HFC-1336eye CHF=CFCHFCF 3 1,2,3,4,4,4-hexafluoro-1-butene HFC-1336eyc CHF=CFCF 2CHF 2 1,2,3,3,4,4-hexafluoro-1-butene HFC-1336pyy CHF2CF=CFCHF 2 1,1,2,3,4,4-hexafluoro-2-butene
HFC-1336gy CH 2FCF=CFCF 3 1,1,1,2,3,4-hexafluoro-2-butene HFC-1336pz CHF 2CH=CFCF 3 1,1,1,2,4,4-hexafluoro-2-butene HFC-1336mzy CF 3 CH=CFCHF 2 1,1,1,3,4,4-hexafluoro-2-butene HFC-1336qc CF 2=CFCF2CH 2F 1,1,2,3,3,4-hexafluoro-1-butene HFC-1336pe CF 2=CFCHFCHF 2 1,1,2,3,4,4-hexafluoro-1-butene HFC-1336ft CH 2=C(CF3) 2 3,3,3-trifluoro-2-(trifluoromethyl)-1 propene HFC-1345qz CH 2 FCH=CFCF 3 1,1,1,2,4-pentafluoro-2-butene HFC-1345mzy CF 3CH=CFCH 2F 1,1,1,3,4-pentafluoro-2-butene HFC-1345fz CF 3CF 2CH=CH 2 3,3,4,4,4-pentafluoro-1-butene HFC-1345mzz CHF 2CH=CHCF 3 1,1,1,4,4-pentafluoro-2-butene HFC-1345sy CH 3CF=CFCF 3 1,1,1,2,3-pentafluoro-2-butene HFC-1345fyc CH 2=CFCF 2CHF 2 2,3,3,4,4-pentafluoro-1-butene HFC-1345pyz CHF 2CF=CHCHF 2 1,1,2,4,4-pentafluoro-2-butene HFC-1345cyc CH 3CF 2CF=CF 2 1,1,2,3,3-pentafluoro-1-butene HFC-1345pyy CH 2 FCF=CFCHF 2 1,1,2,3,4-pentafluoro-2-butene HFC-1345eyc CH 2 FCF 2CF=CF 2 1,2,3,3,4-pentafluoro-1-butene HFC-1345ctm CF 2 =C(CF 3)(CH 3) 1,1,3,3,3-pentafluoro-2-methyl-1 propene HFC-1345ftp CH 2=C(CHF 2)(CF 3) 2-(difluoromethyl)-3,3,3-trifluoro-1 propene HFC1345fye CH 2=CFCHFCF 3 2,3,4,4,4-pentafluoro-1-butene HFC-1345eyf CHF=CFCH 2CF 3 1,2,4,4,4-pentafluoro-1-butene HFC-1345eze CHF=CHCHFCF 3 1,3,4,4,4-pentafluoro-1-butene HFC-1345ezc CHF=CHCF 2CHF 2 1,3,3,4,4-pentafluoro-1-butene HFC-1345eye CHF=CFCHFCHF 2 1,2,3,4,4-pentafluoro-1-butene HFC-1354fzc CH 2=CHCF 2CHF 2 3,3,4,4-tetrafluoro-1-butene HFC-1354ctp CF 2=C(CHF 2)(CH 3) 1,1,3,3-tetrafluoro-2-methyl-1 propene HFC-1354etm CHF=C(CF 3)(CH 3) 1,3,3,3-tetrafluoro-2-methyl-1 propene HFC-1354tfp CH 2 =C(CHF 2 ) 2 2-(difluoromethyl)-3,3-difluoro-1 propene HFC-1354my CF3 CF=CHCH 3 1,1,1,2-tetrafluoro-2-butene HFC-1354mzy CH 3CF=CHCF 3 1,1,1,3-tetrafluoro-2-butene FC-141-10myy. CF3CF=CFCF 2CF3 1,1,1,2,3,4,4,5,5,5-decafluoro-2 pentene FC-141-10cy CF 2=CFCF 2CF 2CF3 1,1,2,3,3,4,4,5,5,5-decafluoro-1 pentene HFC-1429mzt (CF 3 )2C=CHCF 3 1,1,1,4,4,4-hexafluoro-2 (trifluoromethyl)-2-butene HFC-1429myz CF 3CF=CHCF 2CF3 1,1,1,2,4,4,5,5,5-nonafluoro-2 pentene HFC-1429mzy CF 3CH=CFCF 2CF3 1,1,1,3,4,4,5,5,5-nonafluoro-2 pentene HFC-1429eyc CHF=CFCF 2CF2 CF3 1,2,3,3,4,4,5,5,5-nonafluoro-1 pentene HFC-1429czc CF 2=CHCF 2CF 2CF3 1,1,3,3,4,4,5,5,5-nonafluoro-1 pentene HFC-1429cycc CF 2=CFCF 2CF 2CHF 2 1,1,2,3,3,4,4,5,5-nonafluoro-1 pentene HFC-1429pyy CHF 2CF=CFCF 2CF 3 1,1,2,3,4,4,5,5,5-nonafluoro-2 pentene HFC-1429myyc CF 3CF=CFCF 2CHF 2 1,1,1,2,3,4,4,5,5-nonafluoro-2 pentene HFC-1429myye CF 3CF=CFCHFCF 3 1,1,1,2,3,4,5,5,5-nonafluoro-2 pentene HFC-1l429eyym CHF=CFCF(CF 3)2 I,2,3,4,4,4-hexafluoro-3 (trifluoromethIl-1-butene HFC-1429cyzm CF 2=CFCH(CF 3)2 1,1,2,4,4,4-hexafluoro'-3 (trifluoromethyl)-l -butene HFC-1429mzt CF 3CH= C(CF 3)2 1, 1,1,4,4,4-hexafluoro-2 (trifluoromethyl)-2-butene HFC-1429czym CF 2=CHCF(CF 3)2 1,1, 3,4,4,4-hexafluoro-3 HFC-1438fy CH2=CFCF 2CF 2CF3hyl)- 2,,,,,,,-utaflor HFC-1438eyc CHF=CFCF 2CF 2CF 12,3,3,4,4,5,5-octafluoro-1 HFC-1438ftmc CHF=CCF)CF 2CF2 13,3,4,4,-tafluoro-- petriioethn -- btn HFC-1438czzm cF 2=CH(CF 3) 2CF 1,1,4,4,4-pentafluoro-3 (trifluoromethIl-1-butene HFC-1438ezym CF=CHCF(CF 3)2 1,31,4,4,4-pentafluoro-3 (trifluoromethyi)-1 -butene HFC-l438ctm CF=CCF(HCF 3 1,13,4,4,4-pentafluoro-2 (trifluoromethyl)-l -butene HFC-1447fzf (CF 2CCFHCH2CF 1,,4,4,4-etafluoro- (trifluoromethyl)-l -butene HFC-1447fz- CF 3CF 2CF 2CH=CH 2 3,3,4,4,5,5,5-heptafluoro-1-pentene HFC-1447fycc CH 2=CFCFCF 2CHF 2 2,,3,3,4,4,5,5-heptafluoro-1-pentene HFC-1447czcf CF 2=CHCF 2CH 2CF 3 1, 1,3,3,5,5,5-hetafiuoro-1-pentene HFC-1447mytm CF 3CF=C(CF 3)(CH 3) 1,1,1,2,4,4,4-heptafiuoro-3-methyl 2-butene HFC-1447fyz CH 2=CFCH(CF 3)2 2,4,4,4-tetrafluoro-3 (trifluoromethyi)-l -butene HFC-1447ezz CHF=CHCH(CF 3)2 I,4,4,4-tetrafluoro-3 (trifluoromethyl)-l -butene HFC-1447qzt CH 2FCH=C(0F 3)2 I,4,4,4-tetrafluoro-2 (trifluoromethyl)-2-butenia HFC-1447syt CH3cF=C(CF 3)2 2,4,4,4-tetrafluoro-2 (trifluoromethyl)-2-butene HFC-1456szt (0F 3)20=CHCH 3 3-(trifluoromethyl)-4,4,4-trifjuoro-2 butene HFC-1456szy CF CF 2CF=CHCH 3 3,4,4,5,5,5-hexafluoro-2-pentene HFC-1456mstz CF 3C(CH 3)=CHCF 3 1,1, 1,4,4,4-hexafluoro-2-methyi-2 butene HFC-1456fzce CH 2=CHCF 2CHFCF 3 3,3,4,5,5,5-hexafluoro-1-pentene HFC-1456ftmf CH 2=C(CF 3)CH 2CF 3 4,4,4-trifiuoro-2-(trifluoromethyl)-l butene FC-151-12c CF 3(C-F 2)3CF=CF 2 1,1,2,3,3,4,4,5,5,6,6,6 dodecafiuoro-1-hexene (or perfluoro-1-hexene) FC-1 51-l2mcy CF 3CF 2C =-CFCF 2CF, 1, 1,1,2,2,3,4,5,5,6,6,6 dodecafjuoro-3-hexene (or perfluoro-3-hexene) FC-1 51-12mmtt (CF 3)2C=C(CF 3)2 1,1,1,4,4,4-hexafjuoro-2,3 bis(trifluoromethyl)-2-butene FC-1 51-12mmzz (CF 3)2CFCF=CFCF 3 1,1, 1,2,3,4,5,5,5-nonafluoro-4 trifluoromethyl)-2-pentene HFC-1 52-11 mmtz (CF 3)2C=CHC 2F5 1,1,1,4,4,5,5,5-octafiuoro-2 (trifluoromethyl)-2-pentene
HFC-152-11mmyyz (CF 3)2CFCF=CHCF 3 1,1,1,3,4,5,5,5-octafluoro-4 (triflUoromethyl)-2-pentene PFBE CF 3CF 2CF 2CF 2CH=CH 2 3,3,4,4,5,5,6,6,6-nonafluoro-1 (or HFC-1549fz) hexene (or perfluorobutylethylene) HFC-1549fztmm CH 2=CHC(CF 3)3 4,4,4-trifluoro-3,3 bistrifluoromethy)I--butene HFC-1549mmtts (CF 3 ) 2 C=C(CH 3 )(CF 3 ) 1, 1,1,4,4,4-hexafluoro-3-mehy-2 (trifluoromethyl)-2-butene HFC-1549fycz CH 2=CFCF 2CH(CF 3) 2 2,3,3,5,5,5-hexafluoro-4 (trifluoromethy-1-pentene HFC-1549myts CF 3CF=C(CH 3 )CF 2CF 3 1,1,1,2,4,4,5,55-nonafluoro-3 methyl-2-pentene HFC-1549mzzz CF 3CH=CHCH(CF 3)2 1,1,1,5,5,5-hexafluoro-4 (trifluoiromethyl)-2-pentene HFC-1558szy CF 3CF 2CF 2CF=CHCH 3 3 ,4 4 , ,5,5,6 ,6,6-octafluoro-2-hexene HFC-1558fzccc CH 2=CHCF 2CF 2CF 2CHF 2 3 ,3 4 4 , , ,5,5,6 ,6-octafluoro-2-hexene HFC-1558mmtzc (CF 3)2C=CHCF 2CH 3 1,1,1,4,4-pentafluoro-2 (trifluoromethyl)-2-pentene HFC-1558ftmf CH 2=C(CF 3)CH 2C 2F5 4 ,4,5,5,5-pentafluoro-2
HFC-1 567fts CF 3 CF 2CF 2 C(CH 3)=CH 2 23trifluorometh | -p1entene ,3 ,4 , 4 5,5,5-heptafluoro-2-methyl 1-pentene HFC-1567szz CF 3 CF 2 CF 2CH=CHCH 3 4 ,4 ,5,5,6 ,6,6-heptafluoro-2-hexene HFC-1567fzfc CH 2=CHCH 2 CF2 C2 F5 4 ,4 ,5,5,6,6,6-heptafluoro-1-hexene HFC-1567sfyy CF 3CF 2 CF=CFC 2H 5 1,1,1, 2 ,2 ,3,4-heptafluoro-3-hexene HFC-1567fzfy CH 2=CHCH 2CF(CF 3)2 4,5,5,5-tetrafluoro-4 - trifluoromethyl)-1-pentene HFC-1567myzzm CF 3CF=CHCH(CF 3)(CH 3) 1,1,1, 2 ,5,5,5-heptafluoro-4-methyl 2-pentene HFC-1567mmtyf (CF 3)2 C=CFC 2 H5 1,1,1,3-tetrafluoro-2 (trifluoromethyl)-2-pentene FC-161-14myy CF 3CF=CFCF 2CF 2C 2F5 1,1,1,2,3,4,4,5,5,6,6,7,7,7 tetradecafluoro-2-heptene FC-161-14mcyy CF3CF 2CF=CFCF 2C 2Fs 1,1,1,2,2,3,4,5,5,6,6,7,7,7 tetradecafluoro-2-heptene H-fFC-1 62-13mzy CF 3CH=CFCF 2 CF2 C 2F5, 1,1,1,3,4,4,5,5,6,6,7,7,7. tridecafluoro-2-heptene HFC162-13myz CF3CF=CHCF 2CF 2C 2F 1,1,1,2,4,4,5,5,6,6,7,7,7 tridecafluoro-2-heptene HFC-162-13mczy CF 3CF 2 CH=CFCF 2C 2 F5 1,1,1,2,2,4,5,5,6,6,7,77 HFC-162-13m-cyz CF3 CF2 CF=CHCF 2c52F, 1,1, 1,2,2,3,5,5,6,6,7,7,7 tridecafluoro-3-heptene PEVECF 2 =FOCFCF 3 tridecafluoro-3-heptene PEVE CF2=CFOCF2CF3 pentafluoroethyl trifluorovinyl ether PMVE CF 2=CFOCF 3 trifluoromethyl trifluorovinyl ether
The compounds listed in Table 2 and Table 3 are available commercially or may be prepared by processes known in the art or as described herein. 1,1,1, 4 ,4-pentafluoro-2-butene maybe prepared from 1,1,1,2,4,4-hexafluorobutane (CHF 2CH 2CHFCF ) by dehydrofluorination 3 over solid KOH in the vapor phase at room temperature. The synthesis of
1,1,1,2,4,4-hexafluorobutane is described in US 6,066,768, incorporated herein by reference. 1,1,1, 4 ,4,4-hexafluoro-2-butene may be prepared from 1,1,1, 4 ,4,4-hexafluoro-2-iodobutane (CF 3CHICH 2CF 3) by reaction with 5 KOH using a phase transfer catalyst at about 600 C. The synthesis of 1,1,1, 4 ,4,4-hexafluoro-2-iodobutane may be carried out by reaction of perfluoromethyl iodide (CF3 ) and 3,3,3-trifluoropropene (CF CH=CH ) at 3 2 about 2000C under autogenous pressure for about 8 hours. 3 ,4 ,4 ,5,5,5-hexafluoro-2-pentene may be prepared by dehydrofluorination of 1,1,1,2,2,3,3-heptafluoropentane (CF 3CF 2CF 2CH 2CH 3) using solid KOH or over a carbon catalyst at 200 300 °C. 1,1,1, 2 ,2,3,3-heptafluoropentane may be prepared by hydrogenation of 3,3,4,4,5,5,5-heptafluoro-1-pentene (CF 3CF 2 CF 2CH=CH 2). 1,1,1,2,3,4-hexafluoro-2-butene may be prepared by dehydrofluorination of 1,1,1,2,3,3,4-heptafluorobutane (CH FCF CHFCF 2 2 3
) using solid KOH. 1,1,1,2,4,4-hexafluoro-2-butene may be prepared by dehydrofluorination of 1,1,1,2,2,4,4-heptafluorobutane (CHF CH CF CF 2 2 2 3
) using solid KOH. 1,1,1,3,4,4-hexafluoro2-butene may be prepared by dehydrofluorination of 1,1,1,3,3,4,4-heptafluorobutane (CF CH CF CHF 3 2 2 2 using solid KOH. ) 1,1,1,2,4-pentafluoro-2-butene may be prepared by dehydrofluorination of 1,1,1,2,2,3-hexafluorobutane (CH 2FCH CF CF 2 2 3 )
using solid KOH. 1,1,1,3,4-pentafluoro-2-butene may be prepared by dehydrofluorination of 1,1,1,3,3,4-hexafluorobutane (CF 3CH 2CF 2CH 2F) using solid KOH. 1,1,1,3-tetrafluoro-2-butene may be prepared by reacting 1,1,1,3,3-pentafluorobutane ( CF 3CH 2CF 2CH 3) with aqueous KOH at 120 0C. 1,1,1, 4 ,4,5,5,5-octafluoro-2-pentene may be prepared from (CF 3CHICH 2CF 2CF 3) by reaction with KOH using a phase transfer catalyst at about 600C. The synthesis of 4-iodo-1,1,1,2,2,5,5,5-octafluoropentane may be carried out by reaction of perfluoroethyliodide (CF 3CF 2I) and 3,3,3 trifluoropropene at about 200°C under autogenous pressure for about 8 hours. 1,1,1,2,2,5,5,6 ,6 ,6 -decafluoro-3-hexene may be prepared from 1,1,1, 2 ,2 ,5,5,6 ,6 ,6 -decafluoro-3-iodohexane (CF 3CF CHiCH CF CF ) by 2 2 2 3 5 reaction with KOH using a phase transfer catalyst at about 600 C. The synthesis of 1,1,1, 2 ,2 ,5,5,6 ,6 ,6 -decafluoro-3-iodohexane may be carried out by reaction of perfluoroethyliodide (CF 3CF 2 ) and 3,3,4,4,4 pentafluoro-1-butene (CF 3CF 2CH=CH 2) at about 2000C under autogenous pressure for about 8 hours. 10 1,1,1,4,5,5,5-heptafluoro-4-(trifluoromethyl)-2-pentene may be prepared by the dehydrofluorination of 1,1,1,2,5,5,5-heptafluoro-4-iodo-2 (trifluoromethyl)-pentane (CF 3CHICH 2CF(CF 3)2) with KOH in isopropanol. CF 3CHICH 2CF(CF 3)2 is made from reaction of (CF ) CFI with 32 CF 3CH=CH 2 at high temperature, such as about 200 °C. 15 1,1,1, 4 ,4 ,5,5,6,6,6-decafluoro-2-hexene may be prepared by the reaction of 1,1,1,4,4,4-hexafluoro-2-butene (CF 3CH=CHCF ) with 3 tetrafluoroethylene (CF 2=CF 2) and antimony pentafluoride (SbF). 2, 3 ,3,4,4-pentafluoro-1-butene may be prepared by dehydrofluorination of 1,1, 2 ,2,3,3-hexafluorobutane over fluorided alumina 20 at elevated temperature. 2, 3 ,3 ,4 ,4 ,5,5,5-ocatafluoro-1-pentene may be prepared by dehydrofluorination of 2, 2 ,3 ,3 ,4 ,4 ,5,5,5-nonafluoropentane over solid KOH. 1,2,3,3,4,4,5,5-octafluoro-1-pentenemay be prepared by dehydrofluorination of 2,2,3,3 ,4 ,4 ,5,5,5-nonafluoropentane over fluorided alumina at elevated temperature. The compositions of the present invention may comprise a single compound of Formula I, Formula 11, or Table 3 or may comprise a combination of said compounds. Additionally, many of the compounds of Formula I, Formula 11, and Table 3 may exist as different configurational isomers or stereoisomers. The present invention is intended to include all single configurational isomers, single stereoisomers or any combination thereof. For instance, 1, 3 ,3 ,3-tetrafluoropropene (HFC-1234ze) is meant to represent the E-isomer, Z-isomer, or any combination or mixture of both isomers in any ratio. Another example is F12E, by which is represented the E-isomer, Z-isomer, or any combination or mixture of both isomers in any ratio. Compositions of the present invention have zero or low ozone depletion potential and low global warming potential (GWP). The 5 fluoroolefins of the present invention or mixtures of fluoroolefins of this invention with other refrigerants will have global warming potentials that are less than many hydrofluorocarbon refrigerants currently in use. One aspect of the present invention is to provide a refrigerant with a global warming potential of less than 1000, less than 500, less than 150, less 10 than 100, or less than 50. Another aspect of the present invention is to reduce the net GWP of refrigerant mixtures by adding fluoroolefins to said mixtures. The compositions of thepresent invention that are combinations or mixtures may be prepared by any convenient method to 15 combine the desired amounts of the individual components. A preferred method is to weigh the desired component amounts and thereafter combine the components in an appropriate vessel. Agitation may be used, if desired. An alternative means for making compositions of the present 20 invention comprises (i) reclaiming a volume of one or more components of a refrigerant composition from at least one refrigerant container, (ii) removing impurities sufficiently to enable reuse of said one or more of the reclaimed components, (iii) and optionally, combining all or part of said reclaimed volume of components with at least one additional refrigerant composition or component. A refrigerant container may be any container in which is stored a refrigerant blend composition that has been used in a refrigeration apparatus, air-conditioning apparatus or heat pump apparatus. Said refrigerant container may be the refrigeration apparatus, air-conditioning apparatus or heat pump apparatus in which the refrigerant blend was used. Additionally, the refrigerant container may be a storage container for collecting reclaimed refrigerant blend components, including but not limited to pressurized gas cylinders. Residual refrigerant means any amount of refrigerant blend or refrigerant blend component that may be moved out of the refrigerant container by any method known for transferring refrigerant blends or refrigerant blend components. Impurities may be any component that is in the refrigerant blend or refrigerant blend component due to its use in a refrigeration 5 apparatus, air-conditioning apparatus or heat pump apparatus. Such impurities include but are not limited to refrigeration lubricants, being those described earlier herein, particulates such as metal or elastomer that may have come out of the refrigeration apparatus, air-conditioning apparatus or heat pump apparatus, and any other contaminants that may adversely 10 effect the performance of the refrigerant blend composition. Such impurities may be removed sufficiently to allow reuse of the refrigerant blend or refrigerant blend component without adversely effecting the performance or equipment within which the refrigerant blend or refrigerant blend component will be used. 15 It may be necessary to provide 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 specifications required for a given product. For instance, if a refrigerant blend has 3 components in a particular weight percentage range, it may 20 be necessary to add one or more of the components in a given amount in order to restore the composition to within the specification limits. The compositions of the present invention that are useful as refrigerants or heat transfer fluids comprise at least one fluoroolefin selected from the group consisting of: (i) fluoroolefins of the formula E- or Z-RCH=CHR2 , wherein R 1 and R 2 are, independently, C1 to06 perfluoroalkyl groups, and wherein the total number of carbons in the compound is at least 5; (ii) cyclic fluoroolefins of the formulacyclo-[CX=CY(CZW)n-], wherein X, Y, Z, and W, independently, are H or F, and n is an integer from 2 to 5; and (iii) fluoroolefins selected from the group consisting of: 1,2, 3 ,3 ,3 -pentafluoro-1-propene (CF 3CF=CHF);1,1,3,3,3 pentafluoro-1-propene (CF 3CH=CF 2); 1,1,2,3,3-pentafluoro-1 propene (CHF 2CF=CF 2); 1,2,3,3-tetrafluoro-1-propene (CHF 2CF=CHF); 2 ,3 ,3,3-tetrafluoro-1-propene (CF CF=CH 3 2 )
1,1, 2 ,3-tetrafluoro-1-propene (CH 2FCF=CF 2); 1,1,3,3-tetrafluoro-1 propene (CHF 2CH=CF 2); 2,3,3-trifluoro-1-propene (CHF CF=CH 2 2); 3,3,3-trifluoro-1-propene (CF 3CH=CH 2); 1,1,2-trifluoro-1-propene (CH 3CF=CF 2); 1,2,3-trifluoro-i-propene (CH FCF=CF ); 1,1,3 2 2 5 trifluoro-1-propene (CH 2FCH=CF 2); 1,3,3-trifluoro-1-propene (CHF 2CH=CHF); 1,1,1, 2 ,3 ,4 ,4,4-octafluoro-2-butene (CF 3CF=CFCF 3); 1,1, 2 ,3 ,3 ,4 ,4,4-octafluoro-1-butene (CF 3CF 2CF=CF 2); 1,1,1, 2 ,4 ,4,4-heptafluoro-2-butene (CF 3CF=CHCF 3); 1, 2 ,3 ,3 ,4 ,4,4-heptafluoro-1-butene 10 (CHF=CFCF 2CF 3); 1,1,1, 2 ,3 ,4,4-heptafluoro-2-butene (CHF 2CF=CFCF 3); 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=CHCF2CF 3); 1,1, 2 ,3 ,4 ,4 ,4-heptafluoro-1-butene (CF 2=CFCHFCF3); 1,1, 2 ,3 ,3 ,4,4-heptafluoro-1-butene 15 (CF 2=CFCF 2CHF 2); 2,3,3,4,4,4-hexafluoro-1-butene (CF 3CF 2CF=CH 2); 1,3,3,4,4,4-hexafluoro-1-butene (CHF=CHCF 2CF 3); 1,2,3,4,4,4-hexafluoro-1-butene (CHF=CFCHFCF 3); 1,2,3,3,4,4-hexafluoro-1-butene (CHF=CFCF2CHF 2); 1,1,2,3,4,4-hexafluoro-2-butene (CHF 2CF=CFCHF 2); 1,1,1,2,3,4-hexafluoro-2-butene (CH 2FCF=CFCF 3); 1,1,1,2,4,4-hexafluoro-2-butene (CHF 2CH=CFCF 3); 1,1,1,3,4,4-hexafluoro-2-butene (CF 3CH=CFCHF 2); 1,1,2,3,3,4-hexafluoro-1-butene (CF2=CFCF 2CH 2F); 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 FCH=CFCF 2 3); 1,1,1,3,4-pentafluoro-2-butene (CF 3CH=CFCH 2F); 3,3,4,4,4 pentafluoro-1-butene (CF 3CF 2CH=CH 2); 1,1,1,4,4-pentafluoro-2 butene (CHF 2CH=CHCF 3); 1,1,1,2,3-pentafluoro-2-butene (CH 3CF=CFCF 3); 2 ,3 ,3 ,4 ,4-pentafluoro-1-butene (CH 2 =CFCF 2 CHF 2 ); 1,1, 2 ,4,4-pentafluoro-2-butene (CHF 2CF=CHCHF 2); 1,1,2,3,3-pentafluoro-1-butene (CH 3CF 2CF=CF 2); 1,1, 2 ,3 ,4-pentafluoro-2-butene (CH 2FCF=CFCHF 2); 1,1, 3 ,3,3-pentafluoro-2-methyl-1-propene (CF 2 =C(CF 3 )(CH 3)); 2-(difluoromethyl)-3,3,3-trifluoro-1-propene (CH 2=C(CHF 2)(CF 3)); 2 ,3 ,4,4,4-pentafluoro-1-butene
(CH 2=CFCHFCF 3); 1, 2 ,4,4,4-pentafluoro-1-butene (CHF=CFCH 2CF3); 1, 3 ,4,4,4-pentafluoro-1-butene (CHF=CHCHFCF3); 1, 3 ,3 ,4 ,4 -pentafluoro-l-butene (CHF=CHCF 2CHF 2); 1, 2 ,3,4,4-pentafluoro-1-butene 5 (CHF=CFCHFCHF 2); 3 ,3,4,4-tetrafluoro-1-butene (CH 2=CHCF 2CHF 2); 1,1-difluoro-2-(difluoromethyl)-1-propene (CF2=C(CHF 2)(CH 3)); 1,3, 3 ,3-tetrafluoro-2-methyl-1-propene (CHF=C(CF 3)(CH 3)); 3,3-difluoro-2-(difluoromethyl)-1-propene (CH 2 =C(CHF 2 )2 ); 1,1,1,2-tetrafluoro-2-butene (CF CF=CHCH 3 3); 10 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=CFCF2CF 3); 1,1,2,3,3,4,4,5,5,5 decafluoro-1-pentene (CF2=CFCF2CF2CF3); 1,1,1,4,4,4-hexafluoro 2-(trifluoromethyl)-2-butene ((CF 3) 2 C=CHCF 3); 1,1,1,2,4,4,5,5,5 nonafluoro-2-pentene (CF3CF=CHCF2CF 3); 1,1,1,3,4,4,5,5,5 15 nonafluoro-2-pentene (CF3CH=CFCF2CF 3); 1,2,3,3,4,4,5,5,5 nonafluoro-1-pentene (CHF=CFCF2CF2CF 3); 1,1,3,3,4,4,5,5,5 nonafluoro-1-pentene (CF2=CHCF 2CF 2CF3); 1,1,2,3,3,4,4,5,5 nonafluoro-1-pentene (CF2=CFCF2CF2CHF2); 1,1,2,3,4,4,5,5,5 nonafluoro-2-pentene (CHF2CF=CFCF2CF 3); 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 (CF3CF=CFCHFCF 3); 1,2,3,4,4,4-hexafluoro 3-(trifluoromethyl)-1-butene (CHF=CFCF(CF3)2); 1,1,2,4,4,4 hexafluoro-3-(trifluoromethyl)-1-butene (CF 2=CFCH(CF )2); 3 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 (CF2=CHCF(CF 3)2); 2,3,3,4,4 ,5,5,5-octafluoro-1-pentene (CH 2=CFCF2CF 2CF 3); 1,2,3,3,4,4,5,5-octafluoro-1-pentene (CHF=CFCF2CF2CHF2); 3, 3 ,4,4,4-pentafluoro-2-(trifluoromethyl)-1 butene (CH2=C(CF 3)CF 2CF 3 ); 1,1,4,4,4-pentafluoro-3 (trifluoromethyl)-1-butene (CF2=CHCH(CF 3)2); 1,3,4,4,4 pentafluoro-3-(trifluoromethyl)-1-butene (CHF=CHCF(CF ) ); 32 1,1, 4 ,4 ,4 -pentafluoro-2-(trifluoromethyl)-1-butene (CF2=C(CF 3)CH 2CF 3); 3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1 butene ((CF 3)2CFCH=CH 2); 3,3,4,4,5,5,5-heptafluoro-1-pentene (CF 3CF2CF2CH=CH 2); 2,3,3,4,4,5,5-heptafluoro-1-pentene (CH2=CFCF 2CF2CHF2); 1,1,3,3,5,5,5-heptafluoro-1-butene
(CF 2=CHCF 2CH 2CF 3); 1,1,1, 2 ,4 ,4,4-heptafluoro-3-methyl-2-butene (CF 3CF=C(CF 3)(CH 3)); 2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1 butene (CH 2=CFCH(CF 3)2); 1,4,4,4-tetrafluoro-3-(trifluoromethyl)-1 butene (CHF=CHCH(CF 3)2); 1,1,1,4-tetrafluoro-2-(trifluoromethyl) 5 2-butene (CH 2 FCH=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=CHCH 3); 3,4,4,5,5,5-hexafluoro-2-pentene (CF 3CF 2CF=CHCH 3); 1,1,1,4,4,4-hexafluoro-2-methyl-2-butene (CF 3C(CH 3)=CHCF 3); 3 ,3,4,5,5,5-hexafluoro-1-pentene (CH 2=CHCF 2CHFCF 3); 4,4,4-trifluoro-3-(trifluoromethyl)-1-butene (CH 2=C(CF 3)CH 2CF 3); 1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1 hexene (CF 3(CF 2)3CF=CF 2); 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3 hexene (CF 3CF 2CF=CFCF 2CF 3); 1,1,1,4,4,4-hexafluoro-2,3 bis(trifluoromethyl)-2-butene ((CF3) 2 C=C(CF 3 )2 ); 1,1,1,2,3,4,5,5,5 nonafluoro-4-(trifluoromethyl)-2-pentene ((CF 3)2CFCF=CFCF 3); 1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-pentene ((CF 3)2C=CHC 2F5 ); 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2 pentene ((CF 3)2CFCF=CHCF 3); 3,3,4,4,5,5,6,6,6-nonafluoro-1 hexene (CF 3CF 2CF 2CF 2CH=CH 2); 4,4,4-trifluoro-3,3 bis(trifluoromethyl)-1-butene (CH 2=CHC(CF 3)3); 1,1,1,4,4,4 hexafluoro-2-(trifluoromethyl)-3-methyl-2-butene ((CF 3)2C=C(CH 3)(CF3)); 2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1 pentene (CH 2=CFCF 2CH(CF 3)2); 1,1,1,2,4,4,5,5,5-nonafluoro-3 methyl-2-pentene (CF 3CF=C(CH 3)CF 2CF 3); 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 3CF 2CF 2CF=CHCH 3); 3,3,4,4,5,5,6,6-octafluorol-hexene(CH 2=CHCF 2CF 2CF 2 CHF 2); 1,1,1,4,4-pentafluoro-2-(trifluoromethyl)-2-pentene ((CF 3)2C=CHCF 2CH 3); 4,4,5,5,5-pentafluoro-2-(trifluoromethyl)-1 pentene (CH 2=C(CF 3)CH 2C 2F); 3,3,4,4,5,5,5-heptafluoro-2-methyl I-pentene (CF 3CF 2CF 2C(CH 3)=CH 2); 4,4,5,5,6,6,6-heptafluoro-2 hexene (CF 3CF 2CF 2CH=CHCH 3); 4,4,5,5,6,6,6-heptafluoro-1 hexene (CH 2=CHCH 2CF 2C 2F5); 1,1,1,2,2,3,4-heptafluoro-3-hexene (CF 3CF 2CF=CFC 2H5 ); 4,5,5,5-tetrafluoro-4-(trifluoromethyl)-1 pentene (CH 2=CHCH 2CF(CF 3)2); 1,1,1,2,5,5,5-heptafluoro-4 methyl-2-pentene (CF 3CF=CHCH(CF 3)(CH 3)); 1,1,1,3-tetrafluoro-2
(trifluoromethyl)-2-pentene ((CF 3) 2 C=CFC 2 H5 ); 1,1,1,2,3,4,4,5,5,6,6,7,7, 7 -tetradecafluoro-2-heptene
(CF 3CF=CFCF 2CF 2C 2F); 1,1,1,2,2,3,4,5,5,6,6,7,7,7 tetradecafluoro-3-heptene (CF 3CF 2CF=CFCF 2C 2F); 5 1,1,1,3,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene (CF 3CH=CFCF 2CF 2C 2F); 1,1,1, 2 ,4 ,4 ,5,5,6,6,7,7,7-tridecafluoro-2 heptene (CF 3CF=CHCF 2CF 2C 2F5); 1,1,1,2,2,4,5,5,6,6,7,7,7 tridecafluoro-3-heptene (CF 3CF 2CH=CFCF 2 C 2F); 1,1,1, 2 ,2 ,3 ,5,5 ,6 ,6 ,7 ,7,7-tridecafluoro-3-heptene 10 (CF 3CF 2CF=CHCF 2C 2F 5); CF 2=CFOCF 2CF 3 (PEVE) and CF 2=CFOCF 3 (PMVE). 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 selected from the group 15 consisting of: (i) fluoroolefins of the formula E- or Z-R'CH=CHR 2 , wherein R' and R2 are, independently, C 1 to C6 perfluoroalkyl groups, and wherein the total number of carbons in the compound is at least 5; 20 (ii) cyclic fluoroolefins of the formulacyclo-[CX=CY(CZW)n-], wherein X, Y, Z, and W, independently, are H or F, and n is an integer from 2 to 5; and (iii) fluoroolefins selected from the group consisting of: 1, 2 ,3,3,3-pentafluoro-1-propene (CF 3CF=CHF);1,1,3,3,3 pentafluoro-1-propene (CF 3CH=CF 2); 1,1,2,3,3-pentafluoro-1-propene (CHF 2CF=CF 2); 1,2,3,3-tetrafluoro-1-propene (CHF 2CF=CHF); 2,3,3,3 tetrafluoro-1-propene (CF 3CF=CH 2); 1,1,2,3-tetrafluoro-1-propene (CH 2FCF=CF 2); 1,1,3,3-tetrafluoro-1-propene (CHF 2CH=CF 2); 2,3,3 trifluoro-1-propene (CHF 2CF=CH 2); 3,3,3-trifluoro-1-propene (CF 3CH=CH 2); 1,1,2-trifluoro-1-propene (CH 3CF=CF 2); 1,2,3-trifluoro-1 propene (CH 2FCF=CF 2); 1,1,3-trifluoro-1-propene (CH 2FCH=CF ); 1,3,3 2 trifluoro-1-propene (CHF 2CH=CHF); 1,1,1, 2 ,3 ,4,4,4-octafluoro-2-butene (CF 3CF=CFCF 3); 1,1,2,3,3,4,4,4-octafluoro-1-butene(CF CF CF=CF 3 2 2); 1,1,1, 2 ,4,4,4-heptafluoro-2-butene (CF 3CF=CHCF 3); 1,2,3,3,4,4,4 heptafluoro-1-butene (CHF=CFCF 2CF 3); 1,1,1,2,3,4,4-heptafluoro-2 butene (CHF 2CF=CFCF 3); 1,3,3,3-tetrafluoro-2-(trifluoromethyl)-1-propene
((CF 3)2C=CHF); 1,1,3, 3 ,4,4,4-heptafluoro-1-butene (CF =CHCF CF 2 2 3); 1,1, 2 ,3, 4 ,4,4-heptafluoro-1-butene (CF2=CFCHFCF 3); 1,1,2,3,3,4,4 heptafluoro-1-butene (CF 2=CFCF2CHF 2); 2,3,3,4,4,4-hexafluoro-1-butene (CF 3CF 2CF=CH 2); 1, 3 ,3,4,4,4-hexafluoro-1-butene (CHF=CHCF 2CF 3); 5 1,2,3,4,4,4-hexafluoro-1-butene (CHF=CFCHFCF 3); 1,2,3,3,4,4 hexafluoro-1-butene (CHF=CFCF 2CHF 2); 1,1,2,3,4,4-hexafluoro-2-butene (CHF 2CF=CFCHF 2); 1,1,1,2,3,4-hexafluoro-2-butene (CH FCF=CFCF 2 ); 3 1,1,1, 2 ,4,4-hexafluoro-2-butene (CHF 2CH=CFCF 3); 1,1,1,3,4,4-hexafluoro 2-butene (CF 3CH=CFCHF 2); 1,1,2,3,3,4-hexafluoro-1-butene 10 (CF 2=CFCF 2CH 2F); 1,1,2,3,4,4-hexafluoro-1-butene (CF =CFCHFCHF 2 2); 3,3,3-trifluoro-2-(trifluoromethyl)-1-propene (CH 2 =C(CF ) ); 1,1,1,2,4 3 2 pentafluoro-2-butene (CH 2FCH=CFCF 3); 1,1,1,3,4-pentafluoro-2-butene (CF 3CH=CFCH 2F); 3 ,3 ,4 ,4, 4 -pentafluoro-1-butene (CF CF 3 2CH=CH 2); 1,1,1,4,4-pentafluoro-2-butene (CHF 2CH=CHCF 3); 1,1,1,2,3-pentafluoro 2-butene (CH 3CF=CFCF 3); 2,3,3,4,4-pentafluoro-1-butene (CH2=CFCF 2CHF 2); 1,1,2,4,4-pentafluoro-2-butene (CHF CF=CHCHF 2 2); 1,1,2,3,3-pentafluoro-1-butene (CH 3CF 2CF=CF 2); 1,1,2,3,4-pentafluoro-2 butene (CH 2FCF=CFCHF 2); 1,1,3,3,3-pentafluoro-2-methyl-1-propene (CF 2=C(CF3)(CH 3)); 2-(difluoromethyl)-3,3,3-trifluoro-1-propene (CH 2=C(CHF 2)(CF 3)); 2,3,4,4,4-pentafluoro-1-butene (CH =CFCHFCF 2 3); 1,2,4,4,4-pentafluoro-1-butene (CHF=CFCH 2 CF 3); 1,3,4,4,4-pentafluoro-1 butene (CHF=CHCHFCF 3); 1,3,3,4,4-pentafluoro-1-butene (CHF=CHCF 2CHF 2); 1,2,3,4,4-pentafluoro-1-butene (CHF=CFCHFCHF 2); 3,3,4,4-tetrafluoro-1-butene (CH 2=CHCF 2CHF 2); 1,1-difluoro-2 (difluoromethyl)-1-propene (CF 2=C(CHF 2)(CH 3)); 1,3,3,3-tetrafluoro-2 methyl-I-propene (CHF=C(CF 3)(CH 3)); 3,3-difluoro-2-(difluoromethyl)-1 propene (CH 2 =C(CHF 2 )2 ); 1,1,1,2-tetrafluoro-2-butene (CF CF=CHCH 3 3); 1,1,1,3-tetrafluoro-2-butene (CH3CF=CHCF 3); 1,1,1,2,3,4,4,5,5,5 decafluoro-2-pentene (CF 3CF=CFCF 2CF 3); 1,1,2,3,3,4,4,5,5,5-decafluoro 1-pentene (CF 2=CFCF 2CF 2CF 3); 1,1,1, 4 ,4,4-hexafluoro-2-(trifluoromethyl) 2-butene ((CF 3)2C=CHCF 3); 1,1,1, 2 ,4 ,4 ,5,5,5-nonafluoro-2-pentene (CF 3CF=CHCF 2CF 3); 1 , 1 ,1, 3 ,4 ,4,5,5,5-nonafluoro-2-pentene (CF 3CH=CFCF 2CF 3); 1, 2 ,3 ,3 ,4 ,4 ,5,5,5-nonafluoro-1-pentene (CHF=CFCF 2CF 2CF 3); 1,1,3,3,4 ,4 ,5,5,5-nonafluoro-1-pentene (CF 2=CHCF 2CF 2CF 3); 1,1, 2 ,3 ,3, 4 ,4,5,5-nonafluoro-1-pentene (CF 2=CFCF 2CF 2CHF 2); 1,1,2,3,4,4,5,5,5-nonafluoro-2-pentene
(CHF 2CF=CFCF 2CF 3); 1,1,1,2,3,4 ,4 ,5,5-nonafluoro-2-pentene (CF 3CF=CFCF 2CHF 2); 1,1,1,2,3,4,5,5,5-nonafluoro-2-pentene (CF 3CF=CFCHFCF 3); 1,2,3,4, 4 ,4-hexafluoro-3-(trifluoromethyl)-1-butene (CHF=CFCF(CF 3)2); 1,1, 2 ,4 ,4 ,4-hexafluoro-3-(trifluoromethyl)-1-butene 5 (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 =CFCF2CF 2 CF 3); 1,2 ,3 ,3 ,4,4,5,5-octafluoro-1-pentene (CHF=CFCF 2CF 2CHF 2); 3, 3 ,4 ,4 ,4 -pentafluoro-2-(trifluoromethyl)-1-butene 10 (CH 2=C(CF 3)CF 2CF 3); 1,1,4,4 ,4 -pentafluoro-3-(trifluoromethyl)-1-butene (CF 2=CHCH(CF 3)2); 1, 3 ,4 ,4 ,4 -pentafluoro-3-(trifluoromethyl)-1-butene (CHF=CHCF(CF 3)2); 1,1, 4 ,4 ,4 -pentafluoro-2-(trifluoromethyl)-1-butene (CF 2=C(CF 3)CH 2CF 3); 3,4,4,4 -tetrafluoro-3-(trifluoromethyl)-1-butene ((CF 3)2CFCH=CH 2); 3, 3 ,4,4 ,5,5,5-heptafluoro-1-pentene 15 (CF 3CF 2CF 2CH=CH 2); 2 ,3 ,3 ,4,4,5,5-heptafluoro-1-pentene (CH 2=CFCF 2CF 2CHF 2); 1,1, 3 ,3,5,5,5-heptafluoro-1-butene (CF 2=CHCF 2CH 2CF 3); 1,1,1, 2 ,4 ,4 ,4 -heptafluoro-3-methyl-2-butene (CF 3CF=C(CF 3)(CH 3)); 2,4, 4 ,4 -tetrafluoro-3-(trifluoromethyl)-1-butene (CH 2 =CFCH(CF 3 ) 2); 1,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene (CHF=CHCH(CF 3)2); 1,1,1, 4 -tetrafluoro-2-(trifluoromethyl)-2-butene (CH 2 FCH=C(CF 3)2); 1,1,1, 3 -tetrafluoro-2-(trifluoromethyl)-2-butene (CH 3CF=C(CF 3)2); 1,1,1-trifluoro-2-(trifluoromethyl)-2-butene ((CF 3)2C=CHCH 3); 3,4,4,5,5,5-hexafluoro-2-pentene (CF CF CF=CHCH 3 2 3); 1,1,1,4 ,4 ,4 -hexafluoro-2-methyl-2-butene (CF3C(CH )=CHCF 3 3); 3,3,4,5,5,5-hexafluoro-1-pentene (CH2=CHCF 2CHFCF ); 4,4,4-trifluoro-3 3 (trifluoromethyl)-1-butene (CH2=C(CF 3)CH 2CF 3); 1,1,2,3,3,4,4,5,5,6,6,6 dodecafluoro-1-hexene (CF 3(CF 2)3CF=CF 2); 1,1,1,2,2,3,4,5,5,6,6,6 dodecafluoro-3-hexene (CF 3CF 2CF=CFCF 2 CF 3); 1,1,1,4,4,4-hexafluoro 2, 3 -bis(trifluoromethyl)-2-butene ((CF 3) 2 C=C(CF 3 ) ); 1,1,1,2,3,4,5,5,5 2 nonafluoro-4-(trifluoromethyl)-2-pentene ((CF ) CFCF=CFCF 32 3); 1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-pentene ((CF 3) 2 C=CHC 2 F); 1,1,1,3,4,5,5,5 -octafluoro-4-(trifluoromethyl)-2-pentene ((CF3) 2 CFCF=CHCF 3); 3 ,3 ,4 ,4 ,5,5,6,6,6-nonafluoro-1-hexene (CF3CF 2CF 2CF 2CH=CH 2); 4 ,4,4-trifluoro-3,3-bis(trifluoromethyl)-1-butene (CH 2=CHC(CF 3)3); 1,1,1,4,4,4 -hexafluoro-2-(trifluoromethyl)-3-methyl-2 butene ((CF 3)2C=C(CH 3)(CF 3)); 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)CF 2CF 3); 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 3CF 2CF 2CF=CHCH 3); 3,3,4,4,5,5,6,6-octafluoro1 5 hexene (CH 2=CHCF 2CF 2CF 2CHF 2); 1,1,1,4,4-pentafluoro-2 (trifluoromethyl)-2-pentene ((CF 3)2C=CHCF 2CH 3); 4,4,5,5,5-pentafluoro-2 (trifluoromethyl)-1-pentene (CH 2=C(CF 3)CH 2C 2F 5); 3,3,4,4,5,5,5 heptafluoro-2-methyl-1-pentene (CF 3CF 2CF 2C(CH 3)=CH ); 4,4,5,5,6,6,6 2 heptafluoro-2-hexene (CF 3CF 2CF 2CH=CHCH 3); 4,4,5,5,6,6,6-heptafluoro 10 1-hexene (CH 2 =CHCH 2CF 2C 2F 5); 1,1,1, 2 ,2 ,3,4-heptafluoro-3-hexene (CF 3CF 2CF=CFC 2H); 4,5,5,5-tetrafluoro-4-(trifluoromethyl)-1-pentene (CH 2=CHCH 2CF(CF 3)2); 1,1,1,2,5,5,5-heptafluoro-4-methyl-2-pentene (CF 3CF=CHCH(CF 3)(CH 3)); 1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2 pentene ((CF 3) 2 C=CFC 2 H 5); 1,1,1, 2 ,3 ,4 ,4 ,5,5,6,6,7,7,7-tetradecafluoro-2 heptene (CF 3CF=CFCF 2CF 2C 2F 5 ); 1,1,1,2,2,3,4,5,5,6,6,7,7,7 tetradecafluoro-3-heptene (CF 3CF 2CF=CFCF C F); 2 2 1,1,1,3, 4,4 ,5,5,6 ,6 ,7,7,7-tridecafluoro-2-heptene (CF 3CH=CFCF CF C F ); 2 2 25 1,1,1,2,4,4 ,5,5,6 ,6,7,7,7-tridecafluoro-2-heptene (CF CF=CHCF CF C 3 2 2 2F); 1,1,1,2,2,4,5,5,6 ,6, 7 ,7,7-tridecafluoro-3-heptene (CF CF CH=CFCF C 3 2 2 2F5 ); 1,1,1,2,2 ,3 ,5,5,6 ,6,7,7,7-tridecafluoro-3-heptene (CF CF CF=CHCF C F ); 3 2 2 25 CF 2=CFOCF 2CF 3 (PEVE) and CF 2=CFOCF 3 (PMVE). Of particular utility in compositions comprising at least one flammable refrigerant and at least one fluoroolefin are those fluoroolefins that themselves are non-flammable. Flammability of a fluoroolefin appears to be related to the numbers of fluorine atoms and the numbers of hydrogen atoms in the molecule. The equation below provides a flammability factor that may be calculated as an indication of predicted flammability:
flammability factor= F (F + H) wherein: F = the number of fluorine atoms; and H = the number of hydrogen atoms in a molecule.
As certain compounds have been experimentally determined to be flammable, the cut-off for non-flammable fluoroolefin flammability factors has been determined. Fluoroolefins may be determined to be flammable or non-flammable by testing under conditions specified by ASHRAE (American Society of Heating, Refrigerating and Air-Conditioning Engineers, Inc.) Standard 34-2001, under ASTM (American Society of Testing and Materials) E681-01, with an electronic ignition source. Such tests of flammability are. conducted with the compound of interest at 101 kPa (14.7 psia) and a specified temperature (often 100 °C (212 °F)) at various concentrations in air in order to determine the lower flammability limit (LFL) and/or upper flammability limit (UFL) of the test compound in air. The flammability factors for several fluoroolefins are listed in Table 4 along with the experimental determination of flammable or non flammable. Therefore, it can be predicted for the other fluoroolefins of the present disclosure, which will be most useful in combination with the flammable refrigerants of the present disclosure as being in fact non flammable fluoroolefins.
TABLE 4 Experimental Prediction from Compound Formula #F #H F/(F+H) Flammability flammability (LFL, vol% in fa ty air) air) factor HFC- C3HF5 5 1 0.83 non-flammable non-flammable 1225ye HFC- C 3H 2 F4 4 2 0.67 6.0 flammable 1234yf E-HFC- C3H 2F4 4 2 0.67 5.0 flammable 1234ze HFC- C 5HF9 9 1 0.90 non-flammable non-flammable 1429myz/ mzy (mixture of isomers) F12E C 6H 2 F8 8 2 0.75 non-flammable non-flammable
Other fluoroolefins HFC-1243 C 3 H 3 F3 3 3 0.15 na Flammable FC-1318 C 4F8 8 0 1.0 na non-flammable HFC-1327 C 4 HF 7 7 1 0.88 na non-flammable HFC-1336 C 4 H 2 F6 6 2 0.75 na non-flammable HFC-1345 C 4 H 3 F5 5 3 0.63 na flammable HFC-1354 C4 H4 F 4 4 4 0.50 na flammable FC-141-10 C5F 10 10 0 1.0 na non-flammable HFC-1429 C5HF9 9 1 0.90 na non-flammable HFC-1438 C6 H2 F8 8 2 0.80 na non-flammable HFC-1447 C 5H 3F7 7 3 0.70 na non-flammable HFC-1456 C5H 4 Fe 6 4 0.6 na flammable FC-151-12 C6F1 2 12 0 1.0 na non-flammable HFC-152- C 6 HF 11 11 1 0.92 na non-flammable 11 HFC-153- C 6H 2 F10 10 2 0.83 na non-flammable 10 HFC-1549 C6 H 3F1 9 3 0.75 na non-flammable HFC-1558 C 6H 4 F8 8 4 0.67 na flammable HFC-1567 C6 H5 F7 7 5 0.58 na flammable FC-161-14 C 7 F 14 14 0 1.0 na non-flammable HFC-162- C 7HF 13 13 1 0.93 na non-flammable 13 HFC-163- C 7 H 2 F1 2 12 2 0.86 na non-flammable 12 HFC-164- C 7 H 3F11 11 3 0.79 na non-flammable 11 HFC-165- C 7 H4 F10 10 4 0.71 na non-flammable 10 HFC-1669 C 7H 5 F9 9 5 0.64 na flammable HFC- C 4 F6 6 0 1.0 na non-flammable C1316 HFC- C 5F8 8 0 1.0 na non-flammable C1418 HFC- C 6F 10 10 0 1.0 na non-flammable
C151-10 HFC- C 4 H2 F 4 4 2 0.67 na flammable C1334 HFC- C5 H 2F6 6 2 0.75 na non-flammable C1436
The fluoroolefins as listed in Table 4 may be determined to be flammable or non-flammable based upon the value of the flammability factor. If the flammability factor is found to be equal to or greater than 0.70, then the fluoroolefin may be expected to be non-flammable. If the flammability factor is less than 0.70, then the fluoroolefin may be expected to be flammable. In another embodiment of the present invention, the fluoroolefins for use in compositions with flammable refrigerants are those fluoroolefins selected from the group consisting of: (a) fluoroolefins of the formula E- or Z-RCH=CHR 2, wherein R and R 2 are, independently, C1 to C6 perfluoroalkyl groups; (b) cyclic fluoroolefins of the formula cyclo-[CX=CY(CZW)n-], wherein X, Y, Z, and W, independently, are H or F, and n is an integer from 2 to 5, and wherein the flammability factor is greater than or equal to 0.70; and (c) fluoroolefins selected from the group consisting of: 1,2,3,3,3-pentafluoro-1-propene (CF 3CF=CHF); 1,1,3,3,3 pentafluoro-1-propene (CF 3CH=CF 2); 1,1,2,3,3-pentafluoro-1 propene (CHF 2CF=CF 2); 1.,1,1,2,3,4,4,4-octafluoro-2-butene (CF 3CF=CFCF 3); 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF 3CF 2CF=CF 2); 1,1,1,2,4,4,4-heptafluoro-2-butene (CF 3CF=CHCF 3); 1,2,3,3,4,4,4-heptafluoro-1-butene (CHF=CFCF2CF 3); 1,1,1,2,3,4,4-heptafluoro-2-butene (CHF 2CF=CFCF 3); 1,3,3,3-tetrafluoro-2-(trifluoromethyl)-1-propene ((CF3) 2C=CHF); 1,1,3,3,4,4,4-heptafluoro-1-butene (CF 2=CHCF 2CF 3); 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=CFCF 2CHF 2); 2,3,3,4,4,4-hexafluoro-1-butene (CF 3CF 2CF=CH 2); 1,3,3,4,4,4-hexafluoro-1-butene (CHF=CHCF 2CF 3); 1,2,3,4,4,4-hexafluoro-1-butene
(CHF=CFCHFCF3); 1, 2 ,3 ,3 ,4,4-hexafluoro-1-butene (CHF=CFCF2CHF 2); 1,1, 2 ,3 ,4 ,4 -hexafluoro-2-butene (CHF 2CF=CFCHF 2); 1,1,1, 2 ,3 ,4 -hexafluoro-2-butene (CH 2FCF=CFCF 3); 1,1,1, 2 ,4 ,4 -hexafluoro-2-butene 5 (CHF 2CH=CFCF3); 1,1,1, 3 ,4 ,4 -hexafluoro-2-butene (CF 3CH=CFCHF 2); 1,1, 2 ,3 ,3,4-hexafluoro-1-butene (CF 2=CFCF 2CH 2F); 1,1, 2 ,3 ,4,4-hexafluoro-1-butene (CF2=CFCHFCHF 2); 3,3, 3 -trifluoro-2-(trifluoromethyl)-1-propene (CH 2 =C(CF 3) 2 ); 1,1,1,2,3,4,4,5,5,5-decafluoro-2-pentene 10 (CF 3CF=CFCF 2CF 3); 1,1, 2 ,3 ,3 ,4, 4 ,5,5,5-decafluoro-1-pentene (CF2=CFCF 2CF 2CF3); 1,1,1, 4 ,4,4-hexafluoro-2-(trifluoromethyl)-2 butene ((CF 3) 2 C=CHCF 3); 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene (CF 3CF=CHCF 2CF 3); 1,1,1, 3 ,4 ,4 ,5,5,5-nonafluoro-2-pentene (CF 3CH=CFCF 2CF 3); 1, 2 ,3 ,3,4,4,5,5,5-nonafluoro-1-pentene (CHF=CFCF 2CF 2CF 3); 1,1,3,3,4,4,5 ,5,5-nonafluoro-1-pentene (CF2=CHCF 2CF 2CF 3); 1,1, 2 ,3,3,4,4,5,5-nonafluoro-1-pentene (CF 2=CFCF 2CF 2CHF 2); 1,1, 2 ,3 ,4 ,4,5,5,5-nonafluoro-2-pentene (CHF 2CF=CFCF 2CF 3); 1,1,1, 2 ,3 ,4 ,4 ,5,5-nonafluoro-2-pentene (CF 3CF=CFCF 2CHF 2); 1 ,1 ,1, 2 ,3,4,5,5,5-nonafluoro-2-pentene (CF 3CF=CFCHFCF 3); 1, 2 ,3, 4 ,4,4-hexafluoro-3-(trifluoromethyl)-1 butene (CHF=CFCF(CF3)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 ) ); 32 1,1,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene (CF 2=CHCF(CF 3)2); 2 ,3,3,4,4,5,5,5-octafluoro-1-pentene (CH 2=CFCF 2CF 2CF 3); 1,2,3,3,4,4,5,5-octafluoro-1-pentene (CHF=CFCF2CF 2CHF 2); 3 ,3 ,4,4,4-pentafluoro-2-(trifluoromethyl)-1 butene (CH 2=C(CF 3)CF 2CF 3); 1,1,4,4,4-pentafluoro-3 (trifluoromethyl)-1-butene (CF 2=CHCH(CF 3)2); 1,3,4,4,4 pentafluoro-3-(trifluoromethyl)-1-butene (CHF=CHCF(CF ) ); 32 1,1,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene (CF2=C(CF 3)CH 2CF 3); 3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1 butene ((CF 3)2CFCH=CH 2); 3, 3 ,4,4,5,5,5-heptafluoro-1-pentene (CF 3CF 2CF 2CH=CH 2); 2,3,3,4,4,5,5-heptafluoro-1-pentene (CH 2=CFCF2CF 2CHF 2); 1,1, 3 ,3,5,5,5-heptafluoro-1-butene (CF 2=CHCF 2CH 2CF 3); 1,1,1, 2 ,4 ,4 ,4-heptafluoro-3-methyl-2-butene
(CF 3CF=C(CF 3)(CH 3)); 2 ,4,4,4-tetrafluoro-3-(trifluoromethyl)-1
butene (CH 2=CFCH(CF 3)2); 1, 4 ,4,4-tetrafluoro-3-(trifluoromethyl)-1 butene (CHF=CHCH(CF 3)2); 1,1,1,4-tetrafluoro-2-(trifluoromethyl) 2-butene (CH 2FCH=C(CF 3)2); 1,1,1,3-tetrafluoro-2-(trifluoromethyl) 5 2-butene (CH 3CF=C(CF 3)2); 1,1, 2 ,3, 3 ,4 ,4 ,5,5,6 ,6,6-dodecafluoro-1 hexene (CF3(CF2)3CF=CF 2); 1,1,1, 2 ,2,3,4,5,5,6,6,6-dodecafluoro-3 hexene (CF 3CF 2CF=CFCF 2CF 3); 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 ) CFCF=CFCF 32 3); 10 1,1,1, 4 ,4 ,5,5,5-octafluoro-2-(trifluoromethyl)-2-pentene ((CF 3)2C=CHC 2 F); 1,1,1, 3 ,4 ,5,5,5-octafluoro-4-(trifluoromethyl)-2 pentene ((CF 3)2CFCF=CHCF 3); 3 ,3, 4 ,4,5,5,6,6,6-nonafluoro-1 hexene (CF 3CF 2CF 2 CF 2 CH=CH 2); 4,4,4-trifluoro-3,3 bis(trifluoromethyl)-1-butene (CH 2=CHC(CF 3)3); 1,1,1,4,4,4 hexafluoro-2-(trifluoromethyl)-3-methyl-2-butene ((CF 3)2C=C(CH 3)(CF 3)); 2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1 pentene (CH 2=CFCF 2CH(CF 3)2); 1,1,1,2,4,4,5,5,5-nonafluoro-3 methyl-2-pentene (CF 3CF=C(CH 3)CF 2CF 3); 1,1,1,5,5,5-hexafluoro 4-(trifluoromethyl)-2-pentene (CF 3CH=CHCH(CF ) ); 32 1,1,1,2,3,4 ,4 ,5,5, 6 ,6,7,7,7-tetradecafluoro-2-heptene (CF 3CF=CFCF 2CF 2C 2F); 1,1,1,2,2,3,4,5,5,6,6,7,7,7 tetradecafluoro-3-heptene (CF 3CF 2CF=CFCF C F); 2 2 1,1,1,3,4 ,4 ,5,5,6 ,6,7,7,7-tridecafluoro-2-heptene (CF 3CH=CFCF 2CF 2C 2F); 1,1,1, 2 ,4 ,4 ,5,5,6,6,7,7,7-tridecafluoro-2 heptene (CF 3CF=CHCF 2 CF 2C 2F 5); 1,1,1,2,2,4,5,5,6,6,7,7,7 tridecafluoro-3-heptene (CF 3CF 2CH=CFCF 2C 2F 5); and 1,1,1,2,2 ,3 ,5,5,6 ,6,7,7,7-tridecafluoro-3-heptene (CF 3CF 2CF=CHCF 2C 2F5 ). In yet another embodiment, the fluoroolefins of the present disclosure that may be particularly useful in combination with flammable refrigerants, may be at least one fluoroolefin selected from the group consisting of:
(a) fluoroolefins of the formula E- or Z-R'CH=CHR2, wherein R 1 and R 2 are, independently, C 1 to C perfluoroalkyl groups, and wherein the flammability factor is greater than or equal to 0.70; and
(b) cyclic fluoroolefins of the formula cyclo-[CX=CY(CZW)n-], wherein X, Y, Z, and W, independently, are H or F, and n is an integer from 2 to 5, and wherein the flammability factor is greater than or equal to 0.70. 5 While the flammability factor provides a basis for predicting flammability of certain fluoroolefin compounds, there may be certain variables, such as position of the hydrogen atoms on the molecule that would account for certain isomers with a given molecular formula being 10 flammable while other isomers are non-flammable. Therefore, the flammability factor may only be used as a tool for predicting flammability characteristics. Flammable refrigerants of the present invention comprise any compound, which may be demonstrated to propagate a flame under specified conditions of temperature, pressure and composition when mixed with air. Flammable refrigerants may be identified by testing under conditions specified by ASHRAE (American Society of Heating, Refrigerating and Air-Conditioning Engineers, Inc.) Standard 34-2001, under ASTM (American Society of Testing and Materials) E681-01, with an electronic ignition source. Such tests of flammability are conducted with the refrigerant at 101 kPa (14.7 psia) and a specified temperature (typically 100 °C (212 °F), or room temperature, that being about 23°C (73 °F) at various concentrations in air in order to determine the lower flammability limit (LFL) and upper flammability limit (UFL) of the test compound in air. In practical terms, a refrigerant may be classified as flammable if upon leaking from a refrigeration apparatus or air-conditioning apparatus, and contacting an ignition source a fire may result. The compositions of the present invention, during such a leak, have a low probability of causing a fire. Flammable refrigerants of the present invention include hydrofluorocarbons (HFCs), fluoroolefins, fluoroethers, hydrocarbon ethers, hydrocarbons, ammonia (NH 3 ), and combinations thereof. Flammable HFC refrigerants include but are not limited to: difluoromethane (HFC-32), fluoromethane (HFC-41), 1,1,1-trifluoroethane (HFC-143a), 1,1,2-trifluoroethane (HFC-143), 1,1-difluoroethane (HFC
152a), fluoroethane (HFC-161), 1,1,1-trifluoropropane (HFC-263fb), 1,1,1,3,3-pentafluoropropane (HFC-365mfc), and combinations thereof. These flammable HFC refrigerants are commercial products available from a number of sources such as chemical synthesis companies or may 5 be prepared by synthetic processes disclosed in the art. Flammable refrigerants of the present invention further comprise fluoroolefins including but not limited to: 1,2,3,3-tetrafluoro-1 propene (HFC-1234ye); 1,3,3,3-tetrafluoro-1-propene (HFC-1234ze); 2,3,3,3-tetrafluoro-1-propene (HFC-1 2 3 4 y; 1,1,2,3-tetrafluoro-1-propene 10 (HFC-1234yc); 1,1,3,3-tetrafluoro-1-propene (HFC-1234zc); 2,3,3-trifluoro 1-propene (HFC-1243yf); 3,3,3-trifluoro-1-propene (HFC-1243zf); 1,1,2 trifluoro-1-propene (HFC-1243yc); 1,1,3-trifluoro-1-propene (HFC-1243zc); 1,2,3-trifluoro-1-propene (HFC-1243ye); and 1,3,3-trifluoro-1-propene (HFC-1243ze). 15 Flammable refrigerants of the present invention further comprise fluoroethers, compounds similar to hydrofluorocarbons, which also contain at least one ether group oxygen atom. Representative fluoroether refrigerants include but are not limited to C4 FOC 2 H5 , available commercially. Flammable refrigerants of the present invention further comprise hydrocarbon refrigerants. Representative hydrocarbon refrigerants include but are not limited to 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-heptane, methylcyclopentane, and n hexane. Flammable hydrocarbon refrigerants are readily'available from multiple commercial sources. Flammable refrigerants of the present invention further comprise hydrocarbon ethers, such as dimethyl ether (DME, CH 0CH 3 3 )
and methyl t-butyl ether (MTBE, (CH 3) 3 COCH 3 ), both available from multiple commercial sources. Flammable refrigerants of the present invention further comprise ammonia (NH 3), a commercially available compound.
Flammable refrigerants of the present invention may further comprise mixtures of more than one refrigerant such as a mixture of two or more flammable refrigerants (eg. two HFCs or an HFC and a hydrocarbon) or a mixture comprising a flammable refrigerant and a non-flammable 5 refrigerant, such that the overall mixture is still considered to be a flammable refrigerant, identified under the ASTM conditions described herein, or in practical terms. Examples of non-flammable refrigerants that may be combined with other refrigerants of the present invention include R-134a, R-134, R-23, 10 R125, R-236fa, R-245fa, and mixtures of HCFC-22/HFC-152a/HCFC-124 (known by the ASHRAE designations, R401 or R-401A, R-401B, and R 401C), HFC-125/HFC-143a/HFC-134a (known by the ASHRAE designation, R-404 or R-404A), HFC-32/HFC-125/HFC-134a (known by ASHRAE designations, R407 or R-407A, R-407B, and R-407C), HCFC 15 22/HFC-143a/HFC-125 (known by the ASHRAE designation, R408 or R 408A), HCFC-22/HCFC-124/HCFC-142b (known by the ASHRAE designation: R-409 or R-409A), HFC-32/HFC-125 (known by the ASHRAE designation R-410A), and HFC-125/HFC-143a (known by the ASHRAE designation: R-507 or R507A) and carbon dioxide. 20 Examples of mixtures of more than one flammable refrigerant include propane/isobutane; HFC-152a/isobutane, R32/propane; R32/isobutane; and HFC/carbon dioxide mixtures such as HFC-152a/CO 2 One aspect of the present invention is to provide a non . flammable refrigerant with a global warming potential of less than 150, preferably less than 50. Another aspect of the present invention is to reduce the flammability of flammable refrigeration mixtures by'adding non flammable fluoroolefins to said mixtures. It may be demonstrated that while certain refrigerants are flammable, it is possible to produce a non-flammable refrigerant composition by adding to the flammable refrigerant another compound that is not flammable. Examples of such nonflammable refrigerant blends include R-410A (HFC-32 is a flammable refrigerant, while HFC-125 is non-flammable), and R-407C (HFC-32 is a flammable refrigerant, while HFC-125 and HFC-134a are not flammable). The compositions of the present invention that are useful as refrigerants or heat transfer fluids comprising at least one fluoroolefin and at least one flammable refrigerant may contain an effective amount of fluoroolefin to produce a composition that is non-flammable based upon results of ASTM E681-01. The present inventive compositions comprising at least one 5 flammable refrigerant and at least one fluoroolefin may contain about 1 weight percent to about 99 weight percent fluoroolefin and about 99 weight percent to about 1 weight percent flammable refrigerant. In another embodiment, the compositions of the present invention may contain about 10 weight percent to about 80 weight percent 10 fluoroolefin and about 90 weight percent to about 20 weight percent flammable refrigerant. In yet another embodiment, the compositions of the present invention may contain about 20 weight percent to about 70 weight percent fluoroolefin and about 80 weight percent to about 30 weight percent flammable refrigerant. 15 Of particular interest is an embodiment of the present disclosure wherein the fluoroolefin comprises HFC-1225ye and the flammable refrigerant comprises HFC-32 (difluoromethane). It has been determined that compositions comprising up to 37 weight percent HFC-32 are non-flammable, while compositions comprising 38 weight percent 20 HFC-32 or greater are flammable as determined by ASTM 681-01. The present disclosure provides non-flammable compositions comprising about 1.0 weight percent to about 37.0 weight percent HFC-32 and about 99.0 weight percent to about 63 weight percent HFC-1225ye. Also, of particular interest is an embodiment of the present disclosure wherein the composition comprises HFC-1225ye, HFC-32 and HFC-125. This composition of the present invention comprises 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. In another embodiment, the composition comprises about 30 weight percent to about 90 weight percent HFC-1225ye, about 5.0 weight percent to about 55 weight percent HFC-32, and about 1.0 weight percent to about 35 weight percent HFC 125. In yet another embodiment, the composition comprises about 40 weight percent to about 85 weight percent HFC-1225ye, about 10 weight percent to about 45 weight percent HFC-32 and about 1.0 weight percent to about 28 weight percent HFC-125. Those compositions containing less than about 40 weight percent HFC-32 are expected to be non-flammable compositions. This flammability limit will vary from less than about 45 weight percent HFC-32 to less than about 37 weight percent HFC-32 depending on the relative ratios of HFC-1225ye and HFC-125 present in 5 the composition. In another embodiment of particular interest, the flammable refrigerant comprises HFC-1243zf and a non-flammable fluoroolefin intended to reduce the flammability of the overall composition. The composition may comprise about 1.0 weight percent to about 99 weight 10 percent HFC-1243zf and about 99 weight percent to about 1.0 weight percent HFC-1225ye. Alternatively, the composition may comprise about 40 weight percent to about 70 weight percent HFC-1243zf and about 60 weight percent to about 30 weight percent HFC-1225ye. In another embodiment of particular interest, the composition 15 comprises about 1.0 weight percent to about 98 weight percent HFC 1243zf; about 1.0 weight percent to about 98 weight percent HFC-1225ye; and about 1.0 weight percent to about 50 weight percent HFC-125. Alternatively, the composition comprises about 40 weight percent to about 70 weight percent HFC-1243zf; about 20 weight percent to about 60 20 weight percent HFC-1225ye; and about 1.0 weight percent to about 10 weight percent HFC-125. In another embodiment of particular interest the composition comprises about 1.0 weight percent to about 98 weight percent HFC 1243zf; about 1.0 weight percent to about 98 weight percent HFC-1225ye; and about 1.0 weight percent to about 50 weight percent HFC-32. Alternatively, the composition comprisesabout 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. In yet another embodiment of particular interest, the composition comprises about 1.0 weight percent to about 97 weight percent HFC-1243zf; about 1.0 weight percent to about 97 weight percent HFC-1225ye; about 1.0 weight percent to about 50 weight percent HFC 125; and about 1.0 weight percent to about 50 weight percent HFC-32. Alternatively, the composition comprises 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 about 1.0 weight percent to about 10 weight percent HFC-32. The present invention further relates to a method for reducing 5 the flammability of a flammable refrigerant said method comprising combining the flammable refrigerant with at least onefluoroolefin. The amount of fluoroolefin added must be an effective amount to produce a non-flammable compositions as determined by ASTM 681-01. Compositions of the present invention may be used in 10 combination with a desiccant in a refrigeration, air-conditioning, or heat pump system to aid in removal of moisture. Desiccants may be composed of acitivated alumina, silica gel, or zeolite based molecular sieves. Representative molecular sieves include MOLSIV XH-7, XH-6, XH-9 and XH-11 (UOP LLC, Des Plaines, IL). For refrigerants with small molecular 15 size such as HFC-32, XH-1 Idesiccant is preferred. The compositions of the present invention may further comprise at least one lubricant. Lubricants of the present invention comprise those suitable for use with refrigeration or air-conditioning apparatus. Among these lubricants are those conventionally used in compression refrigeration apparatus utilizing chlorofluorocarbon refrigerants. Such lubricants and their properties are discussed in the 1990 ASHRAE Handbook, Refrigeration Systems and Applications, chapter 8, titled "Lubricants in Refrigeration Systems", pages 8.1 through 8.21, herein incorporated by reference. Lubricants of the present invention may comprise those commonly known as "mineral oils" in the field of compression refrigeration lubrication. Mineral oils comprise paraffins (i.e. straight-chain and branched-carbon-chain, saturated hydrocarbons), naphthenes (i.e. cyclic paraffins) and aromatics (i.e. unsaturated, cyclic hydrocarbons containing one or more rings characterized by alternating double bonds). Lubricants of the present invention further comprise those commonly known as "synthetic oils" in the field of compression refrigeration lubrication. Synthetic oils comprise alkylaryls (i.e. linear and branched alkyl alkylbenzenes), synthetic paraffins and naphthenes, and poly(alphaolefins). Representative conventional lubricants of the present invention are the commercially available BVM 100 N (paraffinic mineral oil sold by BVA Oils), Suniso@ 3GS and Suniso@5GS (naphthenic mineral oil sold by Crompton Co.), Sontex@ 372LT (naphthenic mineral oil sold by Pennzoil), Calumet@ RO-30 (naphthenic mineral oil sold by Calumet Lubricants), Zerolo 75, Zerolo 150 and Zerol@ 500 (linear alkylbenzenes sold by Shrieve Chemicals) and HAB 22 (branched alkylbenzene sold by 5 Nippon Oil). Lubricants of the present invention further comprise those, which have been designed for use with hydrofluorocarbon refrigerants and are miscible with refrigerants of the present invention under compression refrigeration and air-conditioning apparatus' operating conditions. Such 10 lubricants and their properties are discussed in "Synthetic Lubricants and High-Performance Fluids", R. L. Shubkin, editor, Marcel Dekker, 1993. Such lubricants include, but are not limited to, polyol esters (POEs) such as Castrol@100 (Castrol, United Kingdom), polyalkylene glycols (PAGs) such as RL-488A from Dow (Dow Chemical, Midland, Michigan), and polyvinyl ethers (PVEs). Lubricants of the present invention are selected by considering a given compressor's requirements and the environment to which the lubricant will be exposed. Commonly used refrigeration system additives may optionally be added, as desired, to compositions of the present invention in order to enhance lubricity and system stability. These additives are generally known within the field of refrigeration compressor lubrication, and include anti wear agents, extreme pressure lubricants, corrosion and oxidation inhibitors, metal surface deactivators, foaming and antifoam control agents, leak detectants and the like. In general, these additives are present only in small amounts relative to the overall lubricant composition. They are typically used at concentrations of from less than about 0.1 % to as much as about 3 %of each additive. These additives are selected on the basis of 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 of thiophosphates. Additionally, the metal dialkyl dithiophosphates (e.g. zinc dialkyl dithiophosphate or ZDDP, Lubrizol 1375) and other members of this family of chemicals may be used in compositions of the present invention. Other antiwear additives include natural product oils and assymetrical polyhydroxyl lubrication additives such as Synergol TMS
(International Lubricants). Similarly, stabilizers such as antioxidants, free radical scavengers, and water scavengers (drying compounds) may be employed. Such additives include but are not limited to, nitromethane, hindered phenols (such as butylated hydroxy toluene, or BHT), 5 hydroxylamines,thiols, phosphites, epoxides or lactones. Water scavengers include but are not limited to ortho esters such as trimethyl-, triethyl-, or tripropylortho formate. Single additives or combinations may be used. In one embodiment, the present invention provides 10 compositions comprising at least one fluoroolefin and at least one stabilizer selected from the group consisting of thiophosphates, butylated triphenylphosphorothionates, organo phosphates, dialkylthiophosphate esters, terpenes, terpenoids, fullerenes, functionalized perfluoropolyethers, polyoxyalkylated aromatics, epoxides, fluorinated 15 epoxides, oxetanes, ascorbic acid, thiols, lactones, thioethers, nitromethanes, alkylsilanes, benzophenone derivatives, arylsulfide, divinyl terephthalate, diphenyl terephthalate, alkylamines, hindered amine antioxidants, and phenols, The alkylamines can include triethylamine, tributylamine, diisopropylamine, triisopropylamine, triisobutylamine, and 20 other members of this family of alkylamine compounds. In another embodiment, the stabilizers of the present invention may comprise specific combinations of stabilizers. One combination of stabilizers of particular interest comprises at least one terpene or terpenoid. These terpenes or terpenoids may be combined with at least one compound selected from epoxides, fluorinated epoxides, and oxetanes. Terpenes are hydrocarbon compounds characterized by structures containing more than one repeating isoprene (2-methyl-1,3 butadiene) unit. Terpenes may be acyclic or cyclic. Representative terpenes include but are not limited to myrcene (2-methyl-6-methyl eneocta-1,7-diene), allo-cimene, beta-ocimene, terebene, limonene (or d limonene), retinal, pinene (or alpha-pinene), menthol, geraniol, farnesol, phyto, Vitamin A, terpinene, delta-3-carene, terpinolene,,phellandrene, fenchene and mixtures thereof. Terpene stabilizers are commercially available or may be prepared by methods known in the art or isolated from natural sources.
Terpenoids are natural products and related compounds characterized by structures containing more than one repeating isoprene unit and optionally contain oxygen. Representative terpenoids include carotenoids, such as lycopene (CAS reg. no. [502-65-8]), betacarotene 5 (CAS reg. no. [7235-40-7]), and xanthophylls, i.e. zeaxanthin (CAS reg. no. [144-68-3]); retinoids, such as hepaxanthin (CAS reg. no. [512-39-0]), and isotretinoin (CAS reg. no. [4759-48-2]); abietane (CAS reg. no. [640 43-7]); ambrosane (CAS reg. no. [24749-18-6]); aristolane (CAS reg. no.
[29788-49-6]); atisane (CAS reg. no. [24379-83-7]);.beyerane (CAS reg. 10 no. [2359-83-3]), bisabolane (CAS reg. no. [29799-19-7]); bornane (CAS reg. no. [464-15-3]); caryophyllane (CAS reg. no. [20479-00-9]); cedrane (CAS reg. no. [13567-54-9]); dammarane (CAS reg. no. [545-22-2]); drimane (CAS reg. no. [5951-58-6]); eremophilane (CAS reg. no. [3242 05-5]); eudesmane (CAS reg. no. [473-11-0]); fenchane (CAS reg. no. 15 [6248-88-0]); gammacerane (CAS reg. no. [559-65-9]); germacrane (CAS reg. no. [645-10-3]); gibbane (CAS reg. no. [6902-95-0]); grayanotoxane (CAS reg. no. [39907-73-8]); guaiane (CAS reg. no. [489-80-5]); himachalane (CAS reg. no. [20479-45-2]); hopane (CAS reg. no. [471-62 5]); humulane (CAS reg. no. [430-19-3]); kaurane (CAS reg. no. [1573-40 6]); labdane (CAS reg. no. [561-90-0]); lanostane (CAS reg. no. [474-20 4]); lupane (CAS reg. no. [464-99-3]); p-menthane (CAS reg. no. [99-82 1]); oleanane (CAS reg. no. [471-67-0]); ophiobolane (CAS reg. no.
[20098-65-1]); picrasane (CAS reg. no. [35732-97-9]); pimarane (CAS reg. no. [30257-03-5]); pinane (CAS reg. no. [473-55-2]); podocarpane (CAS, reg. no. [471-78-3]); protostane (CAS reg. no. [70050-78-1]); rosane (CAS reg. no. [6812-82-4]); taxane (CAS reg. no. [1605-68-1]); thujane (CAS reg. no. [471-12-5]); trichothecane (CAS reg. no. [24706-08-9]); and ursane (CAS reg. no. [464-93-7]). The terpenoids of the present invention are commercially available or may be prepared by methods known in the art or may be isolated from the naturally occurring source. In one embodiment, the terpene or terpenoid stabilizers may be combined with at least one epoxide. Representative epoxides include 1,2 propylene oxide (CAS reg. no. [75-56-9]); 1,2-butylene oxide (CAS reg. no. [106-88-7]); or mixtures thereof. In another embodiment, the terpene or terpenoid stabilizers of the present invention may be combined with at least one fluorinated epoxide. The fluorinated epoxides of the present invention may be depicted by Formula 3, wherein each of R 2 through R 5 is H, alkyl of 1 - 6 carbon atoms or fluoroalkyl of 1-6 carbon atoms with the proviso that at least one of R 2 through R 5 is a fluoroalkyl group. 5 R2 0 R4
R3 R5
Formula 3
Representative fluorinated epoxide stabilizers include but are not limited to trifluoromethyloxirane and 1,1-bis(trifluoromethyl)oxirane. Such compounds may be prepared by methods known in the art, for instance by methods described in, Journal of Fluorine Chemistry, volume 24, pages 93-104 (1984), Journal of Organic Chemistry, volume 56, pages 3187 to 3189 (1991), and Journal of Fluorine Chemistry, volume 125, pages 99 105(2004). In another embodiment, the terpene or terpenoid stabilizers of the present invention may be combined with at least one oxetane. The oxetane stabilizers of the present invention may be compounds with one or more oxetane groups and is represented by Formula 4, wherein R1 -R6 are the same or different and can be selected from hydrogen, alkyl or substituted alkyl, aryl or substituted aryl.
R3 R4
R2 R5
R10 R6
Formula 4 Representative oxetane stabilizers include but are not limited to 3-ethyl-3 hydroxymethyl-oxetane, such as OXT-101 (Toagosei Co., Ltd); 3-ethyl-3 ((phenoxy)methyl)-oxetane, such as OXT-211 (Toagosei Co., Ltd); and 3 ethyl-3-((2-ethyl-hexyloxy)methyl)-oxetane, such as OXT-212 (Toagosei Co., Ltd).
Another embodiment of particular interest is a combination of stabilizers comprising fullerenes. The fullerene stabilizers may be combined with at least one compound selected from the group consisting of epoxides, fluorinated epoxides, and oxetanes. The epoxides, 5 fluorinated epoxides, and oxetanes for combination with fullerenes have been previously described herein as for combination with terpenes or terpenoids. Another embodiment of particular interest is a combination of stabilizers comprising phenols. The fullerene stabilizers may be combined 10 with at least one compound selected from the group consisting of epoxides, fluorinated epoxides, and oxetanes. The epoxides, fluorinated epoxides, and oxetanes for combination with phenols have been previously described herein as for combination with terpenes or terpenoids. 15 Phenol stabilizers comprise any substituted or unsubstituted phenol compound including phenols comprising one or more substituted or unsubstituted cyclic, straight chain, or branched aliphatic substituent group, such as, alkylated monophenols including 2,6-di-tert-butyl-4 methylphenol; 2,6-di-tert-butyl-4-ethylphenol; 2,4-dimethyl-6 tertbutylphenol; tocopherol; and the like, hydroquinone and alkylated hydroquinones including t-butyl hydroquinone, other derivatives of hydroquinone; and the like, hydroxylated thiodiphenyl ethers, including 4,4'-thio-bis(2-methyl-6-tert-butylphenol); 4,4'-thiobis(3-methyl6 tertbutylphenol); 2,2'-thiobis(4methyl-6-tert-butylphenol); and the like, alkylidene-bisphenols including,: 4,4'-methylenebis(2,6-di-tert butylphenol); 4,4'-bis(2,6-di-tert-butylphenol); derivatives of 2,2'- or 4,4 biphenoldiols; 2 ,2'-methylenebis(4-ethyl-6-tertbutylphenol); 2,2' methylenebis(4-methyl-6-tertbutylphenol); 4,4-butylidenebis(3-methyl-6 tert-butylphenol); 4 ,4 -isopropylidenebis(2,6-di-tert-butylphenol); 2,2' methylenebis(4-methyl-6-nonylphenol); 2,2'-isobutylidenebis(4,6 dimethylphenol; 2 ,2 '-methylenebis(4-methyl-6-cyclohexylphenol, 2,2- or 4,4- biphenyldiols including 2,2'-methylenebis(4-ethyl-6-tert-butylphen o); butylated hydroxyl toluene (BHT), bisphenols comprising heteroatoms including 2 ,6-di-tert-alpha-dimethylamino-p-cresol, 4,4-thiobis(6-tert-butyl m-cresol); and the like; acylaminophenols; 2,6-di-tert-butyl-4(N,N' dimethylaminomethylphenol); sulfides including; bis(3-methyl-4-hydroxy-5 tert-butylbenzyl)sulfide; bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide; and the like. In one embodiment of the present invention, these combinations of stabilizers comprising terpenes or terpenoids, or 5 fullerenes or phenols with at least one compound selected from the group consisting of epoxides, fluorinated epoxides, and oxetanes, may further comprise an additional stabilizer compound selected from the group consisting of: areoxalyl bis(benzylidene)hydrazide (CAS reg. no. 6629-10-3); 10 N,N'-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoylhydrazine) (CAS reg. no. 32687-78-8); 2,2'-oxamidobis-ethyl-(3,5-d-tert-butyl-4-hydroxyhydorcinnamate) (CAS reg. no. 70331-94-1); N,N'-(disalicyclidene)-1,2-propanediamine (CAS reg. no. 94-91-1); and 15 ethyenediaminetetraacetic acid (CAS reg. no. 60-00-4) and salts thereof. In another embodiment of the present invention, these combinations of stabilizers comprising terpenes or terpenoids, or fullerenes or phenols with at least one compound selected from the group 20 consisting of epoxides, fluorinated epoxides, and oxetanes, may further comprise at least one alkylamine selected from the group consisting of triethylamine; tributylamine; triisopropylamine; diisobutylamine; triisopropylamine; triisobutylamine; and hindered amine antioxidants. The compositions of the present invention may further comprise a compound or composition that is a tracer and is selected from the group consisting of hydrofluorocarbon (HFCs), deuterated hydrocarbon, deuterated hydrofluorocarbon, perfluorocarbons, fluoroether, brominated compound, iodated compound, alcohol, aldehyde, ketones, nitrous oxide (N 20) and combinations thereof. The tracer used in the present invention are different compositions from those used as refrigerant or heat transfer fluids, are added to the refrigerant and heat transfer compositions in previously determined quantities to allow detection of any dilution, contamination or other alteration of the composition, as described in U. S. Patent application serial no. 11/062,044, filed February 18, 2005. Typical tracer compounds for use in the present compositions are listed in Table 5.
TABLE 5 Cornound Structure -Deuterated hydrocarbons and hydrofluorocarbons Ethane-d6 CD 3CD 3 Propane-d8 CD 3CD 2 CD 3 HFC-32-d2 CD 2F2 HFC-134a-d2 CD 2FCF 3 HFC-143a-d3 CD 3CF 3 HFC-125-d CDF 2CF 3 HFC-227ea-d CF 3CDFCF 3 HFC-227ca-d CF 3CF 2CDF 2 HFC-134-d2 CDF 2CDF 2 HFC-236fa-d2 CF3CD 2CF3 HFC-245cb-d3 CF 3CF 2CD 3 HFC-263fb-d2* CF 3CD 2CH3 HFC-263fb-d3 CF 2CH 2CD3 Fluoroethers HFOC-125E CHF 2OCF 3 HFOC-l 34aE CH 2FOCF 3 HFOC-l43aE CH 300F 3 HFOC-227eaE CF 3OCHF-F 3 HFOC-236faE CF 300H 2 CF 3 HFOC-245faEp3y or HFOC- , CHF 2OCH 2CF 3 245faEa3 (or CHF 2 CH 2 00F 3 )
HFOC-245cbEP7 or HFOC-245cbap CH 3OCF 2CF 3 (or CH3 CF 2 0CF3 )
HFE-42-llmcc (or Freon®)El) CF.3CF 2CF 200HFCF 3 Freon® E2 CF 3 CF 2 CF 2 00F(CF 3)CF 2 00HFCF 3 Hydrofluorocarbons HFC-23 CHF 3 HFC-161 CH 3CH 2F HFC-l52a CH 3CHF 2 HFC-134 CHF 2CHF 2 HFC-227ea CF3CHFCF 3 HFC-227ca CHF 2CF 2 CF3 HFC-236cb CH 2 FCF 2 CF3
HFC-236ea CF 3CHFCHF 2 HFC-236fa OF 3CH 2 CF3 HFC-245cb CF 3 CF2 CH 3 HFC-245fa CHF 2CH 2CF 3 HFC-254cb CHF 2CF 2 CH 3 HFC-254eb CF 3CHFCH 3 HFC-263fb CF 3CH 2 CH 3 HFC-272ca OH 3CF 2 CH 3 HFC-281ea CH 3 CHFCH 3 HFC-281fa CH 2 FCH 2CH 3 HFC-329p CHF 2 CF 2CF 2 CF 3 HFC-329mmz (CH 3) 2CHCF 3 HFC-338mf CF 3CH 2CF 2 CF3 HFC-338pcc CHF 2CF 2CF 2 CHF 2 HFC-347s CH 3CF2CF2CF3 HFC-43-1Omee CF 3CHFCHFCF 2 CF 3 Perfluorocarbons _______________
PFC-1 16 CF 3 CF 3 PFC-C216 Cyclo(-CF 2CF 2 CF 2-) PFC-218 CF 3 CF 2CF 3 PFC-0318 Cyclo(-CF 2CF 2 CF 2CF 2-) PFC-31 -1 Omc CF 3CF 2CF 2 CF 3 PFC-31 -1 Omy (CF 3)2CFCF 3 PFC-C51-12mycm Cyclo(-CF(CF3)CF 2CF(CF 3)CF 2 -) PFC-C5I-12mym, trans Cyclo(-CF 2 CF(CF 3 )CF(CF 3 CF 2-) PFC-C51-l2mym, cis Cyclo(-CF 2CF(CF 3)CF(0F 3)CF 2 -) Perfluorom ethyl cyclo-pentane Cyclo(-CF 2CF 2(CF 3)CF 2CF 2CF2-) Perfluoromethylcyclo-hexane Cyclo(-CF 2CF 2(CF 3)CF 2CF2CF 2CF 2-) Perfluorodimethylcyclo-hexane (ortho, Cyclo(-CF 2CF 2(CF 3)CF 2CF 2(CF 3)CF 2-) meta, or para)______________ _____
Perfluoroethylcyclohexane Cyclo(-CF 2CF 2(CF 2CF 3)CF 2CF 2CF 2CF2
Perfluoroindan C 9F 1 (see structure below) F F F FF
F F F F F
Perfluorotrimethylcyclo-hexane (all Cyclo( possible isomers) CF2(CF 3)CF 2(CF 3)CF 2CF 2(CF 3)CF 2-) Perfluoroisopropylcyclo-hexane Cyclo( CF 2CF 2(CF 2(CF 3)2)CF 2CF 2CF 2CF 2-) Perfluorodecalin (cis or trans, trans C1 0F 1 8 (see structure below) shown) F FF F F FF F F F F F FF
Perfluoromethyldecalin (cis or trans C 11F20 (see structure below) and all additional possible isomers) CF 3 F F F F cFF F rF
F F F F F F FF
Brominated compounds Bromomethane CH 3Br Bromofluoromethane CH 2FBr Bromodifluoromethane CHF 2Br Dibromofluoromethane CHFBr 2 Tribromomethane CHBr3 Bromoethane CH 3CH 2Br Bromoethene CH 2=CHBr 1,2-dibromoethane CH 2BrCH 2Br 1-bromo-1,2-difluoroethene CFBr=CHF lodated compounds lodotrifluoromethane CF31 Difluoroiodomethane CHF 2i Fluoroiodomethane CH 2FI 1,1,2-trifluoro-1-iodoethane CF 2 1CH2F 1,1,2,2-tetrafluoro-1-iodoethane CF 2|CHF2 1,1,2,2-tetrafluoro-1,2-diiodoethane CF 2 1CF21 lodopentafluorobenzene C6 F 5 1 Alcohols Ethanol CH 3CH 2OH n-propanol CH 3CH 2CH 2OH Isopropanol CH 3CH(OH)CH 3 Aldehydes and Ketones Acetone (2-propanone) CH 3 C(O)CH 3 n-propanal CH 3CH 2CHO n-butanal CH 3CH 2CH 2CHO Methyl ethyl ketone (2-butanone) CH 3C(O)CH 2CH 3 Other Nitrous oxide N2 0
The compounds listed in Table 5 are available commercially (from chemical supply houses) or may be prepared by processes known in the art. Single tracer compounds may be used in combination with a refrigeration/heating fluid in the compositions of the present invention or multiple tracer compounds may be combined in any proportion to serve as a tracer blend. The tracer blend may contain multiple tracer compounds from the same class of compounds or multiple tracer compounds from different classes of compounds. For example, a tracer blend may contain 2 or more deuterated hydrofluorocarbons, or one deuterated hydrofluorocarbon in combination with one or more perfluorocarbons. Additionally, some of the compounds in Table 4 exist as multiple isomers, structural or optical. Single isomers or multiple isomers of the same compound may be used in any proportion to prepare the tracer compound. Further, single or multiple isomers of a given compound may be combined in any proportion with any number of other compounds to serve as a tracer blend. The tracer compound or tracer blend may be present in the compositions at a total concentration of about 50 parts per million by weight (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 ultra-violet (UV) dye and optionally a solubilizing agent. The UV dye is a useful component for detecting leaks of the refrigerant composition or heat transfer fluids by permitting one to observe the fluorescence of the dye in the refrigerant or heat transfer fluid composition at or in the vicinity of a leak point in said apparatus in the refrigeration, air-conditioning, heat pump apparatus. One may observe the fluorescence of the dye under an 5 ultra-violet light. Solubilizing agents may be needed due to poor solubility of such UV dyes in some refrigerants and heat transfer fluids. By "ultra-violet" dye is meant a UV fluorescent composition that absorbs light in the ultra-violet or "near" ultra-violet region of the electromagnetic spectrum. The fluorescence produced by the UV fluorescent dye under illumination by a UV light that emits radiation with wavelength anywhere from 10 nanometer to 750 nanometer may be detected. Therefore, if refrigerant or heat transfer fluid containing such a UV fluorescent dye is leaking from a given point in a refrigeration, air conditioning, or heat pump apparatus, the fluorescence can be detected at the leak point, or in the vicinity of the leak point. Such UV fluorescent dyes include but are not limited to naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, and derivatives of said dye or combinations thereof. Solubilizing agents of the present invention comprise at least one compound selected from the group consisting of hydrocarbons, hydrocarbon ethers, polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and 1,1,1-trifluoroalkanes. Hydrocarbon solubilizing agents of the present invention comprise hydrocarbons including straight chained, branched chain or cyclic alkanes or alkenes containing 16 or fewer carbon atoms and'only hydrogen with no other functional groups. Representative hydrocarbon solubilizing agents comprise propane, propylene, cyclopropane, n-butane, isobutane, n-pentane, octane, decane, and hexadecane. It should be noted that if the refrigerant is a hydrocarbon, then the solubilizing agent may not be the same hydrocarbon. Hydrocarbon ether solubilizing agents of the present invention comprise ethers containing only carbon, hydrogen and oxygen, such as dimethyl ether (DME). Polyoxyalkylene glycol ether solubilizing agents of the present invention are represented by the formula R1 [(OR 2 )xOR 3],wherein: x is an integer from 1-3; yis an integer from 1-4; R' is selected from hydrogen and aliphatic hydrocarbon radicals having 1 to 6 carbon atoms and y bonding sites; R2 is selected from aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms; R 3 is selected from hydrogen and aliphatic and 5 alicyclic hydrocarbon radicals having from 1 to 6 carbon atoms; at least one of R1 and R 3 issaid hydrocarbon radical; and wherein said polyoxyalkylene glycol ethers have a molecular weight of from about 100 to about 300 atomic mass units. As used herein, bonding sites mean radical sites available to form covalent bonds with other radicals. 10 Hydrocarbylene radicals mean divalent hydrocarbon radicals. In the present invention, preferred polyoxyalkylene glycol ether solubilizing agents are represented by Rl[(OR 2)xOR 3 ]y: x is preferably 1-2; y is preferably 1; R' and R 3 are preferably independently selected from hydrogen and aliphatic hydrocarbon radicals having 1 to 4 carbon atoms; 15 R2 is preferably selected from aliphatic hydrocarbylene radicals having from 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 mass units, most preferably from about 125 to about 250 atomic mass units. The R1 and Rh ydrocarbon radicals having I to 6 carbon atoms may be linear, branched or cyclic. Representative R, and R 3 hydrocarbon radicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, and cyclohexyl. Where free hydroxyl radicals on the present polyoxyalkylene glycol ether solubilizing agents may be incompatible with certain compression refrigeration apparatus materials of construction (e.g. Mylar@), R 1 and R 3 are preferably aliphatic hydrocarbon radicals having 1 to 4 carbon atoms, most preferably 1 carbon atom. The R2 aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms form repeating oxyalkylene radicals - (OR 2)x - that include oxyethylene radicals, oxypropylene radicals, and oxybutylene radicals. The oxyalkylene radical comprising R 2 in one polyoxyalkylene glycol ether solubilizing agent molecule may be the same, or one molecule may contain different R2 oxyalkylene groups. The present polyoxyakylene glycol ether solubilizing agents preferably comprise at least one oxypropylene radical. Where R is an aliphatic or alicyclic hydrocarbon radical having 1 to 6 carbon atoms and y bonding sites, the radical may be linear, branched or cyclic.
Representative RI aliphatic hydrocarbon radicals having two bonding sites include, for example, an ethylene radical, a propylene radical, a butylene radical, a pentylene radical, a hexylene radical, a cyclopentylene radical and a cyclohexylene radical. Representative R' aliphatic hydrocarbon 5 radicals having three or four bonding sites include residues derived from polyalcohols, such as trimethylolpropane, glycerin, pentaerythritol, 1,2,3 trihydroxycyclohexane and 1,3,5-trihydroxycyclohexane, by removing their hydroxyl radicals. Representative polyoxyalkylene glycol ether solubilizing agents include but are not limited to: CH 30CH 2CH(CH 3)O(H or CH 3) (propylene glycol methyl (or dimethyl) ether), CH 30[CH 2CH(CH 3)O] (H or CH 2 3
) (dipropylene glycol methyl (or dimethyl) ether), CH 3 0[CH 2 CH(CH 3 )O] 3 (H or CH 3 ) (tripropylene glycol methyl (or dimethyl) ether), C 2H 5OCH2CH(CH 3)O(H or C 2 H) (propylene glycol ethyl(or diethyl) ether), C 2H 50[CH 2CH(CH 3)O]2(H or C 2 H) (dipropylene glycol ethyl (or diethyl) ether), C 2 H 5 O[CH 2 CH(CH 3)O] 3(H or C2 H5) (tripropylene glycol ethyl (or diethyl) ether), C 3H7 0CH 2CH(CH 3)O(H or C3H 7 ) (propylene glycol n-propyl (or di-n-propyl) ether), C3H 70[CH 2CH(CH 3)O] 2(H or C3H 7 ) (dipropylene glycol n-propyl (or di-n-propyl) ether) , C 3H 70[CH 2CH(CH 3)O]3(H or C H 3 7
) (tripropylene glycol n-propyl (or di-n-propyl) ether), C 4H0OCH 2CH(CH 3)OH (propylene glycol n-butyl ether), C 4HO[CH 2CH(CH 3)O] 2(H or C 4H9 ) (dipropylene glycol n-butyl (or di-n-butyl) ether), C4HO[CH 2CH(CH)O] 3(H or C 4 H 9) (tripropylene glycol n-butyl (or di-n-butyl) ether), (CH 3)3COCH 2CH(CH 3)OH (propylene glycol t-butyl ether), (CH 3)3CO[CH 2CH(CH 3)O]2(H or (CH 3 ) 3) (dipropylene glycol t-butyl (or di-t butyl) ether), (CH 3)3CO[CH 2CH(CH 3)O] 3(H or (CH 3) 3 ) (tripropylene glycol t butyl (or di-t-butyl) ether), C5 H,1OCH 2CH(CH 3)OH (propylene glycol n pentyl ether), C4 H9 OCH 2CH(C 2H)OH (butylene glycol n-butyl ether), C4 HqO[CH 2 CH(C 2 H)O]2 H (dibutylene glycol n-butyl ether), trimethylolpropane tri-n-butyl ether (C 2 HC(CH 2O(CH 2)3CH 3)3) and trimethylolpropane di-n-butyl ether (C2HC(CH 20C(CH 2)3CH 3)2CH 2OH). Amide solubilizing agents of the present invention comprise those represented by the formulae RIC(O)NR 2 R 3 and cyclo
[R4C(O)N(R 5)], wherein R', R 2, R 3 and R 5 are independently selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms; R 4 is selected from aliphatic hydrocarbylene radicals having from 3 to 12 carbon atoms; and wherein said amides have a molecular weight of from about 100 to about 300 atomic mass units. The molecular weight of said amides is preferably from about 160 to about 250 atomic mass units. R 1, R 2, R 3 and R5 may optionally include substituted hydrocarbon radicals, 5 that is, radicals containing non-hydrocarbon substituents selected from halogens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy). R1, R 2 , R 3 and R5 may optionally include heteroatom-substituted hydrocarbon radicals, that is, radicals, which contain the atoms nitrogen (aza-), oxygen (oxa-) or sulfur (thia-) in a radical chain otherwise composed of carbon 10 atoms. In general, no more than three non-hydrocarbon substituents and heteroatoms, and preferably no more than one, will be present for each 10 carbon atoms in R' 3 , and the presence of any such non-hydrocarbon substituents and heteroatoms must be considered in applying the aforementioned molecular weight limitations. Preferred amide solubilizing 15 agents consist of carbon, hydrogen, nitrogen and oxygen. Representative R', R2 , R 3 and R'aliphatic and alicyclic hydrocarbon radicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers. A preferred embodiment of amide solubilizing agents are those wherein R 4 in the aforementioned formula cyclo-[R4C(O)N(R)-] may be represented by the hydrocarbylene radical (CR6 R 7)n, in other words, the formula: cyclo
[(CR 6R 7 )nC()N(R)-] wherein: the previously-stated values for molecular weight apply; n is an integer from 3 to 5; R is a saturated hydrocarbon radical containing 1 to 12 carbon atoms; R6 and R7 are independently selected (for each n) by the rules previously offered defining R 1 3. In the lactams represented by the formula: cyclo-[(CR 6 R7 )nC(O)N(R)-], all R6 and R 7 are preferably hydrogen, or contain a single saturated hydrocarbon radical among the n methylene units, and R5 is a saturated hydrocarbon radical containing 3 to 12 carbon atoms. For example, 1-(saturated hydrocarbon radical)-5-methylpyrrolidin-2-ones. Representative amide solubilizing agents 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-methylpyrrolidin-2-one, 5-methyl-I pentylpiperid-2-one, 1,3-dimethylpiperid-2-one, 1-methylcaprolactam, 1 butyl-pyrrolidin-2-one, 1,5-dimethylpiperid-2-one, 1-decyl-5 methylpyrrolidin-2-one, 1-dodecylpyrrolid-2-one, N,N-dibutylformamide and N,N-diisopropylacetamide. 5 Ketone solubilizing agents of the present invention comprise ketones represented by the formula R'C(O)R 2, wherein R' and R2 are independently selected from aliphatic, alicyclic and aryl hydrocarbon radicals having from I to 12 carbon atoms, and wherein said ketones have a molecular weight of from about 70 to about 300 atomic mass units. R, 10 and R 2 in said ketones are preferably independently selected from aliphatic and alicyclic hydrocarbon radicals having 1 to 9 carbon atoms. The molecular weight of said ketones is preferably from about 100 to 200 atomic mass units. R' and R 2 may together form a hydrocarbylene radical connected and forming a five, six, or seven-membered ring cyclic ketone, 15 for example, cyclopentanone, cyclohexanone, and cycloheptanone. R and R 2 may optionally include substituted hydrocarbon radicals, that is, radicals containing non-hydrocarbon substituents selected from halogens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy). R' and R 2 may optionally include heteroatom-substituted hydrocarbon radicals, that is, 20 radicals, which contain the atoms nitrogen (aza-), oxygen (keto-, oxa-) or sulfur (thia-) in a radical chain otherwise composed of carbon atoms. In general, no more than three non-hydrocarbon substituents and heteroatoms, and preferably no more than one, will be present for each 10 carbon atoms in R 1 and R2 , and the presence of any such non hydrocarbon substituents and heteroatoms must be considered in applying the aforementioned molecular weight limitations. Representative R1 and R 2 aliphatic, alicyclic and aryl hydrocarbon radicals in the general formula R'C()R2 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers, as well as phenyl, benzyl, cumenyl, mesityl, tolyl, xylyl and phenethyl. Representative ketone solubilizing agents include but are not limited to: 2-butanone, 2-pentanone, acetophenone, butyrophenone, hexanophenone, cyclohexanone, cycloheptanone, 2-heptanone, 3 heptanone, 5-methyl-2-hexanone, 2-octanone, 3-octanone, diisobutyl ketone, 4 -ethylcyclohexanone, 2-nonanone, 5-nonanone, 2-decanone, 4 decanone, 2-decalone, 2-tridecanone, dihexyl ketone and dicyclohexyl ketone. Nitrile solubilizing agents of the present invention comprise 5 nitriles represented by the formula RCN, wherein R1 is selected from aliphatic, alicyclic or aryl hydrocarbon radicals having from 5 to 12 carbon atoms, and wherein said nitriles have a molecular weight of from about 90 to about 200 atomic mass units. R in said nitrile solubilizing agents is preferably selected from aliphatic and alicyclic hydrocarbon radicals 10 having 8 to 10 carbon atoms. The molecular weight of said nitrile solubilizing agents is preferably from about 120 to about 140 atomic mass units. R1 may optionally include substituted hydrocarbon radicals, that is, radicals containing non-hydrocarbon substituents selected from halogens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy). R' may optionally 15 include heteroatom-substituted hydrocarbon radicals, that is, radicals, which contain the atoms nitrogen (aza-), oxygen (keto-, oxa-) or sulfur (thia-) in a radical chain otherwise composed of carbon atoms. In general, no more than three non-hydrocarbon substituents and heteroatoms, and preferably no more than one, will be present for each 10 carbon atoms in R, and the presence of any such non-hydrocarbon substituents and heteroatoms must be considered in applying the aforementioned molecular weight limitations. Representative R' aliphatic,'alicyclic and aryl hydrocarbon radicals in the general formula RCN include pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nony, decyl, undecyl, dodecyl and their configurational isomers, as well as phenyl, benzyl, cumenyl, mesityl, tolyl, xylyl and phenethyl. Representative nitrile solubilizing agents include but are not limited to: 1 cyanopentane, 2,2-dimethyl-4-cyanopentane, 1-cyanohexane, 1 cyanoheptane, 1-cyanooctane, 2-cyanooctane, 1-cyanononane, 1 cyanodecane, 2-cyanodecane, 1-cyanoundecane and 1-cyanododecane. Chlorocarbon solubilizing agents of the present invention comprise chlorocarbons represented by the formula RCx, wherein; x is selected from the integers 1 or 2; R is selected from aliphatic and alicyclic hydrocarbon radicals having 1 to 12 carbon atoms; and wherein said chlorocarbons have a molecular weight of from about 100 to about 200 atomic mass units. The molecular weight of said chlorocarbon solubilizing agents is preferably from about 120 to 150 atomic mass units. Representative R aliphatic and alicyclic hydrocarbon radicals in the general formula RClx include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers. Representative chlorocarbon solubilizing agents 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. Ester solubilizing agents of the present invention comprise esters represented by the general formula R'C0 2 R2 , wherein R1 and R2 are independently selected from linear and cyclic, saturated and unsaturated, alkyl and aryl radicals. Preferred esters consist essentially of the elements C, H and 0, have a molecular weight of from about 80 to about 550 atomic mass units. Representative esters include but are not limited to: (CH 3 )2 CHCH 2 0OC(CH 2 ) 2 4. 0COCH 2CH(CH 3) 2 (diisobutyl dibasic ester), ethyl hexanoate, ethyl heptanoate, n-butyl propionate, n-propyl propionate, ethyl benzoate, di-n-propyl phthalate, benzoic acid ethoxyethyl ester, dipropyl carbonate, "Exxate 700" (a commercial C alkyl acetate), "Exxate 800" (a commercial C8 alkyl acetate), dibutyl phthalate, and tert-butyl acetate. Lactone solubilizing agents of the present invention comprise lactones represented by structures [A], [B], and [C]:
R2R O R1Oj2 ' 1 R3 R5R RR RRR
[A] [B] [C]
These lactones contain the functional group -C02- in a ring of six (A), or preferably five atoms (B), wherein for structures [A] and [B], R1 through R8 are independently selected from hydrogen or linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals. Each R1 through
R 8 may be connected forming a ring with another R1 through R 8. The lactone may have an exocyclic alkylidene group as in structure [C], wherein R 1 through R 6 are independently selected from hydrogen or linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals. Each R 1 though R6 may be connected forming a ring with another R 1 through R 6. The lactone solubilizing agents have a molecular weight range of from about 80 to about 300 atomic mass units, preferred from about 80 to about 200 atomic mass units. Representative lactone solubilizing agents include but are not limited to the compounds listed in Table 6. TABLE 6
Additive Molecular Structure Molecular Molecular Formula Weight (amu) (E,Z)-3-ethylidene-5- 0 o methyl-dihydro-furan-2- C 7H 10 0 2 126 one (E,Z)-3-propylidene-5- 0 o methyl-dihydro-furan-2- C8 H 12 02 140 one (E,Z)-3-butylidene-5- 0 o methyl-dihydro-furan-2- C 9 H1 4 0 2 154 one (E,Z)-3-pentylidene-5- 0 o methyl-dihydro-furan-2- C 10 H160 2 168 one (E,Z)-3-Hexylidene-5- 0 0 methyl-dihydro-furan-2- C 1 H802 182 one (E,Z)-3-Heptylidene-5- 0 o methyl-dihydro-furan-2- C 12 H 20 0 2 196 one (E,Z)-3-octylidene-5- ° methyl-dihydro-furan-2- \ - C 13 H 2 20 2 210 one (E,Z)-3-nonylidene-5- ° methyl-dihydro-furan-2- C 14 H 24 0 2 224 one (E,Z)-3-decylidene-5- ° 0 methyl-dihydro-furan-2- C 15H 2 60 2 238 one (E,Z)-3-(3,5,5- o trimethylhexylidene)-5- C1 4H 24 0 2 224 methyl-dihydrofuran-2 one (E,Z)-3- 0 o cyclohexylmethylidene- C 12 H 18 0 2 194 -methyl-dihydrofuran 2-one gamma-octalactone 0 0 C 8 H1 4 0 2 142 gamma-nonalactone o C C9H1 6O2 156 gamma-decalactone 0 C1 0 H 180 2 170 gamma-undecalactone 0 C11H2002 184 gamma-dodecalactone 0 C12H22O2 198 3-hexyldihydro-furan-2 one 0 C10 H 18 0 2 170 3-heptyldihydro-furan 2-one 0C1H2002 184 cis-3-ethyl-5-methyl dihydro-furan-2-one o C 7H 12 0 2 128 cis-(3-propyl-5-methyl) dihydro-furan-2-one CH1402 142 cis-(3-butyl-5-methyl)- 0 dihydro-furan-2-one 0 CqH 1 6 0 2 156 cis-(3-pentyl-5-methyl) dihydro-furan-2-one 0 C1 0H 180 2 170 cis-3-hexyl-5-methyl dihydro-furan-2-one 0 C 1,H 20 02 184 cis-3-heptyl-5-methyl dihydro-furan-2-one 0 C12H2202 198 cis-3-octyl-5-methyl-0 dihydro-furan-2-one C13H2402 212 cis-3-(3,5,5 trimethylhexyl)-5- o C 14 H 26 0 2 226 methyl-dihydro-furan-2 one cis-3-cyclohexylmethyl 5-methyl-dihydro-furan- oC12H2002 196 2-one 5-methyl-5-hexyl- 0 dihydro-furan-2-one 0 C 11 H 20 0 2 184
5-methyl-5-octyl dihydro-furan-2-one C13H2402 212
Hexahydro- H isobenzofuran-1-one C8H 12 02 140
delta-decalactone o o C10H18O2 170 delta-undecalactone o C1 1H 2 00 2 184 delta-dodecalactone o o C 12 H 22 0 2 198 mixture of 4-hexyl dihydrofuran-2-one and C 10H 180 2 170 3-hexyl-dihydro-furan 2-one
Lactone solubilizing agents generally have a kinematic viscosity of less than about 7 centistokes at 400 C. For instance, gamma undecalactone has kinematic viscosity of 5.4 centistokes and cis-(3-hexyl 5-methyl)dihydrofuran-2-one has viscosity of 4.5 centistokes both at 40°C. Lactone solubilizing agents may be available commercially or prepared by methods as described in U. S. patent application 10/910,495, filed August 3, 2004, incorporated herein by reference. Aryl ether solubilizing agents of the present invention further comprise aryl ethers represented by the formula ROR2 , wherein: R1 is selected from aryl hydrocarbon radicals having from 6 to 12 carbon atoms; R 2 is selected from aliphatic hydrocarbon radicals having from 1 to 4 carbon atoms; and wherein said aryl ethers have a molecular weight of from about 100 to about 150 atomic mass units. Representative R aryl radicals in the general formula ROR 2 include phenyl, biphenyl, cumenyl, mesityl, tolyl, xylyl, naphthyl and pyridyl. Representative R 2 aliphatic hydrocarbon radicals in the general formula ROR 2 include methyl, ethyl, 5 propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl. Representative aromatic ether solubilizing agents include but are not limited to: methyl phenyl ether (anisole), 1,3-dimethyoxybenzene, ethyl phenyl ether and butyl phenyl ether. Fluoroether solubilizing agents of the present invention 10 comprise those represented by the general formula ROCF2CF 2H, wherein R is selected from aliphatic, alicyclic, and aromatic hydrocarbon radicals having from about 5 to about 15 carbon atoms, preferably primary, linear, saturated, alkyl radicals. Representative fluoroether solubilizing agents include but are not limited to: C 8 H 170CF 2CF 2 H and C6 H130CF 2CF 2H. It 15 should be noted that if the refrigerant is a fluoroether, then the solubilizing agent may not be the same fluoroether. Fluoroether solubilizing agents may further comprise ethers derived from fluoroolefins and polyols. The fluoroolefins may be of the type CF 2 =CXY, wherein X is hydrogen, chlorine or fluorine, and Y is chlorine, fluorine, CF 3 or ORf, wherein Rf is CF3 , C F, or C F 2 3 7 . Representative fluoroolefins are tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, and perfluoromethylvinyl ether. The polyols may be linear or branched. Linear polyols may be of the type HOCH 2(CHOH)x(CRR')yCH 2 H, wherein R and R'are hydrogen, or CH 3 , or C 2 H and wherein x is an integer from 0-4, and y is an integer from 0-4. Branched polyols may be of the type C(OH)t(R)u(CH 2 OH)v[(CH 2)mCH 2 OH]w, wherein R may be hydrogen, CH 3 or C 2 H 5, m may be an integer-from 0 to 3, t and u may be 0 or 1, v and w are integers from 0 to 4, and also wherein t + u + v + w = 4. Representative polyols are trimethylol propane, pentaerythritol, butanediol, and ethylene glycol. 1,1,1-Trifluoroalkane solubilizing agents of the present invention comprise 1,1,1-trifluoroalkanes represented by the general formula CF 3R, wherein R 1 is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms, preferably primary, linear, saturated, alkyl radicals. Representative 1,1,1 trifluoroalkane solubilizing agents include but are not limited to: 1,1,1 trifluorohexane and 1,1,1-trifluorododecane. Solubilizing agents of the present invention may be present as a single compound, or may be present as a mixture of more than one 5 solubilizing agent. Mixtures of solubilizing agents may contain two solubilizing agents from the same class of compounds, say two lactones, or two solubilizing agents from two different classes, such as a lactone and a polyoxyalkylene glycol ether. In the present compositions comprising refrigerant and UV 10 fluorescent dye, or comprising heat transfer fluid and UV fluorescent dye, from about 0.001 weight percent to about 1.0 weight percent of the composition is UV dye, preferably from about 0.005 weight percent to about 0.5 weight percent, and most preferably from 0.01 weight percent to about 0.25 weight percent. 15 Solubility of these UV fluorescent dyes in refrigerant and heat' transfer compositions may be poor. Therefore, methods for introducing these dyes into the refrigeration, air-conditioning, or heat pump apparatus have been awkward, costly and time consuming. US patent no. RE 36,951, incorporated herein by reference, describes a method, which 20 utilizes a dye powder, solid pellet or slurry of dye that may be inserted into a component of the refrigeration or air-conditioning apparatus. As refrigerant and lubricant are circulated through the apparatus, the dye is dissolved or dispersed and carried throughout the apparatus. Numerous other methods for introducing dye into a refrigeration or air-conditioning apparatus are described in the literature. Ideally, the UV fluorescent dye could be dissolved in the refrigerant thereby not requiring any specialized method for introduction to the refrigeration, air-conditioning, or heat pump apparatus. The present invention relates to compositions including UV fluorescent dye, which may be introduced into the system dissolved in the refrigerant in combination with a solubilizing agent. The inventive compositions will allow the storage and transport of dye-containing refrigerant and heat transfer fluid even at low temperatures while maintaining the dye in solution. In the present compositions comprising refrigerant, UV fluorescent dye and solubilizing agent, or comprising heat transfer fluid and UV fluorescent dye and solubilizing agent, from about 1 to about 50 weight percent, preferably from about 2 to about 25 weight percent, and most preferably from about 5 to about 15 weight percent of the combined composition is solubilizing agent in the refrigerant or heat transfer fluid. In the compositions of the present invention the UV fluorescent dye is present in a concentration from about 0.001 weight percent to about 1.0 weight percent in the refrigerant or heat transfer fluid, preferably from 0.005 weight percent to about 0.5 weight percent, and most preferably from 0.01 weight percent to about 0.25 weight percent. Solubilizing agents such as ketones may have an objectionable odor, which can be masked by addition of an odor masking agent or fragrance. Typical examples of odor masking agents or fragrances may include Evergreen, Fresh Lemon, Cherry, Cinnamon, Peppermint, Floral or Orange Peel, all of which are commercially available, as well as d limonene and pinene. Such odor masking agents may be used at concentrations of from about 0.001% to as much as about 15% by weight based on the combined weight of odor masking agent and solubilizing agent. The present invention further relates to a method of using the refrigerant or heat transfer fluid compositions comprising ultraviolet fluorescent dye to detect leaks in refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus. The presence of the dye in the compositions allows for detection of leaking refrigerant in the refrigeration, air-conditioning, or heat pump apparatus. Leak detection helps to one to address, resolve and/or prevent inefficient operation of the apparatus or system or equipment failure. Leak detection also helps one contain chemicals used in the operation of the apparatus. The method comprises providing the composition comprising refrigerant, ultra-violet fluorescent dye or comprising heat transfer fluid and UV fluorescent dye, as described herein, and optionally, a solubilizing agent as described herein, to refrigeration, air-conditioning, or heat pump apparatus and employing a suitable means for detecting the UV fluorescent dye-containing refrigerant. Suitable means for detecting the dye include, but are not limited to, ultra-violet lamps, often referred to as a "black light" or "blue light". Such ultra-violet lamps are commercially available from numerous sources specifically designed for detecting UV fluorescent dye. Once the ultra-violet fluorescent dye containing composition has been introduced to the refrigeration, air-conditioning, or heat pump apparatus and has been allowed to circulate throughout the system, a leak point or the vicinity of the leak point can be located by shining said ultra-violet lamp on the apparatus and observing the 5 fluorescence of the dye in the vicinity of anyleak point. Mechanical refrigeration is primarily an application of thermodynamics wherein a cooling medium, such as a refrigerant, goes through a cycle so that it can be recovered for reuse. Commonly used cycles include vapor-compression, absorption, steam-jet or steam-ejector, 10 and air. Vapor-compression refrigeration systems include an evaporator, a compressor, a condenser, and an expansion device. A vapor-compression cycle re-uses refrigerant in multiple steps producing a cooling effect in one step and a heating effect in a different step. The 15 cycle can be described simply as follows. Liquid refrigerant enters an evaporator through an expansion device, and the liquid refrigerant boils in the evaporator at a low temperature to form a gas and produce cooling. The low-pressure gas enters a compressor where the gas is compressed to raise its pressure and temperature. The higher-pressure (compressed) gaseous refrigerant then enters the condenser in which the refrigerant condenses and discharges its heat to the environment. The refrigerant returns to the expansion device through which the liquid expands from the higher-pressure level in the condenser to the low-pressure level in the evaporator, thus repeating the cycle. There are various types of compressors that may be used in refrigeration applications. Compressors can be generally classified as reciprocating, rotary, jet, centrifugal, scroll, screw or axial-flow, depending on the mechanical means to compress the fluid, or as positive displacement (e.g., reciprocating, scroll or screw) or dynamic (e.g., centrifugal or jet), depending on how the mechanical elements act on the fluid to be compressed. The compositions of the present invention comprising fluoroolefins may be useful in any of the compressor types mentioned above. The choice of refrigerant for any given compressor will depend on many factors including for instance, boiling point and vapor pressure requirements.
Either positive displacement or dynamic compressors may be used in the present inventive processes. A centrifugal type compressor is one preferred type of equipment for certain of the refrigerant compositions comprising at least one fluoroolefin. 5 A centrifugal compressor uses rotating elements to accelerate the refrigerant radially, and typically includes an impeller and diffuser housed in a casing. Centrifugal compressors usually take fluid in at an impeller eye, or central inlet of a circulating impeller, and accelerate it radially outward. Some static pressure rise occurs in the impeller, but 10 most of the pressure rise occurs in the diffuser section of the casing, where velocity is converted to static pressure. Each impeller-diffuser set is a stage of the compressor. Centrifugal compressors are built with from 1 to 12 or more stages, depending on the final pressure desired and the volume of refrigerant to be handled. 15 The pressure ratio, or compression ratio, of a compressor is the ratio of absolute discharge pressure to the absolute inlet pressure. Pressure delivered by a centrifugal compressor is practically constant over a relatively wide range of capacities. Positive displacement compressors draw vapor into a chamber, and the chamber decreases in volume to compress the vapor. After being compressed, the vapor is forced from the chamber by further decreasing the volume of the chamber to zero or nearly zero. A positive displacement compressor can build up a pressure, which is limited only by the volumetric efficiency and the strength of the parts to withstand the pressure. Unlike a positive displacement compressor, a centrifugal compressor depends entirely on the centrifugal force of the high-speed impeller to compress the vapor passing through the impeller. There is no positive displacement, but rather what is called dynamic-compression. The pressure a centrifugal compressor can develop depends on the tip speed of the impeller. Tip speed is the speed of the impeller measured at its tip and is related to the diameter of the impeller and its revolutions per minute. The capacity of the centrifugal compressor is determined by the size of the passages through the impeller. This makes the size of the compressor more dependent on the pressure required than the capacity.
Because of its high-speed operation, a centrifugal compressor is fundamentally a high volume, low-pressure machine. A centrifugal compressor works best with a low-pressure refrigerant, such as trichlorofluoromethane (CFC-11) or 1,2,2-trichlorotrifluoroethane (CFC 5 113). Some of the low pressure refrigerant fluids of the present invention may be suitable as drop-in replacements for CFC-113 in existing centrifugal equipment. Large centrifugal compressors typically operate at 3000 to 7000 revolutions per minute (rpm). Small turbine centrifugal compressors (mini 10 centrifugal compressors) are designed for high speeds, from about 40,000 to about 70,000 (rpm), and have small impeller sizes, typically less than 0.15 meters (about 6 inches). A multi-stage impeller may be used in a centrifugal compressor to improve compressor efficiency thus requiring less power in use. For a two-stage system, in operation, the discharge of the first stage impeller goes to the suction intake of a second impeller. Both impellers may operate by use of a single shaft (or axle). Each stage can build up a compression ratio of about 4 to 1; that is, the absolute discharge pressure can be four times the absolute suction pressure. Several examples of two-stage centrifugal compressor systems, particularly for automotive applications, are described in US 5,065,990 and US 5,363,674, both incorporated herein by reference. The present disclosure further relates to a method for producing heating or cooling in a refrigeration, air-conditioning, or heat pump apparatus,.said method comprising introducing a refrigerant or heat transfer fluid composition into said apparatus having (a) a centrifugal compressor; (b) a multi-stage centrifugal compressor, or (c) a single slab/single pass heatexchanger; wherein said refrigerant or heat transfer fluid composition comprises at least one fluoroolefin selected from the group consisting of: (i) fluoroolefins of the formula E- or Z-RCH=CHR 2, wherein R1 and R2 are, independently, C1 to C perfluoroalkyl groups,; (ii) cyclic fluoroolefins of the formula cyclo-[CX=CY(CZW)n-], wherein X, Y, Z, and W, independently, are H or F, and n is an integer from 2 to 5; or (iii) fluoroolefins selected from the group consisting of:
1, 2 ,3 ,3 ,3-pentafluoro-1-propene (CF 3CF=CHF); 1,1,3,3,3-pentafluoro-1 propene (CF 3CH=CF 2); 1,1,2,3,3 -pentafluoro-1-propene (CHF CF=CF 2 2); 1,2,3,3-tetrafluoro-1-propene (CHF 2 CF=CHF); 2,3,3,3-tetrafluoro-1 propene (CF 3CF=CH 2); 1, 3 ,3 ,3 -tetrafiuoro-1-propene (CF CH=CHF); 3 5 1,1, 2 ,3-tetrafluoro-1-propene (CH 2FCF=CF 2); 1,1,3,3-tetrafluoro-1 propene (CHF 2CH=CF 2); 2,3,3-trifluoro-1-propene (CHF CF=CH ); 3,3,3 2 2 trifluoro-1-propene (CF 3CH=CH 2); 1,1,2-trifluoro-1-propene (CH 3CF=CF 2); 1,1,3-trifluoro-1-propene (CH 2FCH=CF 2); 1,2,3-trifluoro-1-propene (CH 2FCF=CHF); 1,3,3-trifluoro-1-propene (CHF 2CH=CHF); 10 1,1,1,2,3,4,4,4-octafluoro-2-butene(CF3CF=CFCF3); 1,1,2,3,3,4,4,4 octafluoro-1-butene (CF 3CF 2CF=CF 2); 1,1,1,2,4,4,4-heptafluoro-2-butene (CF 3CF=CHCF 3); 1,2,3,3,4,4,4-heptafluoro-1-butene (CHF=CFCF CF 2 3); 1,1,1, 2 ,3,4,4-heptafluoro-2-butene (CHF 2CF=CFCF 3); 1,3,3,3-tetrafluoro 2-(trifluoromethyl)-1-propene ((CF 3)2C=CHF); 1,1,3,3,4,4,4-heptafluoro-1 15 butene (CF 2=CHCF 2CF 3); 1,1,2,3,4,4,4-heptafluoro-1-butene (CF 2=CFCHFCF 3); 1,1,2,3,3,4,4-heptafluoro-1-butene (CF =CFCF 2 2CHF 2); 2,3,3,4,4,4-hexafluoro-1-butene (CF 3CF 2CF=CH 2); 1,3,3,4,4,4-hexafluoro 1-butene (CHF=CHCF 2CF 3); 1,2,3,4,4,4-hexafluoro-1-butene (CHF=CFCHFCF 3); 1,2,3,3,4,4-hexafluoro-1-butene (CHF=CFCF CHF 2 2); 20 1,1,2,3,4,4-hexafluoro-2-butene (CHF 2CF=CFCHF 2); 1,1,1,2,3,4 hexafluoro-2-butene (CH 2FCF=CFCF 3); ,1,1,2,4,4-hexafluoro-2-butene (CHF 2CH=CFCF 3); 1,1,1,3,4,4-hexafluoro-2-butene (CF CH=CFCHF 3 2); 1,1,2,3,3,4-hexafluoro-1-butene (CF 2=CFCF2CH 2F); 1,1,2,3,4,4 hexafluoro-1-butene (CF 2=CFCHFCHF 2); 3,3,3-trifluoro-2-(trifluoromethyl) 1-propene (CH 2 =C(CF 3) 2 ); 1,1,1,2,4-pentafluoro-2-butene (CH 2FCH=CFCF 3); 1,1,1,3,4-pentafluoro-2-butene (CF 3CH=CFCH F); 2 3,3,4,4,4-pentafluoro-1-butene (CF 3CF 2CH=CH 2); 1,1,1,4,4-pentafluoro-2 butene (CHF 2CH=CHCF 3); 1,1,1, 2 ,3-pentafluoro-2-butene (CH 3CF=CFCF 3); 2,3,3,4,4-pentafluoro-1-butene (CH =CFCF CHF 2 2 2); 1,1,2,4,4-pentafluoro-2-butene (CHF 2CF=CHCHF 2); 1,1,2,3,3-pentafluoro 1-butene (CH 3CF 2CF=CF 2); 1,1,2,3,4-pentafluoro-2-butene (CH 2FCF=CFCHF 2); 1,1, 3 ,3,3-pentafluoro-2-methyl-1-propene (CF2=C(CF 3)(CH 3)); 2-(difluoromethyl)-3,3,3-trifluoro-1-propene (CH 2=C(CHF 2)(CF 3)); 2,3,4,4,4-pentafluoro-1-butene (CH =CFCHFCF 2 3); 1,2,4,4,4-pentafluoro-1-butene (CHF=CFCH 2CF 3);I1, 3 ,4,4,4-pentafluoro-1 butene (CHF=CHCHFCF 3); 1,3,3,4,4-pentafluoro-1-butene
(CHF=CHCF 2CHF 2); 1, 2 ,3,4,4-pentafluoro-1-butene (CHF=CFCHFCHF 2); 3, 3 ,4,4-tetrafluoro-1-butene (CH 2=CHCF CHF ); 1,1-difluoro-2 2 2 (difluoromethyl)-1-propene (CF 2=C(CHF 2)(CH )); 1,3,3,3-tetrafluoro-2 3 methyl-I-propene (CHF=C(CF 3)(CH 3)); 2 -difluoromethyl-3,3-difluoro-1 5 propene (CH 2 =C(CHF 2 )2 ); 1,1,1, 2 -tetrafluoro-2-butene (CF 3CF=CHCH 3); 1,1,1,3-tetrafluoro-2-butene (CH 3CF=CHCF ); 1,1,1,2,3,4,4,5,5,5 3 decafluoro-2-pentene (CF 3CF=CFCF 2CF ); 1,1,2,3,3,4,4,5,5,5-decafluoro 3 1-pentene (CF 2=CFCF 2CF 2CF 3); 1,1,1,4,4 ,4 -hexafluoro-2-(trifluoromethyl) 2-butene ((CF 3)2C=CHCF 3); 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene 10 (CF 3CF=CHCF 2CF 3); 1,1,1,3,4,4 ,5,5,5-nonafluoro-2-pentene (CF 3CH=CFCF 2CF 3); 1, 2 ,3 ,3 ,4 ,4 ,5,5,5-nonafluoro-1-pentene (CHF=CFCF2 CF2CF 3);1,1,3,3, 4 4 ,5,5,5-nonafluoro-1-pentene , (CF 2=CHCF 2CF 2CF 3); 1,1, 2 ,3 ,3 ,4,4,5,5-nonafluoro-1-pentene (CF2=CFCF 2CF 2CHF 2); 1,1,2,3,4 ,4 ,5,5,5-nonafluoro-2-pentene 15 (CHF2CF=CFCF 2CF 3);1,1,1,2,3,4 4 ,5,5-nonafluoro-2-pentene
(CF 3CF=CFCF 2CHF 2); 1,1,1,2,3,4 ,5,5,5-nonafluoro-2-pentene (CF 3CF=CFCHFCF 3); 1,2,3, 4 ,4 ,4 -hexafluoro-3-(trifluoromethyl)-1-butene (CHF=CFCF(CF 3)2); 1,1,2,4 ,4 ,4-hexafluoro-3-(trifluoromethyl)-1-butene (CF 2=CFCH(CF 3)2); 1,1,1, 4 ,4 ,4 -hexafluoro-2-(trifluoromethyl)-2-butene (CF 3 CH=C(CF 3)2); 1,1, 3 ,4,4 ,4 -hexafluoro-3-(trifluoromethyl)-1-butene (CF 2=CHCF(CF 3)2); 2 ,3 ,3 ,4 ,4,5,5,5-octafluoro-1-pentene (CH 2=CFCF 2CF 2CF 3); 1,2,3,3,4,4 ,5,5-octafluoro-1-pentene (CHF=CFCF 2CF 2CHF 2); 3, 3 ,4,4 ,4 -pentafluoro-2-(trifluoromethyl)-1-butene (CH 2=C(CF 3)CF 2CF 3); 1,1,4,4 ,4 -pentafluoro-3-(trifluoromethyl)-1-butene (CF2=CHCH(CF 3)) ; 1,3,4 ,4 ,4 -pentafluoro-3-(trifluoromethyl)-1-butene (CHF=CHCF(CF 3)2); 1,1, 4 ,4 ,4 -pentafluoro-2-(trifluoromethyl)-1-butene (CF 2=C(CF 3)CH 2CF3); 3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene ((CF 3)2CFCH=CH 2); 3,3,4,4,5,5,5-heptafluoro-1-pentene (CF 3CF 2CF 2CH=CH 2); 2, 3 ,3 ,4 ,4,5,5-heptafluoro-1-pentene (CH 2=CFCF2CF 2CHF 2); 1,1, 3 ,3 ,5,5,5-heptafluoro-1-butene (CF 2 =CHCF 2 CH 2 CF 3 ); 1,1,1,2,4,4 ,4 -heptafluoro-3-methyl-2-butene (CF 3CF=C(CF 3)(CH 3)); 2,4, 4 ,4 -tetrafluoro-3-(trifluoromethyl)-1-butene (CH 2=CFCH(CF 3)2); 1, 4 ,4 ,4 -tetrafluoro-3-(trifluoromethyl)-l-butene (CHF=CHCH(CF 3)2); 1,1,1, 4 -tetrafluoro-2-(trifluoromethyl)-2-butene (CH 2 FCH=C(CF 3)2); 1,1,1, 3 -tetrafluoro-2-(trifluoromethyl)-2-butene (CH 3 CF=C(CF 3)2 ); 1,1,1-trifluoro-2-(trifluoromethyl)-2-butene
((CF 3)2C=CHCH 3); 3,4,4,5,5,5-hexafluoro-2-pentene (CF3CF 2CF=CHCH ); 3 1,1,1,4 ,4,4-hexafluoro-2-methyl-2-butene (CF3C(CH )=CHCF ); 3 3 3,3,4,5,5,5-hexafluoro-1-pentene (CH 2=CHCF 2CHFCF 3); 3 (trifluoromethyl)-4,4,4-trifluoro-1-butene (CH =C(CF )CH CF 2 3 2 3); 5 1,1, 2 ,3 ,3 ,4,4,5,5,6,6,6-dodecafluoro-1-hexene (CF (CF ) CF=CF 3 23 2); 1,1,1, 2 ,2 ,3 ,4 ,5,5,6,6,6-dodecafluoro-3-hexene (CF3CF CF=CFCF 2 2 CF 3); 1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)-2-butene ((CF ) C=C(CF 3 2 3 )2 ); 1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)-2-pentene ((CF 3)2CFCF=CFCF 3); 1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2 10 pentene,((CF 3)2C=CHC 2F); 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl) 2-pentene ((CF 3)2CFCF=CHCF 3); 3 ,3 ,4 ,4,5,5,6,6,6-nonafluoro-1-hexene (CF 3CF 2CF 2CF2CH=CH 2); 4 ,4,4-trifluoro-3,3-bis(trifluoromethyl)-1-butene (CH 2=CHC(CF 3)3); 1,1,1,4,4,4 -hexafluoro-3-methyl-2-(trifluoromethyl)-2 butene ((CF 3)2C=C(CH 3)(CF 3)); 2,3, 3 ,5,5,5-hexafluoro-4-(trifluoromethyl) 15 1-pentene (CH 2=CFCF 2CH(CF 3)2); 1,1,1,2,4,4,5,5,5-nonafluoro-3-methyl 2-pentene (CF 3CF=C(CH 3)CF 2CF 3); 1,1,1,55,5-hexafluoro-4 (trifluoromethyl)-2-pentene (CF 3CH=CHCH(CF 3)2); 3,4,4,5,5,6,6,6 octafluoro-2-hexene (CF 3CF 2CF 2 CF=CHCH 3); 3,3,4,4,5,5,6,6-octafluoro-1 hexene (CH 2=CHCF 2CF 2CF 2CHF 2); 1,1,1,4,4-pentafluoro-2 20 (trifluoromethyl)-2-pentene ((CF 3)2C=CHCF 2CH 3); 4,4,5,5,5-pentafluoro-2 (trifluoromethyl)-1-pentene (CH 2=C(CF 3)CH 2C 2F); 3,3,4,4,5,5,5 heptafluoro-2-methyl-1-pentene (CF3CF 2CF 2C(CH 3)=CH 2); 4,4,5,5,6,6,6 heptafluoro-2-hexene (CF 3CF 2CF 2CH=CHCH 3); 4,4,5,5,6,6,6-heptafluoro 1-hexene (CH 2=CHCH 2CF 2C 2F); 1,1,1, 2 ,2 ,3,4-heptafluoro-3-hexene (CF 3CF 2CF=CFC 2H); 4,5,5,5-tetrafluoro-4-trifluoromethyl-l-pentene (CH 2=CHCH 2CF(CF 3)2); 1,1,1,2,5,5,5-heptafluoro-4-methyl-2-pentene (CF 3CF=CHCH(CF 3)(CH 3)); 1,1,1, 3 -tetrafluoro-2-trifluoromethyl-2-pentene ((CF 3) 2 C=CFC 2 H5 ); 1,1,1,2,3,4 ,4 ,5,5,6,6,7,7,7-tetradecafluoro-2-heptene (CF 3CF=CFCF 2CF 2C 2F); 1,1,1, 2 ,2 ,3 ,4 ,5,5,6,6,7,7,7-tetradecafluoro-3 heptene (CF 3CF 2CF=CFCF 2C 2F5 ); 1,1,1, 3 ,4 ,4 ,5,5,6,6,7,7,7-tridecafluoro 2-heptene (CF 3CH=CFCF 2CF 2C 2 F5); 1,1,1,2,4,4,5,5,6,6,7,7,7 tridecafluoro-2-heptene (CF 3CF=CHCF 2CF 2C2 F); 1,1,1,2,2,4,5,5,6 ,6 ,7 ,7,7-tridecafluoro-3-heptene (CF CF CH=CFCF 3 2 2C 2F); 1,1,1,2,2,3,5,5,6 ,6 ,7,7,7-tridecafluoro-3-heptene (CF 3CF 2CF=CHCF C F); 2 2 CF 2=CFOCF 2CF 3 (PEVE); CF 2=CFOCF 3 (PMVE) and combinations thereof.
The method for producing heating or cooling may be used in stationary air-conditioning, heat pumps or mobile air-conditioning and refrigeration systems. Stationary air-conditioning and heat pump applications include window, ductless, ducted, packaged terminal, chillers 5 and commercial, including packaged rooftop. Refrigeration applications include domestic or home refrigerators and freezers, ice machines, self contained coolers and freezers, walk-in coolers and freezers and transport refrigeration systems. The compositions of the present invention may additionally be 10 used in air-conditioning, heating and refrigeration systems that employ 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. The 15 low operating pressure and density result in high flow velocities and high frictional losses in all components. In these cases, the evaporator design may be modified. Rather than several microchannel slabs connected in series (with respect to the refrigerant path) a single slab/single pass heat exchanger arrangement may be used. Therefore, a preferred heat exchanger for the refrigerant or heat transfer fluid compositions of the present invention is a single slab/single pass heat exchanger. The present invention further relates to a process for producing cooling comprising evaporating the fluoroolefin compositions of the present invention in the vicinity of a body to be cooled, and thereafter condensing said compositions. The present invention further relates to a process for producing heat comprising condensing the fluoroolefin compositions of the present invention in the vicinity of a body to be heated, and thereafter evaporating said compositions. The present invention further relates to a process to produce cooling comprising compressing a composition comprising at least one fluoroolefin in a centrifugal compressor, condensing said composition, and thereafter evaporating said composition in the vicinity of a body to be cooled. Additionally, the centrifugal compressor of the inventive method may bea multi-stage centrifugal compressor and preferably a 2-stage centrifugal compressor.
The present invention further relates to a process to produce cooling in a refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, wherein said apparatus'comprises at least one single slab/single pass heat exchanger, said process comprising condensing a 5 composition of the present invention, and thereafter evaporating said composition in the vicinity of a body to be cooled. The compositions of the present invention are particularly useful in small turbine centrifugal compressors (mini-centrifugal compressors), which can be used in auto and window air-conditioning, 10 heat pumps, or transport refrigeration, as well as other applications. These high efficiency mini-centrifugal compressors may be driven by an electric motor and can therefore be operated independently of the engine speed. A constant compressor speed allows the system to provide a relatively constant cooling capacity at all engine speeds. This provides an 15 opportunity for efficiency improvements especially at higher engine speeds as compared to a conventional R-134a automobile air-conditioning system. When the cycling operation of conventional systems at high driving speeds is taken into account, the advantage of these low pressure systems becomes even greater. Alternatively, rather than use electrical power, the mini centrifugal compressor may be powered by an engine exhaust gas driven turbine or a ratioed gear drive assembly with ratioed belt drive. The electrical power available in current automobile design is about 14 volts, but the new mini-centrifugal compressor requires electrical power of about 50 volts. Therefore, use of an alternative power source would be advantageous. A refrigeration apparatus or air-conditioning apparatus powered by an engine exhaust gas driven turbine is described in detail in U.S. Patent Application serial no. 11/367,517, filed March 3, 2006,. A refrigeration apparatus or air-conditioning apparatus powered by a ratioed gear drive assembly is described in detail in U.S. Patent Application serial no. 11/378,832, filed March 17, 2006. The present invention further relates to a process to produce cooling comprising compressing a composition of the present invention, in a mini-centrifugal compressor powered by an engine exhaust gas driven turbine; condensing said composition; and thereafter evaporating said composition in the vicinity of a body to be cooled.
The present invention further relates to a process to produce cooling comprising compressing a composition of the present invention, in a mini-centrifugal compressor powered by a ratioed gear drive assembly with a ratioed belt drive; condensing said composition; and thereafter 5 evaporating said composition in the vicinity of a body to be cooled. The present invention relates to a process to produce cooling in a refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, wherein said apparatus comprises at least one single slab/single pass heat exchanger, said process comprising compressing a 10 composition of the present invention, in a centrifugal compressor, condensing said composition, and thereafter evaporating said composition in the vicinity of a body to be cooled. The present invention further relates to a method for replacing or substituting for a refrigerant composition having a GWP of about 150 or 15 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 the replacement. In another embodiment of the present invention the refrigerant or heat transfer fluid composition of the present invention, having a lower GWP than the composition being replaced or substituted is introduced into the refrigeration, air conditioning or heat pump apparatus. In some cases, the high GWP refrigerant present in the apparatus will need to be removed from the apparatus before introduction of the lower GWP compositions. In other cases, the fluoroolefin compositions of the present invention may be introduced into the apparatus while the high GWP refrigerant is present. Global warming potentials (GWPs) are an index for estimating relative global warming contribution due to atmospheric emission of a kilogram of a particular greenhouse gas compared to emission of a kilogram of carbon dioxide. GWP can be calculated for different time horizons showing the effect of atmospheric lifetime for a given gas. The GWP for the 100 year time horizon is commonly the value referenced. A high GWP refrigerant would be any compound capable of functioning as a refrigerant or heat transfer fluid having a GWP at the 100 year time horizon of about 1000 or greater, alternatively 500 or greater, 150 or greater, 100 or greater, or 50 or greater. Refrigerants and heat transfer fluids that are in need of replacement, based upon GWP calculations published by the Intergovernmental Panel on Climate Change (IPCC), include but are not limited to HFC-134a (1,1,1,2 tetrafluoroethane). The-present invention will provide compositions that have zero or low ozone depletion potential and low global warming potential (GWP). The fluoroolefins of the present invention or mixtures of fluoroolefins of this invention with other refrigerants will have global warming potentials that are less than many hydrofluorocarbon refrigerants currently in use. Typically, the fluoroolefins of the present invention are expected to have GWP of less than about 25. One aspect of the present invention is to provide a refrigerant with 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 net GWP of refrigerant mixtures by adding fluoroolefins to said mixtures. The present invention further relates to a method for lowering the GWP of a refrigerant or heat transfer fluid, said method comprising combining said refrigerant or heat transfer fluid with at least one fluoroolefin of the present invention. In another embodiment, the method for lowering the global warming potential comprises combining said first composition with a composition comprising at least one fluorolefin, to produce a second composition suitable for use as a refrigerant or heat transfer fluid, and wherein said second composition has a lower global warming potential than said first composition. It may be determined that the GWP of a mixture or combination of compounds may be calculated as a weighted average of the GWP for each of the pure compounds. The present invention further relates to a method of using the composition of the present invention comprising at least one fluoroolefin to lower global warming potential of an original refrigerant or heat transfer fluid composition, said method comprising combining said original refrigerant or heat transfer fluid composition with the composition of the present invention comprising at least one fluoroolefin, to produce a second refrigerant or heat transfer fluid composition wherein said second refrigerant or heat transfer fluid composition has a lower global warming potential than said original refrigerant or heat transfer fluid composition. The present invention further relates to a method for reducing the GWP of an original refrigerant or heat transfer fluid composition in a refrigeration, air-conditioning or heat pump apparatus, wherein said original refrigerant or heat transfer fluid has a GWP of about 150 or higher; said method comprising introducing a second, lower GWP refrigerant or heat transfer fluid composition of the present invention into said 5 refrigeration, air-conditioning or heat pump apparatus.
. The present method for reducing the GWP of an original refrigerant may further comprise removing the original refrigerant or heat transfer fluid composition from said refrigeration, air-conditioning or heat pump apparatus before the second, lower GWP refrigerant or heat transfer 10 fluid is introduced. The present invention further relates to a method for replacing an original refrigerant or heat transfer fluid composition with a second refrigerant or heat transfer fluid composition comprising providing a composition of the present invention as the second refrigerant or heat 15 transfer fluid composition. An original refrigerant may be any refrigerant being used in a refrigeration, air-conditioning or heat pump apparatus in need of replacement The original refrigerant or heat transfer fluid needing replacement may be any of hydrofluorocarbon refrigerants, chlorofluorocarbon refrigerants, hydrochlorofluorocarbon, refrigerants, fluoroether refrigerants, or blends of refrigerant compounds. The hydrofluorocarbon refrigerants of the present invention which may need replacing include but are not limited to: CHF 3 (HFC-23), CH 2F 2 (HFC-32), CH 3F (HFC-41), CHF 2CF 3 (HFC-125), CHF 2CHF 2 (HFC 134), CH 2FCF 3 (HFC-134a), CHF 2CH 2F (HFC143), CF 3CH (HFC-143a), 3 CHF 2CH 3 (HFC-152a), CH 2FCH 3 (HFC-161), CHF 2CF 2CF 3 (HFC-227ca), CF 3CFHCF 3 (HFC-227ea), CHF 2CF 2CHF 2 (HFC-236ca), CH FCF CF 2 2 3 (HFC-236cb), CHF 2CHFCF 3 (HFC-236ea), CF 3CH 2CF 3 (HFC-236fa), CH 2FCF 2CHF 2 (HFC-245ca), CH 3CF 2CF 3 (HFC-245cb), CHF CHFCHF 2 2 (HFC-245ea), CH 2FCHFCF 3 (HFC-245eb), CHF 2CH CF (HFC-245fa), 2 3 CH 2FCF 2CH 2F (HFC-254ca), CH 3CF 2CHF 2 (HFC-254cb), CH FCHFCHF 2 2 (HFC-254ea), CH 3CHFCF 3 (HFC-254eb), CHF 2CH 2CHF (HFC-254fa), 2 CH 2 FCH 2CF 3 (HFC-254fb), CF 3CH 2CH 3 (HFC-263fb), CH 3CF 2CH 2F(HFC 263ca), CH 3CF 2CH 3 (HFC-272ca), CH 3CHFCH 2 F (HFC-272ea), CH 2FCH 2CH 2F (HFC-272fa), CH 3CH 2CF 2H (HFC-272fb), CH CHFCH 3 3 (HFC-28lea), CH 3CH 2CH 2F (HFC-281fa), CHF 2CF 2CF 2CF 2H(HFC
338pcc), CF 3CH 2CF 2CH 3 (HFC-365mfc), CF 3CHFCHFCF 2CF 3 (HFC-43 1Omee). These hydrofluorocarbon refrigerants are available commercially or may be prepared by methods known in the art. Hydrofluorocarbon refrigerants of the present invention may 5 further comprise the azeotropic, azeotrope-like and non-azeotropic compositions, including HFC-125/HFC-143a/HFC-134a (known by the ASHRAE designation, R404 or R404A), HFC-32/HFC-125/HFC-134a (known by ASHRAE designations, R407 or R407A, R407B, or R407C), HFC-32/HFC-125 (R410 or R41OA), and HFC-125/HFC-143a (known by the ASHRAE designation: R507 or R507A), R413A (a blend of R134a/R218/isobutane), R423A (a blend of R134a/R227ea), R507A (a blend of R125/R143a), and others. Chlorofluorocarbon refrigerants of the present invention which may need replacing include R22 (CHF 2C), R123 (CHC 2CF), R124 (CHCIFCF 3 ),R502 (being a blend of CFC- 15 (CCIF 2CF 3) and R22), R503 (being a blend of R23/R13 (CCIF3)), and others. Hydrochlorofluorocarbons of the present invention which may need replacing include R12 (CF2 C 2 ); R1 (CC1 3F), R113 (CCl FCCIF ), 2 2 R114 (CF 2CICF 2CI), R401A or R401B (being blends of R22/R152a/R124), R408A (a blend of R22/R125/R143a), and others, The fluoroether refrigerants of the present invention which may need replacing may comprise compounds similar to hydrofluorocarbons, which also contain at least one ether group oxygen atom. The fluoroether refrigerants include but are not limited to C 4FOCH 3, and C FOC H 4 2 5 (both available commercially). The original refrigerant or heat transfer fluid compositions of the present invention which may need replacement may optionally further comprise combinations of refrigerants that contain up to 10 weight percent of dimethyl ether, or at least one C3 to CO hydrocarbon, e.g., propane, propylene, cyclopropane, n-butane, isobutane, n-pentane, cyclopentane and neopentane (2,2-dimethylpropane). Examples of refrigerants containing such C 3 to C hydrocarbons are azeotrope-like compositions of, HCFC-22/HFC-125/propane (known by the ASHRAE designation, R402 or R402A and R402B), HCFC-22/octafluoropropane/propane (known by the ASHRAE designation, R403 or R403A and R403B), octafluoropropane/HFC-134a/isobutane (known by the ASHRAE designation, R413 or R413A), HCFC-22/HCFC-124/HCFC-142b/isobutane (known by the ASHRAE designation, R414 or R414A and R414B), HFC 134a/HCFC-124/n-butane (known by the ASHRAE designation, R416 or R416A), HFC-125/HFC-134a/n-butane (known by the ASHRAE designation, R417 or R417A), HFC-125/HFC-134a/dimethyl ether (known by the ASHRAE designation, R419 or R419A), and HFC-125/HFC 134a/isobutane (known by ASHRAE designation, R422, R422A, R422B, R422C, R422D). The present invention further relates to a method for replacing an original refrigerant or heat transfer fluid composition, said original composition being R134a (HFC-134a, 1,1,1,2-tetrafluoroethane, CF 3CH 2F) in refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, wherein said method comprises substituting R134a with a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of trifluoromethyl trifluorovinyl ether (PMVE). The present invention further relates to a method for replacing an original refrigerant or heat transfer fluid composition, said original composition being R152a (HFC-152a, 1,1-difluoroethane, CHF 2CH 3) in refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, wherein said method comprises substituting R152a 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 tetrafluoropropene (E-HFC-1234ze), 1,2,3,3,3-pentafluoropropene (HFC 1225ye), 2,3,3,3-tetrafluoropropene (HFC-1234yf), 3,3,3-trifluoropropene (HFC-1243zf), and trifluoromethyl trifluorovinyl ether (PMVE). The present invention further relates to a method for replacing R227ea (HFC-227ea, 1,1,1,2,3,3,3-heptafluoropropane, CF 3CHFCF 3) in refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, wherein said method comprises providing as a substitute a composition comprising at least one compound selected from the group consisting of E-1,3,3,3-tetrafluoropropene (E-HFC-1234ze), 1,2,3,3,3 pentafluoropropene (HFC-1225ye), 2,3,3,3-tetrafluoropropene (HFC 1234yf), 3,3,3-trifluoropropene (HFC-1243zf), and trifluoromethyl trifluorovinyl ether (PMVE).
The present invention further relates to a method for replacing an original refrigerant or heat transfer fluid composition, said original composition being R113 (CFC-113, 1,1,2-trichloro-1,2,2-trifluoroethane, CFCl 2CF 2C) in refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, wherein said method comprises substituting a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 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 ,4,5,5,66,6-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). The present invention further relates to a method for replacing an original refrigerant or heat transfer fluid composition, said original composition being R43-1Omee (HFC-43-1Omee), 1,1,1,2,3,4,4,5,5,5 decafluoropentane, CF 3CHFCHFCF 2CF 3) in refrigeration apparatus, air conditioning apparatus, or heat pump apparatus, wherein said method comprises substituting a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 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-151-12mmt); 1, 2 ,3,3,4,4,5,5,6,6-decafluorocyclohexene(FC-C151-10y); 3,3,4,4,5,5,5 heptafluoro-2-methyl-I-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).
The present invention further relates to a method for replacing an original refrigerant or heat transfer fluid composition, said original composition being C 4 F9 OCH 3 (perfluorobutyl methyl ether) in refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, wherein 5 said method comprises substituting a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 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). The present invention further relates to a method for replacing an original refrigerant or heat transfer fluid composition, said original composition being R365mfc (HFC-365mfc, 1,1,1,3,3-pentafluorobutane, CF 3CH 2CF 2CH 3) in refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, wherein said method comprises substituting a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 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-151-12mmt); 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).
The present inventionfurther relates to a method for replacing an original refrigerant or heat transfer fluid composition, said original composition being RI1 (CFC-11, trichlorofluoromethane, CFC 3 ) in refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, wherein said method comprises substituting a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 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 1,1,1,4,4,5,5,5-octafluoro-2-pentene (Fl2E). The present invention further relates to a method for replacing an original refrigerant or heat transfer fluid composition, said original composition being R123 (HCFC-123, 2,2-dichloro-1,1,-trifluoroethane, CF 3CHCl 2 ) in refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, wherein said method comprises substituting a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 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 1,1,1,4,4,5,5,5-octafluoro-2-pentene(F12E). The present invention further relates to a method for replacing an original refrigerant or heat transfer fluid composition, said original composition being R245fa (HFC-245fa, 1,1,1,3,3-pentafluoropropane, CF 3CH 2CHF 2) in refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, wherein said method comprises substituting a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 2,3,3 trifluoropropene (HFC-1243yf); 1,1,1,4,4,4-hexafluoro-2-butene (F11E); 1,3,3,3-tetrafluoropropene (HFC-1234ze); 1,1,1,2,4,4,4-heptafluoro-2 butene (HFC-1327my); 1, 2 ,3 ,3 -tetrafluoropropene (HFC-1234ye); and pentafluoroethyl trifluorovinyl ether (PEVE). The present invention further relates to a method for replacing an original refrigerant or heat transfer fluid composition, said original 5 composition being R114 (CFC-114, 1, 2 -dichloro-1,1,2,2-tetrafluoroethane, CFC 2CF 2C) in refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, wherein said method comprises substituting a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 1,1,1,2,3,4,4,4-octafluoro 10 2-butene (FC-1318my); 1,2,3,3,4,4-hexafluorocyclobutene (FC-C1316cc); 2,3,3,4,4,4-hexafluoro-1-butene (HFC-1336y); and 3,3,4,4,4-pentafluoro 1-butene (HFC-1345fz). The present invention further relates to a method for replacing an original refrigerant or heat transfer fluid composition, said original 15 composition being R236fa (HFC-236fa, 1,1,1,3,3,3-hexafluoropropane, CF 3CH 2CF 3) in refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, wherein said method comprises substituting a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 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-butene (HFC-1345fz). The present invention relates to a method for replacing an original refrigerant or heat transfer fluid composition, said original composition being R401A in refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, wherein said method comprises substituting a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of E-1,3,3,3-tetrafluoropropene (E-HFC-1234ze); 1,2,3,3,3 pentafluoropropene (HFC-1225ye); 2,3,3,3-tetrafluoropropene (HFC 1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyl trifluorovinyl ether (PMVE).. R401A is the ASHRAE designation for a refrigerant blend containing about 53 weight percent HCFC-22 (chlorodifluoromethane, CHF 2C), about 13 weight percent HFC-152a (1,1-difluoroethane, CHF 2CH 3), and about 34 weight percent HCFC-124 (2-chloro-1,1,1,2-tetrafluoroethane, CF 3CHCIF).
The present invention further relates to a method for replacing an original refrigerant or heat transfer fluid composition, said original composition being R401Bin refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, wherein said method comprises substituting a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of E-1,3,3,3-tetrafluoropropene (E-HFC-1234ze); 1,2,3,3,3 pentafluoropropene (HFC-1225ye); 2,3,3,3-tetrafluoropropene (HFC 1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyl trifluorovinyl ether (PMVE).. R401B is the ASHRAE designation for a refrigerant blend containing about 61 weight percent HCFC-22 (chlorodifluoromethane, CHF 2CI), about 11 weight percent HFC-152a (1,1-difluoroethane, CHF 2CH 3 ),and about 28 weight percent HCFC-124 (2-chloro-1,1,1,2-tetrafluoroethane, CF 3CHCIF). The present invention further relates to a method for replacing an original refrigerant or heat transfer fluid composition, said original composition being R409A in refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, wherein said method comprises substituting a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of E-1,3,3,3-tetrafluoropropene (E-HFC-1234ze); 1,2,3,3,3 pentafluoropropene (HFC-1225ye); 2,3,3,3-tetrafluoropropene (HFC 1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyl trifluorovinyl ether (PMVE).. R409A is the ASHRAE designation for a refrigerant blend containing about 60 weight percent HCFC-22 (chlorodifluoromethane, CHF 2Cl), about 25 weight percent HCFC-124(2 chloro-1,1,1,2-tetrafluoroethane, CF 3CHCIF), and about 15 weight percent HCFC-142b (1-chloro-1,1-difluoroethane, CF 2 CICH 3 ). The present invention further relates to a method for replacing an original refrigerant or heat transfer fluid composition, said original composition being R409B in refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, wherein said method comprises substituting a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of E-1,3,3,3-tetrafluoropropene (E-HFC-1234ze); 1,2,3,3,3 pentafluoropropene (HFC-1225ye); 2,3,3,3-tetrafluoropropene (HFC
1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyl trifluorovinyl ether (PMVE).. R409B is the ASHRAE designation for a refrigerant blend containing about 65 weight percent HCFC-22 (chlorodifluoromethane, CHF 2C), about 25 weight percent HCFC-124 (2 5 chloro-1,1,1,2-tetrafluoroethane, CF 3CHCIF), and about 10 weight percent HCFC-142b (1-chloro-1,1-difluoroethane, CF 2 CICH ). 3 The present invention further relates to a method for replacing an original refrigerant or heat transfer fluid composition, said original composition being R414B in refrigeration apparatus, air-conditioning 10 apparatus, or heat pump apparatus, wherein said method comprises substituting a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of E-1,3,3,3-tetrafluoropropene (E-HFC-1234ze), 1,2,3,3,3 pentafluoropropene (HFC-1225ye), 2,3,3,3-tetrafluoropropene (HFC 1234yf), 3,3,3-trifluoropropene (HFC-1243zf), and trifluoromethyl trifluorovinyl ether (PMVE).. R414B is the ASHRAE designation for a refrigerant blend containing about 50 weight percent HCFC-22 (chlorodifluoromethane, CHF 2CI), about 39 weight percent HCFC-124 (2 chloro-1,1,1,2-tetrafluoroethane, CF 3CHCIF), about 1.5 weight percent isobutane (R600a, CH 3CH(CH 3)CH 3) and about 9.5 weight percent HCFC 142b (1-chloro-1,1-difluoroethane, CF 2 CICH ). 3 The present invention further relates to a method for replacing an original refrigerant or heat transfer fluid composition, said original composition being R416A in refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, wherein said method comprises substituting a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of E-1,3,3,3-tetrafluoropropene (E-HFC-1234ze); 1,2,3,3,3 pentafluoropropene (HFC-1225ye); 2,3,3,3-tetrafluoropropene (HFC 1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyl trifluorovinyl ether (PMVE).. R416A is the ASHRAE designation for a refrigerant blend containing about 59 weight percent HFC-134a (1,1,1,2 tetrafluoroethane, CF 3CH 2F)), about 39.5 weight percent HCFC-124 (2 chloro-1,1,1,2-tetrafluoroethane, CF 3CHCF), and about 1.5 weight percent n-butane (CH 3CH 2CH 2CH 3).
The present invention further relates to a method for replacing an original refrigerant or heat transfer fluid composition, said original composition being R12 (CFC-12, dichlorodifluoromethane, CF 2C 2 ) in refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, wherein said method comprises substituting a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 1,2,3,3,3 pentafluoropropene (HFC-1225ye); 2,3,3,3-tetrafluoropropene (HFC 1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyl trifluorovinyl ether (PMVE).. The present invention further relates to a method for replacing an original refrigerant or heat transfer fluid compositionsaid original composition being R500 in refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, wherein said method comprises substituting a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 1,2,3,3,3-pentafluoropropene (HFC-1225ye); 2,3,3,3-tetrafluoropropene (HFC-1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyl trifluorovinyl ether (PMVE).. R500 is the ASHRAE designation for an azeotropic refrigerant blend containing about 73.8 weight percent R12 ((CFC-12, dichlorodifluoromethane, CF 2 C 2 ) and about 26.2 weight percent R152a (HFC-152a, 1,1-difluoroethane, CHF 2CH 3). The present invention relates to a method for replacing an original refrigerant or heat transfer fluid composition wherein the original refrigerant or heat transfer fluid composition is R134a or R12 and wherein said R134a or R12 is substituted by a second refrigerant or heat transfer fluid composition comprising about 1.0 weight percent to about 37 weight percent HFC-32 and about 99 weight percent to about 63 weight percent HFC-1225ye. In another embodiment, the second refrigerant or heat transfer fluid composition may comprise about 1.0 weight percent to about 10 weight percent HFC-32 and about 99 weight percent to about 90 weight percent HFC-1225ye. The present invention relates to a method for replacing an original refrigerant or heat transfer fluid composition wherein the original refrigerant or heat transfer fluid composition R22, R404A, or R410A and wherein said R22, R404A or R41OA is substituted by a second refrigerant or heat transfer fluid composition comprising about 1.0 weight percent to about 37 weight percent HFC-32 and about 99 weight percent to about 63 weight percent HFC-1225ye. In another embodiment, the second refrigerant or heat transfer fluid composition may comprise about 20 5 weight percent to about 37 weight percent HFC-32 and about 80 weight percent to about 63 weight percent HFC-1225ye. The present inventioni further relates to a method for replacing an original refrigerant or heat transfer fluid composition wherein the original refrigerant or heat transfer fluid composition is R22, R404A, or 10 R41OA and wherein said R22, R404A or R410A is substituted by a second refrigerant or heat transfer fluid composition comprising 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. In another embodiment, the second 15 refrigerant or heat transfer fluid composition comprises about 30 weight percent to about 90 weight percent HFC-1225ye, about 5.0 weight percent to about 55 weight percent HFC-32, and about 1.0 weight percent to about 35 weight percent HFC-125. In yet another embodiment, the second refrigerant or heat transfer fluid composition comprises about 40 weight percent to about 85 weight percent HFC-1225ye, about 10 weight percent to about 45 weight percent HFC-32 and about 1.0 weight percent to about 28 weight percent HFC-125. The present invention relates to a method for replacing an original refrigerant or heat transfer fluid composition wherein the original refrigerant or heat transfer fluid composition is R134a or R12 and wherein said R134a or R12 is substituted by a second refrigerant or heat transfer fluid composition comprising: 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. In all the previously described methods for replacing refrigerants, the fluoroolefins may be used to replace refrigerant in existing equipment. Additionally, the fluorooefins may be used to replace refrigerant in existing equipment designed for use of said refrigerant.
Additionally, the fluoroolefins may be used to replace refrigerant in existing equipment without the need to change or replace the lubricant. The present invention relates to a method for reducing the fire hazard in refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, said method comprising introducing a composition of the present invention into said refrigerant apparatus or air-conditioning apparatus. Refrigerant that may leak from a refrigeration apparatus, air conditioning apparatus, or heat pump apparatus, is a major concern when considering flammability. Should a leak occur in a refrigeration apparatus or air-conditioning apparatus, refrigerant and potentially a small amount of lubricant may be released from the system. If this leaking material comes in contact with an ignition source, a fire may result. By fire hazard is meant the probability that a fire may occur either within or in the vicinity of a refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus. Reducing the fire hazard in a refrigeration apparatus, air conditioning apparatus, or heat pump apparatus may be accomplished by using a refrigerant or heat transfer fluid that is not considered flammable as determined and defined by the methods and standards described previously herein. Additionally, the non-flammable fluoroolefins of the present invention may be added to a flammable refrigerant or heat transfer fluid, either in the apparatus already or prior to adding to the apparatus. The non-flammable fluoroolefins of the present invention reduce the probability of a fire in the event of a leak and/or reduce the degree of fire hazard by reducing the temperature or size of any flame produced. The present invention further relates to a method for reducing fire hazard in or in the vicinity of a refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, said method comprising combining at least one non-flammable fluoroolefin with a flammable refrigerant and introducing the combination into a refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus. The present invention further relates to a method for reducing fire hazard in or in the vicinity of a refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, said method comprising combining at least one non-flammable fluoroolefin with a lubricant and introducing the combination into the refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus comprising flammable refrigerant. The present invention further relates to a method for reducing fire hazard in or in the vicinity of a refrigeration apparatus, air-conditioning 5 apparatus, or heat pump apparatus, said method comprising introducing at least one fluoroolefin into said apparatus. The present invention further relates to a method of using a flammable refrigerant in refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, said method comprising combining 10 said flammable refrigerant with at least one fluoroolefin. The present invention further relates to a method for reducing flammability of a flammable refrigerant or heat transfer fluid, said method comprising combining the flammable refrigerant with at least one fluoroolefin. 15 The present invention further relates to a process for transfer of heat from a heat source to a heat sink wherein the compositions of the present invention serve as heat transfer fluids. Said process for heat transfer comprises transporting the compositions of the present invention from a heat source to a heat sink. 20 Heat transfer fluids are utilized to transfer, move or remove heat from one space, location, object or body to a different space, location, object or body by radiation, conduction, or convection. A heat transfer fluid may function as a secondary coolant by providing means of transfer for cooling (or heating) from a remote refrigeration (or heating) system. In some systems, the heat transfer fluid may remain in a constant state throughout the transfer process (i.e., not evaporate or condense). Alternatively, evaporative cooling processes may utilize heat transfer fluids as well. A heat source may be defined as any space, location, object or body from which it is desirable to transfer, move or remove heat. Examples of heat sources may be spaces (open or enclosed) requiring refrigeration or cooling, such as refrigerator or freezer cases in a supermarket, building spaces requiring air-conditioning, or the passenger compartment of an automobile requiring air-conditioning. A heat sink may be defined as any space, location, object or body capable of absorbing heat. A vapor compression refrigeration system is one example of such a heat sink.
EXAMPLES
EXAMPLE 1 Performance Data Table 7 shows refrigeration performance, as pressure in the evaporator (Evap) and condenser (Cond), discharge temperature (Disch T), energy efficiency (COP), and capacity (Cap), for compounds of the present invention as compared to CFC-113, HFC-43-10mee, C F 0CH 4 9 3
, and HFC-365mfc. The data are based on the following conditions.
Evaporator temperature 40.0°F (4.4°C) Condenser temperature 110.0°F (43.3°C) Subcool temperature 10.0°F (5.5°C) Return gas temperature 75.0°F (23.8°C) Compressor efficiency is 70%
TABLE 7 Evap Evap Cond Cond Comp Comp Cap Cap Compound Pres Pres Pres Pres Disch Disch COP (Btu/min) (kMW .(ia (ka) (Psia) (kPa) T T CFC-113 2.7 18.6 12.8 88.3 156.3 69.1 4.18 14.8 0.26 HFC-43-10mee 2.0 13.4 10.4 71.9 132.8 56.0 3.94 12.2 0.21 C 4F 9oCH 3 1.5 10.1 8.3 57.0 131.3 55.2 3.93 9.5 0.17 HFC-365mfc 3.6 25.1 16.3 112.1 146.3 63.5 4.11 21.4 0.38
1,1,1,3,4,5,5,5-octafluoro-4- 2.1 14.4 10.7 71.9 127.1 52.8 3.83 12.3 0.24 (trifluoromethyl)-2-butene ((HFC-152-11mmyyz) 1,1,1,4,4,5,5,5-octafluoro-2- 2.0 13.4 10.4 71.9 127.3 52.9 3.83 11.8 0.23 (trifluoromethyl)-2-pentene (HFC-152-11mmtz)_ 1,1,1,2,2,3,4,5,5,6,6,6- 2.5 17.3 12.3 85.1 121.8 49.9 3.69 13.8 0.24 dodecafluoro-3-hexene (FC-151-12mcy) 1,1,1,3-tetrafluoro-2-butene 2.5 17.4 11.6 80.1 162.0 72.2 4.25 15.9 0.28 (HFC-1354mzy) 11,1,4,4,4-hexafluoro-2,3- 2.0 13.5 10.0 69.2 122.7 50.4 3.73 11.2 0.20 bis(trifluoromethyl)-2-butene (FC-151-12mmtt) 1,2,3,3,4,4,5,5,6,6- 2.1 14.4 10.6 72.9 126.7 52.6 3.84 12.3 0.22 decafluorocyclohexene (FC-C151-10y) 3,34,4,5,5,5-heptafluoro-2- 2.0 14.1 9.9 68.5 130.0, 54.4 3.92 12.0 0.21 methyl-1-pentene (HFC-1567fts) I 3,3,4,4,5,5,6,6,6-nonafluoro-1- 1.6 11.0 8.6 59.4 130.7 54.8 3.92 10.0 0.18 hexene (PFBE) 4,4,5,5,6,6,6-heptafluoro-2- 1.3 9.2 7.4 51.3 137.8 58.8 4.04 8.9 0.16 hexene (HFC-1567szz) 1,1,1,4,4,5,5,6,6,6-decafluoro- 2.0 13.7 10.7 73.8 131.1 55.1 3.90 12.4 0.22 2-hexene (F13E) 1,1,1,2,3,4,5,5,5-nonafluoro- 2.5 17.3 12.3 85.1 121.8 49.9 3.69 13.8 0.24 4-(trifluoromethyl)-2 pentene(FC-151-12mmzz) 1,1,1,2,2,5,5,6,6,6- 2.4 16.6 12.6 86.7 128.0 53.3 3.83 14.4 0.25 decafluoro-3-hexene (F22E)
EXAMPLE 2 Performance Data Table 8 shows refrigeration performance, as pressure in the evaporator (Evap) and condenser (Cond), discharge temperature (Disch T), energy efficiency (COP), and capacity (Cap), for compounds of the present invention as compared to CFC-1 Iand HCFC-123. The data are based on the following conditions.
Evaporator temperature 40.0°F (4.4°C) Condenser temperature 110.0°F (43.3°C) Subcool temperature 10.0°F (5.5°C) Return gas temperature 75.0°F (23.8°C) Compressor efficiency is 70%
TABLE8 Evap Evap cond Cond comp Comp cap Cap Compound, Pres Pres Pres Pres Disch Disch COP (Btu/min) (w IE|ia| (kPa) EPsia) (kPa) T T (F)LcL CFC-11 7.1 49.0 28.0 192.8 190.5 88.1 4.29 41.1 0.72 HCFC-123 5.8 40.3 25.0 172.4 174.2 79.0 4.25 35.2 0.62
1,2,3,3,4,4,5,5- 6.0 41.6 25.3 174.6 131.7 55.4 3.87 31.6 0.55 octafluorocyclopentene (FC-C1418y) _19 3. 1,1,1,2,3,4,4,5,5,5- 7.5 51.8 30.0 206.6124.9 51.6 3.66 35.3 0.62 decafluoro-2-pentene (FC-141-10myy) 1,1,1,2,4,4,5,5,5- 5.5 37.9 23.7 163.1 132.0 55.6 3.85 29.0 0.51 nonafluoro-2-pentene (HFC-1429myz) 1,1,1,3,4,4,5,5,5- 5.5 37.9 23.7 163.1 132.0 55.6 3.85 29.0 0.51 nonafluoro-2-pentene (HFC-1429mzy)
3,3,4,4,5,5,5- 5.4 37.0 23.1 159.3 135.3 57.4 3.92 29.0 0.51 heptafluoro-1-pentene (HFC-1447fz) 1,1,1,4,4,4-hexafluoro-2- 4.7 32.3 20.8 143.4 150.1 65.6 4.11 27.5 0.48 butene (F11E) 1,1,1,4,4,4-hexafluoro-2- 4.8 33.0 21.0 144.9 132.6 55.9 3.88 25.9 0.45 (trifluoromethyl)-2 butene (HFC-1429mzt) 1,1,1,4,4,5,5,5- 5.5 37.9 24.4 168.0 137.0 58.3 3.93 30.6 0.54 octafluoro-2-pentene (F12E)
EXAMPLE 3 Performance Data Table 9 shows refrigeration performance, as pressure in the evaporator (Evap) and condenser (Cond), discharge temperature (Disch T), energy efficiency (COP), and capacity (Cap), for compounds of the present invention as compared to HFC-245fa. The data are based on the following conditions.
Evaporator temperature 40.0°F (4.4°C) Condenser temperature 110.0°F (43.30 C) Subcool temperature 10.0°F (5.5°C) Return gas temperature 75.0°F (23.8°C) Compressor efficiency is 70%
TABLE 9 Evap Evap C Ind Cond Comp Comp Cap Cap Compound Pres Pres Pres Pres Disch Disch COP (Btu/min) (kw .(Psial (kPa) ,(Psja (kPa) T T (F) _(C)_ HFC- 245fa 10.0 68.81 38.9 268.5 156.7 69.3 4.10 53.3 0.93
2,3,3-trifluoropropene 12.6 87.1 45.4 313.0 172.8 78. 4.19 65.6 1.15 (HFC-1243yf) 1,1,1,4,4,4-hexafluoro-2- 12.5 85.9 47.5 327.4 148.8 64.9 3.99 62.8 1.10 butene (F11E) 1,3,3,3-tetrafluoropropene 12.1 83.4 45.8 315.6 178.8 81.6 4.19 65.6 1.15 (HFC-1234ze) 1,1,1,2,4,4,4-heptafluoro- 10.5 72.5 39.9 275.0 142.3 61.3 3.94 52.0 0.91 2-butene (HFC-1327my) _ I 1,2,3,3-tetrafluoropropene 9.6 66.3 36.9 254.6 176.9 80.5 4.21 53.0 0.93 (HFC-1234ye) pentafluoroethyl 13.1 90.4 49.3 339.8 130.7 54.8 3.69 59.3 1.04 trifluorovinyl ether (PEVE)
EXAMPLE 4 Performance Data Table 10 shows refrigeration performance, as pressure in the evaporator (Evap) and condenser (Cond), discharge temperature (Disch 5 T), energy efficiency (COP), and capacity (Cap), for compounds of the present invention as compared to CFC-114 and HFC-236fa. The data are based on the following conditions.
Evaporator temperature 40.0°F (4.4°C) 10 Condenser temperature 110.0°F (43.3°C) Subcool temperature 10.0°F (5.5°C) Return gas temperature 75.0°F (23.8°C) Compressor efficiency is 70%
TABLE 10 Evap Evap Cond Cond Comp Comp cap Cap Compound Pres Pres Pres Pres Disch Disch COP (Btu/min) (w (Psia) (kPa) Esja (kPa) T T (F) (C) CFC-114 15.4 106.5 54.3 374.2|147.2 64.0 3.97 72.9 1.28 HFC-236fa 18.2 125.8 64.2 442.6 142.8 61.6 3.86 82.9 1.45 1,1,1,2,3,4,4,4-octafluoro-2- 17.2 118.8 59.1 407.4 131.8 55.4 3.68 butene (FC-1318my) 72.1 1.26 1,2,3,3,4,4- __ 16.5 113.5 58.8 405.4141.1 60.6 3.90 76.6 1.34 hexafluorocyclobutene (FC C1316cc) 2,3,3,4,4,4-hexafluoro-1- 14.2 98.2 50.2 346.3 139.4 59.7 3.88 65.3 1.14 butene (HFC-1336yf) 3,3,4,4,4-pentafluoro-1- 14.8 101.8 53.5 368.5 145.5 63.1 3.95 70.7 1.24 butene (HFC-1345fz)
EXAMPLE 5 Performance Data Table 11 shows refrigeration performance, as pressure in the evaporator (Evap) and condenser (Cond), discharge temperature (Disch T), energy efficiency (COP), and capacity (Cap), for compounds of the present invention as compared to HFC-134a, HFC-152a, and HFC-227ea. The data are based on the following conditions.
Evaporator temperature 40.0°F (4.40 C) Condenser temperature 110.0°F (43.3°C) Subcool temperature 10.0°F (5.5°C)
Return gas temperature 75.0°F (23.8°C) Compressor efficiency is 70%
TABLE 11 Evap Evap Cond Cond Comp Comp Cap Cap Compound Pres Pres Pres Pres Disch Disch COP (Btu/min) (kW) iPsja) (kPa) (Esja (kPa) T T HFC-134a 49.6 341.6 161.2 1111.4 168.9 76.1 3.86 213,3 3.73 HFC-152a 46.2 318.8 146.5 1009.9 200.1 93.4 4.02 209.4 3.67 HFC-227ea 32.3 222.7 105.5 727.4 142.9 61.6 3.67 129.3 2.26 2,3,3,3-tetrafluoropropene 47.4 326.7 139.6 962.2 154.8 68.2 3.79 180.5 3.16 (HFC-1234yf) 3,3,3-trifluoropropene (HFC- 39.0 268.8 122.0 841.0 166.2 74.6 3.95 1243zf) 166.3 2.91 1, 2 ,3 ,3,3-pentafluoropropene 36.1 248.9 112.9 778.4 157.8 69.9 3.86 (HFC-1225ye) 148.9 2.61 E-1,3,3,3-tetrafluoropropene 35.5 245.0 115.1 793.9 162.4 72.4 3.90 153.8 2.69 (E-HFC-1234ze) trifluoromethyl trifluorovinyl 39.3 271.1 124.0 855.2 140.9 60.5 3.57 147.6 2.58 ether (PMVE) .
EXAMPLE 6
Flammability Flammable compounds may be identified by testing under ASTM (American Society of Testing and Materials) E681-01, with an electronic ignition source. Such tests of flammability were conducted on compositions of the present disclosure at 101 kPa (14.7 psia), 50 percent relative humidity, and the temperature indicated, at various concentrations in air in order to determine if flammable and if so, find the lower flammability limit (LFL). The results are given in Table 12.
TABLE 12
Composition Temperature LFL (vol % in air) 0C) ( HFC-1225ye 100 Non-flammable HFC-1234yf 100 5.0 E-HFC-1234ze 100 6.0 HFC-1429myz/mzy 23 Non-flammable F12E 23 Non-flammable HFC-1225ye/HFC- 60 Non-flammable 32 (65/35 wt%)
HFC-1225ye/HFC- 60 Non-flammable 32 (63/37 wt%)
HFC-1225ye/HFC- 60 13.0 32 (62/38wt%) HFC-1225ye/HFC- 60 13.0 32 (60/40 wt%)
The results indicate that HFC-1234yf and E-HFC-1234ze are flammable, while HFC-1225ye, HFC-1429myz/mzy, and F12E are non flammable. For mixtures of HFC-1225ye and HFC-32 (which is known to be flammable in the pure state) it has been determined that 37 weight percent HFC-32 is the highest amount that can be present to maintain the non-flammable characteristic. Those compositions comprising fluoroolefins that are non-flammable are more acceptable candidates as refrigerant or heat transfer fluid compositions.
EXAMPLE 7 Tip Speed to Develop Pressure Tip speed can be estimated by making some fundamental relationships for refrigeration equipment that use centrifugal compressors. 5 The torque an impeller ideally imparts to a gas is defined as
T =m*(v 2 *r 2-vl*rl) Equation I where T =torque, Newton-meters 10 m= mass rate of flow, kg/sec V2 =tangential velocity of refrigerant leaving impeller (tip speed), meters/sec r2 =radius of exit impeller, meters v= tangential velocity of refrigerant entering impeller, meters/sec r 1 = radius of inlet of impeller, meters
Assuming the refrigerant enters the impeller in an essentially axial direction, the tangential component of the velocity v1 = 0, therefore
T =m*v 2 *r 2 Equation 2
The power required at the shaft is the product of the torque and the rotative speed P = T* w Equation 3 where P = power, W w = angular velocity, radians/s therefore, P = T*w =m*v 2 *r 2 * w Equation 4
At low refrigerant flow rates, the tip speed of the impeller and the tangential velocity of the refrigerant are nearly identical; therefore
r2*W = v 2 Equation 5 and P =m*v 2*v2 Equation 6
Another expression for ideal power is the product of the mass rate of flow and the isentropic work of compression, P = m*Hi*(1000J/kJ) Equation 7 where 5 Hi = Difference in enthalpy of the refrigerant from a saturated vapor at the evaporating conditions to saturated condensing conditions, kJ/kg. Combining the two expressions Equation 6 and 7 produces, v2 **v = 1000*Hi Equation 8
Although Equation 8 is based on some fundamental assumptions, it provides a good estimate of the tip speed of the impeller and provides an important way to compare tip speeds of refrigerants. Table 13 below shows theoretical tip speeds that are calculated for 1,2,2-trichlorotrifluoroethane (CFC-113) and compositions of the present invention. The conditions assumed for this comparison are:
Evaporator temperature 40.0°F (4.4°C) Condenser temperature 110.0°F (43.3°C) Liquid subcool temperature 10.0°F (5.50 C) Return gas temperature 75.0°F (23.80 C) Compressor efficiency is 70%
These are typical conditions under which small turbine centrifugal compressors perform. TABLE 13
Hi Hi*0.7 Hi*0.7 Tip speed Tip speed Compound Btu/lb Btu/lb KJ/Kg (V2) relative m/s to CFC-113 CFC-113 10.92 7.6 17.8 133.3 n/a HFC-152-11mmyyz 11.56 8.1 18.8 137.2 103% FC-151-12mcy 11.86 8.3 19.3 139.0 104% HFC-1354mzy 13.96 9.8 22.7 150.8 113% FC-151-12mmtt 11.93 8.4 19.4 139.4 105% FC-C151-10y 12.48 8.7 20.3 142.5 107% HFC-1567fm 14.21 9.9 23.1 152.1 114%
PFBE 12.8 9.0 20.8 144.4 108% HFC-1567szz 13.42 9.4 21.9 147.8 111% HFC-1438mzz 11.73 8.2 19.1 138.2 104% FC-151-12mmzz 11.86 8.3 19.3 139.0 104% HFC-153-10mczz 12.23 8.6 19.9 141.1 106%
The example shows that compounds of the present invention have tip speeds within about 15 percent of CFC-113 and would be effective replacements for CFC-113 with minimal compressor design changes. Most preferred compositions have tip speeds within about 10 percent of CFC-113.
EXAMPLE 8 Refrigeration Performance Data Table 14 shows the performance of various refrigerant compositions of the present invention as compared to HFC-134a. In Table 14, Evap Pres is evaporator pressure, Cond Pres is condenser pressure, Comp Disch T is compressor discharge temperature, COP is energy efficiency, and CAP is capacity. The data are based on the following conditions. Evaporator temperature 40.0°F (4.4°C) Condenser temperature 130.0°F (54.40C) Subcool amount 10.0°F (5.5°C) Return gas temperature 60.0°F (15.6°C) Compressor efficiency is 100% Note that the superheat is included in cooling capacity.
TABLE 14 Evap Evap Cond Cond Comp Comp Composition Pres Pres Pres Pres Disch Disch Cap Cap COP (Psia)(kPa) (Psia) (kPa) T T fBtg (kW) .E .(CL min) HFC-134a 50.3 346 214 1476 156 68.9 213 3.73 4.41 HFC-1225ye 37.6 259 165 1138 146 63.3 162 2.84 4.41 HFC-1225ye/HFC-152a (85/15) 39.8 274 173 1193 151 66.1 173 3.03 4.45
HFC-1225ye/HFC-32 43.1 297 184 1269 149 65.0 186 3.26 4.50 (97/3) HFC-1225ye/HFC-32 (96/4) 44.2 305 189 1303 150 65.6 191 3.35 4.51 HFC-1225ye/HFC-32 46.5 321 197 1358 151 66.1 200 3.50 4.53 (95/5) HFC-1225ye/HFC-32 (94/6) 47.3 326 200 1379 153 67.2 203 3.56 4.52 HFC-1225ye/HFC-32 (93/7) 48.8 336 205 1413 154 67.8 210 3.68 4.53 HFC-1225ye/HFC-32 (90/10) 53.0 365 222 1531 157 69.4 227 3.98 4.52 HFC-1243zf/HFC-1225ye 40.8 281 172 1186 148 64.4 170 2.97 4.39 (40/60) 1 HFC-1243zf/HFC-1225ye 41.8 288 174 1200 149 65.0 172 3.02 4.37 (50/50) HFC-1243zf/HFC-1225ye 42.9 296 177 1220 149 65.0 175 (60/40) 3.07 4.36
HFC-1243zf/HFC-1225ye (70/30) 44.1 304 180 1241 150 65.6 178 3.12 4.35
HFC-1243zf/HFC-1225ye/HFC-48 125 (40/56/4) 42.7 294 179 1234 148 64.4 176 3.09 4.38 HFC-1243zf/HFC-1225ye/HFC- 43.7 301 181 1248 149 65.0 179 3.13 4.37 125 (50/46/4) HFC-1243zf/HFC-1225ye/HFC 125 (60/36/4) 44.8 309 184 1269 149 65.0 182 3.18 4.36 HFC-1243zf/HFC-1225ye/HFC- 49.9 344 201 1386 153 67.2 202 3.54 4.40 125 (70/26/4) HFC-1243zf/HFC-1225ye/HFC- 48.4 334 199 1372 153 67.2 202 3.54 4.47 32 (40/55/5) HFC-1 243zf/HFC-1225ye/HFC 324/3)C 45.6 314 189 1303 151 66.1 190 3.33 4.44 32 (42/55/3) HFC-1243zf/HFC-1225ye/HFC- 50.3 347 203 1400 154 67.8 206 3.60 4.43 32 (60/35/5) HFC-1243zf/HFC-1225ye/HFC 32 (62/35/3) 47.7 329 194 1338 152 66.7 195 3.41 4.41 HFC-1243zf/HFC-1225ye/HFC 12/HFC-2(4/5//1) 44.2 305 184 1269 149 65,0 183 3.21 4.41 125/HFC-32 (40/55/4/1) HFC-1243zf/HFC-1225ye/HFC 125/HFC-32 (40/55/3/2) 45.3 312 188 1296 150 65.6 188 3.29 4.42
HFC-1243zf/HFC-1225ye/HFC 125/HFC-32 (60/35/4/1) 46.3 319 189 1303 150 65.6 188 3.29 4.37 HFC-1243zf/HFC-1225ye/HFC 125/HFC-32 (60/35/3/2) 4 326 193 1331 151 66.1 192 3.37 4
Several compositions have even higher energy efficiency (COP) than HFC-134a while maintaining lower or equivalent discharge pressures and temperatures. Capacity for the compositions listed in Table 14 is also similar to R134a indicating these compositions could be replacement refrigerants for R134a in refrigeration and air-conditioning, and in mobile air-conditioning applications in particular. Results also show cooling capacity of HFC-1225ye can be improved with addition of other compounds such as HFC-32.
EXAMPLE 9 Refrigeration Performance Data Table 15 shows the performance of various refrigerant compositions of the present invention as compared to R404A and R422A. In Table 15, Evap Pres is evaporator pressure, Cond Pres iscondenser pressure, Comp Disch T is compressor discharge temperature, EER is energy efficiency, and CAP is capacity. The data are based on the following conditions. Evaporator temperature -17.8 0 C Condenser temperature 46.1°C Subcool amount 5.5 0 C Return gas temperature 15.6°C Compressor efficiency is 70% Note that the superheat is included in cooling capacity.
TABLE 15 Evap Cond P Compr Existing Refrigerant Press Press Disch T CAP EER Product (kPa)) (kPa (C) (kJ/m3) ~
R22 267 1774 144 1697 4.99 R404A 330 2103 101.1 1769 4.64 R507A 342 2151 100.3 1801 4.61 R422A 324 2124 95.0 1699 4.54
Candidate Replacement wt% HFC-32/HFC-1225ye 20/80 200 1620 117 1331 4.91 HFC-32/HFC-1225ye 30/70 246 1879 126 1587 4.85 HFC-32/HFC-1225ye 40/60 284 2101 134 1788 4.74 HFC-32/HFC-1225ye 35/65 256 1948 130.5 1652 4.85 HFC-32/HFC-1225ye 37/63 264 1991 132.2 1694 4.81 HFC-32/HFC-125/HFC 10/10/'80 173 1435 107.0 1159 4.97 1225ye HFC-32/HFC-125/HFC 15/5.5/79.5 184 1509 111.9 1235 4.97 1225ye HFC-32/HFC-125/HFC 24/13.7/62.3 242 1851 119.7 1544 4.85 1225ye HFC-32/HFC-125/HFC 25/25/50 276 2041 120.0 1689 4.73 1225ye HFC-32/HFC-125/HFC 25/40/35 314 2217 119.0 1840 4.66 1225ye HFC-32/HFC-125/HFC 27.5/17.5/55 264 1980 122.8 1653 4.78 1225ye HFC-32/HFC-125/HFC 30/10/60 265 1990 125.0 1664 4.78 1225ye HFC-32/HFC-125/HFC 30/15/55 276 2046 125.0 1710 4.76 1225ye HFC-32/HFC-125/HFC 30/19/51 278 2056 124.8 1724 4.75 1225ye HFC-32IHFC-125/HFC H2 2 5HC 30/20/50 287 2102 124.0 1757 4.73
HFC-32/HFC-125/HFC 30/30/40 311 2218 124.0 1855 4.68 1225ye HFC-32/HFC-125/HFC 1225ye 30/35/35 324 2271 123.0 1906 4.66
-HFC-32/HFC-125/HFC 1225ye 31/20/49 285 2090 125.5 1756 4.74
HFC-32/HFC-125/HFC 33/22/45' 298 2157 127.0 1820 4.72 1225ye HFC-32/HFC-125/HFC 122 35/15/50 296 2157 129.0 1820 4.72 1225ye HFC-32/HFC-125/HFC 122 35/20/45 308 2212 129.0 1868 4.70 1225ye HFC-32/HFC-125/HFC 35/30/35 332 2321 127.0 1968 4.66 1225ye HFC-32/HFC-125/HFC 122 35/40/25 357 2424 126.0 2068 4.64 1225ye HFC-32/HFC-125/HFC 50/30/20 390 2584 138.0 2277 4.54 1225ye HFC-32/HFC-125/HFC 40/30/30 353 2418 131.0 2077 4.66 1225ye HFC-32/HFC-125/HFC 122 40/35/25 364 2465 131.0 2124 4.64 1225ye HFC-32/HFC-125/HFC 45/30/25 372 2505 135.0 2180 4.66 1225ye
Several compositions have energy efficiency (EER) comparable top R404A and R422A. Discharge temperatures are also lower than R404A and R507A. Capacity for the compositions listed in Table 15 is also similar to R404A, R507A, and R422A indicating these compositions could be replacement refrigerants for R404A, R507A, or R422A in refrigeration and air-conditioning.
EXAMPLE10 Refrigeration Performance Data Table 16 shows the performance of various refrigerant compositions of the present invention as compared to HCFC-22 and
R410A. In Table 16, Evap Pres is evaporator pressure, Cond Pres is condenser pressure, Comp Disch T is compressor discharge temperature, EER is energy efficiency, and CAP is capacity. The data are based on the following conditions. Evaporator temperature 40C Condenser temperature 430C Subcool amount 60C Return gas temperature 180C Compressor efficiency is 70% Note that the superheat is included in cooling capacity.
TABLE 16 Evap Cond Compr Existing refrigerant product Press Press Disch CAP EER (kPa) (kPa) Temp (kJ/m3) (C) R22 565 1648 90.9 3808 9.97 R41OA 900 2571 88.1 5488 9.27
Candidate replacement product (Composition wt%) HFC-32/HFC-1225ye (40/60) 630 1948 86.7 4242 9.56 HFC-32/HFC-1225ye (45/55) 666 2041 88.9 4445 9.49 HFC-32/HFC-1225ye (50/50) 701 2127 91.0 4640 9.45 HFC-32/HFC-1225ye (30/70) 536 1700 82.1 3729 9.73 HFC-32/HFC-1225ye (35/65) 575 1805 84.5 3956 9.66 HFC-32/HFC-1225ye (37/63) 590 1845 85.5 4043 9.64 HFC-32/HFC-125/HFC-1225ye (60/5/35) 784 2323 94.6 5087 9.42 HFC-32/HFC-125/HFC-1225ye (60/10/30) 803 2365 94.2 5173 9.42 HFC-32/HFC-125/HFC-1225ye (60/15/25) 822 2407 93.9 5256 9.39 HFC-32/HFC-125/HFC-1225ye (50/10/40) 742 2220 90.3 4820 9.42
HFC-32/HFC-125/HFC-1225ye (50/5/45) 721 2173 90.7 4730 9.45 HFC-32/HFC-125/HFC-1225ye (50/15/35) 762 2266 90.0 4911 9.42 HFC-32/HFC-125/HFC-1225ye (40/15/45) 692 2097 85.9 4518 9.45 HFC-32/HFC-125/HFC-1225ye (40/10/50) 671 2047 86.2 4425 9.49 HFC-32/HFC-125/HFC-1225ye (35/15/50) 654 2001 83.8 4304 9.49 HFC-32/HFC-125/HFC-1225ye (37.5/11.5/51) 643 1976 85.2 4287 9.54 HFC-32/HFC-125/HFC-1225ye (34/6/60) 593 1848 83.8 4028 9.62 HFC-32/HFC-125/HFC-1225ye (30/3/67) 548 1732 82.0 3788 9.70 HFC-32/HFC-125/HFC-1225ye (30/12.7/57.3) 590 1837 81.7 3980 9.60 HFC-32/HFC-125/HFC-1225ye (24/13.7/62.3) 544 1715 78.7 3713 9.66 HFC-32/HFC-125/HFC-1225ye (20/5/75) 471 1522 76.9 3329 9.82 HFC-32/HFC-125/HFC-1225ye (15/5.5/79.5) 427 1398 74.1 3061 9.89
Compositions have energy efficiency (EER) comparable to R22 and R410A while maintaining reasonable discharge temperatures. Capacity for certain compositions listed in Table 16 is also similar to R22 indicating these compositions could be replacement refrigerants for R22 in refrigeration and air-conditioning. Additionally, there are compositions listed in Table 16 with capacity approaching or equivalent to that for R41OA indicating that those compositions could be replacement refrigerants for R41OA in refrigeration and air-conditioning.
EXAMPLE 11 Refrigeration Performance Data
Table 17 shows the performance of various refrigerant compositions of the present invention as compared to HCFC-22, R410A, R407C, and R417A. In Table 17, Evap Pres is evaporator pressure, Cond Pres is condenser pressure, Comp Disch T is compressor discharge 5 temperature, EER is energy efficiency, and CAP is capacity. The data are based on the following conditions. Evaporator temperature 4.40C Condenser temperature 54.40C Subcool amount 5.50 C 10 Return gas temperature 15.6 0 C Compressor efficiency is 100% Note that the superheat is included in cooling capacity. TABLE 17
Existing Refrigerant Evap Cond Compr Product Press Press DischT CAP EER (kPa)) (kPal (C) (kJ/m 3
) R22 573 2149 88.6 3494 14.73 R41OA 911 3343 89.1 4787 13.07 R407C 567 2309 80.0 3397 14.06 R417A 494 1979 67.8 2768 13.78
Candidate Replacement wt% HFC-32/HFC-125/HFC- 30/40/30 732 2823 81.1 3937 13.20 1225ye HFC-32/HFC-125/HFC- 23/25/52 598 2429 78.0 3409 13.54 1225ye
Compositions have energy efficiency (EER) comparable to R22, R407C, R417A, and R41OA while maintaining low discharge temperatures. Capacity for the compositions listed in Table 17 is also similar to R22, R407C and R417A indicating these compositions could be replacement refrigerants for R22, R407C or R417A in refrigeration and air conditioning.

Claims (48)

THE CLAIMS DEFINING THE INVENTION ARE AS FOLLOWS:
1. A fluoroolefin composition comprising 1,3,3,3-tetrafluoro-1-propene and a non-flammable refrigerant wherein the composition is non flammable, and wherein said non-flammable refrigerant is R-236fa and the composition has a global warming potential of less than 150.
2. A method for producing heating or cooling in a refrigeration, air conditioning, or heat pump apparatus, said method comprising introducing a refrigerant or heat transfer fluid composition into said apparatus having (a) a centrifugal compressor; (b) a multi-stage centrifugal compressor, or (c) a single slab/single pass heat exchanger; wherein said refrigerant or heat transfer fluid composition comprises the fluoroolefin composition of claim 1.
3. A method for replacing the use of a high global warming potential refrigerant, said method comprising: providing the composition of claim 1 in refrigeration, air conditioning, or heat pump apparatus in place of, or in combination with, a high global warming potential refrigerant in said apparatus.
4. A method of using the composition of claim 1 to lower global warming potential of an original refrigerant or heat transfer fluid composition, said method comprising combining said original refrigerant or heat transfer fluid composition with the composition of claim 1, to produce a second refrigerant or heat transfer fluid composition wherein said second refrigerant or heat transfer fluid composition has a lower global warming potential than said original refrigerant or heat transfer fluid composition.
5. A method for reducing the GWP of an original refrigerant or heat transfer fluid composition in a refrigeration, air-conditioning or heat pump apparatus, wherein said original refrigerant or heat transfer fluid has a GWP of about 150 or higher; said method comprising introducing a second, lower GWP refrigerant or heat transfer fluid composition of claim 1 into said refrigeration, air-conditioning or heat pump apparatus.
6. The method of claim 5 further comprising removing the original refrigerant or heat transfer fluid composition from said refrigeration, air conditioning or heat pump apparatus before the second, lower GWP refrigerant or heat transfer fluid is introduced.
7. The method of claim 5, wherein said original refrigerant or heat transfer fluid composition is selected from the group consisting of: (i) 1,1-difluoroethane (R152a) and wherein said R152a is substituted by the fluoroolefin composition of claim 1; (ii) 1,1,1,2,3,3,3-heptafluoropropane (R227ea) and wherein said R227ea is substituted by the fluoroolefin composition of claim 1; (iii) 1,1,1,3,3-pentafluoropropane (R245fa) and wherein said R245fa is substituted by the fluoroolefin composition of claim 1; (iv) R401A and wherein said R401A is substituted by the fluoroolefin composition of claim 1; (v) R401B and wherein said R401B is substituted by the fluoroolefin composition of claim 1; (vi) R409A and wherein said R409A is substituted by the fluoroolefin composition of claim 1; (vii) R409B and wherein said R409B is substituted by the fluoroolefin composition of claim 1; (viii) R414B and wherein said R414B is substituted by the fluoroolefin composition of claim 1; and (ix) R416A and wherein said R416A is substituted by the fluoroolefin composition of claim 1.
1. A refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of: (i) fluoroolefins of the formula E- or Z-RCH=CHR2 , wherein R1 and R2 are, independently, Ci to C6 perfluoroalkyl groups, and wherein the total number of carbons in the compound is at least 5; (ii) cyclic fluoroolefins of the formulacyclo-[CX=CY(CZW)n-], wherein X, Y, Z, and W, independently, are H or F, and n is an integer from 2 to 5; and (iii) fluoroolefins selected from the group consisting of: 2,3,3-trifluoro-1-propene (CHF 2CF=CH 2); 1,1,2-trifluoro 1-propene (CH 3CF=CF 2); 1,2,3trifluoro-1-propene (CH 2FCF=CF 2); 1,1,3-trifluoro-1-propene (CH 2FCH=CF 2); 1,3,3-trifluoro-1-propene (CHF2CH=CHF); 1,1,1,2,3,4,4,4 octafluoro-2-butene (CF 3CF=CFCF 3); 1,1,2,3,3,4,4,4 octafluoro-1-butene (CF 3CF 2CF=CF 2); 1,1,1,2,4,4,4 heptafluoro-2-butene (CF 3CF=CHCF 3); 1,2,3,3,4,4,4 heptafluoro-1-butene (CHF=CFCF 2CF 3); 1,1,1,2,3,4,4 heptafluoro-2-butene (CHF 2CF=CFCF 3); 1,3,3,3-tetrafluoro 2-(trifluoromethyl)-1-propene ((CF 3)2C=CHF); 1,1,3,3,4,4,4 heptafluoro-1-butene (CF2=CHCF 2CF 3); 1,1,2,3,4,4,4 heptafluoro-1-butene (CF 2=CFCHFCF 3); 1,1,2,3,3,4,4 heptafluoro-1-butene (CF 2=CFCF 2CHF 2); 2,3,3,4,4,4 hexafluoro-1-butene (CF 3CF 2CF=CH 2); 1,3,3,4,4,4 hexafluoro-1-butene (CHF=CHCF 2CF 3); 1,2,3,4,4,4 hexafluoro-1-butene (CHF=CFCHFCF 3); 1,2,3,3,4,4 hexafluoro-1-butene (CHF=CFCF2CHF 2); 1,1,2,3,4,4 hexafluoro-2-butene (CHF 2CF=CFCHF 2); 1,1,1,2,3,4 hexafluoro-2-butene (CH 2FCF=CFCF3); 1,1,1,2,4,4 hexafluoro-2-butene (CHF2CH=CFCF 3); 1,1,1,3,4,4 hexafluoro-2-butene (CF 3CH=CFCHF 2); 1,1,2,3,3,4 hexafluoro-1-butene (CF 2=CFCF2CH 2F); 1,1,2,3,4,4 hexafluoro-1-butene (CF 2=CFCHFCHF 2); 3,3,3-trifluoro-2 (trifluoromethyl)-1-propene (CH 2 =C(CF 3 )2 ); 1,1,1,2,4 pentafluoro-2-butene (CH 2FCH=CFCF 3); 1,1,1,3,4 pentafluoro-2-butene (CF 3CH=CFCH 2F); 3,3,4,4,4 pentafluoro-1-butene (CF3CF 2CH=CH 2); 1,1,1,4,4 pentafluoro-2-butene (CHF2CH=CHCF3); 1,1,1,2,3 5 pentafluoro-2-butene (CH3CF=CFCF3); 2,3,3,4,4 pentafluoro-1-butene (CH 2=CFCF 2CHF 2); 1,1,2,4,4 pentafluoro-2-butene (CHF2CF=CHCHF 2); 1,1,2,3,3 pentafluoro-1-butene (CH 3CF 2CF=CF2); 1,1,2,3,4 pentafluoro-2-butene (CH 2 FCF=CFCHF 2); 1,1,3,3,3 10 pentafluoro-2-methyl-1-propene (CF2 =C(CF 3)(CH 3 )); 2 (difluoromethyl)-3,3,3-trifluoro-1-propene (CH2=C(CHF 2)(CF 3)); 2,3,4,4,4-pentafluoro-1-butene (CH2=CFCHFCF3); 1,2,4,4,4-pentafluoro-1-butene (CHF=CFCH2CF 3); 1,3,4,4,4-pentafluoro-1-butene (CHF=CHCHFCF 3); 1,3,3,4,4-pentafluoro-1-butene (CHF=CHCF2CHF 2); 1, 2 ,3,4,4-pentafluoro-1-butene (CHF=CFCHFCHF2); 3,3,4,4-tetrafluoro-1-butene (CH 2 =CHCF 2 CHF2 ); 1,1-difluoro-2-(difluoromethyl)-1 propene (CF2=C(CHF 2)(CH 3)); 1,3,3,3-tetrafluoro-2-methyl 1-propene (CHF=C(CF 3)(CH 3)); 3,3-difluoro-2 (difluoromethyl)-1-propene (CH 2 =C(CHF 2 ) 2 ); 1,1,1,2 tetrafluoro-2-butene (CF3CF=CHCH3); 1,1,1,3-tetrafluoro-2 butene (CH 3CF=CHCF3); 1,1,1,2,3,4,4,5,5,5-decafluoro-2 pentene (CF3CF=CFCF2CF3); 1,1,2,3,3,4,4,5,5,5-decafluoro 1-pentene (CF2=CFCF2CF 2CF3); 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=CHCF CF ); 2 3 1,1,1, 3 ,4 ,4,5,5,5-nonafluoro-2-pentene (CF 3CH=CFCF CF ); 2 3 1,2,3,3,4,4,5,5,5-nonafluoro-1-pentene (CHF=CFCF 2CF 2CF 3); 1,1,3,3,4,4,5,5,5-nonafluoro-1 pentene (CF2 =CHCF 2 CF 2 CF3 ); 1,1,2,3,3,4,4,5,5-nonafluoro 1-pentene (CF 2=CFCF 2CF 2CHF2); 1,1,2,3,4,4,5,5,5 nonafluoro-2-pentene (CHF2CF=CFCF2CF3); 1,1,1, 2 ,3 ,4 ,4 ,5,5-nonafluoro-2-pentene (CF 3CF=CFCF 2CHF2); 1,1,1,2,3,4,5,5,5-nonafluoro-2 pentene (CF3CF=CFCHFCF3); 1,2,3,4,4,4-hexafluoro-3 (trifluoromethyl)-1-butene (CHF=CFCF(CF3)2); 1,1,2,4,4,4 hexafluoro-3-(trifluoromethyl)-1-butene (CF 2=CFCH(CF ) 2); 3 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 (CF2=CHCF(CF 3)2); 2,3,3,4,4,5,5,5-octafluoro-1 5 pentene (CH 2=CFCF 2CF 2CF 3); 1,2,3,3,4,4,5,5-octafluoro-1 pentene (CHF=CFCF 2CF 2CHF 2); 3,3,4,4,4-pentafluoro-2 (trifluoromethyl)-1-butene (CH 2=C(CF 3)CF 2CF 3); 1,1,4,4,4 pentafluoro-3-(trifluoromethyl)-1-butene (CF 2=CHCH(CF ) ); 32 1, 3 ,4 ,4,4-pentafluoro-3-(trifluoromethyl)-1-butene (CHF=CHCF(CF 3)2); 1,1,4,4,4-pentafluoro-2 (trifluoromethyl)-1-butene (CF 2=C(CF 3)CH 2CF 3); 3,4,4,4 tetrafluoro-3-(trifluoromethyl)-1-butene ((CF 3)2CFCH=CH ); 2 3,3,4,4,5,5,5-heptafluoro-1-pentene (CF 3CF 2CF 2CH=CH ); 2 2,3,3,4,4,5,5-heptafluoro-1-pentene (CH 2=CFCF 2CF 2CHF ); 2 1,1,3,3,5,5,5-heptafluoro-1-butene (CF 2=CHCF 2CH 2CF 3); 1,1,1,2,4,4,4-heptafluoro-3-methyl-2-butene (CF 3CF=C(CF 3)(CH 3)); 2,4,4,4-tetrafluoro-3-(trifluoromethyl) 1-butene (CH 2=CFCH(CF3)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=CHCH 3); 3,4,4,5,5,5-hexafluoro-2-pentene (CF 3CF 2CF=CHCH 3); 1,1,1,4,4,4-hexafluoro-2-methyl-2 butene (CF 3C(CH 3)=CHCF 3); 3,3,4,5,5,5-hexafluoro-1 pentene (CH 2=CHCF 2CHFCF 3); 4,4,4-trifluoro-3 (trifluoromethyl)-1-butene (CH 2 =C(CF 3 )CH 2 CF ); 3 1,1, 2 ,3,3,4,4,5,5,6,6,6-dodecafluoro-1-hexene (CF 3(CF 2)3CF=CF 2); 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3 hexene (CF 3CF 2CF=CFCF 2CF 3); 1,1,1,4,4,4-hexafluoro-2,3 bis(trifluoromethyl)-2-butene ((CF 3) 2 C=C(CF 3 ) 2 ); 1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)-2-pentene ((CF 3)2CFCF=CFCF 3); 1,1,1,4,4,5,5,5-octafluoro-2 (trifluoromethyl)-2-pentene ((CF 3) 2 C=CHC2 F5 ); 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-pentene ((CF 3)2CFCF=CHCF 3); 3,3,4,4,5,5,6,6,6-nonafluoro-1 hexene (CF 3CF 2CF 2CF 2CH=CH 2); 4,4,4-trifluoro-3,3 bis(trifluoromethyl)-1-butene (CH 2 =CHC(CF 3 ) 3 ); 1,1,1,4,4,4 hexafluoro-2-(trifluoromethyl)-3-methyl-2-butene ((CF 3 )2 C=C(CH 3)(CF 3 )); 2,3,3,5,5,5-hexafluoro-4 (trifluoromethyl)-1-pentene (CH 2=CFCF 2CH(CF 3)2); 5 1,1,1,2,4,4,5,5,5-nonafluoro-3-methyl-2-pentene (CF 3CF=C(CH 3)CF 2CF 3); 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 3CF 2CF 2CF=CHCH 3); 3,3,4,4,5,5,6,6-octafluorol-hexene (CH 2=CHCF 2CF 2CF 2CHF 2); 1,1,1,4,4-pentafluoro-2 (trifluoromethyl)-2-pentene ((CF 3)2C=CHCF 2CH 3); 4,4,5,5,5 pentafluoro-2-(trifluoromethyl)-1-pentene (CH 2=C(CF 3)CH 2C 2F); 3,3,4,4,5,5,5-heptafluoro-2-methyl-1 pentene (CF 3CF 2CF 2C(CH 3)=CH 2); 4,4,5,5,6,6,6 heptafluoro-2-hexene (CF 3CF 2CF 2CH=CHCH 3); 4,4,5,5,6,6,6-heptafluoro-1-hexene(CH 2 =CHCH 2 CF 2 C 2 F); 1,1,1,2,2,3,4-heptafluoro-3-hexene (CF 3CF 2CF=CFC 2 H5 ); 4,5,5,5-tetrafluoro-4-(trifluoromethyl)-1-pentene (CH 2=CHCH 2CF(CF 3)2); 1,1,1,2,5,5,5-heptafluoro-4-methyl 2-pentene (CF 3CF=CHCH(CF 3)(CH 3)); 1,1,1,3-tetrafluoro-2 (trifluoromethyl)-2-pentene ((CF 3)2C=CFC 2H5 ); 1,1,1,2,3 ,4 ,4 ,5,5,6,6,7,7,7-tetradecafluoro-2-heptene (CF 3CF=CFCF 2CF 2C 2F); 1,1,1,2,2,3,4,5,5,6,6,7,7,7 tetradecafluoro-3-heptene (CF 3CF 2CF=CFCF 2C 2F5 ); 1,1,1, 3 ,4 ,4 ,5,5,6,6,7,7,7-tridecafluoro-2-heptene (CF 3CH=CFCF 2CF 2C 2 F); 1,1,1,2,4,4,5,5,6,6,7,7,7 tridecafluoro-2-heptene (CF 3CF=CHCF 2CF 2C 2F5 ); 1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF 3CF 2CH=CFCF 2C 2F); 1,1,1,2,2,3,5,5,6,6,7,7,7 tridecafluoro-3-heptene (CF 3CF 2CF=CHCF 2C 2F); CF 2=CFOCF 2CF 3 (PEVE) and CF 2=CFOCF 3 -(PMVE).
2. A composition comprising: (i) at least one fluoroolefin compound; and (ii) at least one flammable refrigerant; wherein said fluoroolefin is selected from the group consisting of:
(a) fluoroolefins of the formula E- or Z-RCH=CHR2 , wherein R and R 2 are, independently, C1 to C6 perfluoroalkyl groups; (b) cyclic fluoroolefins of the formulacyclo-[CX=CY(CZW)n-], wherein X, Y, Z, and W, independently, are H or F, and n is 5 an integer from 2 to 5; and (c) fluoroolefins selected from the group consisting of: 1, 2 ,3,3,3-pentafluoro-1-propene (CF 3CF=CHF); 1,1,3,3,3 pentafluoro-1-propene (CF 3CH=CF 2); 1,1,2,3,3-pentafluoro-1 propene (CHF 2CF=CF 2); 1,1,1, 2 ,3 ,4,4,4-octafluoro-2-butene (CF 3CF=CFCF 3); 1,1, 2 ,3,3,4,4,4-octafluoro-1-butene (CF 3CF 2CF=CF 2); 1,1,1, 2 ,4 ,4,4-heptafluoro-2-butene (CF 3CF=CHCF 3); 1,2,3,3,4,4,4-heptafluoro-1-butene (CHF=CFCF2CF 3); 1,1,1, 2 ,3,4,4-heptafluoro-2-butene (CHF 2CF=CFCF 3); 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 =CHCF 2 CF 3 ); 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=CFCF2CHF 2); 2,3,3,4,4,4-hexafluoro-1-butene (CF 3CF 2CF=CH 2); 1,3,3,4,4,4-hexafluoro-1-butene (CHF=CHCF 2CF 3); 1,2,3,4,4,4-hexafluoro-1-butene (CHF=CFCHFCF 3); 1,2,3,3,4,4-hexafluoro-1-butene (CHF=CFCF 2CHF 2); 1,1,2,3,4,4-hexafluoro-2-butene (CHF 2CF=CFCHF 2); 1,1,1,2,3,4-hexafluoro-2-butene (CH 2FCF=CFCF 3); 1,1,1,2,4,4-hexafluoro-2-butene (CHF 2CH=CFCF 3); 1,1,1,3,4,4-hexafluoro-2-butene (CF 3CH=CFCHF 2); 1,1,2,3,3,4-hexafluoro-1-butene (CF 2=CFCF2CH 2F); 1,1,2,3,4,4-hexafluoro-1-butene (CF 2=CFCHFCHF 2); 3,3,3-trifluoro-2-(trifluoromethyl)-1-propene (CH 2 =C(CF 3) 2 ); 1,1,1, 2 ,3 ,4,4 ,5,5,5-decafluoro-2-pentene (CF 3CF=CFCF 2CF 3); 1,1,2,3,3,4,4,5,5,5-decafluoro-1-pentene (CF 2=CFCF2CF 2CF 3); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2 butene ((CF 3)2C=CHCF 3); 1,1,1, 2 ,4 ,4 ,5,5,5-nonafluoro-2-pentene (CF 3CF=CHCF 2CF 3); 1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene (CF 3CH=CFCF 2CF 3); 1, 2 ,3 ,3, 4 ,4 ,5,5,5-nonafluoro-1-pentene (CHF=CFCF 2CF 2CF 3); 1,1,3,3,4,4,5,5,5-nonafluoro-1-pentene (CF 2=CHCF 2CF 2CF 3); 1,1,2,3,3,4,4,5,5-nonafluoro-1-pentene (CF 2=CFCF 2CF 2CHF 2); 1,1,2,3,4,4,5,5,5-nonafluoro-2-pentene
(CHF 2CF=CFCF 2CF 3); 1,1,1, 2 ,3,4,4,5,5-nonafluoro-2-pentene (CF 3CF=CFCF 2CHF 2); 1,1,1,2,3 ,4,5,5,5-nonafluoro-2-pentene (CF 3CF=CFCHFCF 3); 1,2,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1 butene (CHF=CFCF(CF 3)2); 1,1,2,4,4,4-hexafluoro-3 (trifluoromethyl)-1-butene (CF 2=CFCH(CF 3)2); 1,1,1,4,4,4 hexafluoro-2-(trifluoromethyl)-2-butene (CF 3CH=C(CF ) ); 32 1,1,3,4 ,4,4-hexafluoro-3-(trifluoromethyl)-1-butene (CF 2=CHCF(CF 3)2); 2 ,3,3,4,4,5,5,5-octafluoro-1-pentene (CH 2=CFCF 2 CF 2 CF 3 ); 1,2,3,3,4,4,5,5-octafluoro-1-pentene (CHF=CFCF 2CF 2CHF 2); 3,3,4,4,4-pentafluoro-2-(trifluoromethyl)-1 butene (CH 2=C(CF 3 )CF 2 CF 3); 1,1,4,4,4-pentafluoro-3 (trifluoromethyl)-1-butene (CF 2=CHCH(CF 3)2); 1,3,4,4,4 pentafluoro-3-(trifluoromethyl)-1-butene (CHF=CHCF(CF 3)2); 1,1,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene (CF 2=C(CF 3)CH 2CF 3); 3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1 butene ((CF 3)2CFCH=CH 2); 3,3,4,4,5,5,5-heptafluoro-1-pentene (CF 3CF 2CF 2CH=CH 2); 2,3,3,4,4,5,5-heptafluoro-1-pentene (CH 2 =CFCF 2 CF 2 CHF 2 ); 1,1,3,3,5,5,5-heptafluoro-1-butene (CF 2=CHCF2CH 2CF 3); 1,1,1,2,4,4,4-heptafluoro-3-methyl-2-butene (CF 3CF=C(CF 3)(CH 3)); 2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1 butene (CH 2=CFCH(CF 3)2); 1,4,4,4-tetrafluoro-3-(trifluoromethyl)-1 butene (CHF=CHCH(CF 3)2); 1,1,1,4-tetrafluoro-2-(trifluoromethyl) 2-butene (CH 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(CF 2)3CF=CF 2); 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3 hexene (CF 3CF 2CF=CFCF 2CF 3); 1,1,1,4,4,4-hexafluoro-2,3 bis(trifluoromethyl)-2-butene ((CF 3 ) 2 C=C(CF 3 ) 2 ); 1,1,1,2,3,4,5,5,5 nonafluoro-4-(trifluoromethyl)-2-pentene ((CF 3)2CFCF=CFCF 3); 1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-pentene ((CF 3 ) 2 C=CHC 2 F); 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2 pentene ((CF 3)2CFCF=CHCF 3); 3,3,4,4,5,5,6,6,6-nonafluoro-1 hexene (CF 3CF 2CF 2CF 2CH=CH 2); 4,4,4-trifluoro-3,3 bis(trifluoromethyl)-1-butene (CH 2=CHC(CF 3)3); 1,1,1,4,4,4 hexafluoro-2-(trifluoromethyl)-3-methyl-2-butene ((CF 3 ) 2 C=C(CH 3 )(CF 3 )); 2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1 pentene (CH 2=CFCF2 CH(CF 3)2); 1,1,1,2,4,4,5,5,5-nonafluoro-3 methyl-2-pentene (CF 3CF=C(CH 3)CF 2CF 3 ); 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=CFCF 2CF 2C 2F); 1,1,1,2,2,3,4,5,5,6,6,7,7,7 tetradecafluoro-3-heptene (CF 3CF 2CF=CFCF 2C 2F); 5 1,1,1, 3 ,4 ,4 ,5,5,6,6,7,7,7-tridecafluoro-2-heptene (CF 3CH=CFCF 2CF 2C 2 F); 1,1,1, 2 ,4 ,4 ,5,5,6 ,6,7,7,7-tridecafluoro-2 heptene (CF 3CF=CHCF 2CF 2C 2F5); 1,1,1,2,2,4,5,5,6,6,7,7,7 tridecafluoro-3-heptene (CF 3CF 2CH=CFCF 2C 2 F 5); and 1,1,1,2,2 ,3 ,5,5,6,6,7,7,7-tridecafluoro-3-heptene 10 (CF 3CF 2CF=CHCF 2C 2F5 ).
3. The composition of claim 2 wherein the flammable refrigerant is selected from the group consisting of hydrofluorocarbons, fluoroethers, hydrocarbon ethers, hydrocarbons, ammonia, and combinations thereof.
4. The composition of claim 3 wherein said flammable refrigerant is selected from the group consisting of: difluoromethane (HFC-32); fluoromethane (HFC-41); 1,1,1 trifluoroethane (HFC-143a); 1,1,2-trifluoroethane (HFC-143); 1,1 difluoroethane (HFC-152a); fluoroethane (HFC-161); 1,1,1 trifluoropropane (HFC-263fb); 1,1, 1,3,3-pentafluorobutane (HFC 365mfc); 1,2,3,3-tetrafluoro-1-propene (HFC-1234ye); 1,3,3,3 tetrafluoro-1-propene (HFC-1234ze); 2,3,3,3-tetrafluoro-1-propene (HFC-1234yf); 1,1,2,3-tetrafluoro-1-propene (HFC-1234yc); 1,1,3,3 tetrafluoro-1-propene (HFC-1234zc); 2,3,3-trifluoro-1-propene (HFC-1243yf; 3,3,3-trifluoro-1-propene (HFC-1243z); 1,1,2 trifluoro-1-propene (HFC-1243yc); 1,1,3-trifluoro-1-propene (HFC 1243zc); 1,2,3-trifluoro-1-propene (HFC-1243ye); and 1,3,3 trifluoro-1-propene (HFC-1243ze) C 4 F9 OC 2 H; propane; propylene; cyclopropane; n-butane; isobutane; n-pentane; 2-methylbutane; 2,2-dimethylpropane; cyclopentane, cyclobutane; 2,2 dimethylbutane; 2,3-dimethylbutane; 2,3-dimethylpentane; 2 methylhexane; 3-methylhexane; 2-methylpentane; 3-ethylpentane; 3-methylpentane; cyclohexane; n-heptane; methylcyclopentane; n hexane; dimethylether; methyl t-butyl ether; ammonia, and combinations thereof.
5. The composition of claim 4 comprising: about 63 weight percent to about 99 weight percent HFC-1225ye and about 37 weight percent to about 1.0 weight percent HFC-32; 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; about 1.0 weight percent to about 99 weight percent HFC-1243zf and about 99 weight percent to about 1.0 weight percent HFC-1225ye; about 1.0 weight percent to about 98 weight percent HFC-1243zf; about 1.0 weight percent to about 98 weight percent HFC-1225ye; and about 1.0 weight percent to about 50 weight percent HFC-125; about 1.0 weight percent to about 98 weight percent HFC-1243zf; about 1.0 weight percent to about 98 weight percent HFC-1225ye; and about 1.0 weight percent to about 50 weight percent HFC-32; or about 1.0 weight percent to about 97 weight percent HFC-1243zf; about 1.0 weight percent to about 97 weight percent HFC-1225ye; about 1.0 weight percent to about 50 weight percent HFC-125; and about 1.0 weight percent to about 50 weight percent HFC-32.
6. The composition of claim 5 comprising: about 90 weight percent to about 99 weight percent HFC-1225ye and about 10 weight percent to about 1.0 weight percent HFC-32; about 30 weight percent to about 90 weight percent HFC-1225ye, about 5.0 weight percent to about 55 weight percent HFC-32, and about 1.0 weight percent to about 35 weight percent HFC-125; about 40 weight percent to about 70 weight percent HFC-1243zf and about 60 weight percent to about 30 weight percent HFC-1225ye; 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; 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; or 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 about 1.0 weight percent to about 10 weight percent HFC-32.. 5 7. The composition of claim 5 comprising: about 63 weight percent to about 80 weight percent HFC-1225ye and about 37 weight percent to about 20 weight percent HFC-32; or about 40 weight percent to about 85 weight percent HFC-1225ye, 10 about 10 weight percent to about 45 weight percent HFC-32 and about 1.0 weight percent to about 28 weight percent HFC-125.
8. The composition of claim 1 or 2 further comprising a lubricant selected from the group consisting of mineral oils, paraffins, naphthenes, synthetic paraffins, alkylbenzenes, poly-alpha-olefins, polyalkylene glycols, polyvinyl ethers, polyol esters and mixtures thereof.
9. The composition of claim 1 or 2 further comprising an additive selected from the group consisting of (i), water scavenger; and (ii) odor masking agent.
10. The composition of claim I or 2 further comprising a tracer compound wherein said tracer is capable of detection and is selected from the group consisting of hydrofluorocarbons, deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodated compounds, alcohols, aldehydes, ketones, nitrous oxide (N 20) and combinations thereof, and wherein said tracer compound is different from said refrigerant or heat transfer fluid.
11. The composition of claim 10 wherein said tracer is selected from the group consisting of CD 3-CD 3, CD -CD -CD , CD 3 2 3 2F2 ,
CF3 -CD 2 CF3 , CD 2 F-CF 3 , CD 3 -CF3 , CDF 2-CF 3, CF -CDF-CF , CF 3 3 3 CF 2CDF 2, CDF2 CDF 2 , CF 3CF 2-CD 3, CF 3CD 2-CH , CF -CH -CD , CF CF 3 2 2 3 3 3 ,
cyclo-CF 2CF 2CF 2-, CF 3CF 2CF 3, cyclo-CF 2CF 2CF 2CF 2-, CF CF CF CF 3 2 2 3 ,
CF 3CF(CF 3)2, cyclo-CF(CF 3)CF 2CF(CF 3)CF 2-, trans-cyclo CF 2CF(CF 3)CF(CF 3)CF 2-, cis-cyclo-CF2CF(CF 3 )CF(CF )CF -, CF 0CHF 3 2 3 2 ,
CF 30CH 2 F, CF 3 0CH 3 , CF 30CHFCF 3, CF 3 0CH 2 CF 3 , CF 30CH 2CHF 2
, CF 3CH 20CHF 2 CH 3 0CF 2 CF 3 , CH3CF 20CF 3 CF 3CF 2CF 20CHFCF 3
, CF 3CF 2CF 20CF(CF 3)CF 20CHFCF3, CHF 3, CH 2FCH 3, CHF 2CH 3
, CHF 2CHF 2 , CF 3CHFCF 3, CF 3CF 2CHF 2, CF 3CF 2CH 2F, CHF 2CHFCF 3
, CF 3CH 2CF 3, CF 3CF 2CH 3, CF 3CH 2CHF 2 , CHF 2CF 2CH 3, CF 3CHFCH 3
, CF 3CH 2CH 3, CH 3CF 2CH 3, CH 3CHFCH 3 , CH 2FCH 2CH 3, CHF 2 CF 2CF 2 CF 3
, (CF 3)2CHCF 3, CF 3 CH2 CF2 CF3 , CHF 2CF 2CF 2CHF 2, CH 3CF 2CF 2CF 3
, CF 3CHFCHFCF 2CF 3, perfluoromethylcyclopentane, perfluoromethylcyclohexane, perfluorodimethylcyclohexane (ortho, meta, or para), perfluoroethylcyclohexane, perfluoroindan, perfluorotrimethylcyclohexane and isomers thereof, perfluoroisopropylcyclohexane, cis-perfluorodecalin, trans perfluorodecalin, cis- or trans-perfluoromethyldecalin and isomers thereof, CH 3Br, CH 2FBr, CHF 2Br, CHFBr 2, CHBr, CH 2BrCH3 , CHBr=CH 2
, CH 2BrCH 2Br, CFBr=CHF, CFA, CHF 2I, CH 2FI, CF 2 CH 2F, CF 2 CHF 2
, CF 21CF21, C6F51, ethanol, n-propanol, isopropanol, acetone, n-propanal, n-butanal, methyl ethyl ketone, nitrous oxide, and combinations thereof.
12. The composition of claim 1 or 2, further comprising at least one ultra-violet fluorescent dye selected from the group consisting of naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, and derivatives of said dye and combinations thereof.
13. The composition of claim 12, further comprising at least one solubilizing agent selected from the group consisting of hydrocarbons, dimethylether, polyoxyalkylene glycol ethers, amides, ketones, nitriles, chlorocarbons, esters, lactones, aryl ethers, fluoroethers, and 1,1,1-trifluoroalkanes.
14. The composition of claim 13, wherein said solubilizing agent is selected from the group consisting of: a) polyoxyalkylene glycol ethers represented by the 2 formula R[(OR )xOR 3]y, wherein: x is an integer from 1 to 3; y is an integer from 1 to 4; R1 is selected from hydrogen and aliphatic hydrocarbon radicals having 1 to 6 carbon atoms and y bonding sites; R 2 is selected from aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms; R 3 is selected from hydrogen, and aliphatic and alicyclic hydrocarbon radicals having from I to 6 carbon atoms; at least one of R and R 3 is selected from said hydrocarbon radicals; and wherein said polyoxyalkylene glycol ethers have a molecular weight of from about 100 to about 300 atomic mass units; b) amides represented by the formulae RC(O)NR 2 R 3 and cyclo-[R4CON(R)-], wherein R', R 2, R 3 and R5 are independently selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms, and at most one aromatic radical having from 6 to 12 carbon atoms; R 4 is selected from aliphatic hydrocarbylene radicals having from 3 to 12 carbon atoms; and wherein said amides have a molecular weight of from about 100 to about 300 atomic mass units; c) ketones represented by the formula RC(O)R2
, wherein R 1 and R 2 are independently selected from aliphatic, alicyclic and aryl hydrocarbon radicals having from 1 to 12 carbon atoms, and wherein said ketones have a molecular weight of from about 70 to about 300 atomic mass units; d) nitriles represented by the formula R1 CN, wherein R1 is selected from aliphatic, alicyclic or aryl hydrocarbon radicals having from 5 to 12 carbon atoms, and wherein said nitriles have a molecular weight of from about 90 to about 200 atomic mass units; e) chlorocarbons represented by the formula RClx, wherein; x is I or 2; R is selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms; and wherein said chlorocarbons have a molecular weight of from about 100 to about 200 atomic mass units; f) aryl ethers represented by the formula R0R 2 ,
wherein: R1 is selected from aryl hydrocarbon radicals having from 6 to 12 carbon atoms; R 2 is selected from aliphatic hydrocarbon radicals having from 1 to 4 carbon atoms; and wherein said aryl ethers have a molecular weight of from about 100 to about 150 atomic mass units; g) 1,1,1-trifluoroalkanes represented by the formula 1 CF 3 R, wherein R is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms; h) fluoroethers represented by the formula R'OCF 2CF 2H, wherein R 1 is selected from aliphatic, alicyclic, and aromatic hydrocarbon radicals having from about 5 to about 15 carbon atoms; or wherein said fluoroethers are derived from fluoroolefins and polyols, wherein said fluoroolefins are of the type CF 2 =CXY, wherein X is hydrogen, chlorine or fluorine, and Y is chlorine, fluorine, CF 3 or ORf, wherein Rf is CF 3 , C 2F, or C 3 F; and said polyols are linear or branched, wherein said linear polyols are of the type HOCH 2 (CHOH)x(CRR' )yCH 2 OH, wherein R and R' are hydrogen, CH 3 or C 2 H 5, x is an integer from 0-4, y is an integer from 0-3 and z is either zero or 1, and said branched polyols are of the type C(OH)t(R)u(CHOH)[(CH 2 2)mCH OH]w, 2 wherein R may be hydrogen, CH 3 or C 2 H5, m is an integer from 0 to 3, t and u are 0 or 1, v and w are integers from 0 to 4, and also wherein t + u
+ v+w=4; and i) lactones represented by structures [B], [C], and [D]:
R2 O 0 R,0 R2 R, O R1 O R1 ' -IRO2 O Rf "R R1 R R R3 R5RR R P R . R6 R4
[B] [C] [D]
wherein, R 1 through R 8 are independently selected from hydrogen, linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals; and the molecular weight is from about 100 to about 300 atomic mass units; and j) esters represented by the general formula R1C0 2 R 2 ,
wherein R 1 and R 2 are independently selected from linear and cyclic, saturated and unsaturated, alkyl and aryl radicals; and wherein said esters have a molecular weight of from about 80 to about 550 atomic mass units.
15. A process for cooling, said process comprising condensing the composition of claim 1 or 2 and thereafter evaporating said composition in the vicinity of a body to be cooled.
16. A process for heating said process comprising evaporating the composition of claim 1 or 2 and thereafter condensing said composition in the vicinity of a body to be heated.
17. A method of using the composition of claim 12 in a compression refrigeration, air-conditioning, or heat pump apparatus, said method comprising providing said composition to said apparatus, and providing a suitable means for detecting the ultra-violet flurescent dye at, or in the vicinity of, a leak point in said apparatus.
18. A method for producing heating or cooling in a refrigeration, air-conditioning, or heat pump apparatus, said method comprising introducing a refrigerant or heat transfer fluid composition into said apparatus having (a) a centrifugal compressor; (b) a multi-stage centrifugal compressor, or (c) a single slab/single pass heat exchanger; wherein said refrigerant or heat transfer fluid composition comprises at least one fluoroolefin selected from the group consisting of: (i) fluoroolefins of the formula E- or Z-RCH=CHR 2 , wherein R' and R2 are, independently, C1 to C6perfluoroalkyl groups,; (ii) cyclic fluoroolefins of the formula cyclo-[CX=CY(CZW)n-], wherein X, Y, Z, and W, independently, are H or F, and n is an integer from 2 to 5; or (iii) fluoroolefins selected from the group consisting of: 1,2,3,3,3-pentafluoro-1-propene (CF 3CF=CHF); 1,1,3,3,3-pentafluoro-1 propene (CF 3CH=CF 2); 1,1,2,3,3-pentafluoro-1-propene (CHF 2CF=CF ); 2 1,2,3,3-tetrafluoro-1-propene (CHF 2CF=CHF); 2,3,3,3-tetrafluoro-1 propene (CF 3CF=CH 2); 1,3,3,3-tetrafluoro-1-propene (CF 3CH=CHF); 1,1,2,3-tetrafluoro-1-propene (CH 2FCF=CF); 1,1,3,3-tetrafluoro-1 propene (CHF 2CH=CF 2); 2,3,3-trifluoro-1-propene (CHF 2CF=CH 2); 3,3,3 trifluoro-1-propene (CF 3CH=CH 2); 1,1,2-trifluoro-1-propene (CH 3CF=CF ); 2 1,1,3-trifluoro-1-propene (CH 2FCH=CF 2); 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(CF3CF=CFCF 3); 1,1,2,3,3,4,4,4 octafluoro-1-butene (CF 3CF 2CF=CF 2); 1,1,1,2,4,4,4-heptafluoro-2-butene (CF 3CF=CHCF 3); 1,2,3,3,4,4,4-heptafluoro-1-butene (CHF=CFCF CF ); 2 3 1,1,1,2,3,4,4-heptafluoro-2-butene(CHF 2CF=CFCF 3); 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=CHCF 2CF 3); 1,1,2,3,4,4,4-heptafluoro-1-butene (CF 2=CFCHFCF 3); 1,1,2,3,3,4,4-heptafluoro-1-butene(CF 2=CFCF CHF ); 2 2 2,3,3,4,4,4-hexafluoro-1-butene (CF 3CF 2CF=CH 2); 1,3,3,4,4,4-hexafluoro 1-butene (CHF=CHCF 2CF 3); 1,2,3,4,4,4-hexafluoro-1-butene
(CHF=CFCHFCF 3); 1,2,3,3,4,4-hexafluoro-1-butene (CHF=CFCF 2CHF 2); 1,1,2,3,4,4-hexafluoro-2-butene (CHF 2CF=CFCHF 2); 1,1,1,2,3,4 hexafluoro-2-butene (CH 2 FCF=CFCF 3); 1,1,1,2,4,4-hexafluoro-2-butene (CHF 2CH=CFCF 3); 1,1,1,3,4,4-hexafluoro-2-butene (CF 3CH=CFCHF 2); 1,1,2,3,3,4-hexafluoro-1-butene (CF 2 =CFCF 2 CH 2 F); 1,1,2,3,4,4 hexafluoro-1-butene (CF 2=CFCHFCHF 2); 3,3,3-trifluoro-2-(trifluoromethyl) 1-propene (CH 2 =C(CF 3) 2 ); 1,1,1,2,4-pentafluoro-2-butene (CH 2FCH=CFCF 3); 1,1,1,3,4-pentafluoro-2-butene (CF 3CH=CFCH 2F); 3,3,4,4,4-pentafluoro-1-butene (CF 3CF 2CH=CH 2); 1,1,1,4,4-pentafluoro-2 butene (CHF 2CH=CHCF 3); 1,1,1,2,3-pentafluoro-2-butene (CH 3CF=CFCF 3); 2,3,3,4,4-pentafluoro-1-butene (CH 2=CFCF 2CHF 2); 1,1,2,4,4-pentafluoro-2-butene (CHF2CF=CHCHF 2); 1,1,2,3,3-pentafluoro I-butene (CH 3CF 2CF=CF 2); 1,1,2,3,4-pentafluoro-2-butene (CH 2FCF=CFCHF 2); 1,1,3,3,3-pentafluoro-2-methyl-1-propene (CF 2=C(CF 3)(CH 3)); 2-(difluoromethyl)-3,3,3-trifluoro-1-propene (CH 2=C(CHF 2)(CF 3)); 2,3,4,4,4-pentafluoro-1-butene (CH 2=CFCHFCF 3); 1,2,4,4,4-pentafluoro-1-butene (CHF=CFCH 2CF 3); 1,3,4,4,4-pentafluoro-1 butene (CHF=CHCHFCF 3); 1,3,3,4,4-pentafluoro-1-butene (CHF=CHCF 2CHF 2); 1,2,3,4,4-pentafluoro-1-butene (CHF=CFCHFCHF 2); 3,3,4,4-tetrafluoro-1-butene (CH 2=CHCF 2CHF 2); 1,1-difluoro-2 (difluoromethyl)-1-propene (CF 2=C(CHF 2)(CH 3)); 1,3,3,3-tetrafluoro-2 methyl-I-propene (CHF=C(CF 3)(CH 3)); 2-difluoromethyl-3,3-difluoro-1 propene (CH 2=C(CHF 2 ) 2 ); 1,1,1,2-tetrafluoro-2-butene (CF 3CF=CHCH ) 3 1,1,1,3-tetrafluoro-2-butene (CH 3CF=CHCF 3); 1,1,1,2,3,4,4,5,5,5 decafluoro-2-pentene (CF 3CF=CFCF 2CF 3); 1,1,2,3,3,4,4,5,5,5-decafluoro 1-pentene (CF 2=CFCF 2CF 2CF 3); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl) 2-butene ((CF 3 ) 2C=CHCF 3); 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene (CF 3CF=CHCF 2CF 3); 1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene (CF 3CH=CFCF 2CF 3); 1,2,3,3,4,4,5,5,5-nonafluoro-1-pentene (CHF=CFCF 2CF 2CF 3); 1,1,3,3,4,4,5,5,5-nonafluoro-1-pentene (CF2=CHCF 2CF 2CF 3); 1,1,2,3,3,4,4,5,5-nonafluoro-1-pentene (CF 2=CFCF2CF 2CHF 2); 1,1,2,3,4,4,5,5,5-nonafluoro-2-pentene (CHF 2CF=CFCF 2CF 3); 1,1,1,2,3,4,4,5,5-nonafluoro-2-pentene (CF 3CF=CFCF 2CHF 2); 1,1,1,2,3,4,5,5,5-nonafluoro-2-pentene (CF 3CF=CFCHFCF 3); 1,2,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene (CHF=CFCF(CF 3)2); 1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene (CF 2=CFCH(CF 3)2); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene
(CF 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=CFCF 2CF 2CF 3); 1, 2 ,3,3,4,4,5,5-octafluoro-1-pentene (CHF=CFCF 2CF 2CHF 2); 3,3,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene (CH 2=C(CF 3)CF 2CF 3); 1,1,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene (CF 2=CHCH(CF 3)2); 1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene (CHF=CHCF(CF 3)2); 1,1,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene (CF2=C(CF 3)CH 2CF 3); 3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene ((CF 3)2CFCH=CH 2); 3,3,4,4,5,5,5-heptafluoro-1-pentene (CF 3CF 2CF 2CH=CH 2); 2,3,3,4,4,5,5-heptafluoro-1-pentene (CH 2 =CFCF 2CF 2 CHF 2 ); 1,1,3,3,5,5,5-heptafluoro-1-butene (CF 2=CHCF 2 CH 2 CF 3); 1,1,1,2,4,4,4-heptafluoro-3-methyl-2-butene (CF 3CF=C(CF 3)(CH 3)); 2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene (CH 2=CFCH(CF 3)2); 1,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene (CHF=CHCH(CF 3)2); 1,1,1,4-tetrafluoro-2-(trifluoromethyl)-2-butene (CH 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=CHCH 3); 3,4,4,5,5,5-hexafluoro-2-pentene (CF 3CF 2CF=CHCH 3); 1,1,1,4,4,4-hexafluoro-2-methyl-2-butene (CF 3C(CH 3)=CHCF 3); 3,3,4,5,5,5-hexafluoro-1-pentene (CH 2=CHCF 2CHFCF 3); 3 (trifluoromethyl)-4,4,4-trifluoro-1-butene (CH 2=C(CF 3)CH 2CF 3); 1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1-hexene(CF 3 (CF 2) 3 CF=CF 2 ); 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene(CF3CF 2CF=CFCF 2CF 3 )
1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)-2-butene ((CF 3 ) 2 C=C(CF 3 ) 2 ); 1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)-2 pentene ((CF 3)2CFCF=CFCF 3); 1,1,1,4,4,5,5,5-octafluoro-2 (trifluoromethyl)-2-pentene ((CF 3)2C=CHC 2 F); 1,1,1,3,4,5,5,5-octafluoro 4-(trifluoromethyl)-2-pentene ((CF 3)2CFCF=CHCF 3); 3,3,4,4,5,5,6,6,6 nonafluoro-1-hexene (CF 3CF 2CF 2CF 2CH=CH 2); 4,4,4-trifluoro-3,3 bis(trifluoromethyl)-1-butene (CH 2=CHC(CF 3)3); 1,1,1,4,4,4-hexafluoro-3 methyl-2-(trifluoromethyl)-2-butene ((CF 3)2C=C(CH 3)(CF 3)); 2,3,3,5,5,5 hexafluoro-4-(trifluoromethyl)-1-pentene (CH 2 =CFCF 2 CH(CF3 ) 2 ); 1,1,1,2,4,4,5,5,5-nonafluoro-3-methyl-2-pentene(CF 3CF=C(CH 3)CF 2CF 3); 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 3CF 2CF 2CF=CHCH 3); 3,3,4,4,5,5,6,6-octafluoro-1-hexene (CH 2=CHCF 2CF 2CF 2CHF 2); 1,1,1,4,4-pentafluoro-2-(trifluoromethyl)-2 pentene ((CF 3)2C=CHCF 2CH 3); 4,4,5,5,5-pentafluoro-2-(trifluoromethyl)-1 pentene (CH 2 =C(CF 3 )CH 2 C 2 F5 ); 3,3,4,4,5,5,5-heptafluoro-2-methyl-1 pentene (CF 3CF 2CF 2C(CH 3)=CH 2); 4,4,5,5,6,6,6-heptafluoro-2-hexene (CF 3CF 2CF 2CH=CHCH 3); 4 ,4 ,5,5,6,6,6-heptafluoro-1-hexene 5 (CH 2=CHCH 2CF 2C 2F); 1,1,1,2,2,3,4-heptafluoro-3-hexene (CF 3CF 2CF=CFC 2H); 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)(CH 3)); 1,1,1,3-tetrafluoro-2-trifluoromethyl-2-pentene ((CF 3)2 C=CFC 2H5 ); 1,1,1,2,3,4 ,4 ,5,5,6,6,7,7,7-tetradecafluoro-2-heptene (CF 3CF=CFCF 2CF 2C 2 F); 1,1,1, 2 ,2 ,3, 4 ,5,5,6,6,7,7,7-tetradecafluoro-3 heptene (CF 3CF 2CF=CFCF 2C 2F); 1,1,1,3,4,4,5,5,6,6,7,7,7-tridecafluoro 2-heptene (CF 3CH=CFCF 2CF 2C 2F); 1,1,1,2,4,4,5,5,6,6,7,7,7 tridecafluoro-2-heptene (CF 3CF=CHCF 2CF 2C 2F); 1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF 3CF 2CH=CFCF 2C 2F 5); 1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3 heptene (CF 3CF 2CF=CHCF 2C 2F5 ); CF 2=CFOCF 2CF 3 (PEVE); CF 2=CFOCF 3 (PMVE) and combinations thereof.
19. The method of claim 18 wherein said method comprises compressing said composition in a centrifugal compressor, condensing said composition, and thereafter evaporating said composition in the vicinity of a body to be heated or cooled.
20. The method of claim 18, wherein said centrifugal compressor is a multi-stage centrifugal compressor.
21. The method of claim 18, wherein said centrifugal compressor is a two-stage centrifugal compressor.
22. The method according to claim 18, wherein said centrifugal compressor is powered by (a) an engine exhaust gas driven turbine; or (b) a ratioed gear drive assembly with a ratioed belt drive.
23. A method of using the composition of claim 1, or 2, to reduce fire hazard in refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus wherein said apparatus comprises a flammable refrigerant, said method comprises introducing said composition into said apparatus, and optionally adding a lubricant to said composition added.
24. The method of claim 23, wherein said flammable refrigerant is selected from the group consisting of: difluoromethane (HFC-32); fluoromethane (HFC-41); 1,1,1-trifluoroethane (HFC-143a);1,1,2-trifluoroethane (HFC-143); 1,1-difluoroethane (HFC 152a); fluoroethane (HFC-161); 1,1,1-trifluoropropane (HFC-263fb); 1,1,1,3,3-pentafluorobutane (HFC-365mfc); 1,2,3,3-tetrafluoro-1-propene (HFC-1234ye); 1,3,3,3-tetrafluoro-1-propene (HFC-1234ze); 2,3,3,3 tetrafluoro-1-propene (HFC-1234yf); 1,1,2,3-tetrafluoro-1-propene (HFC 1234yc); 1,1,3,3-tetrafluoro-1-propene (HFC-1234zc); 2,3,3-trifluoro-1 propene (HFC-1243yf); 3,3,3-trifluoro-1-propene (HFC-1243zf); 1,1,2 trifluoro-1-propene (HFC-1243yc); 1,1,3-trifluoro-1-propene (HFC-1243zc); 1,2,3-trifluoro-1-propene (HFC-1243ye); and 1,3,3-trifluoro-1-propene (HFC-1243ze); C 4 F 9OC 2 H; propane; propylene; cyclopropane; n-butane; isobutane; n-pentane; 2-methylbutane; 2,2-dimethylpropane;cyclopentane, cyclobutane; 2,2-dimethylbutane; 2,3-dimethylbutane; 2,3 dimethylpentane; 2-methylhexane; 3-methyihexane; 2-methylpentane; 3 ethylpentane; 3-methylpentane; cyclohexane; n-heptane; methylcyclopentane; n-hexane; dimethylether; methyl t-butyl ether; ammonia, and combinations thereof.
25. A method of using the refrigerant or heat transfer fluid composition of claim 1 for reducing the flammability of a flammable refrigerant, said method comprising: combining said flammable refrigerant with said composition.
26. The method of claim 25 wherein said flammable refrigerant is selected from the group consisting of hydrofluorocarbons, fluoroethers, hydrocarbon ethers, hydrocarbons, ammonia, and combinations thereof.
27. The method of claim 26, wherein said flammable refrigerant is selected from the group consisting of: Difluoromethane (HFC-32); fluoromethane (HFC-41); 1,1,1-trifluoroethane (HFC-143a); 1,1,2-trifluoroethane (HFC-143); 1,1 difluoroethane (HFC-152a); fluoroethane (HFC-161); 1,1,1 trifluoropropane (HFC-263fb); 1,1,1,3,3-pentafluorobutane (HFC-365mfc); 1,2,3,3-tetrafluoro-1-propene (HFC-1234ye); 1,3,3,3-tetrafluoro-1-propene (HFC-1234ze); 2,3,3,3-tetrafluoro-1-propene (HFC-1234yD; 1,1,2,3 tetrafluoro-1-propene (HFC-1234yc); 1,1,3,3-tetrafluoro-1-propene (HFC 1234zc); 2,3,3-trifluoro-1-propene (HFC-1243yf); 3,3,3-trifluoro-1-propene (HFC-1243zf); 1,1,2-trifluoro-1-propene (HFC-1243yc); 1,1,3-trifluoro-1 propene (HFC-1243zc); 1,2,3-trifluoro-1-propene (HFC-1243ye); and 1,3,3-trifluoro-1-propene (HFC-1243ze); C 4 F9OC 2H; propane; propylene; cyclopropane; n-butane; isobutane; n-pentane; 2-methylpentane; 2,2 dimethylpropane; cyclopentane, cyclobutane; 2,2-dimethylbutane; 2,3 dimethylbutane; 2,3-dimethylpentane; 2-methyihexane; 3-methylhexane; 2-methylpentane; 3-ethylpentane; 3-methylpentane; cyclohexane; n heptane; methylcyclopentane; n-hexane; dimethylether; methyl t-butyl ether; ammonia, and combinations thereof.
28. A method for replacing the use of a high global warming potential refrigerant, said method comprising: providing the composition of claim 1 or 2 in refrigeration, air conditioning, or heat pump apparatus in place of, or in combination with, a high global warming potential refrigerant in said apparatus.
29. A method of using the composition of claim 1 to lower global warming potential of an original refrigerant or heat transfer fluid composition, said method comprising combining said original refrigerant or heat transfer fluid composition with the composition of claim 1, to produce a second refrigerant or heat transfer fluid composition wherein said second refrigerant or heat transfer fluid composition has a lower global warming potential than said original refrigerant or heat transfer fluid composition.
30. A method for reducing the GWP of an original refrigerant or heat transfer fluid composition in a refrigeration, air conditioning or heat pump apparatus, wherein said original refrigerant or heat transfer fluid has a GWP of about 150 or higher; said method comprising introducing a second, lower GWP refrigerant or heat transfer fluid composition of claim 1 or 2 into said refrigeration, air-conditioning or heat pump apparatus..
31. The method of claim 30 further comprising removing the original refrigerant or heat transfer fluid composition from said refrigeration, air-conditioning or heat pump apparatus before the second, lower GWP refrigerant or heat transfer fluid is introduced.
32. A method for replacing an original refrigerant or heat transfer fluid composition with a second refrigerant or heat transfer fluid composition comprising providing a composition of claim 1 or 2 as the second refrigerant or heattransfer fluid composition.
33. The method of claim 30 said original refrigerant or heat transfer fluid composition is selected from the group consisting of: (i) 1,1,1,2-tetrafluoroethane (R134a) and said R134a is substituted by a second refrigerant or heat transfer fluid composition comprising trifluoromethyl trifluorovinyl ether (PMVE);
(ii) 1,1-difluoroethane (R152a) and wherein said R152a is substituted by a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of E-1,3,3,3-tetrafluoropropene (E-HFC-1234ze), 1,2,3,3,3 pentafluoropropene (HFC-1225ye), 2,3,3,3-tetrafluoropropene (HFC 1234yf), 3,3,3-trifluoropropene (HFC-1243zf), and trifluoromethyl trifluorovinyl ether (PMVE);
(iii) 1,1,1,2,3,3,3-heptafluoropropane (R227ea) and wherein said R227ea is substituted by a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of E-1,3,3,3-tetrafluoropropene (E-HFC-1234ze), 1,2,3,3,3-pentafluoropropene (HFC-1225ye), 2,3,3,3-tetrafluoropropene (HFC-1234yf), 3,3,3-trifluoropropene (HFC-1243zf), and trifluoromethyl trifluorovinyl ether (PMVE);
(iv) 1,1,2-trichloro-1,2,2-trifluoroethane (RI13) and wherein said R113 is substituted by a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting 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);
(v) 1,1,1,2,3,4,4,5,5,5-decafluoropentane (R43-10mee) and wherein said R43-10mee is substituted by a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 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- 51 12mmzz); and 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene(F22E);
(vi) C 4 F 9OCH 3 and wherein said C 4 FqOCH 3 is substituted by a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 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);
(vii) 1,1,1,3,3-pentafluorobutane (R365mfc) and wherein said R365mfc is substituted by a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 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-CI51-10y); 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);
(viii) fluorotrichloromethane (R11) and wherein said R11 is substituted by a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 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-141-1Omyy); 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 1,1,1,4,4,5,5,5-octafluoro-2-pentene (F12E);
(ix) 2,2,-dichloro-1,1,1trifluoroethane (R123) and wherein said R123 is substituted by a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 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 (F1IE); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene (HFC-1429mzt); and 1,1,1,4,4,5,5,5-octafluoro-2-pentene (F12E);
(x) 1,1,1,3,3-pentafluoropropane (R245fa) and wherein said R245fa is substituted by a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 2,3,3-trifluoropropene (HFC-1243yf); 1,1,1,4,4,4-hexafluoro 2-butene (F11E); 1,3,3,3-tetrafluoropropene (HFC-1234ze); 1,1,1,2,4,4,4 heptafluoro-2-butene (HFC-1327my); 1,2,3,3-tetrafluoropropene (HFC 1234ye); and pentafluoroethyl trifluorovinyl ether (PEVE);
(xi) 1,2-dichloro-1,I,2,2-tetrafluoroethane (R124) and wherein said R124 is substituted by a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 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-butene (HFC-1345fz);
(xii) 1,1,1,3,3,3-hexafluoropropane (R236fa) and wherein said R236fa is substituted by a second refrigerant or heat-transfer fluid composition comprising at least one compound selected from the group consisting of 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-butene (HFC-1345fz);
(xiii) R401A and wherein said R401A is substituted by a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of E-1,3,3,3 tetrafluoropropene (E-HFC-1234ze); 1,2,3,3,3-pentafluoropropene (HFC 1225ye); 2,3,3,3-tetrafluoropropene (HFC-1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyl trifluorovinyl ether (PMVE);
(xiv) R401B and wherein said R401B is substituted by a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of E-1,3,3,3 tetrafluoropropene (E-HFC-1234ze); 1,2,3,3,3-pentafluoropropene (HFC 1225ye); 2,3,3,3-tetrafluoropropene (HFC-1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyl trifluorovinyl ether (PMVE);
(xv) R409A and wherein said R409A is substituted by a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of E-1,3,3,3 tetrafluoropropene (E-HFC-1234ze); 1,2,3,3,3-pentafluoropropene (HFC 1225ye); 2,3,3,3-tetrafluoropropene (HFC-1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyl trifluorovinyl ether (PMVE);
(xvi) R409B and wherein said R409B is substituted by a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of E-1,3,3,3 tetrafluoropropene (E-HFC-1234ze); 1,2,3,3,3-pentafluoropropene (HFC 1225ye); 2,3,3,3-tetrafluoropropene (HFC-1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyl trifluorovinyl ether (PMVE);
(xvii) R414B and wherein said R414B is substituted by a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of E-1,3,3,3 tetrafluoropropene (E-HFC-1234ze); 1,2,3,3,3-pentafluoropropene (HFC 1225ye); 2,3,3,3-tetrafluoropropene (HFC-1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyl trifluorovinyl ether (PMVE);
(xviii) R416A and wherein said R416A is substituted by a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of E-1,3,3,3 tetrafluoropropene (E-HFC-1234ze); 1,2,3,3,3-pentafluoropropene (HFC 1225ye); 2,3,3,3-tetrafluoropropene (HFC-1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyl trifluorovinyl ether (PMVE);
(xix) dichlorodifluoromethane (R12) and wherein said R12 is substituted by a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 1,2,3,3,3-pentafluoropropene (HFC-1225ye); 2,3,3,3-tetrafluoropropene
(HFC-1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyl trifluorovinyl ether (PMVE); and
(xx) R500 and wherein said R500 is substituted by a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 1,2,3,3,3 pentafluoropropene (HFC-1225ye); 2,3,3,3-tetrafluoropropene (HFC 1234yf; 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyl trifluorovinyl ether (PMVE)-trifluoropropene, 3,3,3-trifluoropropene, and trifluoromethyl trifluorovinyl ether.
34. The method of claim 32 wherein the original refrigerant or heat transfer fluid composition is R134a or R12 and wherein said R134a or R12 is substituted by a second refrigerant or heat transfer fluid composition comprising about 1.0 weight percent to about 37 weight percent HFC-32 and about 99 weight percent to about 63 weight percent HFC-1225ye.
35. The method of claim 34 wherein the second refrigerant or heat transfer fluid composition comprises about 1.0 weight percent to about 10 weight percent HFC-32 and about 99 weight percent to about 90 weight percent HFC-1225ye.
36. The method of claim 32 wherein the original refrigerant or heat transfer fluid composition is R22, R404A, or R41OA and wherein said R22, R404A or R41OA is substituted by a second refrigerant or heat transfer fluid composition comprising about 1.0 weight percent to about 37 weight percent HFC-32 and about 99 weight percent to about 63 weight percent HFC-1225ye.
37. The method of claim 36 wherein the second refrigerant or heat transfer fluid composition comprises about 20 weight percent to about 37 weight percent HFC-32 and about 80 weight percent to about 63 weight percent HFC-1225ye.
38. The method of claim 36 wherein the second refrigerant or heat transfer fluid composition comprises 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.
39. The method of claim 36 wherein the second refrigerant or heat transfer fluid composition comprises about 30 weight percent to about 90 weight percent HFC-1225ye, about 5.0 weight percent to about 55 weight percent HFC-32, and about 1.0 weight percent to about 35 weight percent HFC-125.
40. The method of claim 36 wherein the second refrigerant or heat transfer fluid composition comprises about 40 weight percent to about 85 weight percent HFC-1225ye, about 10 weight percent to about 45 weight percent HFC-32 and about 1.0 weight percent to about 28 weight percent HFC-125.
41. A method of using the composition of claim 1 or 2 as a heat transfer fluid composition, said process comprising comprises transporting said composition from a heat source to a heat sink.
42. A method for making the composition of claim 1 or 2, said method comprising: (i) reclaiming a volume of one or more components of a refrigerant composition from at least one refrigerant container, (ii) removing impurities sufficiently to enable reuse of said one or more of the reclaimed components, (iii) and optionally, combining all or part of said reclaimed volume of components with at least one additional refrigerant composition or component.
43. A refrigeration, air-conditioning or heat pump apparatus containing a composition as claimed in any one of claims 1 or 2.
44. A mobile refrigeration or air-conditioning apparatus containing the composition as claimed in any one of claims 1 or 2.
45. The composition of claims I or 2 further comprising a stabilizer selected from the group consisting of: a. at least one terpenes or terpenoids in combination with at least one selected from the group consisting of epoxides, fluorinated epoxides, and oxetanes. b. at least one fullerene in combination with at least one selected from the group consisting of epoxides, fluorinated epoxides, and oxetanes. c. at least one phenol in combination with at least one selected from the group consisting of epoxides, fluorinated epoxides, and oxetanes.
46. The composition of claim 45 wherein said stabilizer is selected from the group consisting of: a. d-limonene and at least one selected from the group consisting of trifluoromethyloxirane and 3-ethyl-3 hydroxymethyloxetane; b. alpha-pinene and at least one selected from the group consisting of trifluoromethyloxirane and 3-ethy-3 hydroxymethyloxetane; c. a fullerene and at least one selected from the group consisting of trifluoromethyloxirane and 3-ethyl-3 hydroxymethyloxetane; d. tocopherol and at least one selected from the group consisting of trifluoromethyloxirane and 3-ethyl-3 hydroxymethyloxetane; e. hydroquinone and at least one selected from the group consisting of trifluoromethyloxirane and 3-ethyl-3 hydroxymethyloxetane; and f. butylated hydroxyl toluene and at least one selected from the group consisting of trifluoromethyloxirane and 3-ethyl 3-hydroxymethyloxetane.
47. The composition of claim 45 further comprising at least one additional stabilizer selected from the group consisting of: areoxalyl bis(benzylidene)hydrazide; N,N'-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoylhydrazine);
2,2'-oxamidobis-ethyl-(3,5-d-terbutyl-4-hydroxyhydorcinnamate) N,N'-(disalicyclidene)-1,2-propanediamine; and ethyenediaminetetraacetic acid and salts thereof.
48. The composition of claim 45 further comprising at least one alkylamine selected from the group consisting of triethylamine; tributylamine; triisopropylamine; diisobutylamine; triisopropylamine; triisobutylamine; and hindered amine antioxidants.
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