The present invention relates to compositions for use in refrigeration, air-conditioning, and heat pump systems wherein the composition comprises a fluoroolefin and at least one other component. The compositions of the present invention are useful in processes for producing cooling or heat, as heat
The present invention relates to compositions for use in refrigeration, air-conditioning, and heat pump systems wherein the composition comprises a fluoroolefin and at least one other component. The compositions of the present invention are useful in processes for producing cooling or heat, as heat transfer fluids, foam blowing agents, aerosol propellants, and fire suppression and fire extinguishing agents.
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What is claimed is: 1. An azeotropic or near-azeotropic composition comprising about 1 weight percent to about 99 weight percent HFC-1234yf and about 99 weight percent to about 1 weight percent HFC-134a. 2. The composition of claim 1, comprising from about 30 weight percent to about 99 weight per
What is claimed is: 1. An azeotropic or near-azeotropic composition comprising about 1 weight percent to about 99 weight percent HFC-1234yf and about 99 weight percent to about 1 weight percent HFC-134a. 2. The composition of claim 1, comprising from about 30 weight percent to about 99 weight percent HFC-1234yf and from about 70 weight percent to about 1 weight percent HFC-134a. 3. The composition of claim 1, further comprising at least one compound selected from the group consisting of propane, n-butane, isobutane, and dimethyl ether. 4. The composition of claim 3, wherein the azeotropic or near-azeotropic composition is selected from the group consisting of: about 1 weight percent to about 80 weight percent of HFC-1234yf, about 1 weight percent to about 80 weight percent of HFC-134a, and about 19 weight percent to about 98 weight percent of propane; about 1 weight percent to about 98 weight percent of HFC-1234yf, about 1 weight percent to about 98 weight percent of HFC-134a, and about 1 weight percent to about 30 weight percent n-butane; about 1 weight percent to about 98 weight percent of HFC-1234yf, about 1 weight percent to about 98 weight percent HFC-134a, and about 1 weight percent to about 30 weight percent isobutane; and about 1 eight percent to about 98 weight percent of HFC-1234yf, about 1 weight percent to about 98 weight percent of HFC-134a, and about 1 weight percent to about 40 weight percent of dimethyl ether. 5. The composition of claim 3, wherein the composition is an azeotropic composition selected from the group consisting of: about 70.4 weight percent HFC-1234yf and about 29.6 weight percent HFC-134a having a vapor pressure of about 18.4 psia (127 kPa) at a temperature of about-25° C.; about 24.5 weight percent HFC-1234yf, about 31.1 weight percent HFC-134a, and about 44.5 weight percent propane having a vapor pressure of about 34.01 psia (234 kPa) at a temperature of about-25° C.; about 60.3 weight percent HFC-1234yf, about 35.2 weight percent HFC-134a, and about 4.5 weight percent n-butane having a vapor pressure of about 18.58 psia (128 kPa) at about-25° C.; about 48.6 weight percent HFC-1234yf, about 37.2 weight percent HFC-134a, and about 14.3 weight percent isobutane having a vapor pressure of about 19.86 psia (137 kPa) at about-25° C.; and about 24.0 weight percent HFC-1234yf, about 67.9 weight percent HFC-134a, and about 8.1 weight percent dimethyl ether having a vapor pressure of about 17.21 psia (110 kPa) at a temperature of about-25° C. 6. The composition of claim 1, further comprising a lubricant selected from the group consisting of polyol esters, polyalkylene glycols, polyvinyl ethers, mineral oil, alkylbenzenes, synthetic paraffins, synthetic napthenes, and poly(alpha)olefins. 7. The composition of claim 6, further comprising a compatibilizer selected from the group consisting of: a) polyoxyalkylene glycol ethers represented by the formula R1[(OR2)xOR3]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; R2 is selected from aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms; R3 is selected from hydrogen, and aliphatic and alicyclic hydrocarbon radicals having from 1 to 6 carbon atoms; at least one of R1 and R3 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 R1C(O)NR2R3 and cyclo-[R4CON(R5)], wherein R1, R2, R3 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; R4 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 R1C(O)R2, wherein R1 and R2 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 R1CN, 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 1 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 R1OR2, wherein: R1 is selected from aryl hydrocarbon radicals having from 6 to 12 carbon atoms; R2 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 CF3R1, wherein R1 is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms; h) fluoroethers represented by the formula R1OCF2CF2H, wherein R1 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 CF2═CXY, wherein X is hydrogen, chlorine or fluorine, and Y is chlorine, fluorine, CF3 or ORf, wherein Rf is CF3, C2F5, or C3F7; and said polyols are linear or branched, wherein said linear polyols are of the type HOCH2(CHOH)x(CRR')yCH2OH, wherein R and R' are hydrogen, CH3 or C2H5, 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(CH2OH)v[(CH2)m CH2OH]w, wherein R may be hydrogen, CH3 or C2H5, 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]: wherein, R1 through R8 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 R1CO2R2, wherein R1 and R2 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. 8. The composition of claim 7, further comprising a stabilizer or odor masking agent. 9. The composition of claim 8, wherein said stabilizer is selected from the group consisting of nitromethane, hindered phenols, hydroxylamines, thiols, phosphites and lactones. 10. A method for improving oil-return to the compressor in a compression refrigeration, air-conditioning or heat pump apparatus, said method comprising using the composition of claim 7 in said apparatus. 11. The composition of claim 1, further comprising a tracer selected from the group consisting of hydrofluorocarbons, deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodated compounds, alcohols, aldehydes, ketones, nitrous oxide (N2O) and combinations thereof. 12. The composition of claim 11, further comprising a tracer selected from the group consisting of CD3CD3, CD3CD2CD3, CD2F2, CF3CD2CF3, CD2FCF3, CD3CF3, CDF2CF3, CF3CDFCF3, CF3CF2CDF2, CDF2CDF2, CF3CF2CD3, CF3CD2CH3, CF2CH2CD3, CF3CF3, cyclo-CF2CF2CF2--, CF3CF2CF3, cyclo-CF2CF2CF2CF2--, CF3CF2CF2CF3, CF3CF(CF3)2, cyclo-CF(CF3)CF2CF(CF3)CF2--, CF3OCHFCF3, CF3OCH2CF3, CF3OCH2CHF2, CF3CH2OCHF2CH3OCF2CF3 , CH3CF2OCF3CF3CF2CF2 OCHFCF3, CF3CF2CF2OCF(CF3)CF2OCHFCF 3, CHF3, CH2FCH3, CHF2CH3, CHF2CHF2, CF3CHFCF3, CF3CF2CHF2, CF3CF2CH2F, CHF2CHFCF3, CF3CH2CF3, CF3CF2CH3, CF3CH2CHF2, CHF2CF2CH3, CF3CHFCH3, CF3CH2CH3, CH3CF2CH3, CH3CHFCH3, CH2FCH2CH3, CHF2CF2CF2CF3, (CF3)2CHCF3, CF3CH2CF2CF3, CHF2CF2CF2CHF2, CH3CF2CF2CF3, CF3CHFCHFCF2CF3, 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, CH3Br, CH2FBr, CHF2Br, CHFBr2, CHBr3, CH2BrCH3, CHBr═CH2, CH2BrCH2Br, CFBr═CHF, CF3I, CHF2I, CH2FI, CF2ICH2F, CF2ICHF2, CF2ICF2I, C6F5I, ethanol, n-propanol, isopropanol, acetone, n-propanal, n-butanal, methyl ethyl ketone, nitrous oxide, and combinations thereof. 13. The composition of claim 1, further comprising at least one ultra-violet fluorescent dye selected from the group consisting of naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, derivatives of said dye and combinations thereof. 14. The composition of claim 13, further comprising at least one solubilizing agent selected from the group consisting of hydrocarbons, dimethylether, polyoxyalkylene glycol ethers, am ides, ketones, nitriles, chlorocarbons, esters, lactones, aryl ethers, fluoroethers, and 1,1,1-trifluoroalkanes. 15. The composition of claim 14, wherein said solubilizing agent is selected from the group consisting of: a) polyoxyalkylene glycol ethers represented by the formula R1[(OR2)xOR3]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; R2 is selected from aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms; R3 is selected from hydrogen, and aliphatic and alicyclic hydrocarbon radicals having from 1 to 6 carbon atoms; at least one of R1 and R3 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 R1C(O)NR2R3 and cyclo-[R4CON(R5)-], wherein R1, R2, R3 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; R4 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 R1C(O)R2, wherein R1 and R2 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 R1CN, 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 1 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 R1OR2, wherein: R1 is selected from aryl hydrocarbon radicals having from 6 to 12 carbon atoms; R2 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 CF3R1, wherein R1 is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms; h) fluoroethers represented by the formula R1OCF2CF2H, wherein R1 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 CF2═CXY, wherein X is hydrogen, chlorine or fluorine, and Y is chlorine, fluorine, CF3 or ORf, wherein Rf is CF3, C2F5, or C3F7; and said polyols are linear or branched, wherein said linear polyols are of the type HOCH2(CHOH)x(CRR')yCH2OH, wherein R and R' are hydrogen, CH3 or C2H5, 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(CH2OH)v[(CH2)m CH2OH]w, wherein R may be hydrogen, CH3 or C2H5, 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]: wherein, R1 through R8 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 R1CO2R2, wherein R1 and R2 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. 16. A method for detecting the composition of claim 13 in a compression refrigeration, air conditioning, or heat pump apparatus, said method comprising providing said composition including said ultra-violet fluorescent dye to said apparatus, and providing a suitable means for detecting said composition at a leak point or in the vicinity of said apparatus. 17. A method of producing cooling, said method comprising: evaporating said composition of claim 1 in the vicinity of a body to be cooled and thereafter condensing said composition. 18. A method of producing heat, said method comprising: condensing said composition of claim 1 in the vicinity of a body to be heated and thereafter evaporating said composition. 19. A method of solubilizing a refrigerant or heat transfer fluid composition comprising the composition of claim 1 in a refrigeration lubricant selected from the group consisting of mineral oils, alkylbenzenes, synthetic paraffins, synthetic napthenes, and poly(alpha)olefins, wherein said method comprises contacting said lubricant with said composition in the presence of an effective amount of a compatibilizer, wherein said compatibilizer is selected from the group consisting of: a) polyoxyalkylene glycol ethers represented by the formula R1[(OR2)xOR3]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; R2 is selected from aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms; R3 is selected from hydrogen, and aliphatic and alicyclic hydrocarbon radicals having from 1 to 6 carbon atoms; at least one of R1 and R3 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 R1C(O)NR2R3 and cyclo-[R4CON(R5)], wherein R1, R2, R3 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; R4 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 R1C(O)R2, wherein R1 and R2 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 R1CN, 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 1 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 R1OR2, wherein: R1 is selected from aryl hydrocarbon radicals having from 6 to 12 carbon atoms; R2 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 CF3R1, wherein R1 is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms; h) fluoroethers represented by the formula R1OCF2CF2H, wherein R1 is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms; or wherein said fluoroethers are derived from fluoro-olefins and polyols, wherein said fluoro-olefins are of the type CF2═CXY, wherein X is hydrogen, chlorine or fluorine, and Y is chlorine, fluorine, CF3 or ORf, wherein Rf is CF3, C2F5, or C3F7; and said polyols are of the type HOCH2CRR'(CH2)z(CHOH)xCH2(CH 2OH)y, wherein R and R' are hydrogen, CH3 or C2H5, x is an integer from 0-4, y is an integer from 0-3 and z is either zero or 1; and i) lactones represented by structures [B], [C], and [D]: wherein, R1 through R8 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 R1CO2R2, wherein R1 and R2 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. 20. A method for replacing a high GWP refrigerant in a refrigeration, air-conditioning, or heat pump apparatus, wherein said high GWP refrigerant is selected from the group consisting of R134a, R22, R123, R11, R245fa, R114, R236fa, R124, R12, R410A, R407C, R417A, R422A, R507A, R502, and R404A, said method comprising providing the composition of claim 1 to said refrigeration, air-conditioning, or heat pump apparatus that uses, used or is designed to use said high GWP refrigerant. 21. A method of using the composition of claim 1 as a heat transfer fluid composition, said process comprising comprises transporting said composition from a heat source to a heat sink. 22. A method for making the composition of claim 1, 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. 23. A refrigeration, air-conditioning, or heat pump apparatus containing a composition as claimed in claim 1. 24. The apparatus of claim 23 comprising a stationary air-conditioning system. 25. The apparatus of claim 23 comprising a stationary heat pump system. 26. The apparatus of claim 23 comprising a stationary refrigeration system. 27. A method of forming a foam comprising: a) adding to a foamable composition the composition of claim 1; and b) reacting the foamable composition under conditions effective to form a foam. 28. A process for producing aerosol products comprising the step of adding the composition of claim 1 to active ingredients in an aerosol container, wherein said composition functions as a propellant. 29. A method of suppressing a flame comprising contacting the flame with a fluid comprising the composition of claim 1. 30. A method of extinguishing or suppressing a fire in a total-flood application comprising: a) providing an agent comprising the composition of claim 1, b) disposing the agent in a pressurized system; and c) discharging the agent into an area to extinguish or suppress fires in that area. 31. A method of inerting an area to prevent a fire or explosion comprising: a) providing an agent comprising the composition of claim 1; b) disposing the agent in a pressurized discharge system; and c) discharging the agent into the area to prevent a fire or explosion from occurring. 32. The composition of claim 1, wherein the composition is an azeotropic composition comprising about 70.4 weight percent HFC-1234yf and about 29.6 weight percent HFC-134a having a vapor pressure of about 18.4 psia (127 kPa) at a temperature of about-25° C.
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