KR20070015594A - 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone compositions comprising a hydrofluorocarbon and uses thereof - Google Patents

Abstract

Disclosed herein are refrigerant and heat transfer fluid compositions comprising 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and at least one hydrofluorocarbon for use in refrigeration and air conditioning systems employing a centrifugal compressor. The compositions may be azeotropic or near-azeotropic. ® KIPO & WIPO 2007

Description

1,1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone composition comprising hydrofluorocarbons and uses thereof {1,1 , 1,2,2,4,5,5,5-NONAFLUORO-4- (TRIFLUOROMETHYL) -3-PENTANONE COMPOSITIONS COMPRISING A HYDROFLUOROCARBON AND USES THEREOF}

<Cross Reference of Related Application>

This application claims priority to 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 provides at least one hydrofluorocarbon and 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) for use in refrigeration and air conditioning systems. It relates to a composition comprising 3-pentanone (PEIK). In addition, the present invention provides at least one hydrofluorocarbon and 1,1,1,2,2,4,5,5,5-nonnafluoro-4 for use in refrigeration and air conditioning systems using centrifugal compressors. A composition comprising-(trifluoromethyl) -3-pentanone. The composition of the present invention may be an azeotrope or near azeotrope composition and is useful in a method for freezing or generating heat or as a heat transfer fluid.

The refrigeration industry has been trying to find alternative refrigerants for ozone depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) that are being phased out as a result of the Montreal Protocol over the last few decades. The solution for most refrigerant manufacturers has been the commercialization of hydrofluorocarbon (HFC) refrigerants. HFC-134a, the new most widely used HFC refrigerant at present, has no potential for ozone depletion and is therefore not affected by the current phase-out regulations of the Montreal Protocol.

In addition, environmental legislation could ultimately lead to global phase out of certain HFC refrigerants. Currently, the automotive industry is facing legislation on the possibility of global warming for refrigerants used in automotive air conditioning. Thus, there is an urgent need to find new refrigerants with reduced global warming potential for the automotive air conditioning market. If the legislation is more widely applied in the future, there will be a greater need for refrigerants that can be used in all areas of the refrigeration and air conditioning industry.

Currently proposed alternative refrigerants for HFC-134a include HFC-152a, pure hydrocarbons such as butane or propane, or "natural" refrigerants such as CO ₂ or ammonia. Most of the replacements given above are toxic and / or flammable and / or have low energy efficiency. Therefore, new alternatives are always being sought.

It is an object of the present invention to provide novel refrigerant compositions and heat transfer fluids which provide unique properties that meet the requirements of low or no ozone depletion potential and low global warming potential compared to current refrigerants.

<Overview of invention>

The present invention

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1,3-trifluoropropane,

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,3-difluoropropane,

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1,1,3,3-pentafluorobutane ,

1,1,1,2,2,4,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone and 1,1-difluorobutane,

1,1,1,2,2,4,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone and 1,2-difluorobutane,

1,1,1,2,2,4,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone and 1,3-difluorobutane,

1,1,1,2,2,4,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone and 1,4-difluorobutane,

1,1,1,2,2,4,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone and 1,3-difluoro-2-methylpropane,

1,1,1,2,2,4,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone and 1,2-difluoro-2-methylpropane,

1,1,1,2,2,4,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone and 2,3-difluorobutane,

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1,1-trifluoropentane,

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1,1-trifluoro-3-methylbutane ,

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1-difluoropentane,

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,2-difluoropentane,

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 2,2-difluoropentane,

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1,1,2,2,3,4, 5,5,5-decafluoropentane,

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1,1-trifluorohexane, and

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1,2,2-tetrafluorocyclobutane

It relates to a composition comprising a.

In addition, the invention relates to the compositions listed above for use in a refrigeration or air conditioning system utilizing a centrifugal compressor.

In addition, the present invention relates to the compositions listed above for use in characterizing refrigeration or air conditioning systems using multistage or two-stage centrifugal compressors.

In addition, the invention relates to the compositions listed above for use in a refrigeration or air conditioning system using a single passage / slab slab heat exchanger.

In addition, the present invention relates to azeotropic or near-azeotropic refrigerant compositions. These compositions are useful for refrigeration or air conditioning systems. Such compositions are also useful for refrigeration or air conditioning systems using centrifugal compressors.

In addition, the present invention relates to a method for producing heat from a refrigeration, heat, and heat source to a heat sink using the composition of the present invention.

We clearly cite the entire contents of all references cited in this disclosure. In addition, where an amount, concentration, or other value or parameter is given as a list of ranges, preferred ranges, or preferred upper and preferred lower values, whether such ranges are disclosed individually, any of the upper or preferred values and any It is to be understood that all ranges formed from any pair of lower limit values or preferred values of are explicitly disclosed. Unless stated otherwise, where a range of numerical values is mentioned herein, this range is intended to include their endpoints, and all integers and fractions within this range. It is not intended that the scope of the invention be limited to the specific values mentioned when defining the range.

The refrigerant composition of the present invention is 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone (PEIK) and hydrofluorocarbon ( HFC). The composition of the present invention may comprise a mixture of one or more HFCs, after which the mixtures may be 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoro Compound with methyl) -3-pentanone (PEIK).

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

The compounds listed in Table 1 are either commercially available or can be prepared by methods known in the art. 1,1,1,2,2,4,5,5,5-Nonafluoro-4- (trifluoromethyl) -3-pentanone (PEIK) was obtained from 3M ™ (St. Paul, Minn.) Commercially available.

The compositions of the present invention have a low or no ozone depletion potential and a low global warming potential. For example, slightly fluorinated hydrofluorocarbons and PEIK, either alone or in mixtures, will have a lower global warming potential than many HFC refrigerants currently used.

The composition of the present invention may be prepared by any convenient method of combining the desired amounts of the individual components. The preferred method is to weigh the desired amount of ingredients and then combine the ingredients in a suitable container. Agitation can be used if necessary.

The refrigerant composition of the present invention includes the following.

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1,3-trifluoropropane,

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,3-difluoropropane,

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1,1,3,3-pentafluorobutane ,

1,1,1,2,2,4,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone and 1,1-difluorobutane,

1,1,1,2,2,4,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone and 1,2-difluorobutane,

1,1,1,2,2,4,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone and 1,3-difluorobutane,

1,1,1,2,2,4,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone and 1,4-difluorobutane,

1,1,1,2,2,4,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone and 1,3-difluoro-2-methylpropane,

1,1,1,2,2,4,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone and 1,2-difluoro-2-methylpropane,

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 2,3-difluorobutane,

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1,1-trifluoropentane,

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1,1-trifluoro-3-methylbutane ,

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1-difluoropentane,

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,2-difluoropentane,

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 2,2-difluoropentane,

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1,1,2,2,3,4, 5,5,5-decafluoropentane,

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1,1-trifluorohexane,

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1,2,2-tetrafluorocyclobutane, And

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 3,3,4,4,5,5,6, 6,6-nonnafluoro-1-hexene.

The refrigerant or heat transfer composition of the present invention may be an azeotrope or near azeotrope composition. An azeotrope composition is a liquid mixture of two or more substances having a constant boiling point which may be above or below the boiling point of the individual components. The azeotrope composition will not be fractionated which may reduce the efficiency of the system within the refrigeration or air conditioning system during operation. In addition, the azeotrope composition will not be fractionated when leaking from a refrigeration or air conditioning system. If one component of the mixture is flammable, fractionation during the leak may result in a combustible composition inside or outside the system.

By near azeotropic composition is meant a substantially boiling point invariant liquid mixture of two or more materials that behave substantially like a single material. One way of characterizing the azeotropic composition is that the vapor produced by the partial evaporation or distillation of the liquid has a composition that is substantially the same as the liquid evaporated or distilled therefrom. That is, the mixture is distilled / refluxed without substantial change in composition. Another way to characterize the azeotropic composition is that the bubble point vapor pressure and dew point vapor pressure of the composition at a particular temperature are substantially the same. Herein, if 50% by weight of the composition is removed, such as by evaporation or boiling, then the difference in vapor pressure between the composition remaining after the 50% by weight of the original composition and the original composition is removed is less than about 10%. It's public.

The azeotropic refrigerant compositions of the present invention are listed in Table 2 below.

The near azeotropic refrigerant compositions and concentration ranges of the invention are listed in Table 3 below.

The composition of the present invention may further comprise from about 0.01% to about 5% by weight stabilizer, free radical scavenger or antioxidant. Such additives include, but are not limited to, nitromethane, hindered phenols, hydroxylamines, thiols, phosphites, or lactones. Single additives or combinations may be used.

The composition of the present invention may further comprise from about 0.01% to about 5% by weight water scavenger (dry compound). Such water scavengers may include ortho esters such as trimethylortho formate, triethylortho formate, or tripropylortho formate.

The composition of the present invention may further comprise an ultraviolet (UV) dye and optionally a solubilizer. UV dyes are useful components for detecting leaks in refrigerant compositions by allowing fluorescence of the dye in the refrigerant or heat transfer fluid composition to be observed at the leak point of the refrigeration or air conditioning device or near the refrigeration or air conditioning device. Fluorescence of the dye can be observed under ultraviolet light. Since such UV dyes have low solubility in some refrigerants, solubilizers may be required.

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

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

Hydrocarbon solubilizers of the present invention include hydrocarbons, including straight, branched or cyclic alkanes or alkenes containing up to 5 carbon atoms and containing only hydrogen without 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 invention are represented by 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, and R ¹ 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 2 to 4 carbon atoms, R ³ is hydrogen, and 1 carbon atom; Selected from 6 to 6 aliphatic and alicyclic hydrocarbon radicals, at least one of R ¹ and R ³ is the hydrocarbon radical, and the molecular weight of the polyoxyalkylene glycol ether is from about 100 to about 300 atomic mass units. In the polyoxyalkylene glycol ether solubilizer of the present invention represented by R ¹ [(OR ² ) _x OR ³ ] _y , x is preferably 1 to 2, y is preferably 1, and R ¹ and R ³ is preferably independently selected from hydrogen and aliphatic hydrocarbon radicals having 1 to 4 carbon atoms, R ² is preferably selected from aliphatic hydrocarbylene radicals having 2 or 3, most preferably 3 carbon atoms and , The 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. Hydrocarbon radicals of R ¹ and R ³ having 1 to 6 carbon atoms may be linear, branched or cyclic. Representative hydrocarbon radicals of R ¹ and R ³ are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, and cyclohexyl It includes. If the free hydroxyl radicals on the polyoxyalkylene glycol ether solubilizers of the present invention may be incompatible with the particular compressed refrigeration unit material of the structure (eg Mylar®), then R ¹ and R ³ are Preferably it is an aliphatic hydrocarbon radical having 1 to 4 carbon atoms, most preferably 1 carbon atom. The aliphatic hydrocarbylene radical of R ² having 2 to 4 carbon atoms forms a repeating oxyalkylene radical-(OR ² ) _x -comprising an oxyethylene radical, an oxypropylene radical, and an oxybutylene radical. The oxyalkylene radicals comprising R ² in one polyoxyalkylene glycol ether solubilizer molecule may be the same, or one molecule may contain oxyalkylene groups of different R ² . The polyoxyalkylene glycol ether solubilizers of the present invention preferably comprise one or more oxypropylene radicals. When R ¹ is an aliphatic or cycloaliphatic hydrocarbon radical having 1 to 6 carbon atoms and having y bonding sites, the radical may be linear, branched or cyclic. The binding site 2 of the individual aliphatic hydrocarbon radical R ¹ is representative, for example, include ethylene radical, a propylene radical, a butylene radical, a pentylene radical, a hexylene radical, a cyclopentylene radical and a cyclohexylene radical. The binding site 3 or 4 aliphatic hydrocarbon radical R ¹ is a representative personal trimethylolpropane, glycerol, pentaerythritol, 1,2,3-trihydroxy-cyclohexane, and 1,3, 5-trihydroxy cyclohexane, and And residues derived by removing their hydroxyl radicals from the same polyalcohols.

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).

Amide solubilizers of the present invention include those represented by the 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 carbon atoms 1 Independently selected from aliphatic and cycloaliphatic hydrocarbon radicals of 12 to 12, R ⁴ is selected from aliphatic hydrocarbylene radicals of 3 to 12 carbon atoms, and the molecular weight of the amide is from about 100 to about 300 atomic mass units. The molecular weight of the amide is preferably from about 160 to about 250 atomic mass units. R ¹ , R ² , R ³ and R ⁵ optionally substitute substituted hydrocarbon radicals, ie radicals containing non-hydrocarbon substituents selected from halogen (eg fluorine, chlorine) and alkoxides (eg methoxy). May include. R ¹ , R ² , R ³ and R ⁵ are heteroatom-substituted hydrocarbon radicals, ie containing atomic nitrogen (aza-), oxygen (oxa-) or sulfur (thia-) in a radical chain consisting of carbon atoms except for them. Radicals may optionally be included. In general, three or less, preferably one non-hydrocarbon substituents and heteroatoms, the following will be present in ten carbon atoms in R ^{1 -3,} the presence of any such non-hydrocarbon substituents and heteroatoms above-mentioned molecular weight Consideration should be given when applying restrictions. Preferred amide solubilizing agents consist of carbon, hydrogen, nitrogen and oxygen. Representative aliphatic and cycloaliphatic hydrocarbon radicals of R ¹ , R ² , R ³ and R ⁵ are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and coordination isomers thereof. Amide solubilizing agents of the preferred embodiments above-mentioned formula cyclo ^{- [R 4 CON (R 5} ) -] of the R ⁴ is hydrocarbylene radical (CR ⁶ R ⁷⁾ to which may be represented by _n, i.e. the previously mentioned Has a molecular weight value, n is an integer from 3 to 5, R ⁵ is a saturated hydrocarbon radical having 1 to 12 carbon atoms, and R ⁶ and R ⁷ are defined by the law that defines R ^{1 -3} previously provided (each n Is an independently selected formula cyclo-[(CR ⁶ R ⁷ ) _n CON (R ⁵ )-]. In the 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 a single saturated hydrocarbon radical in n methylene units , 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, including but not limited to.

Ketone solubilizers of the invention include ketones represented by the formula 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, The molecular weight is from about 70 to about 300 atomic mass units. R ¹ and R ² in the ketone are preferably independently selected from aliphatic and cycloaliphatic 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 may together form a hydrocarbylene radical and be joined to form a 5, 6 or 7 membered cyclic cyclic ketone 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 heteroatom-substituted hydrocarbon radicals, ie radicals containing atomic nitrogen (aza-), oxygen (keto-, oxa-) or sulfur (thia-) in a radical chain consisting of carbon atoms except for them; May include. In general, up to 3, preferably up to 1 non-hydrocarbon substituents and heteroatoms will be present at 10 carbon atoms in R ¹ and R ² and the presence of any such non-hydrocarbon substituents and heteroatoms may be Consideration should be given when applying molecular weight restrictions. Aliphatic of formula R ¹ COR ² representative of R ¹ and R ^2, alicyclic and aryl hydrocarbon radicals are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec- butyl, tert- butyl, pentyl, isopentyl, neo Pentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their coordination isomers as well as phenyl, benzyl, cumenyl, mesityl, tolyl, xylyl and phenethyl Include.

Representative ketone solubilizing agents 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.

Nitrile solubilizers of the present invention comprise a nitrile 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, the molecular weight of the nitrile being about 90 to about 200 atomic mass units. R ¹ in the nitrile solubilizer is preferably selected from aliphatic and alicyclic hydrocarbon radicals having 8 to 10 carbon atoms. The molecular weight of the nitrile solubilizer is preferably from about 120 to about 140 atomic mass units. R ¹ may optionally include substituted hydrocarbon radicals, that is, radicals containing non-hydrocarbon substituents selected from halogen (eg fluorine, chlorine) and alkoxides (eg methoxy). R ¹ may optionally include a heteroatom substituted hydrocarbon radical, that is, a radical containing atomic nitrogen (aza-), oxygen (keto-, oxa-) or sulfur (thia-) in a radical chain consisting of carbon atoms except for that Can be. In general, up to 3, preferably up to 1 non-hydrocarbon substituents and heteroatoms will be present at 10 carbon atoms in R ¹ and the presence of any such non-hydrocarbon substituents and heteroatoms is subject to the above mentioned molecular weight limitations. Should be considered in the application. Aliphatic, alicyclic and aryl hydrocarbon radicals in the typical R ¹ in the formula R ¹ CN is pentyl, isopentyl, neopentyl, tert- pentyl, cyclopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and Coordination 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.

Carbon chloride solubilizers of the present invention include carbon chloride 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, The molecular weight of the carbon chloride is about 100 to about 200 atomic mass units. The molecular weight of the carbon chloride solubilizer is preferably about 120 to 150 atomic mass units. Representative aliphatic and cycloaliphatic hydrocarbon radicals of R in formula RCl _x are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl , Cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and coordination isomers thereof.

Representative carbon chloride 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, including but not limited to.

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 of 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 hexanoate, ethyl heptanoate, n-butyl propio , N-propyl propionate, ethyl benzoate, di-n-propyl phthalate, benzoic acid ethoxyethyl ester, dipropyl carbonate, "Exxate 700" (commercial C ₇ alkyl acetate), "Ex Acetate 800 "(commercial C ₈ alkyl acetates), dibutyl phthalate, and tert-butyl acetate.

Lactone solubilizers of the present invention include lactones represented by the formulas A, B, and C below.

These lactones contain the functional group -CO ₂ -in the 6-membered ring A, or preferably in the 5-membered ring B, and for structures A and B, R ₁ to R ₈ are hydrogen, or linear, branched, cyclic, Independently from bicyclic, saturated and unsaturated hydrocarbyl radicals. Each R ₁ to R ₈ will be linked to another R ₁ to R ₈ to form a ring. The lactones may have an out-of-cyclic alkylidene group, such as structure C, wherein R ₁ to R ₆ are independently selected from hydrogen or linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals. Each R ₁ to R ₆ may be linked to another R ₁ to R ₆ to form a ring. The molecular weight of the lactone solubilizer is about 80 to about 300 atomic mass units, preferably about 80 to about 200 atomic mass units.

Representative lactone solubilizers include, but are not limited to, the compounds listed in Tables 4A-4C.

The kinematic viscosity of the lactone solubilizer is generally less than about 7 centistokes at 40 ° C. For example, the kinematic viscosity of gamma-undecalactone at 40 ° C. is 5.4 centistokes and the viscosity of cis- (3-hexyl-5-methyl) dihydrofuran-2-one is 4.5 centistokes. Lactone solubilizers are commercially available or may be prepared by methods as described in US Patent Application No. 10 / 910,495 (inventors PJ Fagan and CJ Brandenburg), filed August 3, 2004, which is incorporated herein by reference. Can be.

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

Fluoroether solubilizing agents of the present invention include those represented by the formula R ¹ OCF ₂ CF ₂ H, wherein R ¹ is an aliphatic and cycloaliphatic hydrocarbon radical having about 5 to about 15 carbon atoms, preferably primary linear saturation Selected from alkyl radicals. Representative fluoroether solubilizers include, but are not limited to, C ₈ H ₁₇ OCF ₂ CF ₂ H and C ₆ H ₁₃ OCF ₂ CF ₂ H. It should be noted that when the refrigerant is a fluoroether, the solubilizer may not be the same fluoroether.

The fluoroether solubilizer may further comprise ethers derived from fluoro-olefins and polyols. The fluoro-olefin may be of the form CF ₂ = CXY, where X is hydrogen, chlorine or fluorine, Y is chlorine, fluorine, CF ₃ or OR _f , where R _f is CF ₃ , C ₂ F ₅ , or C ₃ F ₇ . Representative fluoro-olefins are tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, and perfluoromethylvinyl ether. The polyol may be of the type HOCH ₂ CRR '(CH ₂ ) _z (CHOH) _x CH ₂ (CH ₂ OH) _y where R and R' are hydrogen or CH ₃ or C ₂ H ₅ , and x is from 0 to 4 It is an integer, y is an integer of 0-3, z is 0 or 1. Representative polyols are trimethylol propane, pentaerythritol, butane diol, and ethylene glycol.

The 1,1,1-trifluoroalkane solubilizer of the present invention comprises 1,1,1-trifluoroalkane represented by the formula CF ₃ R ¹ , wherein R ¹ has about 5 to about 15 carbon atoms Aliphatic and cycloaliphatic hydrocarbon radicals, preferably primary linear saturated alkyl radicals. Representative 1,1,1-trifluoroalkane solubilizers include, but are not limited to, 1,1,1-trifluorohexane and 1,1,1-trifluorododecane.

The solubilizers of the present invention may be present as a single compound or may be present as a mixture of one or more solubilizers. The mixture of solubilizers may contain two solubilizers from the same class of compounds, for example two lactones, or two solubilizers from two different classes, such as lactones and polyoxyalkylene glycol ethers. Can be.

In the compositions of the present invention comprising a refrigerant and a UV fluorescent dye, the UV dye is from about 0.001% to about 1.0% by weight of the composition, preferably from about 0.005% to about 0.5% by weight, most preferably from 0.01% by weight About 0.25% by weight.

The solubility of these UV fluorescent dyes in the refrigerant can be poor. Thus, methods for introducing these dyes into refrigeration or air conditioning apparatus are difficult, costly and time consuming. U.S. Patent No. RE 36,951 describes a method using dye powders, solid pellets or slurries of dyes that can be inserted as components of a refrigeration or air conditioning apparatus. When the refrigerant and lubricant circulate through the device, the dye is dissolved or dispersed and transported through the device. Numerous other methods for introducing dyes into refrigeration or air conditioning apparatus are described in the literature.

Ideally, UV fluorescent dyes can be dissolved in the refrigerant itself, and should not require any specialized method for introduction into refrigeration or air conditioning apparatus. The present invention relates to a composition comprising a UV fluorescent dye that can be introduced into a system in a refrigerant. The composition of the present invention will enable the storage and delivery of the dye containing refrigerant even at low temperatures while the dye remains in solution.

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

Optionally, refrigeration system additives commonly used to enhance performance and system stability can be added to the compositions of the present invention as needed. These additives are known in the field of refrigeration and include, but are not limited to, antiwear agents, extreme pressure lubricants, corrosion and antioxidants, metal surface deactivators, free radical scavengers, and foam control agents. In general, these additives are present in the compositions of the present invention in small amounts relative to the total composition. 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 based on the individual system requirements. These additives are materials of the triaryl phosphate group of EP (extreme) lubricating additives, for example butylated triphenyl phosphate (BTPP), or other alkylated triaryl phosphate esters, for example Syn-O-Ad 8478 (arczo chemical) Akzo Chemicals), tricresyl phosphate and related compounds. Additionally, metal dialkyl dithiophosphates (eg, zinc dialkyl dithiophosphates (or ZDDPs), Lubrizol 1375 and other materials of the compound group may be used in the compositions of the present invention. Prophylactic additives include natural product oils, and asymmetric polyhydroxyl lubricating additives such as Syngolgol TMS (International Lubricants) Similarly, antioxidants, free radical scavengers, and water scavenger Stabilizers such as benzers may be used Compounds within this category may include, but are not limited to, butylated hydroxy toluene (BHT) and epoxides.

Solubilizers such as ketones can have an unpleasant odor, which can be blocked by the addition of odor masking agents or fragrances. Common examples of odor masks or fragrances include Evergreen, Fresh Lemon, Cherry, Cinnamon, Peppermint, Floral or Orange Peel. As well as d-limonene and pinene. Such malodor masking agents may be used in concentrations of about 0.001% to about 15% by weight, based on the combined weight of the malodor masking agent and the solubilizing agent.

The present invention further relates to a method of using a refrigerant or heat transfer fluid composition further comprising an ultraviolet fluorescent dye, and optionally a solubilizer, in a refrigeration or air conditioning apparatus. Such methods include introducing a refrigerant or heat transfer fluid composition into a refrigeration or air conditioning device. This can be done by dissolving the UV fluorescent dye in the refrigerant or heat transfer fluid composition in the presence of a solubilizer and introducing the blend into the device. Alternatively, this can be done by combining the solubilizer and the UV fluorescent dye and introducing the blend into a refrigeration or air conditioning apparatus containing a refrigerant and / or a heat transfer fluid. The resulting composition can be used in refrigeration or air conditioning apparatus.

In addition, the present invention relates to a method of using a refrigerant or heat transfer fluid composition comprising an ultraviolet fluorescent dye for detecting leaks. The presence of the dye in the composition makes it possible to detect leakage of the refrigerant in the refrigeration or air conditioning apparatus. Leak detection helps to account for, solve or prevent inefficient operation of the device or system or equipment failure. Leak detection also helps to contain the compound used to operate the device.

Such a method is suitable for providing a refrigeration and air conditioning apparatus with a composition comprising a refrigerant as described herein, an ultraviolet fluorescent dye and optionally comprising a solubilizer as described herein and for detecting a UV fluorescent dye containing refrigerant. Using means. Suitable means for sensing a dye include, but are not limited to, ultraviolet lamps, often referred to as "black light" or "blue light". Such ultraviolet lamps are specifically designed for this purpose and are commercially available from numerous suppliers. By introducing a composition containing an ultraviolet fluorescent dye into a refrigeration or air conditioning apparatus and allowing it to circulate through the system, leakage can be found by illuminating the ultraviolet lamp on the apparatus and observing the fluorescence of the dye near any leak point.

Further, the present invention relates to a method of using the composition of the present invention for freezing or generating heat, which method produces a freezing by condensing the composition after evaporating the composition in the vicinity of the object to be cooled. And condensing the composition in the vicinity of the object to be heated to produce heat by evaporating the composition.

Mechanical refrigeration is primarily the application of thermodynamics that are circulated so that cooling media, such as refrigerant, can be recovered for reuse. Commonly used circulation includes steam-compression, absorption, steam-jet or steam-ejector and air.

The vapor compression refrigeration system includes an evaporator, a compressor, a condenser, and an expansion device. The vapor compression circulation reuses the refrigerant in multiple stages, creating a cooling effect in one stage and a heating effect in a different stage. The circulation can be described simply as follows. The liquid refrigerant is introduced into the evaporator through an expansion device, and the liquid refrigerant boils in the evaporator at low temperatures to form gas to produce cooling. Low pressure gas is introduced into the compressor where the gas is compressed to increase pressure and temperature. Thereafter, a higher pressure (compressed) gaseous refrigerant is introduced into the condenser, where the refrigerant condenses and discharges its heat to the surroundings. The refrigerant is returned to the expansion device where the liquid expands from the higher pressure level in the condenser to the lower pressure level in the evaporator, thereby repeating the circulation.

There are various types of compressors that can be used for refrigeration applications. The compressor may be reciprocating, rotating, jetting, centrifugal, scrolling, screwing or axial-flow, or with respect to the fluid being compressed, depending on the mechanical means of compressing the fluid. Depending on how the mechanical part acts, it can generally be classified as either volumetric (eg reciprocating, scrolling or screwing) or dynamic (eg centrifugal or jetting).

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

Centrifugal compressors use a rotating member that radially accelerates the refrigerant and typically includes an impeller and a diffuser embedded in the shell. Centrifugal compressors usually take fluid at the impeller eye or at the central inlet of the circulating impeller and accelerate radially outward. Some static pressure rise occurs in the impeller, but most pressure rise occurs in the diffuser portion of the skin, where speed is converted to static pressure. Each impeller-diffuser set is one stage of the compressor. Centrifugal compressors consist of one to twelve stages or more, depending on the final pressure desired and the volume of refrigerant to be handled.

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

The volumetric compressor draws steam into the chamber and compresses the steam by reducing the volume of the chamber. After compression, the vapor is forced out of the chamber by further reducing the chamber volume to zero or nearly zero. Volumetric compressors can increase pressure, which is limited only by the strength and volumetric efficiency of the components that withstand the pressure.

Unlike volumetric compressors, centrifugal compressors compress the steam passing through the impeller entirely depending on the centrifugal force of the high speed impeller. Although not in volume, there is what is referred to as a dynamic compressor.

The pressure of the centrifugal compressor can develop according to the tip speed of the impeller. Tip velocity is the velocity of the impeller measured at the tip of the impeller and is related to the radius of the impeller and its revolutions per minute. The capacity of the centrifugal compressor is determined by the size of the path through the impeller. For this reason, the size of the compressor is more dependent on the required pressure than on the capacity.

Centrifugal compressors are essentially bulky low pressure equipment because they operate at high speeds. 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 3000 to 7000 revolutions per minute (rpm). Small turbine centrifugal compressors are designed for high speeds of about 40,000 to about 70,000 rpm, and their small impeller sizes are typically less than 0.15 meters.

Multi-stage impellers can be used in centrifugal compressors to improve compressor efficiency, requiring less force in use. In a two-stage system, during operation the exhaust of the first stage impeller enters the intake of the second impeller. Both impellers can be operated using a single shaft (or shaft). Each stage can establish a compression ratio of about 4 to 1 (ie, the absolute absolute pressure can be four times the absolute absolute pressure). In the case of automotive applications, an example of a two-stage centrifugal compressor system is described in US Pat. No. 5,065,990, which is incorporated herein by reference.

Compositions of the invention suitable for use in refrigeration or air conditioning systems utilizing centrifugal compressors

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1,3-trifluoropropane,

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,3-difluoropropane,

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1,1,3,3-pentafluorobutane ,

1,1,1,2,2,4,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone and 1,1-difluorobutane,

1,1,1,2,2,4,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone and 1,2-difluorobutane,

1,1,1,2,2,4,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone and 1,3-difluorobutane,

1,1,1,2,2,4,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone and 1,4-difluorobutane,

1,1,1,2,2,4,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone and 1,3-difluoro-2-methylpropane,

1,1,1,2,2,4,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone and 1,2-difluoro-2-methylpropane,

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 2,3-difluorobutane,

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1,1-trifluoropentane,

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1,1-trifluoro-3-methylbutane ,

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1-difluoropentane,

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,2-difluoropentane,

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 2,2-difluoropentane,

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1,1,2,2,3,4, 5,5,5-decafluoropentane,

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1,1-trifluorohexane,

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1,2,2-tetrafluorocyclobutane, And

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 3,3,4,4,5,5,6, 6,6-nonnafluoro-1-hexene

It is selected from the group consisting of at least one of them.

In addition, these compositions listed above are suitable for use in multistage centrifugal compressors, preferably two-stage centrifugal compressor apparatus.

The compositions of the present invention can be used in stationary air conditioning, heat pumps or mobile air conditioning and refrigeration systems. Stationary air conditioning and heat pump applications include windowed, ductless, ducted, packaged terminals, quenchers, and packaged rooftops. It includes an article. Refrigeration applications include domestic or residential refrigerators and freezers, ice makers, integrally equipped coolers and freezers, walk-in coolers and freezers and transport refrigeration systems.

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

Typical microchannel heat exchangers may not be ideal for the low pressure refrigerant compositions of the present invention. Low working pressures and densities result in high flow rates and high friction reductions in all components. In such cases, the evaporator design may be modified. A single slab / single channel heat exchanger arrangement may be used rather than several microchannel slabs connected in series (for the refrigerant path). Thus, the preferred heat exchanger for low pressure refrigerants of the present invention is a single slab / single passage heat exchanger.

In addition to the two stage compressor system, the following compositions of the present invention are suitable for use in refrigeration or air conditioning systems using a single slab / single passage heat exchanger.

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1,3-trifluoropropane,

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,3-difluoropropane,

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1,1,3,3-pentafluorobutane ,

1,1,1,2,2,4,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone and 1,1-difluorobutane,

1,1,1,2,2,4,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone and 1,2-difluorobutane,

1,1,1,2,2,4,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone and 1,3-difluorobutane,

1,1,1,2,2,4,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone and 1,4-difluorobutane,

1,1,1,2,2,4,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone and 1,3-difluoro-2-methylpropane,

1,1,1,2,2,4,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone and 1,2-difluoro-2-methylpropane,

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 2,3-difluorobutane,

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1,1-trifluoropentane,

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1,1-trifluoro-3-methylbutane ,

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1-difluoropentane,

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,2-difluoropentane,

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 2,2-difluoropentane,

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1,1,2,2,3,4, 5,5,5-decafluoropentane,

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1,1-trifluorohexane,

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1,2,2-tetrafluorocyclobutane,

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 3,3,4,4,5,5,6, 6,6-nonnafluoro-1-hexene.

The compositions of the present invention are particularly useful for small turbine centrifugal compressors, which can be used in automotive and windowed air conditioning or heat pumps as well as other applications. These high efficiency miniature centrifugal compressors can be driven by an electric motor and thus can operate independently of engine speed. Constant compressor speed allows the system to provide a relatively constant cooling capacity at all engine speeds. This offers the possibility of efficiency improvements, especially at higher engine speeds, compared to typical R-134a automotive air conditioning systems. Given the cyclical operation of a typical system at high drive speeds, the benefits of these low pressure systems will be even greater.

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

The present invention relates to a method for producing a freezer comprising evaporating the composition of the invention in the vicinity of an object to be cooled and then condensing the composition.

Further, the present invention relates to a method for generating heat, comprising condensing the composition of the invention in the vicinity of the object to be heated and then evaporating the composition.

In addition, the present invention relates to a method of transferring heat from a heat source to a heat sink, wherein the composition of the present invention acts as a heat transfer fluid. The method for heat transfer includes transferring the composition 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 cooling (or heating) from a remote refrigeration (or heating) system. In some systems, the heat transfer fluid may remain constant (ie, not evaporated or condensed) throughout the transfer process. Alternatively, the evaporative cooling process may also utilize a heat transfer fluid.

The heat source may be defined as any space, place, object or object for which it is desirable to transfer, move or remove heat. Examples of heat sources can be (open or closed) spaces that require refrigeration or cooling, such as refrigerators or freezer cases in supermarkets, building spaces that require air conditioning, or passenger cabins of automobiles that require air conditioning. The heat sink may be defined as any space, place, object or object capable of absorbing heat. The vapor compression refrigeration system is an example of such a heat sink.

Example 1

Impact of Vapor Leakage

At a certain temperature, the composition was first filled into a container and the initial vapor pressure of the composition was measured. The composition was leaked from the container while 50% by weight of the initial composition was removed while maintaining the temperature constant, and the vapor pressure of the composition remaining in the container was measured when 50% by weight of the initial composition was removed. The results are summarized in Tables 5a to 5e below.

The results indicate that the vapor pressure difference between the original composition and the composition remaining after 50% by weight is removed is less than about 10% for the compositions of the present invention. This indicates that the composition of the present invention is azeotropic or near-air. When azeotropic is present, the data indicate that the compositions of the present invention have an initial vapor pressure higher than the vapor pressure of the pure components.

Example  2

Tip speed to generate pressure

Tip speed can be estimated by establishing some basic relationships for refrigeration units using centrifugal compressors. The torque imparted ideally to the gas by the impeller is defined as in Equation 1 below.

In the above formula,

T is the torque (N * m),

m is the mass flow rate (kg / s),

v ₂ is the tangent velocity (tip velocity) of the refrigerant leaving the impeller (m / s),

r ₂ is the radius (m) of the impeller exit,

v ₁ is the tangent speed (m / s) of the refrigerant introduced into the impeller,

r ₁ is the radius (m) of the impeller inlet.

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

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

In the above formula,

P is the force (W),

w is the rotational speed (rez / s),

Therefore, the following equation is established.

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

Another expression of the ideal force is the product of the isentropic work of mass flow rate and compression.

In the above formula,

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

Combining Equations 6 and 7 establishes the following equation.

Equation 8 is based on some fundamental assumptions, but this provides a good estimate of the tip speed of the impeller and provides an important way of comparing the tip speeds of the refrigerants.

Table 6 below shows the theoretical tip rates calculated for 1,2,2-trichlorotrifluoroethane (CFC-113) and the 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 (5.5 ° 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.

This example shows that the compounds of the present invention have a tip speed within about +/- 20% of CFC-113, and are an effective substitute for CFC-113 while minimizing the compressor design. Most preferred compositions have a tip speed within about +/- 10% of CFC-113.

Example 3

Performance Data

The data in Table 7 below shows the performance of various refrigerants compared to CFC-113. Data was 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),

Compressor Efficiency 70%

The data indicate that the compositions of the present invention have evaporator and condenser pressures similar to CFC-113. In addition, some compositions had higher capacity or energy efficiency (COP) than CFC-113.

Claims (18)

1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1,3-trifluoropropane, 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,3-difluoropropane, 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1,1,3,3-pentafluorobutane , 1,1,1,2,2,4,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone and 1,1-difluorobutane, 1,1,1,2,2,4,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone and 1,2-difluorobutane, 1,1,1,2,2,4,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone and 1,3-difluorobutane, 1,1,1,2,2,4,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone and 1,4-difluorobutane, 1,1,1,2,2,4,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone and 1,3-difluoro-2-methylpropane, 1,1,1,2,2,4,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone and 1,2-difluoro-2-methylpropane, 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 2,3-difluorobutane, 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1,1-trifluoropentane, 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1,1-trifluoro-3-methylbutane , 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1-difluoropentane, 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,2-difluoropentane, 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 2,2-difluoropentane, 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1,1,2,2,3,4, 5,5,5-decafluoropentane, 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1,1-trifluorohexane, 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1,2,2-tetrafluorocyclobutane, And 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 3,3,4,4,5,5,6, 6,6-nonnafluoro-1-hexene Composition selected from the group consisting of. suitable for use in refrigeration or air conditioning apparatus utilizing (i) centrifugal compressors, or (ii) multistage centrifugal compressors, or (iii) single slab / single channel heat exchangers, 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1,3-trifluoropropane, 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,3-difluoropropane, 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1,1,3,3-pentafluorobutane , 1,1,1,2,2,4,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone and 1,1-difluorobutane, 1,1,1,2,2,4,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone and 1,2-difluorobutane, 1,1,1,2,2,4,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone and 1,3-difluorobutane, 1,1,1,2,2,4,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone and 1,4-difluorobutane, 1,1,1,2,2,4,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone and 1,3-difluoro-2-methylpropane, 1,1,1,2,2,4,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone and 1,2-difluoro-2-methylpropane, 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 2,3-difluorobutane, 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1,1-trifluoropentane, 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1,1-trifluoro-3-methylbutane , 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1-difluoropentane, 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,2-difluoropentane, 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 2,2-difluoropentane, 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1,1,2,2,3,4, 5,5,5-decafluoropentane, 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1,1-trifluorohexane, 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 1,1,2,2-tetrafluorocyclobutane, And 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and 3,3,4,4,5,5,6, 6,6-nonnafluoro-1-hexene A refrigerant or heat transfer fluid composition selected from the group consisting of: About 1 to about 99 weight percent of 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and about 99 to about 1 weight % 1,1,3-trifluoropropane, About 1 to about 90 weight percent of 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and about 99 to about 10 weight % 1,3-difluoropropane, About 1 to about 99 weight percent of 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and about 99 to about 1 weight % 1,1-difluorobutane, About 54 to about 91 weight percent of 1,1,1,2,2,4,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone and about 46 to about 9 weight % 1,2-difluorobutane, About 65 to about 95 weight percent of 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and about 35 to about 5 weight % 1,3-difluorobutane, About 76 to about 99 weight percent of 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and about 24 to about 1 weight % 1,4-difluorobutane, About 68 to about 95 weight percent 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and about 32 to about 5 weight % 1,3-difluoro-2-methylpropane, About 1 to about 84 weight percent 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoro methyl) -3-pentanone and about 99 to about 16 weight % 1,2-difluoro-2-methylpropane, About 48 to about 90 weight percent 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and about 52 to about 10 weight % 2,3-difluorobutane, About 1 to about 86 weight percent of 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and about 99 to about 14 weight % 1,1,1-trifluoropentane, About 1 to about 84 weight percent of 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and about 99 to about 16 weight % 1,1,1-trifluoro-3-methylbutane, About 62 to about 99 weight percent 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and about 38 to about 1 weight % 1,1-difluoropentane, About 72 to about 99 weight percent of 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and about 28 to about 1 weight % 1,2-difluoropentane, About 51 to about 99 weight percent 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and about 49 to about 1 weight % 2,2-difluoropentane, About 1 to about 99 weight percent of 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and about 99 to about 1 weight % 1,1,1,2,2,3,4,5,5,5-decafluoropentane, About 65 to about 99 weight percent of 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and about 35 to about 1 weight % 1,1,1-trifluorohexane, About 1 to about 99 weight percent of 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and about 99 to about 1 weight % 1,1,2,2-tetrafluorocyclobutane, and About 1 to about 99 weight percent of 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3-pentanone and about 99 to about 1 weight % 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene Azeotropic or azeotropic composition selected from the group consisting of. 78.4% by weight of 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 46.0 ° C -3-pentanone and 21.6% by weight of 1,1,3-trifluoropropane, 74.7% by weight of 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 33.5 ° C. -3-pentanone and 25.3% by weight of 1,3-difluoropropane, 50.6% by weight of 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 37.6 ° C. -3-pentanone and 49.4% by weight of 1,1-difluorobutane, 78.4% by weight of 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 37.2 ° C -3-pentanone and 21.6% by weight of 1,2-difluorobutane, 84.9% by weight of 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 41.3 ° C -3-pentanone and 15.1% by weight of 1,3-difluorobutane, 92.5% by weight of 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 45.8 ° C -3-pentanone and 7.5% by weight of 1,4-difluorobutane, 86.8 wt.% 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 41.7 ° C. -3-pentanone and 13.2% by weight of 1,3-difluoro-2-methylpropane, 55.9 wt.% 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 31.5 ° C. -3-pentanone and 44.1% by weight of 1,2-difluoro-2-methylpropane, 75.0 wt.% 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) -3 having a vapor pressure of about 14.7 psia (101 kPa) at about 36.0 ° C. -Pentanone and 25.0 wt% 2,3-difluorobutane, 47.5% by weight of 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 36.2 ° C. -3-pentanone and 52.5% by weight of 1,1,1-trifluoropentane, 45.4% by weight of 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 35.4 ° C -3-pentanone and 54.6% by weight of 1,1,1-trifluoro-3-methylbutane, 95.2% by weight of 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 48.7 ° C. -3-pentanone and 4.8% by weight of 1,1-difluoropentane, 90.1% by weight of 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 44.8 ° C. -3-pentanone and 9.9% by weight of 1,2-difluoropentane, 82.0% by weight of 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 45.2 ° C -3-pentanone and 18.0% by weight of 2,2-difluoropentane, 73.6% by weight of 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 46.0 ° C. -3-pentanone and 26.4% by weight of 1,1,1,2,2,3,4,5,5,5-decafluoropentane, 96.0 wt.% 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 48.8 ° C. -3-pentanone and 4.0% by weight of 1,1,1-trifluorohexane, and 73.2% by weight of 1,1,1,2,2,4,5,5,5-nonnafluoro-4- (trifluoromethyl) having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 48.7 ° C -3-pentanone and 26.8% by weight of 1,1,2,2-tetrafluorocyclobutane Azeotropic composition selected from the group consisting of. A method of producing a freezer comprising condensing said composition after evaporating the composition of claim 2 in the vicinity of the object to be cooled. The method of generating heat comprising evaporating the composition of any one of claims 2 to 4 in the vicinity of the object to be heated. A method of heat transfer comprising transferring the composition of any one of claims 2 to 4 from a heat source to a heat sink. The compound according to claim 2, which is selected from the group consisting of naphthalimide, perylene, coumarin, anthracene, phenanthracene, xanthene, thioxanthene, naphthoxanthene, fluorescein, derivatives thereof A composition further comprising at least one ultraviolet fluorescent dye selected. The method according to claim 3 or 4, wherein naphthalimide, perylene, coumarin, anthracene, phenanthracene, xanthene, thioxanthene, naphthoxanthene, fluorescein, derivatives of the dyes and combinations thereof The composition further comprises at least one ultraviolet fluorescent dye selected from the group consisting of. The method of claim 8, wherein the hydrocarbon, dimethyl ether, polyoxyalkylene glycol ether, amide, ketone, nitrile, carbon chloride, ester, lactone, aryl ether, hydrofluoroether, and 1,1,1-trifluoro A composition further comprising at least one solubilizer selected from the group consisting of alkanes, wherein the refrigerant and the solubilizer are not the same compound. The method of claim 10 wherein the solubilizer is a) a polyoxyalkylene glycol ether having a molecular weight of about 100 to about 300 atomic mass units and represented by the formula R ¹ [(OR ² ) _x OR ³ ] _y , where x is an integer from 1 to 3 and y is 1 Is an integer from 4 to 4, R ¹ 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 2 to 4 carbon atoms, and R is ³ is selected from hydrogen and aliphatic and alicyclic hydrocarbon radicals having 1 to 6 carbon atoms, at least one of R ¹ and R ³ is selected from said hydrocarbon radicals), b) amides having a molecular weight of about 100 to about 300 atomic mass units and represented by the formula R ¹ CONR ² R ³ and cyclo- [R ⁴ CON (R ⁵ )-], wherein R ¹ , R ² , R ³ and R ⁵ is independently selected from aliphatic and cycloaliphatic hydrocarbon radicals of 1 to 12 carbon atoms, and up to 1 aromatic radical of 6 to 12 carbon atoms, and R ⁴ is selected from aliphatic hydrocarbylene radicals of 3 to 12 carbon atoms ), c) Ketones having a molecular weight of about 70 to about 300 atomic mass units and represented by the formula 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 , d) a nitrile having a molecular weight of about 90 to about 200 atomic mass units and 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, e) carbon chloride represented by the formula RCl _x having a molecular weight of about 100 to about 200 atomic mass units, wherein x is an integer of 1 or 2, and R is selected from aliphatic and cycloaliphatic hydrocarbon radicals having 1 to 12 carbon atoms, f) aryl ethers having a molecular weight of about 100 to about 150 atomic mass units represented by the formula R ¹ OR ² , wherein R ¹ is selected from aryl hydrocarbon radicals having 6 to 12 carbon atoms, and R ² is 1 to 4 carbon atoms; Selected from individual aliphatic hydrocarbon radicals), 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) a fluoroether represented by the formula R ¹ OCF ₂ CF ₂ H, wherein R ¹ is selected from aliphatic and cycloaliphatic hydrocarbon radicals having from about 5 to about 15 carbon atoms, or the fluoroether is a fluoro-olefin And a polyol, wherein the fluoro-olefin is of the form CF ₂ = CXY, where X is hydrogen, chlorine or fluorine, Y is chlorine, fluorine, CF ₃ or OR _f , where R _f is CF ₃ , C ₂ F ₅ , or C ₃ F ₇ , wherein the polyol is of type HOCH ₂ CRR ′ (CH ₂ ) _z (CHOH) _x CH ₂ (CH ₂ OH) _y , wherein R and R ′ are hydrogen, CH ₃ or C ₂ H ₅ , x is an integer from 0 to 4, y is an integer from 0 to 3, z is 0 or 1), j) a lactone having a molecular weight of about 100 to about 300 atomic mass units and represented by the following formulas B, C, and D, and k) esters having a molecular weight of about 80 to about 550 atomic mass units and 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 Composition selected from the group consisting of. <Formula B>

<Formula C>

<Formula D>

(R ¹ to R ⁸ are independently selected from hydrogen and linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals). (i) dissolving an ultraviolet fluorescent dye in the refrigerant composition or heat transfer fluid in the presence of a solubilizer and introducing the formulation into a refrigeration or air conditioning apparatus, or (ii) combining the solubilizer and the UV fluorescent dye and cooling the formulation into a refrigerant. And / or introducing the composition of claim 10 into a compressed refrigeration or air conditioning apparatus by introducing it into a compressed refrigeration or air conditioning apparatus containing a heat transfer fluid. A refrigeration or air conditioning apparatus, comprising providing the composition of claim 8 or 10 to a refrigeration or air conditioning apparatus and providing means suitable for detecting the composition at or near the point of leakage. How to detect leaks on your computer. A method of producing a freezer comprising condensing said composition after evaporating the composition of claim 10 in the vicinity of the object to be cooled. A method of generating heat, comprising evaporating the composition after condensing the composition of claim 10 in the vicinity of the object to be heated. The composition of claim 2 or 10, further comprising a stabilizer, a water scavenger, or a malodor masking agent. The composition of claim 16 wherein the stabilizer is selected from the group consisting of nitromethane, hindered phenols, hydroxylamines, thiols, phosphites and lactones. The composition of claim 16 wherein said water scavenger is an ortho ester.