Fluoroolefin compositions containing dyes and methods for their manufacture, storage, and use - Patents.com

Abstract

The present invention relates to a composition comprising at least one fluoroolefin and an effective amount of at least one inhibitor.The stabilized composition can be useful in cooling equipment such as refrigeration, air conditioning, chillers and heat pumps, as well as in applications as blowing agents, solvents, aerosol propellants and sterilants.

Description

[Technical field]

[0001] The present invention broadly relates to a stabilized composition comprising at least one fluoroolefin, at least one inhibitor comprising at least one member selected from the group consisting of limonene, α-terpinene, α-tocopherol, butylated hydroxytoluene, 4-methoxyphenol, benzene-1,4-diol, at least one dye, and at least one lubricant. [Background technology]

[0002] New environmental regulations on refrigerants are forcing the refrigeration and air conditioning industry to search for new refrigerants with lower global warming potential (GWP).

[0003] There is a need for alternative refrigerants that have low GWP, non-toxicity, non-flammability, reasonable cost, and excellent refrigeration performance.

[0004] Fluoroolefins have been proposed as refrigerants, either alone or in mixtures. These products have been extensively tested for chemical stability and compatibility with materials typically used in air conditioning or refrigeration systems (see "1234yf-A Low GWP Refrigerant For MAC, Honeywell / DuPont Joint Collaboration," JAMA / JAPIA publication, October 3, 2007), and have been shown to be stable under typical operating conditions. However, it has been observed that certain fluoroolefins may exhibit degradation and / or produce unwanted by-products under abnormal conditions, such as extreme temperatures or contact with other compounds in contaminated systems (e.g., excess oxygen, oxidizing chemicals, or radical-generating compounds, among other contaminants), which may occur unexpectedly in a particular use and / or application. Such degradation may occur when utilizing fluoroolefins as refrigerants or heat transfer fluids. This degradation may occur by any number of different mechanisms. Examples of stabilized compositions are disclosed in Application Publication No. JP2009298918, U.S. Pat. No. 6,969,701, U.S. Pat. No. 8,133,407, U.S. Pat. Application Publication No. 2006 / 0022166, U.S. Pat. Application Publication No. 2006 / 0043330, U.S. Pat. Application Publication No. 2008 / 0157022, and WO 2007 / 126760, as well as European Patent No. 2057245, U.S. Pat. No. 8,101,094, U.S. Pat. No. 8,535,555, U.S. Pat. No. 8,097,181, and U.S. Pat. No. 8,075,796, the disclosures of each of which are incorporated herein by reference in their entireties.

[0005] Under certain abnormal conditions and in the presence of undesirable contaminants that can act as initiators, fluoroolefins can oligomerize or homopolymerize.Therefore, there is a need in the art for stabilized fluoroolefin-containing compositions that have reduced, if not eliminated, potential for oligomerization or homopolymerization.

[0006] There is also a need in the art for a refrigerant composition comprising at least one dye. The dye can be used to detect leaks in systems that use refrigerants (e.g., automotive aftermarket refrigerants with dyes for leak detection). Examples of dyes include fluorescent dyes that fluoresce when exposed to UV light, allowing the location of a refrigerant leak to be detected. The dye can be solubilized in the lubricant, and the solubilized dye composition is then blended with the refrigerant. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Publication No. JP2009298918 [Patent Document 2] U.S. Patent No. 6,969,701 [Patent Document 3] U.S. Patent No. 8,133,407 [Patent Document 4] US Patent Application Publication No. 2006 / 0022166 [Patent Document 5] US Patent Application Publication No. 2006 / 0043330 [Patent Document 6] US Patent Application Publication No. 2008 / 0157022 [Patent Document 7] International Publication No. 2007 / 126760 [Patent Document 8] European Patent No. 2057245 [Patent Document 9] U.S. Patent No. 8,101,094 [Patent Document 10] U.S. Patent No. 8,535,555 [Patent Document 11] U.S. Patent No. 8,097,181 [Patent Document 12] U.S. Patent No. 8,075,796 [Non-patent literature]

[0008] [Non-Patent Document 1] See "1234yf-A Low GWP Refrigerant For MAC, Honeywell / DuPont Joint Collaboration," JAMA / JAPIA publication, October 3, 2007. Summary of the Invention [Problem to be solved by the invention]

[0009] Thus, there is a need in the art for compositions in which fluoroolefins (particularly stabilized fluoroolefins), dyes, and lubricants are miscible to provide stable refrigerant compositions. [Means for solving the problem]

[0010] The present invention broadly relates to a stabilized composition comprising at least one fluoroolefin, at least one inhibitor comprising at least one member selected from the group consisting of limonene, α-terpinene, α-tocopherol, butylated hydroxytoluene, 4-methoxyphenol, benzene-1,4-diol, at least one dye, and at least one lubricant.

[0011] The present invention provides a solution to these needs by adding at least one inhibitor to a composition comprising at least one hydrofluoroolefin, at least one dye, and optionally at least one lubricant, improving the hydrofluoroolefin-containing composition to withstand abnormal conditions and also resolving potential problems associated with initiators (e.g., contaminants) that cause the fluoroolefin (e.g., tetrafluoropropene) to oligomerize or homopolymerize. "Inhibitor" is meant to refer to at least one compound according to the present invention that reduces, if not eliminates, the conversion of hydrofluoroolefin to oligomers or polymers. Although the oligomerization or homopolymerization reaction can be accelerated by relatively high temperatures, such reactions can also occur under ambient conditions depending on the concentration and type of initiator (e.g., contaminant). The inhibitor can function as a radical inhibitor without affecting the refrigeration performance of the composition or its compatibility with refrigerant oils and components. The stabilized composition can be useful in cooling systems and as a replacement for existing refrigerants with higher global warming potential.

[0012] To avoid possible instability of fluoroolefins, the addition of certain inhibitor compounds, i.e., hydrocarbons including at least one of cyclic monoterpenes; lipophilic organic compounds including tocopherols such as α-tocopherol; phenols; and aromatic organic compounds having at least one chemical moiety CH(OH), including benzene-1,4-diol, to fluoroolefin-containing compositions increases the stability during packaging, storage, and use in refrigeration or air conditioning system applications. Specific examples of inhibitor compounds include at least one member selected from the group consisting of limomen, α-terpinene, α-tocopherol, butylated hydroxytoluene, 4-methoxyphenol, and benzene-1,4-diol. In one embodiment of the invention, the inhibitor composition of the invention comprises a liquid at a temperature of about -100 to about 220°C, greater than about -80°C, greater than about -70°C, greater than about -50°C, greater than about -40°C, up to about 160°C, up to about 140°C, up to about 120°C, from about -60°C to about 180°C, from about -50°C to about 130°C, and in some cases from about -20 to about 140°C.

[0013] In a specific embodiment, the present invention relates to a fluoroethylene and dye-containing composition comprising an inhibitor capable of interacting or reacting with O2 and fluoroolefin polyperoxides while inhibiting or eliminating the reaction of such compounds with fluoroethylene. Examples of such inhibitors include at least one of limonene, α-pinene, β-pinene, α-terpinene, β-terpinene, γ-terpinene, and δ-terpinene, and mixtures of two or more thereof. Limonene, α-terpinene, α-pinene, and β-pinene have the following structures:

[0014] [ka]

[0015] In one embodiment of the invention, the inhibitor comprises alpha-terpinene. Without being bound by theory or explanation, it is believed that the presence of conjugated double bonds in its structure allows alpha-terpinene to form aromatic rings upon oxidation.

[0016] In one embodiment of the present invention, limonene or alpha-terpinene, optionally containing antioxidants, has a unique fragrance even at a few ppm level. This pleasant odor can be utilized for refrigerant leak detection with refrigerants and blends based on hydrofluoroolefins (e.g., including at least one of 1234yf, 1234ze, and combinations thereof). This is particularly useful for early detection of refrigerant leaks in home or portable air conditioners, since professional electronic leak detectors are often not available everywhere. Furthermore, the dye present in the composition of the present invention can provide improved leak detection.

[0017] One embodiment of the present invention relates to a composition comprising: a. at least one fluoroolefin; b. an effective amount of at least one inhibitor comprising at least one of: a hydrocarbon including a cyclic monoterpene; a lipophilic organic compound including a tocopherol including α-tocopherol; a phenol; and an aromatic organic compound having the chemical formula CH(OH), including benzene-1,4-diol; c. at least one dye; d. at least one lubricant.

[0018] One embodiment of the present invention relates to any of the aforementioned compositions further comprising at least one antioxidant. While any suitable antioxidant can be used, examples of suitable antioxidants include at least one member selected from the group consisting of butylated hydroxytoluene, butylated hydroxyanisole, tertiary butylhydroquinone, gallates, 2-phenyl-2-propanol, 1-(2,4,5-trihydroxyphenyl)-1-butanone, bisphenolmethane derivatives, 2,2'-methylenebis(4-methyl-6-t-butylphenol), and combinations thereof, among others.

[0019] Another embodiment of the present invention relates to any of the aforementioned compositions further comprising at least one acid scavenger.

[0020] A specific embodiment relates to the use of the aforementioned antioxidants in any of the aforementioned compositions together with an inhibitor comprising at least one of limonene and alpha-terpinene.

[0021] Another embodiment of the present invention relates to a method for stabilizing a composition comprising at least one fluoroolefin, the method comprising adding to the composition comprising at least one fluoroolefin an effective amount of at least one inhibitor, the inhibitor being a hydrocarbon comprising at least one member selected from the group consisting of cyclic monoterpenes; lipophilic organic compounds including tocopherols, including α-tocopherol; phenols; aromatic organic compounds having the chemical formula CH(OH), including benzene-1,4-diol; and mixtures thereof.

[0022] Another embodiment of the present invention relates to a method for reducing oligomerization or homopolymerization of a composition comprising at least one fluoroolefin, the oligomerization or homopolymerization being caused by the presence of unintentional or undesirable contaminants present in at least one of the following: conduits, lines, and other systems used to handle the fluoroolefin-containing composition; packaging (containers); and refrigeration, air conditioning, or heat pumps, the method comprising adding an inhibitor comprising at least one hydrocarbon comprising at least one member selected from cyclic monoterpenes; lipophilic organic compounds including tocopherols, including α-tocopherol; phenols; aromatic organic compounds having the chemical formula CH(OH), including benzene-1,4-diol, and mixtures thereof, to at least one of the systems, containers, and compositions comprising at least one fluoroolefin.

[0023] In a further embodiment, the stabilized detectable composition disclosed herein is used as a working fluid in a working fluid heater (which may be an evaporator) that is heated by a second heat transfer medium to form a heated working fluid. The second heat transfer medium is a warm liquid, such as water, that is transferred from a low temperature heat source to the working fluid heater. The warm second heat transfer medium is cooled in the working fluid heater and either returned to a low temperature heat source or passed to a cooling object, such as a building. The heated working fluid is compressed in a compressor to produce a high pressure working fluid. The high pressure working fluid is then cooled in a working fluid cooler by a first heat transfer medium, which is a cooled liquid brought in from the vicinity of the object being heated (heat sink). In this method, the heat pump can also be used to heat domestic or drinking water or process streams. In this method, the heat pump can also be used to heat water for district heating. In another embodiment, the heat pump is a high temperature heat pump, thereby having a working fluid cooler temperature (eg, a condenser when used in a subcritical cycle) of greater than about 50°C.

[0024] Additionally, the stabilized detectable compositions disclosed herein may be useful in mobile air conditioning or heat pump systems in automobiles, trucks, rail cars, or other transportation systems. In particular, mobile heat pumps may be useful in hybrid or electric vehicles that do not include a combustion engine to generate heat.

[0025] In yet another embodiment, the heat pump is a high temperature heat pump, thereby having a working fluid cooler temperature (e.g., condenser) greater than about 75° C. In yet another embodiment, the heat pump is a high temperature heat pump, thereby having a working fluid cooler temperature (e.g., condenser) greater than about 100° C.

[0026] The compositions of the present invention may also be useful as heat transfer fluids or working fluids that may be used in heating and / or cooling modes where heating and cooling are required for cabin and battery management needs.

[0027] In certain embodiments of the invention, the heat pump system is a component of a hybrid electric vehicle (HEV), a mild hybrids electric vehicle (MHEV), a plug-in hybrids electric vehicle (PHEV), or an electric vehicle (EV), and the heat pump system contains the stabilized detectable fluoroolefin compositions disclosed herein.

[0028] In certain embodiments of the present invention, a heat pump system comprises any of the disclosed compositions, wherein the heat pump system is one of a HEV, a MHEV, a PHEV, or an EV heat pump system.

[0029] A further embodiment of the present invention relates to a fluoroolefin-containing composition in a container, wherein the fluoroolefin has a reduced likelihood of oligomerizing or homopolymerizing compared to a composition not including the inhibitor composition of the present invention.

[0030] One embodiment of the present invention relates to a composition comprising at least one fluoroolefin and an effective amount of at least one inhibitor, the composition being substantially free of oligomeric, homopolymeric, or other polymeric products derived from the fluoroolefin.

[0031] Another embodiment of the invention is directed to any of the preceding compositions, wherein the composition comprises less than about 0.03% by weight of oligomeric products, homopolymers, or other polymeric products.

[0032] Another embodiment of the invention relates to any of the aforementioned compositions, further comprising at least one member selected from the group consisting of air, oxygen, cumene hydroperoxide, fluoroolefin polyperoxide, peroxides, hydroperoxides, persulfates, percarbonates, perborates, and hydropersulfates.

[0033] Another embodiment of the invention relates to any of the aforementioned compositions, wherein the inhibitor comprises at least one member selected from the group consisting of limomen, alpha-terpinene, alpha-tocopherol, butylated hydroxytoluene, 4-methoxyphenol, and benzene-1,4-diol.

[0034] Another embodiment of the present invention is directed to any of the aforementioned compositions further comprising at least one lubricant.

[0035] Another embodiment of the invention relates to any of the aforementioned compositions, wherein the fluoroolefin comprises, consists essentially of, or comprises at least one member selected from the group consisting of HFO-1234yf and HFO-1234ze.

[0036] Another embodiment of the present invention is directed to any of the aforementioned compositions further comprising at least one component selected from the group consisting of HFC-32, HFC-125, HFC-134a, HFC-152a, HFC-227ea, and carbon dioxide.

[0037] Another embodiment of the invention is directed to any of the aforementioned compositions further comprising at least one component selected from the group consisting of HFC-134a, HFO-1243zf, HFO1225ye, HFO-1234ze, 3,3,3-trifluoro-1-propyne, HCFO-1233xf, HFC-244bb, and HFC-245cb.

[0038] Another embodiment of the invention is directed to any of the aforementioned compositions further comprising at least one component selected from the group consisting of HCC-40, HCFC-22, CFC-115, HCFC-124, HCFC-1122, and CFC-1113.

[0039] Another embodiment of the invention relates to any of the aforementioned compositions wherein the inhibitor is present in an amount of about 10 to about 3,000 ppm, or about 30 ppm to about 3,000 ppm, preferably less than 2,000 ppm, and most preferably less than 1,000 ppm.

[0040] Another embodiment of the invention relates to any of the aforementioned compositions further comprising at least one member selected from the group consisting of butylated hydroxytoluene, butylated hydroxyanisole, tertiary butylhydroquinone, gallate, 2-phenyl-2-propanol, 1-(2,4,5-trihydroxyphenyl)-1-butanone, phenol, bisphenolmethane derivatives, and 2,2'-methylenebis(4-methyl-6-t-butylphenol).

[0041] Another embodiment of the invention relates to any of the aforementioned compositions, wherein the inhibitor comprises at least one of limonene and alpha-terpinene.

[0042] Another embodiment of the invention relates to any of the aforementioned compositions, wherein the inhibitor comprises a liquid at temperatures from about -80°C to about 180°C, from about -70°C to about 150°C, from about -60°C, or from about -40°C to about 120°C, and all ranges therebetween.

[0043] Another embodiment of the present invention relates to any of the aforementioned compositions, optionally further comprising at least one antioxidant.

[0044] Another embodiment of the invention relates to any of the aforementioned compositions, further comprising at least one component selected from the group consisting of HFO-1225yeZ, HFO-1243zf, HFO-1234ze, HFC-236ea, HFC-245fa, and 3,3,3-trifluoropropyne.

[0045] Another embodiment of the invention relates to the aforementioned composition, wherein the at least one component comprises at least one of HFO-1234ze, HFO-1225yeZ, and 3,3,3-trifluoropropyne.

[0046] Another embodiment of the invention relates to any of the aforementioned compositions, wherein the composition is substantially free of at least one of ammonia and CF3I.

[0047] Another embodiment of the invention relates to any of the aforementioned compositions, wherein the composition consists essentially of HFO-1234yf and limonene, and contains no ammonia or CF3I.

[0048] Another embodiment of the invention relates to any of the aforementioned compositions, wherein the composition consists essentially of HFO-1234yf, 3,3,3-trifluoropropyne, and limonene.

[0049] Another embodiment of the present invention relates to any of the aforementioned compositions, wherein the composition has a Total Acid Number (TAN) of less than 3.

[0050] Another embodiment of the invention relates to any of the aforementioned compositions, wherein the composition has from about 100 to about 0.1 ppm of F-anions.

[0051] Another embodiment of the invention relates to any of the aforementioned compositions, wherein the dye comprises at least one compound that contains a fluorescein species.

[0052] Another embodiment of the invention relates to any of the aforementioned compositions, wherein the dye species comprises at least one compound selected from derivatives of 6-hydroxy-3H-xanthen-3-one.

[0053] Another embodiment of the invention relates to any of the aforementioned compositions, wherein the dye has a first absorbance peak at about 425 to about 433 nm and a second absorbance peak at about 292 to about 295 nm.

[0054] Another embodiment of the invention relates to any of the aforementioned compositions, wherein the amount of dye can range from about 30 to about 0.001% by weight.

[0055] One embodiment of the present invention relates to a method for reducing the formation of oligomers and homopolymers comprising contacting a composition comprising at least one fluoroolefin with an effective amount to reduce the formation of oligomers or homopolymers of at least one member selected from the group consisting of limomen, alpha-terpinene, alpha-tocopherol, butylated hydroxytoluene, 4-methoxyphenol, and benzene-1,4-diol.

[0056] Another embodiment of the invention relates to any of the aforementioned methods, wherein the composition is exposed to at least one member selected from the group consisting of air, oxygen, cumene hydroperoxide, and fluoroolefin polyperoxides, peroxides, hydroperoxides, persulfates, percarbonates, perborates, and hydropersulfates prior to the contacting.

[0057] Another embodiment of the invention relates to any of the aforementioned methods using any of the aforementioned compositions for heating or cooling.

[0058] Another embodiment of the invention is directed to a container containing a refrigerant comprising any of the aforementioned compositions.

[0059] Another embodiment of the present invention relates to any combination of the preceding embodiments, wherein the composition of the present invention comprises a UV dye, an inhibitor, a lubricant (e.g., PAG, POE, PVE), and 1234yf or a 1234yf blend.

[0060] Another embodiment of the present invention relates to any combination of the preceding embodiments, including a process of delivering UV dyes to a vehicle A / C system using a low GWP refrigerant or low GWP refrigerant blend of the present invention, further comprising at least one acid scavenger. In a specific embodiment, a compromised or damaged A / C or refrigeration system may also be experiencing additional acid generation. The compositions of the present invention can be used to introduce an acid scavenger to reduce the effects of such acid generation and to aid in leak detection.

[0061] Another embodiment of the invention relates to any combination of the preceding embodiments and includes a process of using the low GWP refrigerant or low GWP refrigerant blends of the invention to deliver a UV dye containing a polymer inhibitor to a vehicle A / C system. Another embodiment of the invention relates to any combination of the preceding embodiments and includes a process of using the low GWP refrigerant or low GWP refrigerant blends of the invention to deliver a performance enhancer to a vehicle A / C system. Another embodiment of the invention relates to any combination of the preceding embodiments and includes a process of using the low GWP refrigerant or low GWP refrigerant blends of the invention to deliver a flame suppressant to a vehicle A / C system.

[0062] Another embodiment of the present invention relates to servicing an A / C or refrigeration system by replacing at least a portion of the refrigerant in the system with the composition of the present invention. In one specific embodiment of the present invention, air may enter a leaking HFO-1234yf system, which in turn may cause low levels of polymer to form. Thus, the introduction of the composition of the present invention may not only reduce the formation of additional polymer, but may also aid in leak detection.

[0063] Another embodiment of the present invention relates to any combination of the above embodiments, in which the composition of the present invention is packaged in a container. In one embodiment, such a container includes a container disclosed in US Patent No. 10,131,486 or US Patent Application Publication No. 2015 / 0108176, the disclosures of which are incorporated herein by reference in their entirety, such as a housing having a body, a lower end with an inlet, an upper end with an outlet, and a throat between the lower end and the upper end; a lower end located within the housing and fixed to the housing body, a pin having a blunt depressor suitable for contacting a can having an upper portion with a valve located thereon, the lower end being capable of operating the valve of the can, and a flow portion between the upper end and the lower end of the pin located within the housing throat, allowing fluid to flow between the housing and the pin; a gasket located adjacent to the housing at or near the housing inlet and further located so as to be able to contact the can when the tap is attached to the can; and a tap outlet in fluid communication with the housing outlet at the upper end of the housing.

[0064] In one embodiment of the present invention, the stabilized detectable composition disclosed herein containing at least one homopolymerization inhibitor is packaged in a container suitable for charging or recharging a stationary or mobile air conditioning or heat pump system.

[0065] In another embodiment of the invention, the refrigerant composition used in the heat transfer system is removed or recovered and then recycled and subsequently reclaimed (i.e., removed of any impurities and returned to the required quality level).

[0066] Any of the embodiments of the present invention disclosed herein can be used alone or in combination with each other. Those skilled in the art will understand that different embodiments discussed herein can be combined to form part of the present invention. Also, those skilled in the art will understand that certain specific aspects of different embodiments discussed herein can be combined to form part of the present invention. [Brief description of the drawings]

[0067] [Figure 1] 1 depicts a partial cross-sectional view of an exemplary container containing a composition according to an embodiment of the present invention. [Diagram 2] 1 depicts an exemplary heat transfer system including or connected to a vessel containing a composition according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0068] The present invention provides a stabilized composition comprising at least one fluoroolefin, an effective amount of at least one inhibitor, at least one dye, typically at least one lubricant, and optionally at least one acid scavenger. By "stabilized" it is meant that the composition comprises an effective amount of at least one inhibitor compound that inhibits, but does not eliminate, the interaction of the fluoroolefin with another compound to form a dimer, oligomer, homopolymer, or polymer product. Examples of such compounds that may cause such interactions include air, oxygen, cumene hydroperoxide, and oxidizing agents such as fluoroolefin polyperoxides, peroxides, hydroperoxides, persulfates, percarbonates, perborates, and hydropersulfates, among other initiators. The initiator compounds may be present in an amount of about 10 to about 15,000 ppm, about 1,000 to about 10,000 ppm, and in some cases about 1,000 to about 3,000 ppm, and in some embodiments, 30 to 2,000 ppm, by weight. Such initiator compounds may be present as contaminants in at least one of conduits, lines, and other systems used to handle fluoroolefin-containing compositions; packaging (containers), and refrigeration, air conditioning, or heat pump systems. Without being bound by theory or explanation, it is believed that certain contaminants function as radical initiators, thereby causing fluoroolefins to oligomerize, homopolymerize, or form other polymeric products.

[0069] In one embodiment of the present invention, the composition of the present invention is substantially free of oligomeric and polymeric products (including, but not limited to, oligomers and homopolymers) derived from hydrofluoroolefins such as 2,3,3,3-tetrafluoropropene. By "substantially free," it is meant that the composition contains less than about 1% by weight, less than about 0.07% by weight, less than about 0.03% by weight, or in some cases about 0 ppm of such products as measured by IR or NMR.

[0070] In another embodiment of the present invention, the composition of the present invention comprises at least one member selected from the group consisting of phenols, phosphorus-containing compounds, thiophosphates, butylated triphenyl phosphorothioate, organic phosphates, or phosphites; sesquiterpene compounds, such as at least one member selected from the group consisting of farnesol and farnesene; ionic liquids, such as [CH3CO2] - , [HSO4] - , [CH3OSO3] - , [C2H5OSO3] - , [AlCl4] - , [CO3] 2- , [HCO3] - , [NO2] - , [NO3] - , [SO4] 2- , [PO4] 3- , [HPO4] 2- , [H2PO4] - , [HSO3], and a particular fluorinated anion, wherein the fluorinated anion is [BF4] - , PF6 - , [SbF6] - , [CF3SO3] - , [HCF2CF2SO3] - , [CF3HFCCF2SO3] - , [HCClFCF2SO3] - , [(CF3SO2)2N] - , [(CF3CF2SO2)2N] - , [(CF3SO2)3C] - , [CF3CO2] - , [CF3OCFHCF2SO3] - , [CF3CF2OCFHCF2SO3] - , [CF3CFHOCF2CF2SO3] - , [CF2HCF2OCF2CF2SO3] - , [CF2ICF2OCF2CF2SO3] - , [CF3CF2OCF2CF2SO3] - , [(CF2HCF2SO2)2N] -, [(CF3CFHCF2SO2)2N] - and mixtures thereof. By "substantially free," it is meant that the compositions of the present invention contain less than about 500 ppm, typically less than about 250 ppm, in some cases less than about 100 ppm, and in some cases about 0 ppm of such conventional inhibitors.

[0071] The present invention includes a composition comprising at least one stabilized fluoroolefin, at least one dye, and at least one lubricant, wherein the fluoroolefin, dye, and lubricant are miscible. By "miscible" it is meant that the dye is solubilized in the lubricant and refrigerant containing the inhibitor. Miscibility can be measured by visual detection according to ASHRAE 218. In one embodiment, miscibility is determined using ASHRAE 218 at temperatures ranging from about -65°C to about 90°C.

[0072] The present invention further includes the aforementioned compositions, wherein the composition is stable. By "stable" it is meant that the composition contains less than 100 ppm of F-anions and has a total acid number (TAN) of less than 3. For example, the composition can have about 10 to about 0.1 ppm, about 5 to about 0.05 ppm, and in some cases about 3 to about 0.01 ppm of F-anions, and a TAN in the range of about 3 to about 0.1 mg / KOH / g, about 2.5 to about 0.05 mg / KOH / g, and in some cases about 2 to about 0.01 mg / KOH / g.

[0073] The compositions of the invention have a variety of utilities including, inter alia, blowing agents, solvents, aerosol propellants, sterilants, or working fluids including heat transfer media, such as heat transfer fluids and refrigerants for use in refrigeration systems, refrigerators, air conditioning systems, heat pumps, chillers, etc. The compounds of the invention are particularly suitable for use in portable air conditioning systems and as components for making refrigerant blends for use in stationary heat transfer systems.

[0074] A blowing agent is a volatile composition that causes a polymer matrix to expand and form a cellular structure.

[0075] A solvent is a fluid that removes dirt from a substrate or deposits material onto a substrate or carries material.

[0076] An aerosol propellant is a volatile composition of one or more components that exerts a pressure greater than one atmosphere to expel the material from a container.

[0077] The sterilant is a volatile germicidal fluid or blend that contains a volatile germicidal fluid that destroys biologically active materials and the like.

[0078] A heat transfer medium (also referred to herein as a heat transfer fluid, heat transfer composition, or heat transfer fluid composition) is a working fluid used to transport heat from a heat source to a heat sink.

[0079] The compositions according to the present invention can be used as power cycle working fluids for use in Organic Rankine Cycle (ORC) systems for the efficient conversion of heat from various sources into mechanical energy, such as that disclosed in U.S. Pat. No. 8,961,811, the disclosure of which is incorporated herein by reference in its entirety.

[0080] A refrigerant is a compound or mixture of compounds that acts as a heat transfer fluid in a cycle in which the fluid changes phase from a liquid to a gas and back again.

[0081] As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," or any other variation thereof, are intended to cover non-exclusive inclusions. For example, a composition, process, method, article, or device that includes recited elements is not necessarily limited to only those elements, but may include other elements not expressly recited or inherent in such composition, process, method, article, device, etc. Furthermore, unless expressly stated to the contrary, "or" refers to an inclusive "or," not an exclusive "or." For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or absent), A is false (or absent) and B is true (or present), and both A and B are true (or present).

[0082] The transitional phrase "consisting of" excludes any element, step, or ingredient not specified. In the claims, such phrases limit the claims to include materials other than those recited, except for impurities normally accompanying the materials. When the phrase "consisting of" appears within a clause in the body of a claim rather than immediately following the preamble, the phrase limits only the elements set forth in that clause and does not exclude other elements from the claim as a whole.

[0083] The transitional phrase "consisting essentially of" is used to define compositions, methods, and methods that include materials, steps, features, ingredients, or elements in addition to those literally disclosed, provided that these additionally included materials, steps, features, ingredients, or elements have a substantial effect on the basic and novel characteristics of the claimed invention, particularly the mode of action for achieving any desired result of the inventive process. The term "consisting essentially of" has a meaning intermediate between "comprising" and "consisting of."

[0084] It should be readily understood that where applicants have defined an invention or a portion thereof with open-ended terms such as "comprising," the description should be construed to also include inventions using the terms "consisting essentially of" or "consisting of" (unless otherwise expressly stated).

[0085] Additionally, the use of "a" or "an" is used to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be interpreted to include one or at least one, and the singular also includes the plural unless it is clear that a different meaning is intended.

[0086] As used herein, the term fluoroolefin describes a compound that contains carbon atoms, fluorine atoms, and optionally hydrogen atoms. In one embodiment, the fluoroolefins used in the compositions of the present invention include compounds having 2 to 12 carbon atoms. In another embodiment, the fluoroolefins include compounds having 3 to 10 carbon atoms, and in yet another embodiment, the fluoroolefins include compounds having 3 to 7 carbon atoms. Representative fluoroolefins include, but are not limited to, all of the compounds listed in Table 1, Table 2, and Table 3.

[0087] One embodiment of the present invention is a compound of formula E- or ZR 1 CH=CHR 2 (I), wherein R 1 and R 2 R is independently a C1 to C6 perfluoroalkyl group. 1 and R 2 Examples of groups include CF, C2F 5、Examples of fluoroolefins include, but are not limited to, CF2CF2CF3, CF(CF3)2, CF2CF2CF2CF3, CF(CF3)CF2CF3, CF2CF(CF3)2, C(CF3)3, CF2CF2CF2CF2CF3, CF2CF2CF(CF3)2, C(CF3)2C2F5, CF2CF2CF2CF2CF2CF3, CF(CF3)CF2CF2C2F5, and C(CF3)2CF2C2F5. In one embodiment, the fluoroolefin of formula I has at least about 4 carbon atoms in the molecule. In another embodiment, the fluoroolefin of formula I has at least about 5 carbon atoms in the molecule. Exemplary non-limiting compounds of formula I are provided in Table 1.

[0088] [Table 1-1]

[0089] [Table 1-2]

[0090] Compounds of formula I have the formula R 1 I is a perfluoroalkyl iodide of formula R 2 by contacting with a perfluoroalkyltrihydroolefin of formula R 1 CH2CHIR 2 This trihydroiodoperfluoroalkane can then be dehydroiodinated to give R 1 CH=CHR 2 Alternatively, the olefin R 1 CH=CHR 2 is the formula R 2 I is a perfluoroalkyl iodide of formula R 1 with a perfluoroalkyltrihydroolefin of formula R 1 CHICH2R 2can be prepared by dehydroiodination of trihydroiodoperfluoroalkanes of formula (I).

[0091] The contacting of the perfluoroalkyl iodide with the perfluoroalkyl trihydroolefin may be carried out in a batch mode by combining the reactants in a suitable reaction vessel capable of operating at the reaction temperature and under the autogenous pressure of the reactants and products. Suitable reaction vessels include vessels made of stainless steel (particularly austenitic) and well-known high nickel alloys, such as Monel® nickel-copper alloy, Hastelloy® nickel-based alloy, and Inconel® nickel-chromium alloy.

[0092] Alternatively, the reaction may be carried out in a semi-batch mode in which the perfluoroalkyltrihydroolefin reactant is added to the perfluoroalkyliodide reactant by a suitable addition device, such as a pump, at the reaction temperature.

[0093] The ratio of perfluoroalkyl iodide to perfluoroalkyl trihydroolefin should be about 1:1 to about 4:1, preferably about 1.5:1 to 2.5:1. Ratios less than 1.5:1 tend to produce large amounts of the 2:1 adduct, as reported by Jeanneaux, et.al., Journal of Fluorine Chemistry, Vol. 4, pp. 261-270 (1974).

[0094] The preferred temperature for contacting the perfluoroalkyl iodide with the perfluoroalkyltrihydroolefin is preferably within the range of about 150° C. to 300° C., preferably about 170° C. to about 250° C., and most preferably about 180° C. to about 230° C. The preferred contact time for the reaction of the perfluoroalkyl iodide with the perfluoroalkyltrihydroolefin is about 0.5 hours to 18 hours, preferably about 4 to about 12 hours.

[0095] The trihydroiodoperfluoroalkane prepared by the reaction of the perfluoroalkyl iodide with the perfluoroalkyltrihydroolefin may be used directly in the dehydroiodination step or, preferably, may be recovered and purified by distillation prior to the dehydroiodination step.

[0096] The dehydroiodination step is carried out by contacting the trihydroiodoperfluoroalkane with a basic substance. Suitable basic substances include alkali metal hydroxides (e.g., sodium hydroxide or potassium hydroxide), alkali metal oxides (e.g., sodium oxide), alkaline earth metal hydroxides (e.g., calcium hydroxide), alkaline earth metal oxides (e.g., calcium oxide), alkali metal alkoxides (e.g., sodium methoxide or sodium ethoxide), aqueous ammonia, sodium amide, or a mixture of basic substances such as soda lime. Preferred basic substances are sodium hydroxide and potassium hydroxide. The contact of the trihydroiodoperfluoroalkane with a basic substance may be carried out in liquid phase, preferably in the presence of a solvent capable of dissolving at least a portion of both reactants. Suitable solvents for the dehydroiodination step include one or more polar organic solvents such as alcohols (e.g., methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and tertiary butanol), nitriles (e.g., acetonitrile, propionitrile, butyronitrile, benzonitrile, or adiponitrile), dimethylsulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, or sulfolane. The choice of solvent may depend on the boiling point of the product and the ease of separating traces of solvent from the product during purification. Typically, ethanol or isopropanol are good solvents for this reaction.

[0097] Typically, the dehydroiodination reaction can be carried out by adding one of the reactants (either the basic material or the trihydroiodoperfluoroalkane) to the other reactant in a suitable reaction vessel, which may be constructed from glass, ceramic, or metal, and is preferably agitated with an impeller or stirring mechanism.

[0098] Suitable temperatures for the dehydroiodination reaction are from about 10° C. to about 100° C., preferably from about 20° C. to about 70° C. The dehydroiodination reaction may be carried out at ambient pressure or at reduced or elevated pressure. Of note in the dehydroiodination reaction is that the compound of formula I distills from the reaction vessel as it is formed.

[0099] Alternatively, the dehydroiodination reaction may be carried out by contacting an aqueous solution of the basic material with a solution of the trihydroiodoperfluoroalkane in the presence of a phase transfer catalyst in one or more less polar organic solvents such as an alkane (e.g., hexane, heptane, or octane), an aromatic hydrocarbon (e.g., toluene), a halogenated hydrocarbon (e.g., methylene chloride, chloroform, carbon tetrachloride, or perchloroethylene), or an ether (e.g., diethyl ether, methyl tert-butyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, dimethoxyethane, diglyme, or tetraglyme). Suitable phase transfer catalysts include quaternary ammonium halides (e.g., tetrabutylammonium bromide, tetrabutylammonium hydrosulfate, triethylbenzylammonium chloride, dodecyltrimethylammonium chloride, and tricaprylyl ammonium chloride), quaternary phosphonium halides (e.g., triphenylmethylphosphonium bromide and tetraphenylphosphonium chloride), or cyclic polyether compounds known in the art as crown ethers (e.g., 18-crown-6 and 15-crown-5).

[0100] Alternatively, the dehydroiodination reaction may be carried out in the absence of a solvent by adding the trihydroiodoperfluoroalkane to a solid or liquid basic substance.

[0101] Suitable reaction times for the dehydroiodination reaction are from about 15 minutes to about 6 hours, or more, depending on the solubility of the reactants. Typically, the dehydroiodination reaction is rapid, requiring from about 30 minutes to about 3 hours for completion.

[0102] The compound of formula I can be recovered from the dehydroiodination reaction mixture by phase separation after addition of water, by distillation, or by a combination of these.

[0103] In another embodiment of the present invention, the fluoroolefin is a cyclic fluoroolefin (cyclo-[CX=CY(CZW) n -] (Formula II), where X, Y, Z, and W are independently selected from H and F, and n is an integer from 2 to 5. In one embodiment, the fluoroolefin of Formula II has at least about 3 carbon atoms in the molecule. In another embodiment, the fluoroolefin of Formula II has at least about 4 carbon atoms in the molecule. In yet another embodiment, the fluoroolefin of Formula II has at least about 5 carbon atoms in the molecule. Representative cyclic fluoroolefins of Formula II are listed in Table 2.

[0104] [Table 2]

[0105] The compositions of the invention may include a single compound of formula I or formula II, such as one of the compounds in Table 1 or Table 2, or may include a combination of compounds of formula I or formula II.

[0106] In another embodiment, the fluoroolefin may include the compounds listed in Table 3.

[0107] [Table 3-1]

[0108] [Table 3-2]

[0109] [Table 3-3]

[0110] [Table 3-4]

[0111] In one embodiment, the composition may include a combination of one or more compounds of Table 1, Table 2, and / or Table 3.

[0112] The compounds listed in Tables 1, 2, and 3 are either commercially available or can be prepared by processes known in the art or as described herein.

[0113] 1,1,1,4,4-Pentafluoro-2-butene can be prepared from 1,1,1,2,4,4-hexafluorobutane (CHF2CH2CHFCF3) by dehydrofluorination with solid KOH in the vapor phase at room temperature. The synthesis of 1,1,1,2,4,4-hexafluorobutane is described in U.S. Patent No. 6,066,768, the entire disclosure of which is incorporated herein by reference.

[0114] 1,1,1,4,4,4-Hexafluoro-2-butene can be prepared from 1,1,1,4,4,4-hexafluoro-2-iodobutane (CF3CHICH2CF3) by reaction with KOH using a phase transfer catalyst at about 60° C. The synthesis of 1,1,1,4,4,4-hexafluoro-2-iodobutane can be carried out by reaction of perfluoromethyl iodide (CF3I) with 3,3,3-trifluoropropene (CF3CH=CH2) at about 200° C. under autogenous pressure for about 8 hours.

[0115] 3,4,4,5,5,5-Hexafluoro-2-pentene can be prepared by dehydrofluorination of 1,1,1,2,2,3,3-heptafluoropentane (CF3CF2CF2CH2CH3) using solid KOH or over a carbon catalyst at about 200° C. to 300° C. 1,1,1,2,2,3,3-heptafluoropentane can be prepared by hydrogenation of 3,3,4,4,5,5,5-heptafluoro-1-pentene (CF3CF2CF2CH=CH2).

[0116] 1,1,1,2,3,4-Hexafluoro-2-butene can be prepared by dehydrofluorination of 1,1,1,2,3,3,4-heptafluorobutane (CH2FCF2CHFCF3) using solid KOH.

[0117] 1,1,1,2,4,4-Hexafluoro-2-butene can be prepared by dehydrofluorination of 1,1,1,2,2,4,4-heptafluorobutane (CHF2CH2CF2CF3) using solid KOH.

[0118] 1,1,1,3,4,4-Hexafluoro-2-butene can be prepared by dehydrofluorination of 1,1,1,3,3,4,4-heptafluorobutane (CF3CH2CF2CHF2) using solid KOH.

[0119] 1,1,1,2,4-Pentafluoro-2-butene can be prepared by dehydrofluorination of 1,1,1,2,2,3-hexafluorobutane (CH2FCH2CF2CF3) using solid KOH.

[0120] 1,1,1,3,4-Pentafluoro-2-butene can be prepared by dehydrofluorination of 1,1,1,3,3,4-hexafluorobutane (CF3CH2CF2CH2F) using solid KOH.

[0121] 1,1,1,3-Tetrafluoro-2-butene can be prepared by reacting 1,1,1,3,3-pentafluorobutane (CF3CH2CF2CH3) with aqueous KOH at about 120°C.

[0122] 1,1,1,4,4,5,5,5-Octafluoro-2-pentene can be prepared from (CF3CHICH2CF2CF3) by reaction with KOH using a phase transfer catalyst at about 60° C. The synthesis of 4-iodo-1,1,1,2,2,5,5,5-octafluoropentane can be carried out by reaction of perfluoroethyl iodide (CF3CF2I) with 3,3,3-trifluoropropene at about 200° C. under autogenous pressure for about 8 hours.

[0123] 1,1,1,2,2,5,5,6,6,6-Decafluoro-3-hexene can be prepared from 1,1,1,2,2,5,5,6,6,6-decafluoro-3-iodohexane (CF3CF2CHICH2CF2CF3) by reaction with KOH using a phase transfer catalyst at about 60° C. The synthesis of 1,1,1,2,2,5,5,6,6,6-decafluoro-3-iodohexane can be carried out by reaction of perfluoroethyl iodide (CF3CF2I) with 3,3,4,4,4-pentafluoro-1-butene (CF3CF2CH=CH2) at about 200° C. under autogenous pressure for about 8 hours.

[0124] 1,1,1,4,5,5,5-Heptafluoro-4-(trifluoromethyl)-2-pentene can be prepared by dehydrofluorination of 1,1,1,2,5,5,5-heptafluoro-4-iodo-2-(trifluoromethyl)-pentane (CF3CHICH2CF(CF3)2) with KOH in isopropanol. CF3CHICH2CF(CF3)2 is made from the reaction of (CF3)2CFI with CF3CH=CH2 at elevated temperatures, such as about 200°C.

[0125] 1,1,1,4,4,5,5,6,6,6-Decafluoro-2-hexene can be prepared by the reaction of 1,1,1,4,4,4-hexafluoro-2-butene (CF3CH=CHCF3) with tetrafluoroethylene (CF2=CF2) and antimony pentafluoride (SbF5).

[0126] 2,3,3,4,4-Pentafluoro-1-butene can be prepared by dehydrofluorination of 1,1,2,2,3,3-hexafluorobutane with fluorinated alumina at elevated temperatures.

[0127] 2,3,3,4,4,5,5,5-Octafluoro-1-pentene can be prepared by dehydrofluorination of 2,2,3,3,4,4,5,5,5-nonafluoropentane with solid KOH.

[0128] 1,2,3,3,4,4,5,5-Octafluoro-1-pentene can be prepared by dehydrofluorination of 2,2,3,3,4,4,5,5,5-nonafluoropentane with fluorinated alumina at elevated temperatures.

[0129] 2,3,3,3-tetrafluoro-1-propene can be prepared by converting at least one of HCFC-244bb or HFC-245eb to HFO-1234yf.

[0130] 1,3,3,3-Tetrafluoro-1-propene can be prepared by converting HFC-245fa to HFO-1234ze.

[0131] Many of the compounds of Formula I, Formula II, Table 1, Table 2, and Table 3 exist as different configurational isomers or stereoisomers. If no particular isomer is specified, the present invention is intended to include all single configurational isomers, single stereoisomers, or any combination thereof. For example, F11E is meant to represent the E isomer, the Z isomer, or any combination or mixture of both isomers in any ratio. As another example, HFO-1225ye is meant to represent the E isomer, the Z isomer, or any combination or mixture of both isomers in any ratio.

[0132] In one specific embodiment, the fluoroolefin component of the compositions of the invention comprises HFO-1234yf and / or HFO-1234ze. In another specific embodiment, the fluoroolefin comprises HFO-1234yf and / or HFO-1234ze having a purity of greater than 99% by weight, greater than 99.5% by weight, and in some cases greater than 99.5 to 99.98 percent. In another specific embodiment, the fluoroolefin comprises at least 99.5% by weight of 1234yf or 1234ze and less than 0.5 and greater than 0.0001%, less than 0.3%, and in some cases less than 0.2% by weight of other fluoroolefins.

[0133] In another specific embodiment, the fluoroolefin component may include compositions disclosed in US Pat. Nos. 8,147,709 and 8,877,086, the disclosures of which are incorporated herein by reference in their entireties.

[0134] In another specific embodiment, the fluoroolefin component comprises greater than about 99.5 wt% HFO-1234yf and one or more members selected from the group consisting of HFO-1225ye, HFO-1243zf, HFO-1234ze, HFC-236ea, HFC-244bb, HFC-245fa, HFC-245eb, HFC-245cb, 3,3,3-trifluoropropyne, and mixtures thereof. The amount of HFO-1225ye (E / Z isomer) can range from greater than 0 to about 200 ppm by weight, from about 1 to about 150 ppm by weight, and in some cases from about 5 to about 50 ppm by weight. The amount of HFO-1243zf can range from about 0.1 to about 250 ppm, from about 10 to about 200 ppm, and in some cases from about 15 to about 150 ppm by weight. The amount of HFO-1234ze (E isomer) may range from about 1 to about 1,500 ppm, about 5 to about 1,000 ppm, and in some cases about 50 to 500 ppm. The amount of HFC-236ea may range from about 1 to about 50 ppm, about 5 to about 25, and in some cases about 10 to about 20 ppm. The amount of HFC-245fa, HFC-245eb, and / or HFC-245cb may range from about 0 to about 20, about 1 to about 15, and in some cases about 5 to about 10 ppm. The amount of 3,3,3-trifluoropropyne may range from about 0 to about 500 ppm, about 1 to about 300 ppm, and in some cases about 5 to about 100 ppm.

[0135] In another embodiment, the fluoroolefin component comprises HFO-1234yf and at least one additional compound selected from the group consisting of 1114, 1123, 1131a, 1131trans, 1132, 1123, 1140, 1214ya, 1216, 1224yd, 1225ye(E), 1233zd(E), 1234ze(E), 1252, 143a, 225, 245eb, 254eb, 263fb, CFCFI, 236fa, 142b, 244cc, 1223, 1132a, 2316, 1327 isomers, 1336mzzE, 1336 isomers, 1234zeZ, and 1224 isomers. In one specific embodiment, the fluoroolefin component includes HFO-1234yf and greater than 0 and less than about 1 wt %, less than about 0.5 wt %, and in some cases less than 0.25 wt % of additional compounds.

[0136] In further embodiments, the inhibitors of the present invention can be used with compositions of at least one of HCFO-1233zd and HCFO-1224yd, and blends comprising at least one of HCFO-1233zd and HCFO-1224yd.

[0137] Any suitable effective amount of inhibitor can be used in the aforementioned composition comprising at least one fluoroolefin. As described herein, the phrase "effective amount" refers to an amount of the inhibitor of the present invention that, when added to a composition comprising at least one fluoroolefin, results in a composition in which the fluoroolefin does not interact with the initiator and / or degrade, e.g., does not significantly reduce performance when used in a cooling device, compared to a composition without an inhibitor. In the case of a cooling device, such an effective amount of inhibitor can be determined by testing under the conditions of standard test ASHRAE 97-2007 (RA 2017). In certain embodiments of the invention, an effective amount is an amount of inhibitor that, when combined with a composition comprising at least one fluoroolefin, reduces the amount of 1,1,1,2-tetrafluoroethane (R-134a) or other standard refrigerants (R-12, R-22, R-502, R-507A, R-508, R401A, R401B, R402A, R402B, R408, R-410A, R-510B, R-510C, R-510D, R-510E, R-510F, R-510G, R-510H, R-510I, R-510H ... In one embodiment, the present invention relates to a refrigeration equipment that utilizes a composition comprising at least one fluoroolefin (R-404A, R-407C, R-413A, R-417A, R-422A, R-422B, R-422C, R-422D, R-423, R-114, R-11, R-113, R-123, R-124, R236fa, or R-245fa) as a working fluid.

[0138] The present invention employs an effective amount of at least one of the aforementioned inhibitors. While any suitable effective amount can be used, the effective amount of at least one inhibitor comprises from about 0.001 weight percent to about 10 weight percent, from about 0.01 weight percent to about 5 weight percent, from about 0.3 weight percent to about 4 weight percent, from about 0.3 weight percent to about 1 weight percent based on the total weight of the composition comprising at least one fluoroolefin described herein. In one embodiment, the effective amount comprises from about 1 to about 3,000 weight ppm, or from about 1 to about 2,000 weight ppm, or from about 10 to about 3,000 weight ppm, or from about 10 to about 2,000 weight ppm, or from about 30 ppm to about 3,000 weight ppm, or from about 30 ppm to about 2,000 weight ppm, or from about 5 to about 1,000 ppm, and in some cases from about 10 to about 500 ppm of at least one inhibitor based on the total weight of the composition. The amount of inhibitor in the overall composition can be reduced if the additional components added to the 1234yf blend do not contain inhibitors.

[0139] While any compatible dye can be included in the compositions of the present invention, examples of compatible dyes include at least one compound containing a fluorescein species selected from derivatives of 6-hydroxy-3H-xanthen-3-one and having an absorbance peak at about 425 to about 433 nm, another absorbance peak at about 292 to about 295 nm, and optionally a third absorbance peak at about 243 to about 250 nm. The absorbance peaks were measured using UV-Vis. Compatible dyes can also be characterized using (FTIR) and have an absorbance peak at about 700 to about 800 cm. -1 , about 1000~1100cm -1 , about 1200~1300cm -1 , and about 1400 to about 1600 cm -1The amount of dye may range from about 30 to about 0.001% by weight, from about 20 to about 0.001% by weight, and in some cases from about 5 to about 0.001% by weight, based on the total weight of the composition. The dye, lubricant, fluoroolefin, and inhibitor, among other components of the composition of the present invention, may be combined in any suitable order. For example, the dye is solubilized in the lubricant, followed by the addition of the HFO-1234yf-containing inhibitor. The dye is solubilized in the lubricant containing the inhibitor, followed by the addition of the HFO-1234yf.

[0140] In one embodiment, a solubilizing agent may be included. Solubilizing agents for use in the present invention include, but are not limited to, those disclosed in US Patent Publication No. 20070138433, the disclosure of which is incorporated herein by reference in its entirety. These agents enhance the solubility of the UV dye in the refrigerant and are suitable for "ultraviolet" dyes that absorb light in the ultraviolet or "near" ultraviolet region of the electromagnetic spectrum. Under irradiation with UV light that emits radiation having a wavelength in the range of 10 nanometers to about 750 nanometers, the fluorescence produced by the UV fluorescent dye can be visually detected. Thus, if a refrigerant containing such a UV fluorescent dye is leaking from a given point in a refrigeration or air conditioning device, the fluorescence will be visible at the leak point when illuminated with light of the appropriate wavelength. Such UV fluorescent dyes include, but are not limited to, naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, and derivatives or mixtures thereof. UV dyes for leak detection include perylene and naphthalimide. Perylene fluoresces a bright yellow color when illuminated with a long wave ultraviolet lamp. Naphthalimide fluoresces a bright green color when exposed to UV and blue light.

[0141] The solubilizers of the present invention include compounds selected from the group consisting of hydrocarbons, dimethyl ethers, polyoxyalkylene glycol ethers, amides, ketones, nitriles, chlorocarbons, esters, lactones, aryl ethers, fluoroethers, 1,1,1-trifluoroalkanes, and mixtures thereof. In any of the embodiments disclosed herein, the solubilizer may be present in an amount of about 1 ppm to about 2%, based on the total weight of the composition.

[0142] In one embodiment, the aforementioned compositions of the present invention may further comprise at least one lubricant. Lubricants of the present invention include those suitable for use with refrigeration or air conditioning equipment. Among these lubricants are those conventionally used in compression refrigeration equipment utilizing chlorofluorocarbon refrigerants. Such lubricants and their properties are discussed in the 1990 ASHRAE Handbook, Refrigeration Systems and Applications, Chapter 8, entitled "Lubricants in Refrigeration Systems", pages 8.1-8.21, which is incorporated herein by reference. Lubricants of the present invention may include those commonly known in the field of compression refrigeration lubrication as "mineral oils". Mineral oils include paraffins (i.e., saturated hydrocarbons of straight and branched carbon chains), naphthenes (i.e., cyclic or ring structured saturated hydrocarbons that may be paraffins), and aromatics (i.e., unsaturated cyclic hydrocarbons containing one or more rings characterized by alternating double bonds). Lubricants of the present invention further include those commonly known in the field of compression refrigeration lubrication as "synthetic oils". Synthetic oils include alkylaryls (i.e., linear and branched alkyl alkylbenzenes), synthetic paraffins and naphthenes, silicones, and poly-alpha-olefins. Representative conventional lubricants of the present invention are commercially available BVM 100 N (paraffinic mineral oil sold by BVA Oils), naphthenic mineral oils sold by Crompton Co. under the trade names Suniso® 3GS and Suniso® 5GS, naphthenic mineral oils sold by Pennzoil under the trade name Sontex® 372LT, naphthenic mineral oils sold by Calumet Lubricants under the trade name Calumet® RO-30, linear alkyl benzenes sold by Shrieve Chemicals under the trade names Zerol® 75, Zerol® 150, and Zerol® 500, and branched alkyl benzenes sold by Nippon Oil under the trade name HAB 22.

[0143] In another embodiment, the lubricants of the present invention include those designed for use with hydrofluorocarbon refrigerants and miscible with the refrigerants of the present invention under the operating conditions of compression refrigeration and air conditioning equipment. Such lubricants and their properties are discussed in "Synthetic Lubricants and High-Performance Fluids", edited by RLShubkin and Marcel Dekker, 1993. Such lubricants include, but are not limited to, polyol esters (POE), such as Castrol® 100 (Castrol, United Kingdom), polyalkylene glycols (PAG), such as RL-488A manufactured by Dow (Dow Chemical, Midland, Michigan), and polyvinyl ethers (PVE).

[0144] The lubricant of the present invention is selected by considering the requirements of a given compressor and the environment to which the lubricant will be exposed. The amount of lubricant may range from about 0.1 to about 50% by weight, from about 0.1 to about 20% by weight, and in some cases from about 0.1 to about 3% by weight. In one specific embodiment, the aforementioned composition is combined with a PAG lubricant for use in an A / C system for a vehicle having an internal combustion engine. In another specific embodiment, the aforementioned composition is combined with a POE lubricant for use in an A / C system for a vehicle having an electric or hybrid electric drivetrain. In any of the embodiments disclosed herein, the amount of lubricant may range from about 0.1 to about 50% by weight, from about 0.1 to about 20% by weight, and in some cases from about 0.1 to about 3% by weight.

[0145] One embodiment of the present invention relates to any of the aforementioned compositions further comprising at least one antioxidant. While any suitable antioxidant can be used, examples of suitable antioxidants include at least one member selected from the group consisting of butylated hydroxytoluene, butylated hydroxyanisole, tertiary butylhydroquinone, gallate, 2-phenyl-2-propanol, 1-(2,4,5-trihydroxyphenyl)-1-butanone, phenol, bisphenolmethane derivatives, 2,2'-methylenebis(4-methyl-6-t-butylphenol), and combinations thereof. The amount of antioxidant can range from about 0.01 to about 5,000 ppm, about 0.03 to about 2,000 ppm, and in some cases from about 0.05 to about 1,000 ppm by weight. A specific example embodiment relates to the use of any of the aforementioned antioxidants with at least one inhibitor comprising alpha-terpinene and limonene. One specific embodiment example relates to the use of any of the aforementioned antioxidants together with an inhibitor comprising at least one of alpha-terpinene and limonene.

[0146] In one embodiment, the aforementioned composition of the present invention may further comprise at least one acid scavenger. An example of an acid scavenger comprises at least one member selected from the group consisting of epoxides and hindered amines. The amount of the acid scavenger may range from about 0.005 to about 3% by weight based on the total weight of the composition. For example, the amount of the acid scavenger may be adjusted to interact with a higher TAN number.

[0147] In one embodiment, the aforementioned compositions of the present invention may further comprise at least one additional compound selected from the group consisting of fluoroolefins (as previously described herein), hydrofluorocarbons, hydrocarbons, dimethyl ether, CF3I, ammonia, carbon dioxide (CO2), and mixtures thereof, i.e., mixtures of any of the additional compounds listed in this paragraph. The amount of the additional compound may range from about 1 to about 90% by weight, from about 5 to about 75% by weight, and in some cases from about 10 to about 50% by weight, based on the total weight of the composition.

[0148] In one embodiment, the additional compound comprises a hydrofluorocarbon. The hydrofluorocarbon (HFC) compounds of the present invention include saturated compounds containing carbon, hydrogen, and fluorine. Particularly useful are hydrofluorocarbons having 1 to 7 carbon atoms and normal boiling points of about -90°C to about 80°C. Hydrofluorocarbons are commercially available from a number of sources or can be prepared by methods known in the art. Representative hydrofluorocarbon compounds include fluoromethane (CH3F, HFC-41), difluoromethane (CH2F2, HFC-32), trifluoromethane (CHF3, HFC-23), pentafluoroethane (CF3CHF2, HFC-125), 1,1,2,2-tetrafluoroethane (CHF2CHF2, HFC-134), 1,1,1,2-tetrafluoroethane (CF3CH2F, HFC- 134a), 1,1,1-trifluoroethane (CF3CH3, HFC-143a), 1,1-difluoroethane (CHF2CH3, HFC-152a), fluoroethane (CH3CH2F, HFC-161), 1,1,1,2,2,3,3-heptafluoropropane (CF3CF2CHF2, HFC-227ca), 1,1,1,2,3,3,3-heptafluoropropane (CF3CHFCF3, HFC-227e a), 1,1,2,2,3,3,-Hexafluoropropane (CHF2CF2CHF2, HFC-236ca), 1,1,1,2,2,3-Hexafluoropropane (CF3CF3CH2F, HFC-236cb), 1,1,1,2,3,3-Hexafluoropropane (CF3CHFCHF2, HFC-236ea), 1,1,1,3,3,3-Hexafluoropropane (CF3CH2CF3, HFC-236fa ), 1,1,2,2,3-pentafluoropropane (CHF2CF2CH2F, HFC-245ca), 1,1,1,2,2-pentafluoropropane (CF3CF2CH3, HFC-245cb), 1,1,2,3,3-pentafluoropropane (CHF2CHFCHF2, HFC-245ea), 1,1,1,2,3-pentafluoropropane (CF3CHFCH2F, HFC-245eb), 1,1,1,3,3-Pentafluoropropane (CF3CH2CHF2, HFC-245fa), 1,2,2,3-Tetrafluoropropane (CH2FCF2CH2F, HFC-254ca), 1,1,2,2-Tetrafluoropropane (CHF2CF2CH3, HFC-254cb), 1,1,2,3-Tetrafluoropropane (CHF2CHFCH2F, HFC-254ea), 1,1,1,2-Tetrafluoropropane (CF3CHFCH3, HFC-254eb), 1,1,3, 3-Tetrafluoropropane (CHF2CH2CHF2, HFC-254fa), 1,1,1,3-Tetrafluoropropane (CF3CH2CH2F, HFC-254fb), 1,1,1-Trifluoropropane (CF3CH2CH3, HFC-263fb), 2,2-Difluoropropane (CH3CF2CH3, HFC-272ca), 1,2-Difluoropropane (CH2FCHFCH3, HFC-272ea), 1,3-Difluoropropane (CH2FCH2CH 2F, HFC-272fa), 1,1-difluoropropane (CHF2CH2CH3, HFC-272fb), 2-fluoropropane (CH3CHFCH3, HFC-281ea), 1-fluoropropane (CH2FCH2CH3, HFC-281fa), 1,1,2,2,3,3,4,4-octafluorobutane (CHF2CF2CF2CHF2, HFC-338pcc), 1,1,1,2,2,4,4,4-octafluorobutane (CF3CH2CF2CF3, HF C-338mf), 1,1,1,3,3-pentafluorobutane (CF3CH2CHF2, HFC-365mfc), 1,1,1,2,3,4,4,5,5,5-decafluoropentane (CF3CHFCHFCF2CF3, HFC-43-10mee), and 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoroheptane (CF3CF2CHFCHFCF2CF2CF3, HFC-63-14mee).

[0149] In another embodiment, the additional compound comprises a hydrocarbon. The hydrocarbon of the present invention includes compounds having only carbon and hydrogen. In particular, compounds having 3 to 7 carbon atoms are useful. Hydrocarbons are commercially available through a number of chemical sources. Representative hydrocarbons include, but are not limited to, propane, n-butane, isobutane, cyclobutane, n-pentane, 2-methylbutane, 2,2-dimethylpropane, cyclopentane, n-hexane, 2-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, 3-methylpentane, cyclohexane, n-heptane, and cycloheptane.

[0150] In another embodiment, the additional compound comprises a hydrocarbon containing a heteroatom, such as dimethyl ether (DME, CH3OCH3). DME is commercially available.

[0151] In another embodiment, the additional compound includes iodotrifluoromethane (CF3I), which is commercially available from a variety of sources or can be prepared by methods known in the art.

[0152] In another embodiment, the additional compound includes carbon dioxide (CO2), which is commercially available from a variety of sources or can be prepared by methods known in the art.

[0153] In another embodiment, the aforementioned composition of the present invention is substantially free of additional compounds, specifically substantially free of at least one of dimethyl ether, CF3I, ammonia, and carbon dioxide. In a preferred aspect of this embodiment, the aforementioned composition is substantially free of CF3I. By "substantially free of additional compounds" is meant that the fluoroolefin composition and inhibitor comprises less than about 10%, typically less than about 5%, and in some cases 0% of additional compounds.

[0154] In one embodiment, the composition of the invention comprises HFO-1234yf and other HFOs, such as those listed in Tables 1, 2, and 3. In one embodiment, the composition comprises 1 to 99 wt% HFO-1234yf, 1 to 99 wt% other HFOs, or 20 to 80 wt% HFO-1234yf, 20 to 80 wt% other HFOs. Of particular note are stabilized fluoroolefin compositions comprising HFO-1234yf and / or HFO-1234ze and additional compounds including HFO-1132E; HFC-32 and HFO-1132Z; HFO-1225ye and HFC-32; HFC-32 and HFC-152a; HFO-1225ye and HFC-134a; HFO-1225ye, HFC-134a, and HFC-32; HFO-1225ye and HFO-1234yf; HFO-1225ye, HFC-32; HFO-1225ye, HFO-1225ye, and HFC-125. Further fluoroolefin compositions include blends of at least one of HFO-1234yf and HFO-1234ze with at least one of i) 134a, 32, and 125; ii) 134a; iii) 227ea; iv) 236fa, and v) 134.

[0155] In other embodiments of the invention, the fluoroolefin comprises at least about 99% by weight HFO-1234yf and greater than 0 but less than 1% by weight of at least one member selected from the group consisting of HFC-134a, HFO-1243zf, HFO-1225ye, HFO-1234ze, 3,3,3-trifluoro-1-propyne, HCFO-1233xf, HFC-245cb, and combinations thereof.

[0156] In other embodiments of the invention, the fluoroolefin comprises at least about 99% by weight HFO-1234ze and greater than 0 but less than 1% by weight of at least one member selected from the group consisting of HFO-1234yf, HFC-245fa, HFC-236fa, HFO-1234ye, and combinations thereof.

[0157] In another embodiment of the present invention, the fluoroolefin comprises one or more of the aforementioned fluoroolefins blended with at least one hydrofluorocarbon. Examples of suitable hydrofluorocarbons include at least one member selected from the group consisting of HFC-32, HFC-125, HFC-134a, HFC-152a, 236fa, and HFC-227ea. The amount of hydrofluorocarbon may range from about 10 to about 90 weight percent, from about 20 to about 80 weight percent, and in some cases from about 30 to about 60 weight percent, based on the total weight of the composition. In a specific embodiment, the aforementioned amount of hydrofluorocarbon is blended with at least one of HFO-1234yf and HFO-1234ze.

[0158] Optionally, the blended composition may further comprise at least one additional component selected from the group consisting of HCC-40, HCFC-22, CFC-115, HCFC-124, HCFC-1122, and CFC-1113. The amount of the additional component may comprise from greater than 0 to about 5% by weight, greater than about 0 to about 2% by weight, and in some cases greater than about 0 to about 0.5% by weight, based on the total weight of the composition. In a specific embodiment, the aforementioned amount of the additional component is blended with at least one of HFO-1234yf and HFO-1234ze. In another specific embodiment, the aforementioned amount of the additional component is blended with at least one of HFO-1234yf and HFO-1234ze, and at least one hydrofluorocarbon selected from the group consisting of HFC-32, HFC-125, HFC-134a, HFC-152a, 236fa, and HFC-227ea, and optionally combined with carbon dioxide.

[0159] In one embodiment of the present invention, in addition to the inhibitor of the present invention, the composition may include at least one additive that can improve the life of refrigerants and air conditioning systems and compressor durability. In one aspect of the present invention, the aforementioned composition includes at least one component selected from the group consisting of acid scavengers, performance enhancers, and flame suppressants.

[0160] Additives that can improve refrigerant and A / C life and compressor durability are desirable. In one aspect of the present invention, refrigerants containing the compositions of the present invention are used to introduce lubricants into A / C systems, as well as other additives such as a) acid scavengers, b) performance enhancers, and / or c) flame suppressants.

[0161] The acid scavenger may include a siloxane, an activated aromatic compound, or a combination of both. Serrano et al. (US 2011 / 0272624 A1, paragraph 38), the entirety of which is incorporated herein by reference, disclose that the siloxane can be any molecule having a siloxy functional group. The siloxane may include an alkyl siloxane, an aryl siloxane, or a siloxane containing a mixture of aryl and alkyl substituents. For example, the siloxane may be an alkyl siloxane, including a dialkyl siloxane or a polydialkyl siloxane. Preferred siloxanes include groups having an oxygen atom bonded to two silicon atoms, i.e., the structure: SiOSi. For example, the siloxane may be a siloxane of formula IV: R1[Si(R2R3)4O]nSi(R2R3)R4, where n is 1 or greater. Siloxanes of formula IV preferably have n that is 2 or greater, more preferably 3 or greater (e.g., about 4 or greater). Siloxanes of formula IV preferably have n that is about 30 or less, more preferably about 12 or less, and most preferably about 7 or less. Preferably, the R1 group is an aryl or alkyl group. Preferably, the R2 group is an aryl or alkyl group, or a mixture thereof. Preferably, the R3 group is an aryl or alkyl group, or a mixture thereof. Preferably, the R4 group is an aryl or alkyl group. Preferably, R1, R2, R3, R4, or any combination thereof is not hydrogen. The R2 groups in a molecule may be the same or different. Preferably, the R2 groups in a molecule are the same. The R2 groups in a molecule may be the same or different from the R3 groups. Preferably, the R2 and R3 groups in a molecule are the same. Preferred siloxanes include those of Formula IV, where R1, R2, R3, R4, or any combination thereof, is a methyl, ethyl, propyl, or butyl group, or any combination thereof.Exemplary siloxanes that may be used include hexamethyldisiloxane, polydimethylsiloxane, polymethylphenylsiloxane, dodecamethylpentasiloxane, decamethylcyclopentasiloxane, decamethyltetrasiloxane, octamethyltrisiloxane, or any combination thereof.

[0162] From paragraph

[0039] of Serrano et al., which is incorporated by reference, it is noted that in one aspect of the invention, the siloxane is an alkyl siloxane containing from about 1 to about 12 carbon atoms, e.g., hexamethyldisiloxane. The siloxane may also be a polymer, such as a polydialkylsiloxane, where the alkyl group is methyl, ethyl, propyl, butyl, or any combination thereof. Suitable polydialkylsiloxanes have a molecular weight of from about 100 to about 10,000. Highly preferred siloxanes include hexamethyldisiloxane, polydimethylsiloxane, and combinations thereof. The siloxane may consist essentially of polydimethylsiloxane, hexamethyldisiloxane, or combinations thereof.

[0163] The activated aromatic compound may be any aromatic molecule, or mixture thereof, that is activated toward a Friedel-Crafts addition reaction. An aromatic molecule activated toward a Friedel-Crafts addition reaction is defined as any aromatic molecule that can undergo an addition reaction with a mineral acid. In particular, any aromatic molecule that can undergo an addition reaction with a mineral acid either in the application environment (AC system) or during the thermal stabilization test of ASHRAE 97:2007 "Sealed Glass Tube Method to Test the Chemical Stability of Materials for Use within Refrigerant Systems". Such molecules or compounds are typically activated by replacing a hydrogen atom of the aromatic ring with one of the following groups: NH2, NHR, NRz, ADH, AD, NHCOCH3, NHCOR, 4OCH3, OR, CH3, 4C2H5, R, or CH6H5, where R is a hydrocarbon, preferably a hydrocarbon containing from about 1 to about 100 carbon atoms. The activated aromatic molecule may be an alcohol or ether in which an oxygen atom (i.e., an oxygen atom of an alcohol or ether group) is directly bonded to an aromatic group. The activated aromatic molecule may be an amine in which a nitrogen atom (i.e., a nitrogen atom of an amine group) is directly bonded to an aromatic group. For example, the activated aromatic molecule may have the formula ArXRn, where X is O (i.e., oxygen) or N (i.e., nitrogen), when X=O, n is 1, when X=N, n is 2, Ar is an aromatic group (i.e., a CH group), R may be H or a carbon-containing group, and when n=2, the R groups may be the same or different. For example, R may be H (i.e., hydrogen), Ar, an alkyl group, or any combination thereof, and exemplary activated aromatic molecules that may be used in the refrigerant compositions according to the teachings herein include diphenyl oxide (i.e., diphenyl ether), methyl phenyl ether (e.g., anisole), ethyl phenyl ether, butyl phenyl ether, or any combination thereof.One aromatic molecule that is highly favored for activation toward Friedel-Crafts addition reactions is diphenyl oxide.

[0164] From paragraph

[0045] of Serrano et al., which is incorporated by reference, the acid scavenger (e.g., activated aromatic compound, siloxane, or both) may be present at any concentration that results in a relatively low total acid number, a relatively low total halide concentration, a relatively low total organic acid concentration, or any combination thereof. The acid scavenger is preferably present at a concentration of greater than about 0.0050 wt%, more preferably greater than about 0.05 wt%, and even more preferably greater than about 0.1 wt% (e.g., greater than about 0.5 wt%) based on the total weight of the refrigerant composition. The acid scavenger is preferably present at a concentration of less than about 3 wt%, more preferably less than about 2.5 wt%, and most preferably less than about 2 wt% (e.g., less than about 1.8 wt%) based on the total weight of the refrigerant composition.

[0165] Additional examples of acid scavengers that may be included in, and preferably excluded from, the refrigerant composition include those described by Kaneko (U.S. Patent Application No. 11 / 575,256, published as U.S. Patent Application Publication No. 2007 / 0290164, paragraph 42, which is expressly incorporated herein by reference), such as one or more of phenyl glycidyl ethers, alkyl glycidyl ethers, alkylene glycol glycidyl ethers, cyclohexene oxides, otolenoxides, or epoxy compounds such as epoxidized soybean oil, and those described by Singh et al. (U.S. Patent Application No. 11 / 250,219, published as U.S. Patent Application Publication No. 2006 / 0116310, paragraphs 34-42, which are expressly incorporated herein by reference).

[0166] Preferred additives include those described in U.S. Patent Nos. 5,152,926 and 4,755,316, which are incorporated herein by reference in their entirety.Specifically, preferred extreme pressure additives include a mixture of (A) tolyltriazole or its substituted derivatives, (B) an amine (e.g., Jeffamine M-600), and (C) a third component that is (i) an ethoxylated phosphate ester (e.g., Antara LP-700 type), or (ii) an alcohol phosphate (e.g., ZELEC 3337 type), or (iii) a zinc dialkyldithiophosphate (e.g., Lubrizol 5139, 5604, 5178, or 5186 type), or (iv) a mercaptobenzothiazole, or (v) a 2,5-dimercapto-1,3,4-tridiazole derivative (e.g., Curvan 826), or a mixture thereof. Additional examples of additives that can be used are described in US Pat. No. 5,976,399 (Schnur, 5:12-6:51, incorporated herein by reference).

[0167] Acid number is measured in mgKOH / g according to ASTM D664-01. Total halide, fluoride, and total organic acid concentrations are measured by ion chromatography. Chemical stability of the refrigerant system is measured according to ASHRAE 97:2007 (RA 2017) "Sealed Glass Tube Method to Test the Chemical Stability of Materials for Use within Refrigerant Systems". Viscosity of the lubricant is tested at 40°C according to ASTM D-7042.

[0168] Mouli et al. (WO 2008 / 027595 and WO 2009 / 042847) teach the use of alkylsilanes as stabilizers in refrigerant compositions containing fluoroolefins. Phosphates, phosphites, epoxides, and phenolic additives have also been used in certain refrigerant compositions. These are described, for example, by Kaneko (U.S. Patent Application Serial No. 11 / 575,256, published as U.S. Patent Application Publication No. 2007 / 0290164) and Singh et al. (U.S. Patent Application Serial No. 11 / 250,219, published as U.S. Patent Application Publication No. 2006 / 0116310). All of these aforementioned applications are expressly incorporated herein by reference in their entirety.

[0169] Preferred flame suppressants include those described in Canadian Patent Publication No. 2,557,873(A1), entitled "Compositions containing fluorine substituted olefins," which is incorporated by reference in its entirety, as well as fluorinated products such as HFC-125 and / or Krytox® lubricants, such as those described in International Publication No. 2009018117(A1), entitled "Compositions comprising fluoroolefins and uses thereof," which is incorporated by reference in its entirety.

[0170] In one embodiment, for example, a composition according to the present invention comprises, consists essentially of, or consists of about 99 to about 99.9 wt.% of at least one fluoroolefin, about 0.01 to about 0.5 wt.% of at least one UV dye, and about 0.001 to about 0.5 wt.% of at least one inhibitor.

[0171] The compositions of the present invention can be prepared by any convenient method for combining the desired amounts of the individual components. A preferred method is to weigh the desired amounts of the components and then combine the components in a suitable vessel. Agitation may be used if desired.

[0172] The present invention further relates to a process for producing cooling comprising condensing a composition comprising at least one fluoroolefin and an effective amount of an inhibitor, and then evaporating the composition in the vicinity of the body to be cooled.

[0173] The body to be cooled may be any space, location, or object requiring refrigeration or air conditioning. In stationary applications, the body may reside inside a structure, i.e., a residential or commercial structure, or a storage location for perishable goods such as food or medicine. In mobile refrigeration applications, the object may be incorporated into a transportation unit for road, rail, sea, or air. Certain refrigeration systems operate independently on any mobile carrier, and these are known as "intermodal" systems. Such intermodal systems include "containers" (sea / land intermodal transport), and "swap bodies" (road and rail intermodal transport).

[0174] The present invention further relates to a process for producing heating comprising condensing a composition comprising at least one fluoroolefin and an effective amount of an inhibitor comprising at least one of limonene and alpha-terpinene near a body to be heated, and then evaporating the composition.

[0175] The object to be heated may be any space, location, or object that requires heat. They may be located inside either residential or commercial structures in a similar manner to the objects to be cooled. Additionally, portable units such as those described for cooling may be similar to those requiring heating. Certain transport units require heating to prevent the materials being transported from solidifying within the transport container.

[0176] Another embodiment of the present invention relates to an air conditioning or refrigeration device comprising the aforementioned composition.

[0177] In one embodiment, the present invention relates to a heat transfer system that includes the composition. More specifically, referring to Figure 2, an exemplary heat transfer system is shown that includes, in sequence, a service valve 102, an expansion valve 104, an evaporator 106, a compressor 108, and a heat exchanger / condenser 110. The system is connected to a vessel 100 that contains the stabilized composition.

[0178] Another embodiment of the present invention relates to storing the aforementioned compositions in the gas and / or liquid phase in a sealed container in which the oxygen and / or water concentration in the gas and / or liquid phase ranges from about 3 ppm to less than about 3,000 ppm by volume, from about 5 ppm to less than about 1,000 ppm by volume, and in some cases from about 5 ppm to less than about 500 ppm by volume at a temperature of about 25° C.

[0179] The container for storing the aforementioned compositions can be constructed of any suitable material and design that can seal the composition while maintaining the gas and liquid phases. Examples of suitable containers include pressure vessels such as tanks, charge cylinders, and secondary charge cylinders. The containers can be constructed from any suitable material such as carbon steel, manganese steel, chromium-molybdenum steel, particularly low alloy steel, stainless steel, and possibly aluminum alloys. The containers may be equipped with a perforated top or valve suitable for dispensing flammable materials. In one embodiment, the compositions of the present invention are used to service existing A / C or refrigerant systems, and the compositions are stored in a container with a threaded seal. Examples of suitable containers for compositions that can be used to service automobiles are described in U.S. Pat. No. 10,131,486 and U.S. Patent Application Publication No. 2015 / 0108176(A1), the disclosures of which are incorporated herein by reference in their entireties. An exemplary container containing the composition is shown in FIG. 1.

[0180] In another embodiment, the compositions of the present invention are introduced into an A / C or refrigeration system suspected of having a refrigerant leak. The leak can be detected by using a kit in which a dye contained in the composition fluoresces when exposed to UV light (e.g., a UV detection kit available commercially as tracerline UV detection kit). Once introduced into the system, the compositions of the present invention can also amerliorate the adverse effects caused by exposure to polymerization initiators, acids, among other conditions.

[0181] According to any of the foregoing embodiments, also disclosed herein is the use of the refrigerant composition in a hybrid electric vehicle (HEV), a mild hybrid electric vehicle (MHEV), a plug-in hybrid electric vehicle (PHEV), or an electric vehicle (EV) heat pump system.

[0182] According to any of the foregoing embodiments, also disclosed herein is the use of the refrigerant composition in a HEV, MHEV, PHEV, or EV heat pump system in combination with a vehicle electrical system, including battery management.

[0183] Also disclosed herein, in accordance with any of the preceding embodiments, is a method of charging a refrigerant composition into an automotive system, comprising providing a composition of any of the preceding embodiments to a heating or cooling system of the automotive vehicle.

[0184] In accordance with any of the foregoing embodiments, also disclosed herein is a method for servicing the refrigerant composition of any of the foregoing embodiments using conventional on-site vehicle recovery, recycling, and recharging equipment.

[0185] Any suitable method can be used to stabilize the fluorocarbon-containing composition, examples of such methods include blending the inhibitor with the fluoroolefin composition, purging lines and vessels with a material containing the inhibitor (e.g., an inhibitor comprising a nitrogen carrier, or a stabilized composition of the present invention), among other suitable methods.

[0186] The following examples are provided to illustrate certain embodiments of the invention and are not intended to limit the scope of the appended claims. EXAMPLES

[0187] HFO-1234yf (at least 99.5% by weight purity) * A mixture of 30 g of HFO-1234yf and initiator (and no inhibitor) was heated in a 210 mL shaker tube at the temperature and time shown in Table 4. The shaker tube was visually inspected for polymer formation and by detecting the HFO-1234yf polymer peak using IR according to conventional methods. Polymer can also be detected by using conventional NMR methods. To compare this control experiment with the composition of the present invention, the same test and inspection was repeated using mixtures with various concentrations and types of inhibitors. * The HFO-1234yf contained 99.7 wt% HFO-1234yf, 1,000 ppm HFO-1234ze, 150 ppm HFO-1225yeZ, 3 ppm trifluoropropyne, and the remainder contained compounds that did not affect the performance of the mixture or initiator.

[0188] [Table 4] EXAMPLES

[0189] Refrigerant blends containing a mixture of HFO-1234yf (30 g having the composition of Example 1), at least one additional compound, and an initiator (and no inhibitor) were heated in a 210 mL shaker tube at the temperatures and times shown in Table 5. Examples 1-6 evaluate inhibitors containing Opteon™ XP-10 refrigerant (R513a) and a commercially available lubricant. Examples 7-12 evaluate inhibitors containing Opteon™ XP-40 refrigerant (R449a) and a commercially available lubricant. Examples 13-18 evaluate inhibitors containing HFO-1234yf and a commercially available lubricant. XP10 refrigerant contains 56% by weight of HFO1234yf and 44% by weight of HFC-134a, and XP40 refrigerant contains 24.3% by weight of R32, 24.7% by weight of R125, 25.3% by weight of 1234yf, and 25.7% by weight of 134a. XP10 and XP40 refrigerants are commercially available from Chemours Company. The shaker tubes were inspected visually for polymer formation and by using IR. Data reported below are ppm by weight.

[0190] [Table 5] EXAMPLES

[0191] This example demonstrates that compositions containing inhibitors exhibit superior stability (low acidity) performance. Commercially available dyes and lubricants were evaluated as shown in Table 6, and the results of the evaluation are shown in Table 7.

[0192] Experimental Procedure: 15mL of dye+oil solution or oil prepared as follows was mixed with 50mL of 1234yf containing 24ppm air in a glass bottle. The glass bottle was heated at 50°C for 6 months. After 6 months of aging, the F concentration of the refrigerant was checked and the acidity (TAN) of the dye-oil solution was investigated.

[0193] [Table 6] *Tracerline TP-9761-0108 Bigez Oil Pag Lubricant, 8z., 46 Visc. Cartridges

[0194] [Table 7] * 1234yf containing 200ppm d-limonene EXAMPLES

[0195] Experimental Procedure: 2mL of the dye+oil solution prepared above was mixed with 2mL of 1234yf+1340ppm air in a sealed tube. The sealed tube was heated at 175°C for 2 weeks. The acidity (TAN) of the refrigerant oil was investigated and the F concentration of the refrigerant was determined.

[0196] Example 4 demonstrates that refrigerant + dye and oil in the presence of inhibitor has better stability (lower TAN and F-) compared to without inhibitor. The results of these evaluations are shown in Table 8.

[0197] [Table 8]

[0198] While certain aspects, embodiments, and principles have been described above, it is understood that this description is made by way of example only and is not intended to limit the scope of the invention or the appended claims. The various aspects, embodiments, and principles described above can be used alone and in combination with each other.

Claims

1. A composition comprising at least one fluoroolefin, an effective amount of at least one liquid fluoroolefin homopolymerization inhibitor, and at least one dye, the composition being substantially free of oligomeric and polymeric products derived from said at least one fluoroolefin.

2. 10. The composition of claim 1, wherein the composition comprises less than about 0.03% by weight of oligomeric and polymeric products.

3. 10. The composition of claim 1 further comprising at least one member selected from air, oxygen, cumene hydroperoxide, and fluoroolefin polyperoxides, peroxides, hydroperoxides, persulfates, percarbonates, perborates, and hydropersulfates.

4. 4. The composition of claim 3, wherein the inhibitor comprises at least one member selected from limomen, alpha-terpinene, alpha-tocopherol, butylated hydroxytoluene, 4-methoxyphenol, and benzene-1,4-diol.

5. The composition of claim 3 further comprising at least one lubricant.

6. The composition of claim 3 , wherein the fluoroolefin, the dye, and the lubricant are miscible.

7. The composition of claim 3, wherein the at least one fluoroolefin comprises at least HFO-1234yf.

8. 8. The composition of claim 7 further comprising at least one component selected from HFO-1132E, HFC-32, HFC-125, HFC-134a, HFC-152a, HFC-236fa, HFC-227ea, and carbon dioxide.

9. 9. The composition of claim 7 or 8, further comprising at least one component selected from HFC-134a, HFO-1243zf, HFO-1225ye, HFO-1234ze, 3,3,3-trifluoro-1-propyne, HCFO-1233xf, HFC-244bb, and HFC-245cb.

10. 9. The composition of claim 7 or 8, further comprising at least one component selected from HCC-40, HCFC-22, CFC-115, HCFC-124, HCFC-1122, and CFC-1113.

11. 10. The composition of claim 1, wherein the inhibitor is present in an amount of from about 10 ppm to about 3,000 ppm, preferably less than 2,000 ppm, and most preferably less than 1000 ppm.

12. 5. The composition of claim 4, further comprising at least one component selected from butylated hydroxytoluene, butylated hydroxyanisole, tertiary butylhydroquinone, gallates, 2-phenyl-2-propanol, 1-(2,4,5-trihydroxyphenyl)-1-butanone, phenol, bisphenolmethane derivatives, and 2,2'-methylenebis(4-methyl-6-t-butylphenol).

13. 8. The composition of claim 7, wherein the inhibitor comprises at least one of limonene and alpha-terpinene.

14. 2. The composition of claim 1, wherein the liquid inhibitor comprises a liquid at a temperature of about -80°C to 180°C, preferably above -60°C, more preferably above -40°C.

15. The composition of claim 1 further comprising at least one antioxidant.

16. 8. The composition of claim 7 further comprising at least one component selected from HFO-1132E, HFO-1225yeZ, HFO-1243zf, HFO-1234ze, HFC-236ea, HFC-245fa, and 3,3,3-trifluoropropyne.

17. 17. The composition of claim 16, wherein the components include HFO-1234ze, HFO-1225yeZ, and 3,3,3-trifluoropropyne.

18. 10. The composition of claim 1, wherein the composition is substantially free of at least one of ammonia and CF3I.

19. 10. The composition of claim 1, wherein the composition consists essentially of HFO-1234yf and limonene and contains no ammonia or CF3I.

20. 17. The composition of claim 16, wherein the composition consists essentially of HFO-1234yf, 3,3,3-trifluoropropyne, and limonene.

21. The composition of claim 1 , wherein the composition has a total acid number (TAN) of less than 3.

22. 2. The composition of claim 1, wherein the composition has about 10 to about 0.1 ppm of F-anions.

23. The composition of claim 1 , wherein the dye comprises at least one compound containing a fluorescein species.

24. 24. The composition of claim 23, wherein the fluorescein species comprises at least one compound selected from derivatives of 6-hydroxy-3H-xanthen-3-one.

25. The composition of claim 1 , wherein the dye has a first absorbance peak at about 425 to about 433 nm and a second absorbance peak at about 292 to about 295 nm.

26. The composition of claim 1, wherein the amount of dye ranges from about 30% to about 0.001% by weight, based on the total weight of the composition.

27. 13. A method for reducing the formation of oligomers and homopolymers comprising contacting the composition of claim 1 comprising at least one fluoroolefin with an effective amount to reduce the formation of oligomers or homopolymers of at least one member selected from limomene, alpha-terpinene, alpha-tocopherol, butylated hydroxytoluene, 4-methoxyphenol, and benzene-1,4-diol.

28. 28. The method of claim 27, wherein the composition is exposed to at least one member selected from air, oxygen, cumene hydroperoxide, and fluoroolefin polyperoxides, peroxides, hydroperoxides, persulfates, percarbonates, perborates, and hydropersulfates prior to said contacting.

29. 13. A method for heating or cooling using the composition of claim 1, comprising: condensing the composition of claim 1; and evaporating said composition.

30. 24. A container comprising a refrigerant comprising the composition of any one of claims 1, 13, or 23.

31. 31. The container of claim 30, wherein the composition is maintained under a minimum pressure of 662 kPa (96 psia).

32. 31. The container of claim 30, wherein the concentration of oxygen and / or water in the gas and / or liquid phase within the container ranges from about 3 ppm by volume to less than about 3,000 ppm by volume at a temperature of about 25°C.

33. 24. A heat transfer system comprising the composition of any one of claims 1, 14, and 23.

34. 34. The heat transfer system of claim 33 comprising at least a refrigerator, an air conditioner, a chiller, and a heat pump.

35. 24. A process for stabilizing a heat transfer system comprising purging the lines of the system with the composition of any one of claims 1, 14, and 23.

36. 24. A process comprising circulating the composition of any one of claims 1, 14, and 23 through a heat transfer system.

37. 24. A process for detecting leaks in a heat transfer system comprising circulating the composition of any one of claims 1, 14, and 23 through the system and exposing the system to UV light to detect the presence of the dye.

38. 26. A leak detection process comprising exposing a system containing the composition of any one of claims 1, 14, or 23 to UV light.

39. 24. Use of the refrigerant composition according to any one of claims 1, 14 and 23 in a heat pump system.

40. 24. Use of the refrigerant composition according to any one of claims 1, 14 and 23 in a HEV, MHEV, PHEV or EV heat pump system.

41. 24. Use of the refrigerant composition according to any one of claims 1, 14 and 23 in a HEV, MHEV, PHEV or EV heat pump system in combination with a vehicle electrical system.

42. 24. A heat pump system comprising the refrigerant composition of any one of claims 1, 14, and 23, wherein the heat pump system is one of a HEV, a MHEV, a PHEV, or an EV heat pump system.

43. 26. A process comprising: removing an existing refrigerant composition from a heat transfer system; and providing the refrigerant composition of any one of claims 1, 14, and 23 to the heat transfer system.

44. Recovering the refrigerant composition of any one of claims 1, 14, and 23 from a heat transfer system; Recycling the recovered refrigerant composition; and and reclaiming said recycled refrigerant composition.

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