Stabilized fluoroethylene compositions and methods for storing and using same

Abstract

The present invention relates to a stabilized composition comprising at least one fluoroethylene and an effective amount of at least one inhibitor.The composition is substantially free of oligomers, homopolymers, or other polymer products derived from fluoroethylene.The stabilized composition can be useful in cooling devices such as refrigeration, air conditioning, chillers, and heat pumps, as well as in applications as foaming agents, solvents, aerosol propellants, fire extinguishing agents, and sterilizing agents.

Description

[Technical field]

[0001] The present invention relates generally to stabilized compositions comprising at least one fluoroethylene and at least one inhibitor, and methods for storing and using the same. [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] Fluoroethylenes have been proposed as refrigerants, either alone or in mixtures, in some cases due to their low boiling points. However, it has been observed that certain fluoroethylenes may exhibit degradation and / or produce unwanted by-products under certain conditions, such as extreme temperatures or contact with other compounds in contaminated systems (e.g., excess oxygen, oxidizing chemicals, or radical-producing compounds, among other contaminants), which may occur unexpectedly in certain uses and / or applications. Such degradation may occur when utilizing fluoroethylenes as refrigerants or heat transfer fluids. This degradation may occur by any number of different mechanisms.

[0005] Under certain conditions and / or in the presence of undesirable contaminants which may act as initiators, fluoroethylene can oligomerize or homopolymerize. Summary of the Invention [Problem to be solved by the invention]

[0006] Thus, there is a need in the art for stabilized fluoroethylene-containing compositions that reduce, if not eliminate, the potential for oligomerization or homopolymerization, and copolymerization with compounds such as hydrofluoroolefins (such as HFO-1234yf and HFO-1132A). [Means for solving the problem]

[0007] The present invention can improve the ability of fluoroethylene-containing compositions to withstand abnormal conditions by adding at least one inhibitor to the fluoroethylene-containing composition and also solves potential problems associated with initiators (e.g., contaminants) that oligomerize or homopolymerize fluoroethylene. The present invention can also solve problems associated with initiation of polymerization by providing at least one inhibitor present in liquid and / or vapor fluoroethylene-containing compositions and lubricants. "Inhibitor" is meant to refer to at least one compound according to the present invention that reduces, if not eliminates, the conversion of fluoroethylene 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 refrigeration systems and as a replacement for existing refrigerants with higher global warming potential.

[0008] To avoid possible instability of fluoroethylene, it has been found that 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, or aromatic organic compounds having at least one chemical moiety -C6H4(OH), including phenols, benzene-1,4-diol, to fluoroethylene-containing compositions increases stability during packaging, storage, and use, such as 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 (BHT), 4-methoxyphenol, benzene-1,4-diol.

[0009] In a specific embodiment, the present invention relates to a fluoroethylene-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 and α-terpinene. Limonene and α-terpinene have the following structures:

[0010] [ka]

[0011] In one embodiment of the invention, the inhibitor comprises alpha-terpinene. Without being bound by any 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.

[0012] In one embodiment of the present invention, limonene or alpha-terpinene, optionally containing antioxidants, has a unique aroma even at a few ppm level. This pleasant odor can be utilized for refrigerant leak detection using at least one fluoroethylene-based refrigerant and blends. This is particularly useful for early detection of refrigerant leaks in home or portable air conditioners, since paraprofessional electronic leak detectors are often not available everywhere.

[0013] In another embodiment of the invention, at least one of the following inhibitors can be used alone or in combination with the aforementioned inhibitors: meta-xylene, ortho-xylene, para-xylene, α-methylstyrene, α-meta-methylstyrene, α-ortho-methylstyrene, and α-para-methylstyrene.

[0014] One embodiment of the present invention comprises: a. at least one fluoroethylene; and b. an effective amount of at least one inhibitor, wherein the composition is substantially free of oligomers, homopolymers, or other polymeric products derived from fluoroethylene.

[0015] One embodiment relates to at least one fluoroethylene, including at least one difluoroethylene.

[0016] One specific embodiment relates to at least one difluoroethylene, including 1,1-difluoroethylene (HFO-1132a).

[0017] Another specific embodiment relates to at least one difluoroethylene, including 1,1-difluoroethylene, (E)-1,2-difluoroethylene, and (Z)-1,2-difluoroethylene. Another specific embodiment relates to any of the aforementioned compositions in combination with at least one of HFO-1234yf and HFC-32. The amount of HFO-1234yf and / or HFC-32 can range from about 50 to about 95% by weight, about 60 to about 90% by weight, and in some cases about 65 to about 80% by weight. In one aspect of this specific embodiment, the composition comprises R1132(E) / R1234yf at 23 / 77% by weight, which is useful in a wide range of applications, including, for example, heat pumps for electric vehicles, hybrid electric vehicles, or fuel cell vehicles. In another aspect of this specific embodiment, the composition comprises R1132a / R32 / R1234yf in a ratio of 5 / 44 / 51, or R1132(E) / R32 / R1234yf in a ratio of 32 / 44 / 24, which is useful in a wide range of applications, including those where a GWP<300 is desired. In another aspect of this specific embodiment, the aforementioned compositions can be used for residential, commercial, and industrial space heating, water heating, among other applications where the boiling point of the composition allows operation at low ambient temperatures.

[0018] Another embodiment of the invention relates to any of the aforementioned compositions, wherein the at least one inhibitor is selected from the group consisting of terpenes, terpenoids, straight chain unsaturated hydrocarbons, and phenols.

[0019] Another embodiment of the invention relates to any of the aforementioned compositions, wherein the at least one inhibitor is selected from the group consisting of D-limonene, terpinene, pinene, p-cymene, terpineol, myrcene, farnesene, 4-methoxyphenol, butylated hydroxytoluene, butylated hydroxyanisole, and tert-butylhydroquinone.

[0020] Another embodiment of the invention relates to any of the aforementioned compositions, wherein at least one inhibitor is present in an amount ranging from about 5 ppm to about 3,000 ppm, from about 50 to about 2,000 ppm, and in some cases from about 75 to about 500 ppm.

[0021] Another embodiment of the present invention is directed to any of the aforementioned compositions further comprising at least one lubricant.

[0022] 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 oligomers, homopolymers, or other polymeric products.

[0023] Another embodiment of the invention relates to any of the aforementioned compositions, further comprising at least one initiator selected from the group consisting of air, oxygen, cumene hydroperoxide, fluoroolefin polyperoxides, peroxides, hydroperoxides, persulfates, percarbonates, perborates, and hydropersulfates.

[0024] Another embodiment of the present invention relates to any of the aforementioned compositions, further comprising at least one antioxidant.

[0025] A specific embodiment relates to the at least one antioxidant selected from the group consisting of butylated hydroxytoluene, butylated hydroxyanisole, tert-butylhydroquinone, gallates, 2-phenyl-2-propanol, 1-(2,4,5-trihydroxylphenyl)-1-butanone, phenol, bisphenolmethane derivatives, and 2,2′-methylenebis(4-methyl-6-t-butylphenol).

[0026] One embodiment of the present invention relates to a composition comprising: a. at least one of fluoroethylene, in an amount of at least 99.5% by weight; vinyl fluoride (HFO-1141); and b. In an amount greater than 0.0% by weight, and in some cases at least 0.1% by weight, of chlorotrifluoromethane (CFC-13), trifluoromethane (CFC-23), difluoromethane (CFC-32), 1-chloro-1,1-difluoroethane (HFC-142b), 1,1,1-trifluoroethane (HFC-143a), tetrafluoroethylene (HFO-1114), 1-chloro-2,2-difluoroethylene (HFO-1122), acetylene, ethylene, 1, at least one additional compound selected from the group consisting of 2-dichloro-1,2-difluoroethane (HFC-132), 1,1,2-trifluoroethane (HFC-143), 1-chloro-1,2-difluoroethylene (HFO-1122a), trifluoroethylene (HFO-1123), 1-chloro-2-fluoroethylene (HFO-1131), (Z)-1,2-difluoroethylene ((Z)-HFO-1132), and combinations thereof.

[0027] One embodiment relates to at least one fluoroethylene, including at least one difluoroethylene.

[0028] One specific embodiment relates to at least one difluoroethylene, including 1,1-difluoroethylene (HFO-1132).

[0029] Another specific embodiment relates to at least one additional compound selected from the group consisting of chlorotrifluoromethane (CFC-13), trifluoromethane (HFC-23), difluoromethane (HFC-32), 1-chloro-1,1-difluoroethane (HCFC-142b), 1,1,1-trifluoroethane (HFC-143a), tetrafluoroethylene (HFO-1114), 1-chloro-2,2-difluoroethylene (HFO-1122), and combinations thereof.

[0030] Another specific embodiment relates to at least one difluoroethylene, including (E)-1,2-difluoroethylene.

[0031] Another specific embodiment relates to at least one additional compound above selected from the group consisting of acetylene, ethylene, 1,2-dichloro-1,2-difluoroethane (HCFC-132), 1,1,2-trifluoroethane (HFC-143), 1,1,1-trifluoroethane (HFC-143a), 1-chloro-1,2-difluoroethylene (HFO-1122a), trifluoroethylene (HFO-1123), trifluoroethylene (HFO-1123), 1-chloro-2-fluoroethylene (HFO-1131), 1,2-difluoroethylene (HFO-Z-1132), and combinations thereof.

[0032] Another specific embodiment relates to any of the aforementioned compositions having at least one additional compound comprising a C2-C5 hydrocarbon, including linear, branched, and cyclic compounds. Examples of such additional compounds include at least one selected from the group consisting of propane, cyclopropane, propylene, isobutene, butane, and butene.

[0033] Another embodiment of the invention relates to any of the aforementioned compositions further comprising an effective amount of at least one inhibitor such that the composition is substantially free of oligomers, homopolymers, or other polymeric products derived from fluoroethylene.

[0034] A specific embodiment relates to at least one inhibitor selected from the group consisting of terpenes, terpenoids, straight chain unsaturated hydrocarbons, and phenols.

[0035] Another specific embodiment relates to at least one inhibitor as described above being present in an amount of from about 30 ppm to about 3,000 ppm.

[0036] Another specific embodiment relates to at least one inhibitor as described above selected from the group consisting of D-limonene, terpinene, pinene, p-cymene, terpineol, myrcene, farnesene, 4-methoxyphenol, butylated hydroxytoluene, butylated hydroxyanisole, and tert-butylhydroquinone.

[0037] Another specific embodiment relates to a composition comprising greater than 0% and less than about 0.03% by weight of oligomer, homopolymer, or other polymeric product.

[0038] A specific embodiment relates to a composition further comprising at least one member selected from the group consisting of air, oxygen, cumene hydroperoxide, and fluoroolefin polyperoxides, peroxides, hydroperoxides, persulfates, percarbonates, perborates, and hydropersulfates.

[0039] Another embodiment of the present invention is directed to any of the aforementioned compositions further comprising at least one lubricant.

[0040] Another embodiment of the present invention relates to any of the aforementioned compositions comprising at least one fluoroethylene, at least one terpene inhibitor, and one or more oxidation products, wherein the oxidation products are oxidation products of a terpene inhibitor.

[0041] One embodiment of the present invention is a method of heating or cooling, the method comprising: a. condensing in a refrigerant loop a refrigerant composition from a vapor phase to a liquid phase in the refrigerant loop, the refrigerant composition comprising at least one fluoroethylene and an effective amount of an inhibitor, the effective amount being effective to reduce oligomer or homopolymer formation from said at least one fluoroethylene; b. thereafter, evaporating the refrigerant composition from the liquid phase to a vapor phase in the refrigerant loop.

[0042] A specific embodiment of the invention relates to any of the above methods, wherein the refrigerant 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 said contacting.

[0043] Another embodiment of the invention relates to any of the aforementioned methods, further comprising providing a lubricant to the refrigerant loop, wherein the inhibitor is in the liquid phase and in the lubricant.

[0044] One particular embodiment of the above method relates to a vapor phase that is substantially free of inhibitors.

[0045] One embodiment of the present invention is a method for reducing the formation of oligomers and homopolymers, the method comprising: and a method for producing said at least one fluoroethylene comprising contacting said composition with an effective amount of at least one member selected from the group consisting of limomen, alpha-terpinene, alpha-tocopherol, butylated hydroxytoluene, 4-methoxyphenol, benzene-1,4-diol, meta-xylene, ortho-xylene, para-xylene, alpha-methylstyrene, alpha-meta-methylstyrene, alpha-ortho-methylstyrene, and alpha-para-methylstyrene, said effective amount being an amount effective to reduce the formation of oligomers or homopolymers from said at least one fluoroethylene.

[0046] Another embodiment of the invention relates to a container containing a refrigerant comprising any of the aforementioned compositions.

[0047] Another embodiment of the present invention relates to a composition comprising at least one terpene and at least one oxidation product of the at least one terpene.

[0048] The embodiments of the invention can be used alone or in combination with each other, and different embodiments thereof can be combined and form part of the invention. [Brief description of the drawings]

[0049] [Figure 1A] 1 is a chart showing refrigerated COP, Cap, and glide performance of compositions containing 1234yf, 1132(E), 32, and 143a, respectively. [Figure 1B] 1 is a chart showing refrigerated COP, Cap, and glide performance of compositions containing 1234yf, 1132(E), 32, and 143a, respectively. [Figure 1C] 1 is a chart showing refrigerated COP, Cap, and glide performance of compositions containing 1234yf, 1132(E), 32, and 143a, respectively. [Figure 2A] 1 is a chart showing the refrigeration COP, Cap, and glide performance of compositions including 1234yf, 1132(E), and 32, which can be used under similar conditions to the conventionally used R-404A. [Figure 2B] 1 is a chart showing the refrigeration COP, Cap, and glide performance of compositions including 1234yf, 1132(E), and 32, which can be used under similar conditions to the conventionally used R-404A. [Figure 2C] 1 is a chart showing the refrigeration COP, Cap, and glide performance of compositions including 1234yf, 1132(E), and 32, which can be used under similar conditions to the conventionally used R-404A. [Figure 3A] 1 is a chart showing the refrigeration COP, Cap, and glide performance of compositions including 1234yf, 1132(E), and 32, which can be used under similar conditions to the conventionally used R-123. [Figure 3B] 1 is a chart showing the refrigeration COP, Cap, and glide performance of compositions including 1234yf, 1132(E), and 32, which can be used under similar conditions to the conventionally used R-123. [Figure 3C] 1 is a chart showing the refrigeration COP, Cap, and glide performance of compositions including 1234yf, 1132(E), and 32, which can be used under similar conditions to the conventionally used R-123. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0050] In some embodiments, the present invention provides a stabilized composition comprising at least one fluoroethylene and an effective amount of at least one inhibitor. By "stabilized" it is intended to mean that the composition comprises an effective amount of at least one inhibitor compound that inhibits, if not precludes, the fluoroethylene from interacting with another compound to form a dimer, oligomer, homopolymer, or polymer product. Examples of such compounds that may cause such interactions include oxidizing agents such as air, oxygen, cumene hydroperoxide, and fluoroolefin polyperoxides, peroxides, hydroperoxides, persulfates, percarbonates, perborates, and hydropersulfates, among other initiators. The initiator compound may be present in an amount of about 10 to about 15,000 ppm, about 1,000 to about 10,000 ppm, in some cases about 1,000 to about 3,000 ppm, and in some cases 30 to 2,000 ppm by weight. Such initiator compounds may be present as contaminants in at least one of the following: conduits, lines, and other systems used to handle fluoroethylene-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 act as radical initiators, thereby causing fluoroethylene to oligomerize, homopolymerize, or form other polymer products.

[0051] In one embodiment of the present invention, the composition of the present invention is substantially free of oligomers, homopolymers, or other polymeric products derived from fluoroethylene. By "substantially free" is meant that the composition contains more than 0% and less than about 1% by weight, more than 0% and less than about 0.07% by weight, more than 0% and less than about 0.03% by weight, or even about 0 ppm of such products as measured by IR or NMR.

[0052] In another embodiment of the present invention, the composition of the present invention comprises: farnesol; farnesene; [CH3CO2] - , [HSO4] - , [CH3OSO3] - , [C2H5OSO3] - , [AICI4] - , [CO3] 2- , [HCO3] - , [NO2] - , [NO3] - , [SO4] 2- , [PO4] 3- , [HPO4] 2- , [H2PO4] - , [HSO3] - and a specific fluorinated anion, wherein the fluorinated anion is [BF4] - , PF6 - , [SbF6] - , [CF3SO3] - ,[HCF2CF2SO3] - , [CF3HFCCF2SO3] - , [HCCIFCF2SO3] - , [(CF3SO2)2N] - , [(CF3CF2SO2)2N] - , [(CF3SO2)3C] - , [CF3CO2] - , [CF3OCFHCF2SO3] - , [CF3CF2OCFHCF2SO3] - , [CF3CFHOCF2CF2SO3] - , [CF2HCF2OCF2CF2SO3] -, [CF2ICF2OCF2CF2SO3] - , [CF3CF2OCF2CF2SO3] - , [(CF2HCF2SO2)2N] - , [(CF3CFHCF2SO2)2N] - The composition is substantially free of certain conventional inhibitor compounds, including sesquiterpene compounds, such as at least one member selected from the group consisting of ionic liquids, such as ionic liquids containing fluorinated anions, selected from the group consisting of: ...

[0053] In one embodiment of the present invention, the composition of the present invention comprises at least one fluoroethylene, at least one terpene inhibitor, and one or more oxidation products, the oxidation products being oxidation products of the terpene inhibitor. The terpene inhibitor may be selected from one or more of limonene, α-terpinene, α-pinene, and β-pinene.

[0054] The oxidation product can be an oxidation product of limonene selected from at least one of carvone, carveol (Z- and E-), and limonene oxide (Z- and E-), as shown below.

[0055] [ka]

[0056] When the inhibitor comprises limonene, the composition may further comprise one or more of an alpha-terpene, cymene, 1-octanol, gamma-terpinene, terpinolene, and beta-terpinene.

[0057] The oxidation product can be an oxidation product of α-terpinene selected from at least one of 3-isopropyl-6-methyl-7-oxabicyclo[4.1.0]hept-2-ene, 6-isopropyl-3-methyl-7-oxabicyclo[4.1.0]hept-2-ene, 1-isopropyl-4-methyl-cyclohex-2-ene-1,4-diol, E-3-isopropyl-6-methylhepta-2,6-dienal, p-cymene, and propane, all of which are as shown below except for propane.

[0058] [ka]

[0059] When the inhibitor comprises alpha-terpinene, the composition may further comprise one or more of camphene, isocamphene, terpinolene, menthomenthene, phellandrene, sabinene, beta-terpinene, 1,4-cineole, carbomenthene oxide, d-limonene, 1,8-cineole, -terpinene.

[0060] The oxidation product may be an oxidation product of α-pinene, where the oxidation product is α-pinene oxide, as shown below.

[0061] [ka]

[0062] When the inhibitor includes α-pinene, the composition may further include one or more of 5-methyl-4-nonene, -thujene, tricyclene (1,7,7-trimethyltricyclo[2.2.1.02,6]heptane), α-fenkene, camphene, cymene, d-limonene, α-camphorenal.

[0063] The oxidation product may be an oxidation product of β-pinene selected from at least one of pinocarveol and myrtenol, as shown below.

[0064] [ka]

[0065] When the inhibitor comprises β-pinene, the composition may further comprise one or more of α-pinene, α-fencene, camphene, verbenene, myrcene, phellandrene, camphane, cymene, and 2-menthene.

[0066] The composition disclosed herein comprises one or more oxidation products of terpene inhibitors.The oxidation products can be selected from one or more of carvone, carveol, limonene oxide, 3-isopropyl-6-methyl-7-oxabicyclo[4.1.0]hept-2-ene, 6-isopropyl-3-methyl-7-oxabicyclo[4.1.0]hept-2-ene, 1-isopropyl-4-methyl-cyclohex-2-ene-1,4-diol, E-3-isopropyl-6-methylhepta-2,6-dienal, p-cymene, propane, α-pinene oxide, pinocarveol, and myrtenol.

[0067] When the inhibitor comprises limonene, the oxidation product may be at least one of carvone, carveol, and limonene oxide, as shown above. In one embodiment, when the inhibitor is limonene, the oxidation product is limonene oxide. In one embodiment, when the inhibitor is limonene, the oxidation product is carvone. In one embodiment, when the inhibitor is limonene, the oxidation product is carveol. In one embodiment, when the inhibitor is limonene, the oxidation product is two or more of limonene oxide, carvone, and carveol.

[0068] When the inhibitor is α-terpinene, the oxidation product is at least one of 3-isopropyl-6-methyl-7-oxabicyclo[4.1.0]hept-2-ene, 6-isopropyl-3-methyl-7-oxabicyclo[4.1.0]hept-2-ene, 1-isopropyl-4-methyl-cyclohex-2-ene-1,4-diol, E-3-isopropyl-6-methylhepta-2,6-dienal, p-cymene, and propane, all of which are as exemplified above except for propane. In one embodiment, when the inhibitor is α-terpinene, the oxidation product is 3-isopropyl-6-methyl-7-oxabicyclo[4.1.0]hept-2-ene. In one embodiment, when the inhibitor is α-terpinene, the oxidation product is 6-isopropyl-3-methyl-7-oxabicyclo[4.1.0]hept-2-ene. In one embodiment, when the inhibitor is alpha-terpinene, the oxidation product is 1-isopropyl-4-methyl-cyclohex-2-ene-1,4-diol. In one embodiment, when the inhibitor is alpha-terpinene, the oxidation product comprises E-3-isopropyl-6-methylhepta-2,6-dienal. In one embodiment, when the inhibitor is alpha-terpinene, the oxidation product comprises p-cymene. In one embodiment, when the inhibitor is alpha-terpinene, the oxidation product comprises propane. In one embodiment, when the inhibitor is alpha-terpinene, the oxidation products include combinations of two or more of 3-isopropyl-6-methyl-7-oxabicyclo[4.1.0]hept-2-ene, 6-isopropyl-3-methyl-7-oxabicyclo[4.1.0]hept-2-ene, 1-isopropyl-4-methyl-cyclohex-2-ene-1,4-diol, E-3-isopropyl-6-methylhepta-2,6-dienal, p-cymene, and propane.

[0069] When the inhibitor comprises α-pinene, the oxidation product comprises α-pinene oxide as shown above.

[0070] When the inhibitor comprises β-pinene, the oxidation product comprises at least one of pinocarveol and myrtenol as shown above. In one embodiment, when the inhibitor comprises β-pinene, the oxidation product comprises pinocarveol. In one embodiment, when the inhibitor is β-pinene, the oxidation product comprises myrtenol. In one embodiment, when the inhibitor is β-pinene, the oxidation product comprises pinocarveol and myrtenol.

[0071] While any suitable amount of oxidation product can be used, effective amounts of oxidation product include from 0.0001% to 10%, from 0.01% to 5%, from 0.3% to 4%, from 0.3% to 1% by weight based on the total weight of the composition, hi one embodiment, an effective amount includes from 1 to 2000 ppm, or from 1 to 1000 ppm, or from 1 to 500 ppm of at least one oxidation product.

[0072] When two or more oxidation products are present, the total amount of oxidation products may also be in the range of 0.0001 wt.% to 10 wt.%, 0.01 wt.% to 5 wt.%, 0.3 wt.% to 4 wt.%, 0.3 wt.% to 1 wt.%, based on the total weight of the composition.

[0073] In some embodiments, the present invention provides a fluoroethylene compound comprising at least one fluoroethylene and at least one additional compound. In some embodiments, the at least one additional compound comprises at least one fluoroolefin. In some embodiments, the at least one additional compound comprises at least two additional compounds. In another embodiment, the at least one additional compound comprises a hydrocarbon, such as propane and butane.

[0074] The compositions of the invention have a variety of utilities including, inter alia, as foam blowing agents, solvents, aerosol propellants, fire extinguishing agents, 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.

[0075] A blowing agent is a volatile composition that causes a polymer matrix to expand and form a cellular structure.

[0076] A solvent is a fluid that removes dirt from a substrate or deposits material onto a substrate or carries material.

[0077] 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.

[0078] Fire extinguishing agents are volatile compositions that extinguish or suppress flames.

[0079] The sterilant is a volatile germicidal fluid or blend that contains a volatile germicidal fluid that destroys biologically active materials and the like.

[0080] 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.

[0081] A refrigerant is a compound or mixture of compounds that functions as a heat transfer fluid in a cycle in which the fluid changes phase from liquid to gas (or vapor) and back again. The inhibitor is present in at least the liquid fluoroethylene-containing phase of the refrigerant as well as in the lubricant component of the refrigerant. In one embodiment, about 10 to about 80 weight percent, about 25 to about 75 weight percent, and in some cases, about 45 to about 60 weight percent of the inhibitor is present in the liquid fluoroethylene-containing phase, with the remainder being primarily in the lubricant phase. In one embodiment, the vapor phase is substantially free of inhibitor. By "substantially free," it is meant that the amount of inhibitor in the vapor fluoroethylene-containing phase is less than about 10 ppm, in some cases less than about 5, and typically less than about 2 ppm. In one embodiment, the refrigerant includes a vapor phase containing at least one fluoroethylene, and a liquid phase containing at least one fluoroethylene, at least one lubricant, and at least one inhibitor, and in some cases the vapor phase is substantially free of inhibitor. In other embodiments, the inhibitor is present in the fluoroethylene-containing vapor phase.

[0082] 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" and 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).

[0083] 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.

[0084] 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 operation for achieving the desired results of any of the inventive processes. The term "consisting essentially of" has a meaning intermediate between "comprising" and "consisting of."

[0085] It should be readily understood that where applicants have defined an invention or portions 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).

[0086] 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.

[0087] The term fluoroethylene, as used herein, refers to a compound comprising two carbon atoms connected by a double bond and further comprising at least one fluorine atom, optionally at least one hydrogen atom, and optionally at least one chlorine atom. In one embodiment, the fluoroethylene is represented by the formula CR1R2=CR3R4, where R1 is fluorine and R2, R3, and R4 are independently selected from hydrogen, fluorine, and chlorine. In one embodiment, the fluoroethylene is hydrofluoroethylene. In one embodiment, the fluoroethylene is difluoroethylene. In one embodiment, the difluoroethylene is (Z)-1,2-difluoroethylene (HFO-Z-1132). In one embodiment, the difluoroethylene is (E)-1,2-difluoroethylene (HFO-E-1132). In one embodiment, the difluoroethylene is 1,2-difluoroethylene (HFO-1132). In one embodiment, the difluoroethylene is 1,1-difluoroethylene (HFO-1132a). In another embodiment the fluoroethylene comprises 1141 (CFH=CH2).

[0088] In some embodiments, the composition comprises at least 99.5% by weight of fluoroethylene.

[0089] In some embodiments, the composition is a refrigerant blend comprising fluoroethylene and at least one other compound, in some embodiments, the at least one other compound comprises a fluoroolefin.

[0090] 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.

[0091] Many of the compounds of the present composition 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 any combination or mixture of the E-isomer, Z-isomer, or both isomers in any ratio of 1,1,1,4,4,4-hexafluorobut-2-ene. As another example, HFO-1132a is meant to represent any combination or mixture of the E-isomer, Z-isomer, or both isomers in any ratio of 1,2-difluoroethylene.

[0092] In one specific embodiment, the fluoroethylene component of the compositions of the invention comprises HFO-1132 and / or HFO-1132a. In another specific embodiment, the fluoroethylene comprises HFO-1132 and / or HFO-1132a having a purity of greater than 99 weight percent, greater than 99.5 weight percent, and in some cases greater than 99.5 to 99.98 weight percent. In another specific embodiment, the fluoroethylene comprises at least 99.5 weight percent HFO-1132 and / or HFO-1132a and less than 0.5 and greater than 0.0001 weight percent, less than 0.3, and in some cases less than 0.2, of another fluoroethylene.

[0093] In some embodiments, the fluoroethylene component of the compositions or processes of the present invention is formed, purified, and / or obtained by processes known in the art.

[0094] In some embodiments, the fluoroethylene component is (E)-1,2-difluoroethylene, which is formed and / or purified by the process described in U.S. Patent Application Publication No. 2021 / 0107850, the disclosure of which is incorporated herein by reference.

[0095] In some embodiments, the fluoroethylene component is 1,1-difluoroethylene formed and / or purified by the process described in US Pat. No. 7,294,747, which is incorporated herein by reference.

[0096] In some embodiments, the composition comprises greater than about 99.5% by weight of the fluoroethylene component and vinyl fluoride (HFO-1141) and any of the following: chlorotrifluoromethane (CFC-13), trifluoromethane (CFC-23), difluoromethane (CFC-32), 1-chloro-1,1-difluoroethane (HFC-142b), 1,1,1-trifluoroethane (HFC-143a), tetrafluoroethylene (HFO-1114), 1-chloro-2,2-difluoroethylene (HFO-1122), and at least one additional compound selected from the group consisting of acetylene, ethylene, 1,2-dichloro-1,2-difluoroethane (HFC-132), 1,1,2-trifluoroethane (HFC-143), 1-chloro-1,2-difluoroethylene (HFO-1122a), trifluoroethylene (HFO-1123), 1-chloro-2-fluoroethylene (HFO-1131), (Z)-1,2-difluoroethylene ((Z)-HFO-1132), and combinations thereof. The amount of HFO-1141 and the at least one additional compound can be in the range of about 1 to about 2000 ppm, about 10 to about 1000 ppm, about 100 to about 500 ppm, about 50 to about 200 ppm, about 10 to about 100 ppm, greater than about 0.1%, by weight, or any value, range, or subrange therebetween.

[0097] In some specific embodiments, the fluoroethylene component is 1,1-difluoroethylene (HFO-1132) and the at least one additional compound is selected from the group consisting of chlorotrifluoromethane (CFC-13), trifluoromethane (CFC-23), difluoromethane (CFC-32), 1-chloro-1,1-difluoroethane (HFC-142b), 1,1,1-trifluoroethane (HFC-143a), tetrafluoroethylene (HFO-1114), 1-chloro-2,2-difluoroethylene (HFO-1122), and combinations thereof.

[0098] In some specific embodiments, the fluoroethylene component is (E)-1,2-difluoroethylene ((E)-HFO-1132a) and the at least one additional compound is selected from the group consisting of acetylene, ethylene, 1,2-dichloro-1,2-difluoroethane (HFC-132), 1,1,2-trifluoroethane (HFC-143), 1,1,1-trifluoroethane (HFC-143a), 1-chloro-1,2-difluoroethylene (HFO-1122a), trifluoroethylene (HFO-1123), 1-chloro-2-fluoroethylene (HFO-1131), 1,2-difluoroethylene (HFO-Z-1132), and combinations thereof.

[0099] In some embodiments, the fluoroethylene component in the refrigerant blend composition is 1,1-difluoroethylene as described in WO 2020 / 035690(A1) or WO 2020 / 135569(A1), the disclosures of which are incorporated herein by reference.

[0100] In some embodiments, the fluoroethylene component is (Z)-1,2-difluoroethylene in a refrigerant blend composition as described in U.S. Pat. No. 8,961,812, which is incorporated herein by reference.

[0101] In some embodiments, the refrigerant blend comprises fluoroethylene and at least one refrigerant compound selected from 2,3,3,3-tetrafluoropropene (HFO1234yf), difluoromethane (HFC-32), 1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), and 1,1-difluoroethane (HFC-152a). In some embodiments, the refrigerant blend further comprises at least one refrigerant compound selected from trifluoroethylene (HFO-1123), trifluoroiodomethane (CF3I), carbon dioxide (R-744, CO2), and 1,1,1,2-tetrafluoroethane (HFC-134a).

[0102] In some embodiments, the refrigerant blend composition comprises from about 1 to about 96% by weight fluoroethylene and from about 4% to about 99% by weight of at least one other refrigerant compound, or from about 1 to about 20% by weight fluoroethylene and from about 80% to about 99% by weight of at least one other refrigerant compound, or from about 2 to about 14% by weight fluoroethylene and from about 86% to about 98% by weight of at least one other refrigerant compound, or from about 20% by weight or more fluoroethylene and from about 80% to about 80% by weight of at least one other refrigerant compound, or from about 72 to about 96% by weight fluoroethylene and from about 4% to about 28% by weight of at least one other refrigerant compound, or any value, range, or subrange therebetween.

[0103] In some specific embodiments, the refrigerant blend composition comprises 2-14 wt.% fluoroethylene, 2-96 wt.% of a second refrigerant compound (such as HFC-152a), and 2-96 wt.% of a third refrigerant compound (such as HFO-1234yf), such as 4-10 wt.% fluoroethylene, 2-30 wt.% of the second refrigerant compound, and 60-94 wt.% of the third refrigerant compound.

[0104] In some specific embodiments, the refrigerant blend composition comprises 1-20 wt.% fluoroethylene, 1-21 wt.% of a second refrigerant compound, such as, for example, HFC-32, and 59-98 wt.% of a third refrigerant compound, such as, for example, HFO-1234yf (e.g., as disclosed in International Patent Application Publication No. WO 2020 / 035690 A1, the disclosure of which is incorporated herein by reference).

[0105] In further embodiments, the inhibitors of the present invention can be used with at least one of HFO-1132 and HFO-1132a, and with blend compositions that include at least one of HFO-1132 and HFO-1132a.

[0106] Any suitable effective amount of inhibitor can be used in the aforementioned composition comprising at least one fluoroethylene. 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 fluoroethylene, results in a composition in which the fluoroethylene does not interact with the initiator and / or degrades to significantly reduce performance, for example, when stored at high purity (e.g., at least 99.5% by weight) or used as part of a refrigerant blend in a cooling device, compared to a composition that does not contain the 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 fluoroethylene, 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 accordance with the present invention, it can be said that a cooling device utilizing a composition comprising at least one fluoroethylene can exhibit the same level of refrigeration performance and cooling capacity as if the composition comprising at least one fluoroethylene was utilized as the working fluid.

[0107] The present invention employs an effective amount of at least one of the aforementioned inhibitors. While any suitable effective amount can be used, an effective amount 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, or from about 0.3 weight percent to about 1 weight percent based on the total weight of the composition, including the at least one fluoroethylene-containing composition described herein. In one embodiment, an effective amount comprises from about 10 to about 2,000 ppm by weight, from about 10 to about 1,000 ppm, and in some cases from about 10 to about 500 ppm of at least one inhibitor.

[0108] In one embodiment, an effective amount of inhibitor stabilizes the composition in the presence of about 10 to about 10,000 ppm by weight, about 10 to about 1,000 ppm, about 10 to about 500 ppm, and in some cases, about 10 to about 100 ppm of at least one initiator.

[0109] 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 butyl hydroquinone, gallates, 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 by weight, from about 0.03 to about 2,000 ppm, and in some cases from about 0.05 to about 1,000 ppm. One specific embodiment relates to the use of the aforementioned antioxidants with at least one inhibitor comprising alpha-terpinene and limonene. One particular embodiment relates to the use of the aforementioned antioxidants together with an inhibitor comprising at least one of alpha-terpinene and limonene.

[0110] 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, 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 aforementioned 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.

[0111] 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.

[0112] 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, HFC227ca), 1,1,1,2,3,3,3-heptafluoropropane (CF3CHFCF3, HFC-227ea), 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, HFC254fb), 1,1,1-Trifluoropropane (CF3CH2CH3, HFC-263fb), 2,2-Difluoropropane (CH3CF2CH3, HFC-272ca), 1,2-Difluoropropane (CH2FCHFCH3, HFC-272ea), 1,3-Difluoropropane (CH2FCH2CH2F, HFC-272fa), 1,1-Difluoropropane (CHF2CH2CH3, HFC-272fb), 2-Fluoropropane (CH3CHFCH3, HFC-281ea), 1-Fluoropropane (CHF2CH2CH3, HFC-281ea), 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, HFC-338mf), 1,1,1,3,3-Pentafluorobutane (CF3CH2CHF2, HFC-338mf), FC-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).

[0113] 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.

[0114] In another embodiment, the additional compound comprises a hydrocarbon containing a heteroatom, such as dimethyl ether (DME, CH3OCH3). DME is commercially available.

[0115] 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.

[0116] 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.

[0117] In another embodiment, the additional compound comprises at least one member selected from the group of HFC-23, HFC-41, HFC-134a, HCFC-22, CFC-12, HCC-40, and 143a.

[0118] In another embodiment, the additional compound comprises at least one member selected from the group of water, air (with a N2 / O2 ratio of 78 / 21), air (with a N2 / O2 ratio of greater than 78 / 21), O2, N2, Ar, CO2, CH4, and He.

[0119] In one particular aspect of the above embodiment, the additional compound may include a tracer. While any suitable tracer may be used, examples of suitable tracers include at least one member selected from the group consisting of: E-1336mzz, 1233zd, 1224yd, 1112, 1327, Z-1336mzz, 1336yf, 1336ze, and 263fb as a tracer.

[0120] In another embodiment, the composition of the present invention is substantially free of additional compounds, in particular substantially free of at least one of dimethyl ether, CF3I, ammonia, and carbon dioxide. In a preferred aspect of this embodiment, the composition is substantially free of CF3I. "Substantially free of additional compounds" means that the composition and inhibitor contain less than about 10%, usually less than about 5%, and in some cases 0% of additional compounds.

[0121] Of particular note are vinyl fluoride (HFO-1141), chlorotrifluoromethane (CFC-13), trifluoromethane (CFC-23), difluoromethane (CFC-32), 1-chloro-1,1-difluoroethane (HFC-142b), 1,1,1-trifluoroethane (HFC-143a), tetrafluoroethylene (HFO-1114), 1-chloro-2,2-difluoroethylene (HFO-1122), acetylene, ethylene, 1,2-difluoroethane ... and at least one additional compound selected from chloro-1,2-difluoroethane (HFC-132), 1,1,2-trifluoroethane (HFC-143), 1-chloro-1,2-difluoroethylene (HFO-1122a), trifluoroethylene (HFO-1123), 1-chloro-2-fluoroethylene (HFO-1131), and (Z)-1,2-difluoroethylene ((Z)-HFO-1132).

[0122] In other embodiments of the invention, the fluoroethylene comprises at least about 99% by weight fluoroethylene, greater than 0% and less than 1% by weight vinyl fluoride (HFO-1141), and at least one member selected from chlorotrifluoromethane (CFC-13), trifluoromethane (CFC-23), difluoromethane (CFC-32), 1-chloro-1,1-difluoroethane (HFC-142b), 1,1,1-trifluoroethane (HFC-143a), tetrafluoroethylene (HFO-1114), and 1-chloro-2,2-difluoroethylene (HFO-1122).

[0123] In other embodiments of the invention, the fluoroethylene comprises at least about 99% by weight fluoroethylene, greater than 0% and less than 1% by weight vinyl fluoride (HFO-1141), and at least one member selected from acetylene, ethylene, 1,2-dichloro-1,2-difluoroethane (HFC-132), 1,1,2-trifluoroethane (HFC-143), 1,1,1-trifluoroethane (HFC-143a), 1-chloro-1,2-difluoroethylene (HFO1122a), trifluoroethylene (HFO-1123), 1-chloro-2-fluoroethylene (HFO-1131), and 1,2-difluoroethylene (HFO-Z-1132).

[0124] In another embodiment of the invention, the refrigerant blend comprises one or more of the aforementioned fluoroethylenes 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, HFC-236fa, and HFC-227ea. The amount of hydrofluorocarbon may range from about 25 to about 75% by weight, from about 30 to about 60% by weight, and in some cases from about 30 to about 50% by weight.

[0125] 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 greater than 0 to about 5% by weight, about 0 to about 2% by weight, and in some cases about 0 to about 0.5% by weight. In a specific embodiment, the aforementioned amount of the additional component is blended with at least one of HFO-1132 and HFO-1132a. In another specific embodiment, the aforementioned amount of the additional component is blended with at least one of HFO1132 and HFO-1132a and at least one hydrofluorocarbon selected from the group consisting of HFC-32, HFC-125, HFC-134a, HFC-152a, 236fa, and HFC-227ea, and in some cases, in combination with carbon dioxide.

[0126] Lubricants 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.

[0127] 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 (POEs) such as Castrol® 100 (Castrol, United Kingdom), polyalkylene glycols (PAGs) such as RL-488A manufactured by Dow (Dow Chemicals, Midland, Michigan), and polyvinyl ethers (PVEs).

[0128] 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 can range from about 1 to about 50% by weight, from about 1 to about 20% by weight, and in some cases from about 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.

[0129] In embodiments that include a refrigerant composition that further comprises an inhibitor and a lubricant, the inhibitor may be present in the liquid phase of the refrigerant composition, the vapor phase of the refrigerant composition, and / or the lubricant. In one embodiment of the invention, the inhibitor is distributed between the two liquid phases, i.e., the liquid phase fluoroolefin and the lubricant. The amount of inhibitor present in the liquid phase of the fluoroolefin can range from about 10 to about 80% by weight, about 25 to about 75% by weight, and in some cases about 45 to about 60% by weight, while the remaining inhibitor is primarily present in the lubricant phase.

[0130] In an exemplary embodiment, the inhibitor has sufficient miscibility in the lubricant such that a portion of the inhibitor is present in the lubricant. The amount of inhibitor present in the lubricant may vary when the refrigerant composition is used as a working fluid or a heat transfer medium.

[0131] Additives In one embodiment of the present invention, in addition to the inhibitor of the present invention, the composition may desirably 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.

[0132] Additives that can improve refrigerant and A / C life and compressor durability are desirable. In one aspect of the present invention, the refrigerant-containing 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 c) flame suppressants.

[0133] The acid scavenger may include a siloxane, an activated aromatic compound, or a combination of both. Serrano et al. (U.S. Patent Application Publication No. 2011 / 0272624(A1), paragraph 38, incorporated herein by reference) disclose that the siloxane can be any molecule with siloxy functionality. The siloxane may include alkylsiloxanes, arylsiloxanes, or siloxanes containing a mixture of aryl and alkyl substituents. For example, the siloxane may be an alkylsiloxane, including a dialkylsiloxane or a polydialkylsiloxane. 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 R4 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, R5, 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.

[0134] Incorporated by reference from Serrano et al., paragraph

[0039] notes 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, in which the alkyl groups are 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.

[0135] 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 stability 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 -C6H5, 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.

[0136] Incorporated by reference from Serrano et al. at paragraph

[0045] , 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. Preferably, the acid scavenger is present at a concentration of greater than about 0.0050 wt%, more preferably greater than about 0.05 wt%, 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. Preferably, the acid scavenger is 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.

[0137] 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 Serial 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 Serial No. 11 / 250,219, published as U.S. Patent Application Publication No. 20060116310, paragraphs 34-42, which are expressly incorporated herein by reference).

[0138] Preferred additives include those described in U.S. Patents 5,152,926 and 4,755,316, which are incorporated herein by reference. In particular, 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).

[0139] 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.

[0140] Mouli et al. (International Patent Application Publications WO 2008 / 027595 and WO 2009 / 042847) teach the use of alkylsilanes as stabilizers in refrigerant compositions containing fluoroethylene. Phosphates, phosphites, epoxides, and phenolic additives have also been used in certain refrigerant compositions. These are described, for example, in Kaneko (U.S. Patent Application Publication WO 2007 / 0290164) and Sign et al. (U.S. Patent Application Publication WO 2006 / 0116310). All of these aforementioned applications are expressly incorporated herein by reference.

[0141] Preferred flame suppressants include those described in Canadian Patent No. 2,557,873, entitled "Compositions containing fluorine substituted olefins," which is incorporated herein by reference, along with fluorinated products such as HFC-125 and / or Krytox® lubricants, which are described in International Patent Application Publication No. 2009 / 018117A1, entitled "Compositions comprising fluoroolefins and uses thereof," which are expressly incorporated herein by reference.

[0142] 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.

[0143] The present invention further relates to a process for producing cooling comprising condensing a composition comprising at least one fluoroethylene and an effective amount of an inhibitor, and then evaporating the composition in the vicinity of an object to be cooled.

[0144] The object to be cooled may be any space, location, or object requiring refrigeration or air conditioning. In stationary applications, the object 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 for 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).

[0145] The present invention further relates to a process for producing heat comprising condensing a composition comprising at least one fluoroethylene and an effective amount of an inhibitor comprising at least one of limonene and alpha-terpinene near a target to be heated, and then evaporating the composition.

[0146] The objects 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.

[0147] Another embodiment of the present invention relates to an air conditioning or refrigeration device comprising the aforementioned composition.

[0148] 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.

[0149] The container for storing the aforementioned composition 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 container can be constructed from any suitable material, such as, for example, carbon steel, manganese steel, or chrome-molybdenum steel, among other low alloy steels, stainless steels, and possibly aluminum alloys. The container can be equipped with a perforated top or valve suitable for dispensing flammable materials.

[0150] Any suitable method can be used to stabilize the fluorocarbon-containing composition, examples of such methods include blending the inhibitor with the fluoroethylene 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.

[0151] In one embodiment, the composition of the present invention is prepared by adding the inhibitor to at least one of the fluoroethylene component and the lubricant, and then combining the fluoroethylene component with the lubricant. If the inhibitor is added to only one of the fluoroethylene or the lubricant, and then the fluoroethylene and the lubricant are combined, the inhibitor is distributed such that the inhibitor is present in the fluoroolefin and the lubricant. In another embodiment, the inhibitor can be added to a composition that includes at least one fluoroethylene component and at least one lubricant.

[0152] Another embodiment of the present invention relates to storing the aforementioned compositions in the gas and / or liquid phase in a sealed container having a concentration of oxygen and / or water in the gas and / or liquid phase ranging 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, in some cases from about 5 ppm to less than about 500 ppm by volume, and all values ​​therebetween, at a temperature of about 25° C.

[0153] The container for storing the aforementioned composition 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 container can be constructed from any suitable material, such as carbon steel, manganese steel, chromium-molybdenum steel, among various low alloy steels, stainless steels, and possibly aluminum alloys. The container can be equipped with a perforated top or valve suitable for dispensing flammable materials. EXAMPLES

[0154] The following examples are provided to illustrate certain embodiments of the invention and are not intended to limit the scope of the appended claims.

[0155] Example 1 In control 1, the lock bomb was evacuated and then blanketed with nitrogen gas (N2). 0.2 g of initiator (azobisisobutyronitrile, AlBN) was then placed in the lock bomb. The lock bomb was then evacuated and charged with 200 g of the test composition, HFO-1132a (having a purity of at least 99.5% by weight) and 0.1% AlBN initiator (without inhibitor). The lock bomb was then heated at the temperature and time shown in Table 1. The lock bomb was visually inspected for polymer formation and by detecting the HFO-1132a polymer peak using IR according to conventional methods. Polymer can also be detected by using conventional NMR methods.

[0156] In Examples 1-3, the test compositions contained 200 g of HFO-1132 or HFO-1132a (having a purity of at least 99.5% by weight), 0.1% AIBN initiator, and d-limonene as an inhibitor in the amounts listed in Table 1.

[0157] Table 1 shows that about 3.7 wt% fluoroethylene was polymerized without an inhibitor under the test conditions of Control 1. In Example 1, the addition of 500 ppm d-limonene as an inhibitor reduced the amount of fluoroethylene polymerization to 0.25 wt%. In Examples 2 and 3, the addition of 1500 ppm and 3000 ppm d-limonene as an inhibitor, respectively, further reduced the amount of fluoroethylene polymerization to less than 0.1 wt%.

[0158] [Table 1]

[0159] For Control 2, 40 g of HFO-1132a (having a purity of at least 99.5% by weight) was added to 200 mL of deionized water containing 0.6 g of ammonium persulfate and 0.6 g of a fluorosurfactant as initiators. The mixture was stirred at the temperature and for the time shown in Table 1.

[0160] In Example 4, the test sample included 40 g of HFO-1132a (having a purity of at least 99.5% by weight) added to 200 mL of deionized water containing 0.6 g of ammonium persulfate as an initiator, 0.6 g of a fluorosurfactant, and 0.34 g (8000 ppm) of d-limonene as an inhibitor.

[0161] Table 1 shows that about 90 wt% of the fluoroethylene was polymerized without an inhibitor under the test conditions for Control 2. The addition of 8000 ppm of d-limonene as an inhibitor in Example 4 stabilized the refrigerant blend and reduced the amount of polymerization of fluoroethylene to less than 0.1 wt%.

[0162] Example 2 For Control 3, 30 g of HFO-1132a (having a purity of at least 99.5% by weight) and 3300 ppm of initiator (air) were added to the shaker tube. The shaker tube was maintained at the temperature and for the time indicated in Table 2. The shaker tube was then cooled to room temperature and examined for polymer formation.

[0163] For Examples 5-7, the mixtures also contained d-limonene or α-terpinene in the amounts listed in Table 2 as inhibitors.

[0164] Table 2 shows that greater than 3 wt.% fluoroethylene polymerized without an inhibitor under the control test conditions. The inclusion of an inhibitor in the amounts listed in Examples 5-7 for the conditions listed in Table 2 is expected to stabilize the refrigerant blends and reduce the amount of fluoroethylene polymerization to less than 0.1 wt.%.

[0165] [Table 2]

[0166] For Control 4, 30 g of HFO-1132a (having a purity of at least 99.5% by weight) and 10,000 ppm of initiator (air) are added to the shaker tube. The shaker tube is maintained at the temperature and for the time shown in Table 2.

[0167] In Examples 8-10, the mixture also contains an inhibitor in the amount listed in Table 2.

[0168] Greater than 10 wt.% fluoroethylene is expected to polymerize without an inhibitor under the test conditions of Control 4. The inclusion of an inhibitor in the amounts listed in Examples 8-10 for the conditions listed in Table 2 is expected to stabilize the refrigerant blends and reduce the amount of polymerization of fluoroethylene to less than 1 wt.%.

[0169] For Control 5, 30 g of HFO-1132a (having a purity of at least 99.5% by weight) and 1700 ppm of initiator (cumene hydroperoxide) are added to a 210 mL shaker tube. The shaker tube is maintained at the temperature and for the time indicated in Table 2.

[0170] In Examples 11-12, the mixtures also contain inhibitors in the amounts listed in Table 2.

[0171] More than 3 wt.% fluoroethylene is expected to polymerize without an inhibitor under the test conditions of Control 5. The inclusion of an inhibitor in the amounts listed in Examples 11-12 for the conditions listed in Table 2 is expected to stabilize the refrigerant blend and reduce the amount of polymerization of fluoroethylene to less than 0.1 wt.%.

[0172] Example 3 For Control 6, a refrigerant blend containing a mixture of (E)-HFO-1132, HFC-32, and HFO-1234yf (30 g) (i.e., equivalent to 32 wt. % 1132, 44.2 wt. % HFC-32, and 23.8 wt. % 1234yf) and 2000 ppm initiator (air) is added to a 210 mL shaker tube. The shaker tube is maintained at the temperature and for the time shown in Table 3.

[0173] In Examples 13-18, the inhibitors and lubricants listed in Table 3 are added to the same refrigerant blend and initiator as Control 6 in a 210 mL shaker tube. The shaker tube is maintained at the temperature and for the time indicated in Table 3.

[0174] Greater than 0.5 wt. % of the refrigerant is expected to polymerize without an inhibitor under the test conditions of Control 7. The inclusion of an inhibitor in the amounts listed in Examples 13-18 for the conditions listed in Table 3 is expected to stabilize the refrigerant blends and not produce detectable amounts of polymerization of the refrigerant.

[0175] [Table 3]

[0176] For Control 7, a refrigerant blend containing the above mixture of (E)-HFO-1132, CFC-32, and HFO-1234yf (30 g) and 10,000 ppm of initiator (air) is added to a 210 mL shaker tube. The shaker tube is maintained at the temperature and for the time shown in Table 3.

[0177] In Examples 19-24, the inhibitors and lubricants listed in Table 3 are added to the same refrigerant blend and initiator as Control 7 in a 210 mL shaker tube. The shaker tube is maintained at the temperature and for the time indicated in Table 3.

[0178] Greater than 3 wt. % of the refrigerant is expected to polymerize without an inhibitor under the test conditions of Control 7. The inclusion of inhibitors in the amounts listed in Examples 19-24 for the conditions listed in Table 3 will stabilize the refrigerant blends and is not expected to produce detectable amounts of refrigerant polymerization.

[0179] Example 4 The stabilized fluoroethylene compositions of the present invention can be used in refrigerant applications. Figures 1A, 1B, and 1C are charts showing the refrigeration performance of compositions containing 1234yf, 1132(E), 32, and 143a.

[0180] Example 5 The stabilized fluoroethylene composition of the present invention can be used for refrigeration applications. Figures 2A, 2B, and 2C are charts showing the refrigeration performance of compositions containing 1234yf, 1132(E), and 32, and show that the composition of the present invention can be used under similar conditions as the conventionally used R-404A.

[0181] Example 6 The stabilized fluoroethylene composition of the present invention can be used for refrigeration. Figures 3A, 3B and 3C are charts showing the refrigeration capacity of compositions containing 1234yf, 1132(E) and 32, showing that the composition of the present invention can be used under the same conditions as the conventionally used R-123.

[0182] Example 7 (E) A mixture of 1132a (30 g) and initiator is heated in a 210 mL shaker tube with or without inhibitor for a certain period of time. The shaker tube is cooled to room temperature and visually inspected for polymer formation. The results are shown in Table 4.

[0183] [Table 4]

[0184] Example 8 The following blends are evaluated according to the method of Example 7: E-1132 / 1234yf (23 / 77 by weight), E-1132 / 32 (56 / 44 by weight), and E-1132 / 32 / 1234yf (32 / 44.2 / 23.8 by weight). The results of the evaluation of these blends are shown in Table 5.

[0185] [Table 5-1]

[0186] [Table 5-2]

[0187] Example 9 The refrigeration performance of the composition disclosed in Example 8 was This was evaluated using computer modeling, and the results are reported in Table 6.

[0188] [Table 6]

[0189] [Table 7-1]

[0190] [Table 7-2]

[0191] Example 10 The refrigeration performance of compositions containing 1132E, 1234yf, and propane was evaluated using computer modeling, and the results are shown in Table 7 below.

[0192] [Table 8]

[0193] [Table 9-1]

[0194] [Table 9-2]

[0195] While certain aspects, embodiments, and principles have been described above, it is understood that this description is made by way of example only and does not 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 stabilized composition comprising at least one fluoroethylene and an effective amount of at least one inhibitor, said composition being substantially free of oligomers, homopolymers, or other polymeric products derived from said fluoroethylene.

2. The composition of claim 1 , wherein the at least one fluoroethylene comprises at least one difluoroethylene.

3. 3. The composition of claim 2, wherein the at least one difluoroethylene comprises one of 1,1-difluoroethylene (HFO-1132a) and (E)-1,2-difluoroethylene ((E)-HFO-1132).

4. 2. The composition of claim 1, wherein the at least one inhibitor is selected from the group consisting of (i) terpenes, terpenoids, and straight chain unsaturated hydrocarbons or (ii) D-limonene, terpinene, pinene, p-cymene, terpineol, myrcene, farnesene, 4-methoxyphenol, butylated hydroxytoluene, butylated hydroxyanisole, tert-butylhydroquinone, meta-xylene, ortho-xylene, para-xylene, α-methylstyrene, α-meta-methylstyrene, α-ortho-methylstyrene, and α-para-methylstyrene.

5. 10. The composition of claim 1, wherein the at least one inhibitor is present in an amount from about 30 ppm to about 3,000 ppm.

6. The composition of claim 1 further comprising at least one lubricant.

7. 10. The composition of claim 1, wherein the composition comprises less than about 0.03% by weight of an oligomer, homopolymer, or other polymer product.

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

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

10. 10. The composition of claim 9, wherein the at least one antioxidant is selected from the group consisting of butylated hydroxytoluene, butylated hydroxyanisole, tert-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).

11. At least one fluoroethylene, vinyl fluoride (HFO-1141), chlorotrifluoromethane (CFC-13), trifluoromethane (CFC-23), difluoromethane (CFC-32), 1-chloro-1,1-difluoroethane (HFC-142b), 1,1,1-trifluoroethane (HFC-143a), tetrafluoroethylene (HFO-1114), 1-chloro-2,2-difluoroethylene (HFO-1122), acetylene, ethylene, 1,2-dichloro-1,2-difluoroethylene, ...

10. The composition of claim 1, further comprising at least 0.001 wt. % of at least one additional compound selected from the group consisting of fluoroethane (HFC-132), 1,1,2-trifluoroethane (HFC-143), 1-chloro-1,2-difluoroethylene (HFO-1122a), trifluoroethylene (HFO-1123), 1-chloro-2-fluoroethylene (HFO-1131), (Z)-1,2-difluoroethylene ((Z)-HFO-1132), and combinations thereof. (i) the at least one fluoroethylene comprises 1,1-difluoroethylene (HFO-1132a); and the at least one additional compound is selected from the group consisting of chlorotrifluoromethane (CFC-13), trifluoromethane (CFC-23), difluoromethane (CFC-32), 1-chloro-1,1-difluoroethane (HFC-142b), 1,1,1-trifluoroethane (HFC-143a), tetrafluoroethylene (HFO-1114), 1-chloro-2,2-difluoroethylene (HFO-1122), and combinations thereof; or (ii) the at least one difluoroethylene comprises (E)-1,2-difluoroethylene ((E)-HFO-1132); and 12. The composition of claim 11, wherein the at least one additional compound is selected from the group consisting of acetylene, ethylene, 1,2-dichloro-1,2-difluoroethane (HFC-132), HFC-32, 1,1,2-trifluoroethane (HFC-143), 1,1,1-trifluoroethane (HFC-143a), 1-chloro-1,2-difluoroethylene (HFO-1122a), trifluoroethylene (HFO-1123), 1-chloro-2-fluoroethylene (HFO-1131), (Z)-1,2-difluoroethylene ((Z)-HFO-1132)), propane, and combinations thereof.

13. 1. A method for heating or cooling comprising: The method includes condensing a refrigerant composition from a vapor phase to a liquid phase in a refrigerant loop, the refrigerant composition comprising at least one fluoroethylene and an effective amount of an inhibitor, the effective amount being effective to reduce oligomer or homopolymer formation from the at least one fluoroethylene; thereafter evaporating said refrigerant composition from said liquid phase to said vapor phase in said refrigerant loop.

14. 14. The method of claim 13, wherein the refrigerant composition has been exposed to at least one selected from the group consisting of air, oxygen, cumene hydroperoxide, and fluoroolefin polyperoxides, peroxides, hydroperoxides, persulfates, percarbonates, perborates, and hydropersulfates prior to said contacting.

15. 14. The method of claim 13, further comprising supplying a lubricant to the refrigerant loop, wherein the inhibitor is present in the liquid phase and in the lubricant, and wherein the vapor phase is substantially free of the inhibitor.

16. 1. A method for reducing the formation of oligomers and homopolymers comprising the step of contacting a composition comprising at least one fluoroethylene with an effective amount of at least one member selected from the group consisting of limonene, alpha-terpinene alpha-tocopherol, butylated hydroxytoluene, 4-methoxyphenol, benzene-1,4-diol, meta-xylene, ortho-xylene, para-xylene, alpha-methylstyrene, alpha-meta-methylstyrene, alpha-ortho-methylstyrene, and alpha-para-methylstyrene, wherein the effective amount is effective to reduce the formation of oligomers or homopolymers from the at least one fluoroethylene.

17. 17. The method of claim 16, wherein the composition further comprises at least one or more oxidation products, the oxidation products being oxidation products of the constituents.

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