KR20060122917A - Hydrofluorocarbon refrigerant compositions and uses thereof - Google Patents

Abstract

Disclosed herein are hydrofluorocarbon refrigerant or heat transfer fluid compositions that are useful in refrigerain or air conditioning apparatus or as heat transfer fluids. The compositions of the present invention are also useful in centrifugal compressor apparatus that employ two-stage compressors or single slab.single pass heat exchangers.

Description

HYDROFLUOROCARBON REFRIGERANT COMPOSITIONS AND USES THEREOF

Cross Reference to Related Application

This application is published in US Provisional Application No. 60 / 536,819, filed Jan. 14, 2004; US Provisional Application No. 60 / 537,453, filed January 15, 2004; US Provisional Application No. 60 / 549,978, filed March 4, 2004; US Provisional Application No. 60 / 575,037, filed May 26, 2004; And US Provisional Application No. 60 / 584,785, filed June 29, 2004.

The present invention relates to a composition suitable for use in a cooling and air conditioning apparatus comprising at least one hydrofluorocarbon (HFC) or combinations thereof. The invention also relates to a composition for use in a cooling and air conditioning apparatus using a centrifugal compressor comprising at least one hydrofluorocarbon (HFC) or combinations thereof. The compositions of the present invention are useful in cooling or heat generating processes or as heat transfer fluids.

The refrigeration industry has been trying to find refrigerants to replace ozone layer depleting chlorofluorocarbons (CFCs) and hydrogen fluorocarbons (HCFCs), which are being phased out as a result of the Montreal Protocol over the past decades. The solution for most refrigerant manufacturers has been to commercialize fluorocarbon (HFC) refrigerants. The new HFC refrigerant, HFC-134a, which is currently the most widely used, is not applicable to the current regulations on phase-out, according to the Montreal Protocol, because it is unlikely to destroy the ozone layer.

By further environmental regulation, certain HFC refrigerants can ultimately be phased out worldwide. Currently, the automotive industry is faced with regulations relating to the global warming potential of refrigerants used in automotive air conditioning. Thus, there is currently a strong desire for the automotive air conditioning market to find new refrigerants with reduced global warming potential. If regulations are to be applied more broadly in the future, refrigerants that can be used in all areas of the cooling and air conditioning industry will become even more necessary.

Alternative refrigerants for HFC-134a that are currently being presented include HFC-152a, pure hydrocarbons such as butane or propane, or "natural" refrigerants such as CO ₂ or ammonia. Many of these suggested alternatives have toxicity, flammability, and / or low energy efficiency. Thus, new alternatives are constantly being sought.

It is an object of the present invention to provide novel refrigerant compositions and heat transfer fluids having properties which meet the requirement that there is little or no ozone depletion potential and a lower global warming potential than existing refrigerants.

Summary of the Invention

The present invention is 1,1,3-trifluoropropane; 1,1,1,3,3-pentafluorobutane; 1,3-difluoropropane; 1,1-difluorobutane; 1,3-difluoro-2-methylpropane; 1,2-difluoro-2-methylpropane; 1,2-difluorobutane; 1,3-difluorobutane; 1,4-difluorobutane; 2,3-difluorobutane; 1,1,1-trifluoropentane; 1,1,1-trifluoro-3-methylbutane; 1,1-difluoropentane; 1,2-difluoropentane; 2,2-difluoropentane; 1,1,1-trifluorohexane; 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene; And a refrigerant or heat transfer fluid selected from the group consisting of:

In the present invention, 1,1,3-trifluoropropane; 1,3-difluoropropane; 1,1,1,3,3-pentafluorobutane; 1,1-difluorobutane; 1,3-difluoro-2-methylpropane; 1,2-difluoro-2-methylpropane; 1,2-difluorobutane; 1,3-difluorobutane; 1,4-difluorobutane; 2,3-difluorobutane; 1,1,1-trifluoropentane; 1,1,1-trifluoro-3-methylbutane; 1,1-difluoropentane; 1,2-difluoropentane; 2,2-difluoropentane; 1,1,1-trifluorohexane; 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene; And a refrigerant or heat transfer fluid suitable for use in a cooling or air conditioning apparatus using a centrifugal compressor, selected from the group consisting of, and combinations thereof.

In the present invention, 1,1,2,2,3-pentafluoropropane; 1,1,1,3,3-pentafluoropropane; 1,1,3-trifluoropropane; 1,3-difluoropropane; 2- (difluoromethyl) -1,1,1,2,3,3-hexafluoropropane; 1,1,2,2,3,3,4,4-octafluorobutane; 1,1,1,2,2,4-hexafluorobutane; 1,1,1,3,3-pentafluorobutane; 1,1-difluorobutane; 1,3-difluoro-2-methylpropane; 1,2-difluoro-2-methylpropane; 1,2-difluorobutane; 1,3-difluorobutane; 1,4-difluorobutane; 2,3-difluorobutane; 1,1,1,2,3,3,4,4-octafluoro-2- (trifluoromethyl) butane; 1,1,1,2,2,3,3,4,4,5,5-undecafluoropentane; 1,1,1,2,2,3,4,5,5,5-decafluoropentane; 1,1,1,2,2,3,3,5,5,5-decafluoropentane; 1,1,1,4,4,4-hexafluoro-2- (trifluoromethyl) butane; 1,1,1-trifluoropentane; 1,1,1-trifluoro-3-methylbutane; 1,1-difluoropentane; 1,2-difluoropentane; 2,2-difluoropentane; 1,1,1-trifluorohexane; 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane; 1,1,1,2,2,5,5,5-octafluoro-4- (trifluoromethyl) pentane; 1,1,2,2-tetrafluorocyclobutane; 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene; And a refrigerant or heat transfer fluid composition suitable for use in a cooling or air conditioning apparatus using a two stage centrifugal compressor selected from the group consisting of, or a combination thereof, or using a single slab / single pass heat exchanger. .

Also disclosed herein are cooling methods, heat generation methods, and methods for transferring heat from a heat source to a heat sink using the compositions of the present invention.

The refrigerant composition of the present invention comprises at least one hydrofluorocarbon (HFC) or a combination thereof. The refrigerant composition of the present invention may be a single compound or a mixture comprising more than one compound.

Hydrofluorocarbons of the present invention include compounds containing hydrogen, fluorine and carbon. Such hydrofluorocarbons may be represented by the formula C _x H _{2x + 2-y} F _y or C _x H _2x-y F _y . In this formula, x may be 3 to 8 and y may be 1 to 17. The hydrofluorocarbons may be saturated or unsaturated compounds having about 3 to 8 carbon atoms, straight, branched or cyclic. Representative hydrofluorocarbons are listed in Table 1.

compound Chemical formula Compound name CAS registration number Hydrogen Fluorocarbon HFC-245ca CHF ₂ CF ₂ CH ₂ F 1,1,2,2,3-pentafluoropropane 679-86-7 HFC-245fa CF ₃ CH ₂ CHF ₂ 1,1,1,3,3-pentafluoropropane 460-73-1 HFC-263fa CHF ₂ CH ₂ CH ₂ F 1,1,3-trifluoropropane 24270-67-5 HFC-272fa CH ₂ FCH ₂ CH ₂ F 1,3-difluoropropane 462-39-5 HFC-392p CF ₂ HCH ₂ CH ₂ CH ₃ 1,1-difluorobutane 2358-38-5 HFC-392qqz (CH ₂ F) ₂ CHCH ₃ 1,3-difluoro-2-methylpropane 62126-93-6 HFC-392qy CH ₂ FCF (CH ₃ ) ₂ 1,2-difluoro-2-methylpropane 62126-92-5 HFC-392qe CH ₂ FCHFCH ₂ CH ₃ 1,2-difluorobutane 686-65-7 HFC-392qfe CH ₂ FCH ₂ CHFCH ₃ 1,3-difluorobutane 691-42-9 HFC-392qff CH ₂ FCH ₂ CH ₂ CH ₂ F 1,4-difluorobutane 372-90-7 HFC-392see CH ₃ CHFCHFCH ₃ 2,3-difluorobutane 666-21-7 HFC-4-10-3m CF ₃ (CH ₂ ) ₃ CH ₃ 1,1,1-trifluoropentane 402-82-6 HFC-4-10-3mfsz CF ₃ CH ₂ CH (CH ₃ ) ₂ 1,1,1-trifluoro-3-methylbutane 406-49-5 HFC-4-11-2p CHF ₂ (CH ₂ ) ₃ CH ₃ 1,1-difluoropentane 62127-40-6 HFC-4-11-2qe CH ₂ FCHF (CH ₂ ) ₂ CH ₃ 1,2-difluoropentane 62126-94-7 HFC-4-11-2sc CH ₃ CF ₂ CH ₂ CH ₂ CH ₃ 2,2-difluoropentane 371-65-3 HFC-5-12-3m CF ₃ (CH ₂ ) ₄ CH ₃ 1,1,1-trifluorohexane 17337-12-1 PFBE CF ₃ (CF ₂ ) ₃ CH = CH ₂ 3,3,4,4,5,5,6,6,6-nonnafluoro-1-hexene (or perfluorobutylethylene) 19430-93-4

The compounds listed in Table 1 are either commercially available or can be prepared by processes known in the art.

The composition of the present invention has no possibility of destroying the ozone layer and has a low possibility of global warming. Lightly fluorinated hydrofluorocarbons, for example alone or as a mixture, will have a lower global warming potential than many HFC refrigerants currently used.

The compositions of the present invention as a combination or a mixture can be prepared by any convenient method of mixing the desired amounts of the individual components. The preferred method is to weigh the desired amount of ingredients and then mix the ingredients in a suitable container. If desired, stirring can be performed.

Refrigerant or heat transfer compositions of the present invention that can be used in cooling or air conditioning using two stage centrifugal compressors or single slab / single pass heat exchangers include 1,1,2,2,3-pentafluoropropane; 1,1,1,3,3-pentafluoropropane; 1,1,3-trifluoropropane; 1,3-difluoropropane; 2- (difluoromethyl) -1,1,1,2,3,3-hexafluoropropane; 1,1,2,2,3,3,4,4-octafluorobutane; 1,1,1,2,2,4-hexafluorobutane; 1,1,1,3,3-pentafluorobutane; 1,1-difluorobutane; 1,3-difluoro-2-methylpropane; 1,2-difluoro-2-methylpropane; 1,2-difluorobutane; 1,3-difluorobutane; 1,4-difluorobutane; 2,3-difluorobutane; 1,1,1,2,3,3,4,4-octafluoro-2- (trifluoromethyl) butane; 1,1,1,2,2,3,3,4,4,5,5-undecafluoropentane; 1,1,1,2,2,3,4,5,5,5-decafluoropentane; 1,1,1,2,2,3,3,5,5,5-decafluoropentane; 1,1,1,4,4,4-hexafluoro-2- (trifluoromethyl) butane; 1,1,1-trifluoropentane; 1,1,1-trifluoro-3-methylbutane; 1,1-difluoropentane; 1,2-difluoropentane; 2,2-difluoropentane; 1,1,1-trifluorohexane; 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane; 1,1,1,2,2,5,5,5-octafluoro-4- (trifluoromethyl) pentane; 1,1,2,2-tetrafluorocyclobutane; 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene; And combinations thereof.

The composition of the present invention has no possibility of destroying the ozone layer and has a low possibility of global warming. Lightly fluorinated hydrofluorocarbons, for example, alone or as a mixture, will have a lower global warming potential than many HFC refrigerants currently used.

Compositions of the present invention may also include ultraviolet (UV) dyes and optionally solubilizers. Ultraviolet dyes are useful components that allow leakage of the refrigerant composition to be observed in the cooling or air conditioning system by allowing the fluorescence of the dye to be observed in the presence of ultraviolet light at this point of leakage. Since such ultraviolet dyes have low solubility in some refrigerants, solubilizers may be required.

By "ultraviolet" dye is meant an ultraviolet fluorescent composition that absorbs light in the ultraviolet region of the electromagnetic spectrum or light in the "near" ultraviolet region. Fluorescence generated by ultraviolet fluorescent dyes can be sensed when ultraviolet light emitting radiation having a wavelength of 10 to 750 nanometers is illuminated. Therefore, when a refrigerant containing such ultraviolet fluorescent dye leaks at a certain point in the cooling or air conditioning apparatus, fluorescence can be detected at this leak point. Such ultraviolet fluorescent dyes include, but are not limited to, naphthalimide, perylene, coumarin, anthracene, phenanthracene, xanthene, thioxanthene, naphthoxanthene, fluorescein and derivatives or combinations thereof.

Solubilizing agents of the present invention consist of hydrocarbons, hydrocarbon ethers, polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluorinated ethers and 1,1,1-trifluoroalkanes At least one compound selected from the group.

Hydrocarbon solubilizers of the present invention include hydrocarbons comprising straight, branched or cyclic alkanes or alkenes containing no more than 5 carbon atoms and hydrogen and no other functional groups. Representative hydrocarbon solubilizers include propane, propylene, cyclopropane, n-butane, isobutane and n-pentane. It should be noted that when the refrigerant is a hydrocarbon, the solubilizer may not be the same hydrocarbon.

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

Polyoxyalkylene glycol ether solubilizers of the present invention are of the formula R ¹ [(OR ² ) _x OR ³ ] _y where x is an integer from 1 to 3; y is an integer from 1 to 4; R ¹ is hydrogen, And an aliphatic hydrocarbon radical having 1 to 6 carbon atoms and y bonding sites; R ² is selected from an aliphatic hydrocarbylene radical having 2 to 4 carbon atoms; R ³ is hydrogen, and 1 to 6 Selected from aliphatic and alicyclic hydrocarbon radicals having 2 carbon atoms; at least one of R ¹ and R ³ is the hydrocarbon radical), and the polyoxyalkylene glycol ether is from about 100 to about 300 atomic mass units Has a molecular weight. In the present invention, the polyoxyalkylene glycol ether solubilizer is of the formula R ¹ [(OR ² ) _x OR ³ ] _y (where x is preferably 1 or 2; y is preferably 1; R ¹ and R ³ is preferably independently selected from hydrogen and an aliphatic hydrocarbon radical having 1 to 4 carbon atoms; R ² is preferably aliphatic hydro having 2 or 3, most preferably 3 carbon atoms; And a molecular weight of the polyoxyalkylene glycol ether is preferably from about 100 to about 250 atomic mass units, most preferably from about 125 to about 250 atomic mass units. R ¹ and R ³ hydrocarbon radicals having 1 to 6 carbon atoms may be linear, branched or cyclic. Representative R ¹ and R ³ hydrocarbon radicals are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl and cyclo Hexyl. If the free hydroxyl radicals on the polyoxyalkylene glycol ether solubilizing agent of the present invention are incompatible with the material of a particular compression cooling device (eg Mylar®), then R ¹ and R ³ are preferably Aliphatic hydrocarbon radicals having 1 to 4 carbon atoms, most preferably 1 carbon atom. R ² aliphatic hydrocarbylene radicals having 2 to 4 carbon atoms form a repeating oxyalkylene radical-(OR ² ) _x -comprising an oxyethylene radical, an oxypropylene radical and an oxybutylene radical. The R ² -comprising oxyalkylene radicals in one polyoxyalkylene glycol ether solubilizer molecule may be the same, or one molecule may contain different R ² oxyalkylene groups. The polyoxyalkylene glycol ether solubilizer of the present invention preferably comprises one or more oxypropylene radicals. When R ¹ is an aliphatic or cycloaliphatic hydrocarbon radical having 1 to 6 carbon atoms and y bonds, these radicals may be linear, branched or cyclic. Representative R ¹ aliphatic hydrocarbon radicals having two bonding sites include, for example, ethylene radicals, propylene radicals, butylene radicals, pentylene radicals, hexylene radicals, cyclopentylene radicals and cyclohexylene radicals. Representative R ¹ aliphatic hydrocarbon radicals having 3 or 4 binding sites include trimethylolpropane, glycerin, pentaerythritol, 1,2,3-trihydroxycyclohexane and 1,3,5-trihydroxycyclohexane It includes residues derived by the removal of hydroxyl radicals from polyalcohols such as.

Representative polyoxyalkylene glycol ether solubilizers are CH ₃ OCH ₂ CH (CH ₃ ) O (H or CH ₃ ) (propylene glycol methyl (or dimethyl) ether), CH ₃ O [CH ₂ CH (CH ₃ ) O] ₂ (H or CH ₃ ) (dipropylene glycol methyl (or dimethyl) ether), CH ₃ O [CH ₂ CH (CH ₃ ) O] ₃ (H or CH ₃ ) (tripropylene glycol methyl (or dimethyl) ether) , C ₂ H ₅ OCH ₂ CH (CH ₃ ) O (H or C ₂ H ₅ ) (propylene glycol ethyl (or diethyl) ether), C ₂ H ₅ O [CH ₂ CH (CH ₃ ) O] ₂ ( H or C ₂ H ₅ ) (dipropylene glycol ethyl (or diethyl) ether), C ₂ H ₅ O [CH ₂ CH (CH ₃ ) O] ₃ (H or C ₂ H ₅ ) (tripropylene glycol ethyl ( Or diethyl) ether), C ₃ H ₇ OCH ₂ CH (CH ₃ ) O (H or C ₃ H ₇ ) (propylene glycol n-propyl (or di-n-propyl) ether), C ₃ H ₇ O [ CH ₂ CH (CH ₃ ) O] ₂ (H or C ₃ H ₇ ) (dipropylene glycol n-propyl (or di-n-propyl) ether), C ₃ H ₇ O [CH ₂ CH (CH ₃ ) O ] ₃ (H or C ₃ H ₇ ) (Tripropylene glycol n-propyl (or di-n-propyl) ether), C ₄ H ₉ OCH ₂ CH (CH ₃ ) OH (propylene glycol n-butyl ether), C ₄ H ₉ O [CH ₂ CH ( CH ₃ ) O] ₂ (H or C ₄ H ₉ ) (dipropylene glycol n-butyl (or di-n-butyl) ether), C ₄ H ₉ O [CH ₂ CH (CH ₃ ) O] ₃ (H Or C ₄ H ₉ ) (tripropylene glycol n-butyl (or di-n-butyl) ether), (CH ₃ ) ₃ COCH ₂ CH (CH ₃ ) OH (propylene glycol t-butyl ether), (CH ₃ ) ₃ CO [CH ₂ CH (CH ₃ ) O] ₂ (H or (CH ₃ ) ₃ ) (dipropylene glycol t-butyl (or di-t-butyl) ether), (CH ₃ ) ₃ CO [CH ₂ CH (CH ₃ ) O] ₃ (H or (CH ₃ ) ₃ ) (tripropylene glycol t-butyl (or di-t-butyl) ether), C ₅ H ₁₁ OCH ₂ CH (CH ₃ ) OH (propylene glycol n -Pentyl ether), C ₄ H ₉ OCH ₂ CH (C ₂ H ₅ ) OH (butylene glycol n-butyl ether), C ₄ H ₉ O [CH ₂ CH (C ₂ H ₅ ) O] ₂ H (di Butylene glycol n-butyl ether), trimethylolpropane tri-n-butyl ether (C ₂ H ₅ C (CH ₂ O (CH ₂ ) ₃ CH ₃ ) ₃ ) and trimethylolpropane di-n-butyl ether (C ₂ H ₅ C (CH ₂ OC (CH ₂ ) ₃ CH ₃ ) ₂ CH ₂ OH), but are not limited thereto.

The amide solubilizing agent of the present invention is formula R ¹ CONR ² R ³ and cyclo- [R ⁴ CON (R ⁵ )-], wherein R ¹ , R ² , R ³ and R ⁵ are independently 1 to 12 carbons Selected from aliphatic and alicyclic hydrocarbon radicals having atoms; R ⁴ is selected from aliphatic hydrocarbylene radicals having from 3 to 12 carbon atoms), and the amide is from about 100 to about 300 atomic mass units Phosphorus molecular weight. The molecular weight of the amide is preferably from about 160 to about 250 atomic mass units. R ¹ , R ² , R ³ and R ⁵ optionally represent substituted hydrocarbon radicals, ie radicals containing non-hydrocarbon substituents selected from halogen (eg fluorine, chlorine) and alkoxides (eg methoxy). It may include. R ¹ , R ² , R ³ and R ⁵ are optionally a heteroatom-substituted hydrocarbon radical, ie a nitrogen atom (aza-), an oxygen atom (oxa-) or a sulfur atom (thia- Radicals containing). In general, up to 3, preferably up to 1 non-hydrocarbon substituent and heteroatom will be present for every 10 carbon atoms in R ^1-3 and the presence of any such non-hydrocarbon substituent and heteroatom is determined by the molecular weight described above. Should be taken into account when applying the scope. Preferred amide solubilizing agents consist of carbon, hydrogen, nitrogen and oxygen. Representative R ¹ , R ² , R ³ and R ⁵ aliphatic and cycloaliphatic hydrocarbon radicals are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary-butyl, tert-butyl, pentyl, isopentyl, neopentyl , Tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and coordination isomers thereof. A preferred embodiment of amide solubilizing agents are, cycloalkyl formula mentioned earlier ^{- [R 4 CON (R 5} ) -] R 4 is hydrocarbylene radicals in the (CR ⁶ R ⁷⁾ will be indicated by _n, in other words, the formula cyclo -[(CR ⁶ R ⁷ ) _n CON (R ⁵ )-] (where the above mentioned values apply for molecular weight; n is an integer from 3 to 5; R ⁵ contains from 1 to 12 carbon atoms Is a saturated hydrocarbon radical; R ⁶ and R ⁷ are independently selected (for each n) by the law applied when defining R ^1-3 above. For lactams represented by the formula cyclo-[(CR ⁶ R ⁷ ) _n CON (R ⁵ )-], all R ⁶ and R ⁷ are preferably hydrogen or contain one saturated hydrocarbon radical in n methylene units And R ⁵ is a saturated hydrocarbon radical containing 3 to 12 carbon atoms. For example, 1- (saturated hydrocarbon radical) -5-methylpyrrolidin-2-one.

Representative amide solubilizers include 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-1-pentylpiperid-2-one, 1,3-dimethylpiperid-2-one, 1-methylcaprolactam, 1-butyl-pyrrolidine-2 -One, 1,5-dimethylpiperid-2-one, 1-decyl-5-methylpyrrolidin-2-one, 1-dodecylpyrrolid-2-one, N, N-dibutylformamide and N, N-diisopropylacetamide, but is not limited thereto.

Ketone solubilizers of the present invention comprise ketones represented by R ¹ COR ² , wherein R ¹ and R ² are independently selected from aliphatic, cycloaliphatic and aryl hydrocarbon radicals having 1 to 12 carbon atoms, and Ketones have a molecular weight that is about 70 to about 300 atomic mass units. R ¹ and R ² in the ketone are preferably independently selected from aliphatic and alicyclic hydrocarbon radicals having 1 to 9 carbon atoms. The molecular weight of the ketone is preferably about 100 to 200 atomic mass units. R ¹ and R ² together may form a hydrocarbylene radical to form 5-, 6- or 7-membered cyclic ketones such as cyclopentanone, cyclohexanone and cycloheptanone. R ¹ and R ² may optionally include substituted hydrocarbon radicals, ie, radicals containing non-hydrocarbon substituents selected from halogen (eg fluorine, chlorine) and alkoxides (eg methoxy). R ¹ and R ² optionally contain a nitrogen atom (aza-), an oxygen atom (keto-, oxa-) or a sulfur atom (thia-) in a heteroatom-substituted hydrocarbon radical, ie a radical chain consisting of carbon atoms It may include radicals. In general, up to 3, preferably up to 1 non-hydrocarbon substituent and heteroatom will be present for every 10 carbon atoms in R ¹ and R ² , and the presence of any of these non-hydrocarbon substituents and heteroatoms is described above. Should be taken into account when applying the molecular weight range. Representative R ¹ and R ² aliphatic, cycloaliphatic and aryl hydrocarbon radicals in formula R ¹ COR ² are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary-butyl, tert-butyl, pentyl, isopentyl, Neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and coordination isomers thereof, as well as phenyl, benzyl, cumenyl, mesityl, tolyl, xylyl and pelican Netyl.

Representative ketone solubilizers are 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-decalon , 2-tridecanone, dihexyl ketone and dicyclohexyl ketone, but are not limited thereto.

Nitrile solubilizers of the invention include nitriles represented by the formula R ¹ CN, wherein R ¹ is selected from aliphatic, cycloaliphatic or aryl hydrocarbon radicals having 5 to 12 carbon atoms, wherein the nitrile is about 90 to about It has a molecular weight of 200 atomic mass units. R ¹ in the nitrile solubilizer is preferably selected from aliphatic and alicyclic hydrocarbon radicals having 8 to 10 carbon atoms. The molecular weight of the nitrile solubilizer is preferably from about 120 to about 140 atomic mass units. R ¹ may optionally include a substituted hydrocarbon radical, that is, a radical containing a non-hydrocarbon substituent selected from halogen (eg fluorine, chlorine) and alkoxide (eg methoxy). R ¹ optionally comprises a heteroatom-substituted hydrocarbon radical, ie a radical containing a nitrogen atom (aza-), an oxygen atom (keto-, oxa-) or a sulfur atom (thia-) in a radical chain consisting of carbon atoms can do. In general, up to 3, preferably up to 1 non-hydrocarbon substituent and heteroatom will be present for every 10 carbon atoms in R ¹ , and the presence of any such non-hydrocarbon substituent and heteroatom is in the range of molecular weight described above. Should be considered in the application. Representative R ¹ aliphatic, cycloaliphatic and aryl hydrocarbon radicals in formula R ¹ CN include pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and Co-isomers thereof, as well as phenyl, benzyl, cumenyl, mesityl, tolyl, xylyl and phenethyl. Representative nitrile solubilizers include 1-cyanopentane, 2,2-dimethyl-4-cyanopentane, 1-cyanohexane, 1-cyanoheptane, 1-cyanooctane, 2-cyanooctane, 1-cya Nononane, 1-cyanodecane, 2-cyanodecane, 1-cyanooundecan and 1-cyanododecane, but are not limited thereto.

Chlorocarbon solubilizing agents of the present invention include chlorocarbon represented by the formula RCl _x where x is selected from integers of 1 or 2; R is selected from aliphatic and alicyclic hydrocarbon radicals having 1 to 12 carbon atoms. And the chlorocarbon has a molecular weight of about 100 to about 200 atomic mass units. The molecular weight of the chlorocarbon solubilizer is preferably about 120 to 150 atomic mass units. Representative R aliphatic and cycloaliphatic hydrocarbon radicals in the formula RCl _x are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, Cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and coordination isomers thereof.

Representative chlorocarbon solubilizers include 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, but are not limited thereto.

Ester solubilizing agents of the present invention include esters represented by the formula R ¹ CO ₂ R ² , wherein R ¹ and R ² are independently selected from linear and cyclic, saturated and unsaturated, alkyl and aryl radicals. Preferred esters consist essentially of the elements C, H and O and have a molecular weight that is about 80 to about 550 atomic mass units.

Representative esters include (CH ₃ ) ₂ CHCH ₂ OOC (CH ₂ ) _2-4 OCOCH ₂ CH (CH ₃ ) ₂ (diisobutyl dibasic ester), ethyl hexaneoate, ethyl heptanoate, n-butyl propionate , n-propyl propionate, ethyl benzoate, di-n-propyl phthalate, benzoic acid ethoxyethyl ester, dipropyl carbonate, "Exxate 700" (commercial C ₇ alkyl acetate), "Exate 800 "(Commercial C ₈ alkyl acetates), dibutyl phthalate, and tert-butyl acetate, but are not limited thereto.

Lactone solubilizing agents of the present invention include lactones represented by the following formulas (A), (B) and (C):

Such lactones contain a functional group -CO ₂ -in the six-membered ring of formula A, or preferably the five-membered ring of formula B, wherein in formulas A and B, R ₁ to R ₈ are independently hydrogen and linear, minute Topographic, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals. Each R ₁ to R ₈ may combine with another R ₁ to R ₈ to form a ring. Lactones can have exocyclic alkylidene groups as in Formula C, wherein R ₁ to R ₆ are independently hydrogen and linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl Selected from radicals. Each R ₁ to R ₆ may combine with another R ₁ to R ₆ to form a ring. The lactone solubilizer has a molecular weight that is about 80 to about 300, preferably about 80 to about 200 atomic mass units.

Representative lactone solubilizers include, but are not limited to, the compounds listed in Table 2.

Lactone solubilizers generally have a kinematic viscosity at 40 ° C. of less than about 7 centistokes. For example, gamma-undecalactone has a kinematic viscosity of 5.4 centistokes at 40 ° C. and cis- (3-hexyl-5-methyl) dihydrofuran-2-one has a kinematic viscosity of 4.5 centistokes at 40 ° C. . Lactone solubilizers are commercially available or as described in U.S. Patent Application Serial No. 10 / 910,495 filed on August 3, 2004 (inventors: PJFagan and CJBrandenburg), which is hereby incorporated by reference. It can be produced by the method.

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

Fluorinated ether solubilizers of the present invention are selected from formulas R ¹ OCF ₂ CF ₂ H, wherein R ¹ is an aliphatic and cycloaliphatic hydrocarbon radical having from about 5 to about 15 carbon atoms, preferably a primary linear saturated alkyl radical It includes what is represented by). Representative fluorinated ether solubilizers include, but are not limited to, C ₈ H ₁₇ OCF ₂ CF ₂ H and C ₆ H ₁₃ OCF ₂ CF ₂ H. It should be noted that when the refrigerant is a fluorinated ether, the solubilizer may not be the same fluorinated ether.

The 1,1,1-trifluoroalkane solubilizers of the present invention are formulated with the formula CF ₃ R ¹ , wherein R ¹ is an aliphatic and cycloaliphatic hydrocarbon radical having from about 5 to about 15 carbon atoms, preferably linear linear saturation. 1,1,1-trifluoroalkane, selected from alkyl radicals). Representative 1,1,1-trifluoroalkane solubilizers include, but are not limited to, 1,1,1-trifluorohexane and 1,1,1-trifluorododecane.

The solubilizers of the present invention may exist as a single compound or as a mixture of more than one solubilizers. The mixture of solubilizers may contain two solubilizers selected from the same group of compounds, such as two lactones, or two solubilizers selected from two different groups, such as lactones and polyoxyalkylene glycol ethers.

The composition of the present invention may also comprise from about 0.01 to about 5 weight percent of a heat stabilizer, such as nitromethane. In the compositions of the present invention comprising a refrigerant and an ultraviolet fluorescent dye, about 0.001 to about 1.0 weight percent of the composition, preferably about 0.005 to about 0.5 weight percent, and most preferably 0.01 to about 0.25 weight percent of the composition is an ultraviolet dye.

The solubility of the ultraviolet fluorescent dye in the refrigerant may be low. Therefore, the method of incorporating such dye into a cooling or air conditioning apparatus is difficult, costly and time consuming. U. S. Patent No. RE 36,951 describes a process using dye powders, solid pellets or dye slurries that can be inserted into one part of a cooling or air conditioning apparatus. As the refrigerant and lubricant circulate through the device, the dye is dissolved or dispersed and transported throughout the device. Numerous other methods for incorporating dyes into cooling or air conditioning devices are described in the literature.

Ideally, dissolving the ultraviolet fluorescent dye in the refrigerant itself eliminates the need to use any special method for incorporating the dye into the cooling or air conditioning apparatus. The present invention relates to a composition comprising an ultraviolet fluorescent dye which can be incorporated into the system directly via a refrigerant. The composition of the present invention will allow storage and transport of the dye-containing refrigerant even at low temperatures while maintaining the dye in solution form.

 In compositions of the present invention comprising a refrigerant, an ultraviolet fluorescent dye and a solubilizer, about 1 to about 50 weight percent, preferably about 2 to about 25 weight percent, most preferably about 5 to about 15 weight percent of the combined composition % Is a solubilizer in the refrigerant. In the compositions of the present invention, the ultraviolet fluorescent dye is present in the refrigerant at a concentration of about 0.001 to about 1.0 weight percent, preferably 0.005 to about 0.5 weight percent, most preferably 0.01 to about 0.25 weight percent.

Optionally, commonly used cooling system additives may optionally be added to the compositions of the present invention, if desired, to improve performance and system stability. Such additives are known in the cooling arts and include, but are not limited to, antiwear agents, extreme pressure lubricants, corrosion and antioxidants, metal surface deactivators, free radical scavengers and antifoam agents. Generally such additives are present in minor amounts relative to the total composition in the composition of the present invention. Typically each additive is used at a concentration of less than about 0.1 weight percent to about 3 weight percent. These additives are selected to suit the individual system requirements. Such additives are members of the triaryl phosphate group of EP (extreme) lubricants such as butylated triphenyl phosphate (BTPP) or other alkylated triaryl phosphate esters such as Syn-derived from Akzo Chemicals. 0-Ad 8478, tricresyl phosphate and related compounds. In addition, metal dialkyl dithiophosphates such as zinc dialkyl dithiophosphate (or ZDDP), Lubrizol 1375 and other members of this group of chemicals may be used in the compositions of the present invention. Still other antiwear agents include natural oils and asymmetric polyhydroxyl lubricants such as Syngolgol TMS (International Lubricants). Likewise, stabilizers such as antioxidants, free radical scavengers and water scavengers can be used. Compounds of this category include, but are not limited to, butylated hydroxy toluene (BHT) and epoxides.

Solubilizers such as ketones can have an unpleasant odor that can be concealed by the addition of odor masking agents or fragrances. Typical examples of odor masks or fragrances are Evergreen, Fresh Lemon, Cherry, Cinnamon, Peppermint and Floral sold by Intercontinental Fragrance. ) Or orange peel (Orange Peel), or may include di-limonene (pinene) and pinene (pinene). Such malodor masking agents may be used in concentrations of from about 0.001 to about 15 weight percent based on the total weight of the malodor masking agent and the solubilizer.

The compounds of the present invention may also include thermal stabilizers such as nitromethane.

The invention further relates to a method for use in a cooling or air conditioning apparatus of a refrigerant or heat transfer fluid composition comprising an ultraviolet fluorescent dye and optionally a solubilizer. The method includes incorporating a refrigerant or heat transfer fluid composition into a cooling or air conditioning apparatus. This can be done by dissolving the ultraviolet fluorescent dye in the refrigerant or heat transfer fluid composition in the presence of a solubilizer and incorporating this combination into the device. Alternatively, this can be done by combining the solubilizer with the ultraviolet fluorescent dye and incorporating the combination into a cooling or air conditioning apparatus containing a refrigerant and / or heat transfer fluid. The resulting composition can be used in a cooling or air conditioning apparatus.

The invention also relates to a method of detecting leaks using a refrigerant or heat transfer fluid composition comprising an ultraviolet fluorescent dye. The dyes in the composition allow for detection of leakage of the refrigerant in the cooling or air conditioning apparatus. Detection of leaks helps to correct, solve or prevent inefficient operation of the device or system or damage to the device. Detection of leaks helps to add chemicals used in the operation of the device.

The method provides a composition comprising a refrigerant, an ultraviolet fluorescent dye as described herein, and optionally a solubilizer as described herein, in a cooling and air conditioning apparatus and suitable for sensing an ultraviolet fluorescent dye-containing refrigerant. Use of means. Suitable means for sensing the dye include, but are not limited to, ultraviolet lamps, often referred to as "black light" or "blue light". Such ultraviolet lamps are commercially available from a number of specialty manufacturers for this purpose. After incorporating an ultraviolet fluorescent dye-containing composition into a cooling or air conditioning device and allowing it to circulate throughout the system, the ultraviolet lamp is illuminated on the device to observe the fluorescence of the dye near any leak point to detect leakage. Can be.

The invention also achieves cooling by evaporating the composition of the invention near the object of cooling and then condensing the composition; A method of cooling or generating heat using the composition of the invention, comprising generating heat by evaporating the composition after condensing the composition near a heating object.

Mechanical cooling is primarily the application of thermodynamics that regenerate the refrigerant for recycling by applying a cooling medium, such as a refrigerant, to the cycle. Commonly used cycles include steam-compression, absorption, steam-jet or steam-exhaust, and air.

Vapor-compression cooling devices include evaporators, compressors, condensers and diffusion devices. The vapor-compression cycle reuses the refrigerant through a multistage process that achieves a cooling effect in one step and a heating effect in another different step. The cycle can simply be described as follows. The liquid refrigerant enters the evaporator through the diffusion device and the liquid refrigerant boils at low temperature in the evaporator to form gas and achieve cooling. This low pressure gas enters the compressor, which compresses the gas to raise pressure and temperature. A higher pressure gaseous refrigerant then enters the condenser, which condenses the refrigerant and releases heat to the surrounding environment. The refrigerant returns to the diffusion device, which repeats the cycle by diffusing the liquid from the high pressure level in the condenser to the low pressure level in the evaporator.

There are various types of compressors that can be used in cooling applications. Compressors are generally classified as reciprocating, rotating, jetting, centrifugal, scrolling, screwing, or axial-flow, depending on the mechanical means for compressing the fluid, Depending on how it acts on the compressed fluid, it may be classified as volumetric (eg reciprocating, scrolling or screwing) or dynamic (eg centrifugal or jetting).

Volumetric or dynamic compressors may be used in the process of the present invention. Centrifugal compressors are preferred as apparatus for the refrigerant composition of the present invention.

Centrifugal compressors use a rotating element that radially accelerates the refrigerant and typically includes an impeller and diffuser embedded in the case. Centrifugal compressors typically accept fluid at the central inlet of the impeller eye or circulation impeller and accelerate it radially outward. Some steady pressure is generated in the impeller, but most of the pressure is in the diffuser portion of the case, where the speed is converted to normal pressure. Each impeller-diffuser set constitutes one compressor stage. Centrifugal compressors consist of one to twelve or more stages, depending on the desired final pressure and the volume of refrigerant to be handled.

The pressure ratio or compression ratio of the compressor is the ratio of the absolute outflow pressure to the absolute inflow pressure. The pressure delivered by the centrifugal compressor is substantially constant over a relatively wide range of capacities.

The volumetric compressor pushes steam into the chamber and the chamber compresses the vapor by reducing its volume. The chamber further reduces the volume to zero or nearly zero, thereby forcing the compressed vapor out of the chamber. Volumetric compressors can increase pressure, which is limited only by volumetric efficiency and the strength of the components that withstand these pressures.

Unlike volumetric compressors, centrifugal compressors rely entirely on the centrifugal force of the high speed impeller to compress the steam passing through the impeller. In centrifugal compressors volumetric compression does not occur but what is called dynamic compression occurs.

The pressure a centrifugal compressor can generate is dependent on the tip speed of the impeller. Blade tip velocity is the velocity of the impeller measured at the blade 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 amount of passage through the impeller. For this reason, the size of the compressor is more dependent on the required pressure than on the capacity.

Centrifugal compressors operate at high speeds and are essentially high volume, low pressure equipment. Centrifugal compressors work best when using low pressure refrigerants such as trichlorofluoromethane (CFC-11) or 1,2,2-trichlorotrifluoroethane (CFC-113).

Large centrifugal compressors typically operate at revolutions per minute (rpm) of 3000 to 7000. Small turbine centrifugal compressors are designed to operate at high speeds of about 40,000 to about 70,000 (rpm) and typically have a small impeller size of less than 0.15 meters.

Multistage impellers can be used in centrifugal compressors to improve compressor efficiency, requiring less power. In a two-stage system, in operation, the discharge of the first stage impeller enters the suction of the second impeller. Both impellers can be operated by a single shaft (or shaft). Each stage may be stacked at a compression ratio of about 4 to 1 (ie the absolute absolute pressure may be four times the absolute absolute pressure). For automotive applications, examples of two-stage centrifugal compressor systems are described in US Pat. No. 5,065,990, which is incorporated herein by reference.

Compositions of the present invention suitable for use in refrigeration or air conditioning systems using two stage centrifugal compressor devices include 1,1,2,2,3-pentafluoropropane; 1,1,1,3,3-pentafluoropropane; 1,1,3-trifluoropropane; 1,3-difluoropropane; 2- (difluoromethyl) -1,1,1,2,3,3-hexafluoropropane; 1,1,2,2,3,3,4,4-octafluorobutane; 1,1,1,2,2,4-hexafluorobutane; 1,1,1,3,3-pentafluorobutane; 1,1-difluorobutane; 1,3-difluoro-2-methylpropane; 1,2-difluoro-2-methylpropane; 1,2-difluorobutane; 1,3-difluorobutane; 1,4-difluorobutane; 2,3-difluorobutane; 1,1,1,2,3,3,4,4-octafluoro-2- (trifluoromethyl) butane; 1,1,1,2,2,3,3,4,4,5,5-undecafluoropentane; 1,1,1,2,2,3,4,5,5,5-decafluoropentane; 1,1,1,2,2,3,3,5,5,5-decafluoropentane; 1,1,1,4,4,4-hexafluoro-2- (trifluoromethyl) butane; 1,1,1-trifluoropentane; 1,1,1-trifluoro-3-methylbutane; 1,1-difluoropentane; 1,2-difluoropentane; 2,2-difluoropentane; 1,1,1-trifluorohexane; 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane; 1,1,1,2,2,5,5,5-octafluoro-4- (trifluoromethyl) pentane; 1,1,2,2-tetrafluorocyclobutane; 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene; And combinations thereof.

All compositions of the present invention can be used in stationary air conditioning, heat pumps or mobile air conditioning and cooling devices. Fixed air conditioning and heat pump applications include commercial, including windowed, ductless, ducted, packaged terminals, quenchers, and packaged rooftops. Includes uses. Cooling devices include household refrigerators and freezers, ice makers, self-built coolers and freezers, walk-in refrigerators and freezers, and transportation refrigeration systems.

The compositions of the present invention can also be used in air conditioning, heat generating and cooling devices, using fin and tube heat exchangers, microchannel heat exchangers and vertical or horizontal single pass tube or plate heat exchangers.

Conventional microchannel heat exchangers may not be ideal for the low pressure refrigerant compositions of the present invention. Low operating pressures and densities result in high flow rates and high friction losses for all components. In this case, the evaporator design can be changed. Rather than several microchannel slabs connected in series (for the refrigerant path), a single slab / single pass heat exchanger arrangement may be used. Thus, preferred heat exchangers for the low pressure refrigerants of the present invention are single slab / single pass heat exchangers.

In addition, in addition to the two stage compressor system, the compositions of the present invention suitable for use in cooling or air conditioning systems using single slab / single pass heat exchangers include 1,1,2,2,3-pentafluoropropane; 1,1,1,3,3-pentafluoropropane; 1,1,3-trifluoropropane; 1,3-difluoropropane; 2- (difluoromethyl) -1,1,1,2,3,3-hexafluoropropane; 1,1,2,2,3,3,4,4-octafluorobutane; 1,1,1,2,2,4-hexafluorobutane; 1,1,1,3,3-pentafluorobutane; 1,1-difluorobutane; 1,3-difluoro-2-methylpropane; 1,2-difluoro-2-methylpropane; 1,2-difluorobutane; 1,3-difluorobutane; 1,4-difluorobutane; 2,3-difluorobutane; 1,1,1,2,3,3,4,4-octafluoro-2- (trifluoromethyl) butane; 1,1,1,2,2,3,3,4,4,5,5-undecafluoropentane; 1,1,1,2,2,3,4,5,5,5-decafluoropentane; 1,1,1,2,2,3,3,5,5,5-decafluoropentane; 1,1,1,4,4,4-hexafluoro-2- (trifluoromethyl) butane; 1,1,1-trifluoropentane; 1,1,1-trifluoro-3-methylbutane; 1,1-difluoropentane; 1,2-difluoropentane; 2,2-difluoropentane; 1,1,1-trifluorohexane; 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane; 1,1,1,2,2,5,5,5-octafluoro-4- (trifluoromethyl) pentane; 1,1,2,2-tetrafluorocyclobutane; 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene; And combinations thereof.

The compositions of the present invention are particularly useful in small turbine centrifugal compressors that can be used in automotive and windowed air conditioners or heat pumps as well as other applications. Such high efficiency compact centrifugal compressors can be driven by an electric motor and therefore can be operated regardless of engine speed. Constant compressor speed allows the system to provide a relatively constant cooling capacity at all engine speeds. This allows for improved efficiency, especially at higher engine speeds, compared to conventional R-134a automotive air conditioning systems. Given the periodic operation of a conventional system at high drive speeds, the benefits of such low pressure systems are even greater.

Some of the low pressure refrigerant fluids of the present invention may be suitable as drop-in replacements for CFC-113 in existing centrifugal devices.

The present invention relates to a cooling method comprising condensing the composition after evaporating any one of the compositions of the invention in the vicinity of the object to be cooled.

The invention also relates to a method of generating heat comprising evaporating the composition after condensing any one of the compositions of the invention near a heating object.

The invention also relates to a method of transferring heat from a heat source to a heat sink using the composition of the invention as a heat transfer fluid. The heat transfer method includes transferring any one of the compositions of the present invention from a heat source to a heat sink.

Heat transfer fluids are used to transfer, move, or remove heat from one space, place, object or object to another space, place, object or object by radiation, conduction or convection. The heat transfer fluid may function as a secondary refrigerant by providing a means for transferring cold air (or heat) from a remote cooling (or heating) system. In some systems, the heat transfer fluid may remain constant throughout the transfer process (ie neither evaporate nor condense). Alternatively, heat transfer fluids can be used in the evaporative cooling process.

A heat source can be defined as any space, place, object, or object that needs to transfer, move, or remove heat. Examples of heat sources may be (open or closed) spaces that require cooling or refrigeration, such as supermarket or freezer cases in supermarkets, building spaces that require air conditioning, or automobile compartments that require air conditioning. The heat sink can be any space, place, object or object capable of absorbing heat. The vapor compression cooling system is an example of such a heat sink.

Example 1

Wing tip speed to generate pressure

In the case of a cooling device using a centrifugal compressor, the blade tip speed can be estimated by establishing some fundamental relationships. The torque that the impeller ideally imparts to the gas is defined as in Equation 1 below.

T = m * (v ₂ * r ₂ -v ₁ * r ₁ )

Where T is the torque (N * m), m is the mass flow rate (kg / s), v ₂ is the tangent velocity (wing tip speed) (m / s) of the refrigerant leaving the impeller, and r ₂ is the impeller Is the radius m of the outlet, v ₁ is the tangent velocity (m / s) of the refrigerant entering the impeller, and r ₁ is the radius m of the impeller inlet.

Assuming that the refrigerant enters the impeller essentially radially, the tangent component v ₁ of velocity is zero, so the following equation is established.

T = m * v ₂ * r ₂

The force required on the shaft is the product of the torque and the rotational speed.

P = T * w

In the above formula, P is the force (W), and w is the rotational speed (rez / s), the following formula is established.

P = T * w = m * v ₂ * r ₂ * w

At low refrigerant flow rates, the blade tip speed of the impeller and the tangent speed of the refrigerant are about the same. Therefore, the following equations are established.

r ₂ * w = v ₂

P = m * v ₂ * v ₂

Another equation for the ideal force is the product of mass velocity and isentropic work of compression.

P = m * H _i * (1000J / kJ)

Wherein H _i is the difference in enthalpy of the refrigerant in saturated condensation (kJ / kg) from the enthalpy of the refrigerant derived from saturated steam in the evaporation state.

Combining Equations 6 and 7 establishes the following equation.

v ₂ * v ₂ = 1000 * H _i

Equation 8 is based on some fundamental assumptions, but this provides a good estimate of the impeller vane speed and provides an important way to compare the vane speed of the refrigerant.

Table 3 below shows the theoretical wing tip velocities calculated for 1,2,2-trichlorotrifluoroethane (CFC-113) and the compositions of the present invention. Conditions assumed for this comparison include: evaporator temperature 40.0 ° F. (4.4 ° C.); Condenser temperature 110.0 ° F. (43.3 ° C.); Liquid subcool temperature of 10.0 ° F. (5.5 ° C.); Return gas temperature 75.0 ° F. (23.8 ° C.); Compressor efficiency is 70%.

This is the typical condition under which a small turbine centrifugal compressor is carried out.

Refrigerant Hi Btu / lb Hi * 0.7 Btu / lb Hi * 0.7 kJ / kg v ₂ m / s ₂ compared to CFC-113 CFC-113 10.92 7.6 17.8 133.3 n / a HFC-263fa 15.57 10.9 25.4 159.2 119% HFC-272fa 18.18 12.7 29.6 172.0 129% HFC-365mfc 14.45 10.1 23.5 153.4 115% HFC-392p 19.18 13.4 31.2 176.7 133% HFC-392qe 19.41 13.6 31.6 177.8 133% HFC-392qfe 19.58 13.7 31.9 178.6 134% HFC-392qff 20.28 14.2 33.0 181.7 136% HFC-392qqz 19.63 13.7 32.0 178.8 134% HFC-392qy 19.41 13.6 31.6 177.8 133% HFC-392see 18.83 13.2 30.7 175.1 131% HFC-4-10-3m 18.48 12.9 30.1 173.5 130% HFC-4-10-3mfsz 18.12 12.7 29.5 171.8 129% HFC-4-11-2p 20.83 14.6 33.9 184.2 138% HFC-4-11-2qe 20.90 14.6 34.0 184.5 138% HFC-4-11-2sc 21.00 14.7 34.2 184.9 139% HFC-5-12-3m 19.97 14.0 32.5 180.3 135% PFBE 12.80 9.0 20.8 144.4 108% HFC-c354cc 15.33 10.7 25.0 158.0 119%

This example shows that the compounds of the present invention have vane speeds within about ± 30% of CFC-113 and are effective replacements for CFC-113 while allowing for minimal changes in compressor design.

Example 2

Performance data

Table 4 shows the performance of various refrigerants compared to CFC-113. 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 70%.

Refrigerant Evaporator pressure (psia) Evaporator pressure (kPa) Condenser pressure (psia) Condenser Pressure (kPa) Compressor Exhaust Temperature (℉) Compressor Discharge Temperature (℃) COP Capacity (Btu / min) Capacity (kW) CFC-113 2.7 19 12.8 88 156.3 69.1 4.2 14.8 0.26 HFC-263fa 2.9 20 13.6 94 179.2 81.8 4.3 18.8 0.33 HFC-272fa 3.4 23 15.6 107 181.8 83.2 4.3 21.9 0.38 HFC-365mfc 3.6 25 16.3 112 146.3 63.5 4.11 21.4 0.38 HFC-392p 3.6 24 16.2 111 160.4 71.3 4.2 22.0 0.39 HFC-392qe 2.4 16 11.5 79 163.6 73.1 4.3 15.5 0.27 HFC-392qfe 1.6 11 8.2 56 167.0 75.0 4.3 10.8 0.19 HFC-392qff 0.7 5 4.3 30 173.5 78.6 4.3 5.5 0.10 HFC-392qqz 1.4 10 7.4 51 168.0 75.6 4.3 9.7 0.17 HFC-392qy 4.5 31 19.0 131 154.3 67.9 4.2 26.2 0.46 HFC-392see 3.1 21 14.1 97 161.5 71.9 4.3 19.4 0.34 HFC-4-10-3m 3.7 25 16.9 116 141.9 61.1 4.1 21.7 0.38 HFC-4-10-3-mfsz 3.9 27 17.4 120 141.5 60.8 4.1 22.6 0.40 HFC-4-11-2p 1.1 7 5.9 41 155.0 68.3 4.2 7.5 0.13 HFC-4-11-2qe 0.8 6 4.8 33 156.8 69.3 4.2 6.0 0.10 HFC-4-11-2sc 1.7 11 8.3 57 148.4 64.7 4.2 10.7 0.19 HFC-5-12-3m 0.8 6 4.8 33 142.0 61.1 4.1 5.7 0.10 PFBE 1.6 11 9.6 66 130.7 54.8 3.9 10.0 0.18 HFC-c354cc 2.6 18 11.7 80 153.1 67.3 4.21 15.9 0.28

The data show that the compositions of the present invention have evaporator and condenser pressures similar to CFC-113. Some compositions have higher capacity and / or energy efficiency (as measured by COP) than CFC-113.

Claims (16)

1,1,3-trifluoropropane; 1,3-difluoropropane; 1,1,1,3,3-pentafluorobutane; 1,1-difluorobutane; 1,3-difluoro-2-methylpropane; 1,2-difluoro-2-methylpropane; 1,2-difluorobutane; 1,3-difluorobutane; 1,4-difluorobutane; 2,3-difluorobutane; 1,1,1-trifluoropentane; 1,1,1-trifluoro-3-methylbutane; 1,1-difluoropentane; 1,2-difluoropentane; 2,2-difluoropentane; 1,1,1-trifluorohexane; 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene; And a refrigerant or heat transfer fluid composition selected from the group consisting of: 1,1,3-trifluoropropane; 1,3-difluoropropane; 1,1,1,3,3-pentafluorobutane; 1,1-difluorobutane; 1,3-difluoro-2-methylpropane; 1,2-difluoro-2-methylpropane; 1,2-difluorobutane; 1,3-difluorobutane; 1,4-difluorobutane; 2,3-difluorobutane; 1,1,1-trifluoropentane; 1,1,1-trifluoro-3-methylbutane; 1,1-difluoropentane; 1,2-difluoropentane; 2,2-difluoropentane; 1,1,1-trifluorohexane; 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene; And a refrigerant or heat transfer fluid composition suitable for use in a cooling or air conditioning apparatus using a centrifugal compressor selected from the group consisting of: and combinations thereof. 1,1,2,2,3-pentafluoropropane; 1,1,1,3,3-pentafluoropropane; 1,1,3-trifluoropropane; 1,3-difluoropropane; 2- (difluoromethyl) -1,1,1,2,3,3-hexafluoropropane; 1,1,2,2,3,3,4,4-octafluorobutane; 1,1,1,2,2,4-hexafluorobutane; 1,1,1,3,3-pentafluorobutane; 1,1-difluorobutane; 1,3-difluoro-2-methylpropane; 1,2-difluoro-2-methylpropane; 1,2-difluorobutane; 1,3-difluorobutane; 1,4-difluorobutane; 2,3-difluorobutane; 1,1,1,2,3,3,4,4-octafluoro-2- (trifluoromethyl) butane; 1,1,1,2,2,3,3,4,4,5,5-undecafluoropentane; 1,1,1,2,2,3,4,5,5,5-decafluoropentane; 1,1,1,2,2,3,3,5,5,5-decafluoropentane; 1,1,1,4,4,4-hexafluoro-2- (trifluoromethyl) butane; 1,1,1-trifluoropentane; 1,1,1-trifluoro-3-methylbutane; 1,1-difluoropentane; 1,2-difluoropentane; 2,2-difluoropentane; 1,1,1-trifluorohexane; 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane; 1,1,1,2,2,5,5,5-octafluoro-4- (trifluoromethyl) pentane; 1,1,2,2-tetrafluorocyclobutane; 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene; And a refrigerant or heat transfer fluid composition suitable for use in a cooling or air conditioning apparatus using a multistage centrifugal compressor, or a cooling or air conditioning apparatus using a single slab / single pass heat exchanger, selected from the group consisting of a combination thereof. A method of using the composition of claim 3 comprising generating heat or achieving cooling in a cooling or air conditioning apparatus using a multistage centrifugal compressor. A method of cooling comprising condensing said composition after evaporating the composition of any one of claims 1 to 4 near the object of cooling. A method of generating heat comprising evaporating the composition after condensing the composition of any one of claims 1 to 4 near the heating target. A method of heat transfer using the composition of any one of claims 1 to 4 comprising transferring the composition from a heat source to a heat sink. The at least one ultraviolet fluorescent dye according to claim 1, which is selected from the group consisting of naphthalimide, perylene, coumarin, anthracene, phenanthracene, xanthene, thioxanthene, naphthoxanthene, fluorescein, derivatives and combinations thereof. Further comprising composition. The group according to any one of claims 2 to 4, consisting of naphthalimide, perylene, coumarin, anthracene, phenanthracene, xanthene, thioxanthene, naphthoxanthene, fluorescein, derivatives and combinations thereof. The composition further comprises at least one ultraviolet fluorescent dye selected from. 9. The composition of claim 8 comprising hydrocarbons, hydrocarbon ethers, polyoxyalkylene glycol ethers, amides, ketones, nitriles, chlorocarbons, esters, lactones, aryl ethers, fluorinated ethers and 1,1,1-trifluoroalkanes And at least one solubilizer different from the refrigerant selected from the group. The method of claim 10 wherein the solubilizer is (a) Formula R ¹ [(OR ² ) _x OR ³ ] _y (where x is an integer from 1 to 3; y is an integer from 1 to 4; R ¹ is hydrogen and 1 to 6 carbon atoms and y Selected from aliphatic hydrocarbon radicals having two bonding sites; R ² is selected from aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms; and R ³ is hydrogen and aliphatic and alicyclic having 1 to 6 carbon atoms. Polyoxyalkylene glycol ethers having a molecular weight of about 100 to about 300 atomic mass units, selected from hydrocarbon radicals, at least one of R ¹ and R ³ is selected from the above hydrocarbon radicals; (b) Formulas R ¹ CONR ² R ³ and cyclo- [R ⁴ CON (R ⁵ )-], wherein R ¹ , R ² , R ³ and R ⁵ are independently aliphatic having 1 to 12 carbon atoms And alicyclic hydrocarbon radicals and at most one aromatic radical having 6 to 12 carbon atoms; R ⁴ is selected from aliphatic hydrocarbylene radicals having 3 to 12 carbon atoms). Amides having a molecular weight of 300 atomic mass units; (c) from about 70 to about 300 atomic mass units represented by R ¹ COR ² , wherein R ¹ and R ² are independently selected from aliphatic, alicyclic and aryl hydrocarbon radicals having 1 to 12 carbon atoms Ketones having a molecular weight; (d) a nitrile having a molecular weight of about 90 to about 200 atomic mass units represented by the formula R ¹ CN, wherein R ¹ is selected from aliphatic, alicyclic, or aryl hydrocarbon radicals having 5 to 12 carbon atoms; (e) about 100 to about 200 atomic mass units represented by the formula RCl _x , wherein x is selected from integers of 1 or 2; R is selected from aliphatic and alicyclic hydrocarbon radicals having 1 to 12 carbon atoms Chlorocarbon having a phosphorus molecular weight; (f) represented by the formula R ¹ OR ² , wherein R ¹ is selected from aryl hydrocarbon radicals having 6 to 12 carbon atoms; R ² is selected from aliphatic hydrocarbon radicals having 1 to 4 carbon atoms; Aryl ethers having a molecular weight of about 100 to about 150 atomic mass units; (g) 1,1,1-trifluoroalkane represented by the formula CF ₃ R ¹ , wherein R ¹ is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms; (i) fluorinated ethers represented by the formula R ¹ OCF ₂ CF ₂ H, wherein R ¹ is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms; (j) Formulas (A), (B) and (C) wherein R ₁ to R ₈ are independently selected from hydrogen and linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals Lactones having a molecular weight of about 100 to about 300 atomic mass units represented by; And <Formula A>

<Formula B>

<Formula C>

(k) from about 80 to about 550 atomic mass units represented by the formula R ¹ CO ₂ R ² , wherein R ¹ and R ² are independently selected from linear and cyclic, saturated and unsaturated, alkyl and aryl radicals Ester with molecular weight The composition is selected from the group consisting of. (i) dissolving the ultraviolet fluorescent dye in the refrigerant composition or heat transfer fluid in the presence of a solubilizer and incorporating this combination into a compression cooling or air conditioning apparatus, or (ii) combining the solubilizer and the ultraviolet fluorescent dye, A method of using the composition of claim 10 comprising incorporating the composition into a compression cooling or air conditioning device by incorporating it into a cooling or air conditioning device containing a refrigerant and / or heat transfer fluid. A method of using the composition of claim 8 or 10 in a compression cooling or air conditioning apparatus comprising placing the composition in a compression cooling or air conditioning apparatus and providing a suitable means for sensing the composition in the vicinity of the apparatus. a cooling is performed by condensing the composition after evaporating the composition near the cooling object, or (ii) generating heat by evaporating the composition after condensing the composition near the heating object. A method of using the composition of claim 10. The composition of claim 10 further comprising a malodor masking agent or a heat stabilizer. 5. The method of claim 4 wherein the multistage centrifugal compressor is a two stage centrifugal compressor.