Hydrocarbon additives for 1234YF compositions and methods for their production, 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 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] (Related Applications) This application relates to and incorporates by reference the entire disclosures of the applicants' concurrently filed application No. FL2039-WO01, as well as U.S. Provisional Applications Nos. 63 / 321,120 and 63 / 321,118, each filed on March 18, 2022, and U.S. Patent Applications Nos. 63 / 344,904 and 63 / 344,899, each filed on May 23, 2022, by like-named inventors, Sheng Peng and Barbara Haviland Minor of The Chemours Company FC, LLC.

[0002] FIELD OF THEINVENTION The present invention broadly relates to a stabilized composition comprising at least one fluoroolefin and at least one oligomerization / polymerization inhibitor or chain transfer agent comprising at least one member selected from one or more of xylene, methylstyrene, C2-C5 hydrocarbons, and mixtures of two or more thereof, and optionally including an air component, a tracer, a lubricant, and moisture. [Background technology]

[0003] New environmental regulations regarding refrigerants are forcing the refrigeration and air conditioning industry to search for new refrigerants with lower global warming potential (GWP), resulting in the development of new alternative refrigerants that have low GWP, are non-toxic, non-flammable, reasonable cost and excellent refrigeration performance.

[0004] Fluoroolefins have been proposed as refrigerants, either alone or in mixtures, and several are commercially available. 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 / JARIA 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 JP 2009298918, U.S. Pat. Nos. 6,969,701, 8,133,407, U.S. Patent Application Publication Nos. 2006 / 0022166, 2006 / 0043330, 2008 / 0157022, and WO 2007 / 126760, as well as EP 2057245, U.S. Pat. Nos. 8,101,094, 8,535,555, 8,097,181, and 8,075,796, the disclosures of which are incorporated herein by reference. Other stabilized compositions are disclosed in related, co-pending U.S. Patent Publication Nos. 2021 / 0108119, 2021 / 0040368, and 202110340421, each of which is incorporated by reference in its entirety into this specification. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] U.S. Provisional Application No. 63 / 321,120 [Patent Document 2] U.S. Provisional Application No. 63 / 321,118 [Patent Document 3] U.S. Patent Application No. 63 / 344,904 [Patent Document 4] U.S. Patent Application No. 63 / 344,899 [Patent Document 5] Patent Publication No. 2009298918 [Patent Document 6] U.S. Patent No. 6,969,701 [Patent Document 7] U.S. Patent No. 8,133,407 [Patent Document 8] US Patent Application Publication No. 2006 / 0022166 [Patent Document 9] US Patent Application Publication No. 2006 / 0043330 [Patent Document 10] US Patent Application Publication No. 2008 / 0157022 [Patent Document 11] International Publication No. 2007 / 126760 [Patent Document 12] European Patent No. 2057245 [Patent Document 13] U.S. Patent No. 8,101,094 [Patent Document 14] U.S. Patent No. 8,535,555 [Patent Document 15] U.S. Patent No. 8,097,181 [Patent Document 16] U.S. Patent No. 8,075,796 [Patent Document 17] U.S. Patent Publication No. 2021 / 0108119 [Patent Document 18] U.S. Patent Publication No. 2021 / 0040368 [Patent Document 19] U.S. Patent Publication No. 202110340421 [Non-patent literature]

[0006] [Non-Patent Document 1] "1234yf-A Low GWP Refrigerant For MAC, Honeywell / DuPont Joint Collaboration", JAMA / JARIA, October 3, 2007 Summary of the Invention [Problem to be solved by the invention]

[0007] Thus, there is a continuing need in the art for stabilized fluoroolefin-containing compositions that have reduced, if not eliminated, potential for oligomerization or homopolymerization. [Means for solving the problem]

[0008] The present invention improves the hydrofluoroolefin-containing composition's ability to withstand abnormal conditions by adding at least one inhibitor to the fluoroolefin-containing composition, and also solves the potential problem associated with initiators (e.g., contaminants) that oligomerize or homopolymerize fluoroolefins (e.g., tetrafluoropropene). "Inhibitor" is meant to refer to at least one compound according to the present invention that reduces, if not eliminates, the conversion of hydrofluoroolefins to oligomers or polymers. 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 or chain transfer agent, or both, without affecting the refrigeration performance of the composition or its compatibility with refrigerant oils and components. The addition of an oligomer inhibitor to the fluoroolefin-containing composition will increase its stability during packaging, storage, and use in refrigeration or air conditioning system applications. The stabilized composition can be useful in refrigeration systems and as a replacement for existing refrigerants with higher global warming potential.

[0009] In a specific embodiment, the present invention relates to one or more C3 tetrafluoropropene compounds containing compositions such as HFO-1234yf alone or in combination with HFO-1234ze as a mixture of the two isomers or trans-1234ze, including inhibitors capable of interacting or reacting with fluoroolefins, e.g., O2 and fluoroolefin polyperoxides, and then inhibiting or eliminating the reaction of such compounds with hydrofluoroolefins. Examples of such inhibitors include (1) ethane, propane, cyclopropane, propylene, butane, butene, isobutane, isobutene, 2-methylbutane, and (2) meta-, ortho-, or para-xylene, alpha (α)-methylstyrene, 2-methyl-alpha-methylstyrene (α,2-dimethylstyrene), 3-methyl-alpha-methylstyrene (α,3-dimethylstyrene), and 4-methyl-alpha-methylstyrene (α,4) dimethylstyrene), which have the following chemical structures:

[0010] [Table 1-1]

[0011] [Table 1-2]

[0012] In another specific embodiment, the present invention relates to fluoroolefin compositions, for example, one or more tetrafluoropropene-containing compositions, comprising a fluoroolefin / olefin inhibitor capable of interacting or reacting with O2 and fluoroolefin polyperoxides, and then inhibiting or eliminating the reaction of such compounds with hydrofluoroolefins, including C2-C5 hydrocarbons, such as ethane, propane, propylene, butane, butene, isobutane, isobutene, and 2-methylbutane, in amounts up to 0.5% by weight.

[0013] In another specific embodiment, the invention relates to a fluoroolefin composition, e.g., one or more tetrafluoropropene-containing compositions, e.g., HFO-1234yf alone or in combination with HFO-1234ze, further comprising a xylene or methylstyrene oligomerization inhibitor in an amount of up to 0.5 wt. % inhibitor that can interact or react with O2 and fluoroolefin polyperoxides and in turn inhibit or eliminate the reaction of such compounds with at least C3 fluoroolefins.

[0014] In another specific embodiment, high purity HFO-1234yf or HFO-1234ze having a purity of at least 99.5 weight percent comprises at least one additional refrigerant component comprising an HFO, HCFO, HFC, HCFC, nitrogen, and carbon dioxide, and an effective stabilizing amount of at least one oligomerization inhibitor comprising one or more of xylene, α-methylstyrene, C3-C4 hydrocarbons, and mixtures of two or more.

[0015] In a further specific embodiment, the present invention relates to at least one C3 fluoroolefin composition that also contains at least one additional HFC, HCC, HFO, HCFO, and refrigerant gas component, and at least one of xylene, alpha (α)-methylstyrene, 2-methyl-alpha-methylstyrene (α,2-dimethylstyrene), 3-methyl-alpha-methylstyrene (α,3-dimethylstyrene), and 4-methyl-alpha-methylstyrene (α,4) dimethylstyrene), and a C2-C5 hydrocarbon oligomerization inhibitor.

[0016] Also disclosed herein is a method for reducing the formation of oligomeric and homopolymeric products or by-products comprising contacting a composition comprising at least 2,3,3,3-tetrafluoropropene (HFO-1234yf) with an effective amount of a radical inhibiting additive selected from d-limonene, l-limonene, β-pinene, α-pinene, α-terpinene, β-terpinene, γ-terpinene, and δ-terpinene, and mixtures of two or more, alone or in combination with propane.

[0017] Limonene has the following structure:

[0018] [ka]

[0019] One component is selected from at least one of C2 to C5 hydrocarbons and the other component is d-limonene, l-limonene, β-pinene, α-pinene, α-terpinene, β-terpinene, γ-terpinene, and δ-terpinene, as well as up to 0.1 weight percent of d-limonene / propane, l-limonene / propane, β-pinene / propane, α-pinene / propane, , α-terpinene / propane, β-terpinene / propane, γ-terpinene / propane, and δ-terpinene / propane, d-limonene / cyclopropane, l-limonene / cyclopropane, β-pinene / cyclopropane, α-pinene / cyclopropane, α-terpinene / cyclopropane, β-terpinene / cyclopropane, γ-terpinene / cyclopropane, and δ-terpinene / / cyclopropane, d-limonene / butane, l-limonene / butane, β-pinene / butane, α-pinene / propane, α-terpinene / butane, β-terpinene / butane, γ-terpinene / butane, and δ-terpinene / butane, d-limonene / isobutane, l-limonene / isobutane, β-pinene / isobutane, α-pinene / isobutane, α-terpinene / isobutane, β-terpinene / isobutane, Also disclosed herein are oligomeric inhibitor pairs selected from mixtures of two or more including: d-pinene / isobutane, gamma-terpinene / isobutane, and delta-terpinene / isobutane, d-limonene / butene, l-limonene / butene, beta-pinene / butene, alpha-pinene / butene, alpha-terpinene / butene, beta-terpinene / butene, gamma-terpinene / butene, or delta-terpinene / butene.

[0020] One embodiment of the present invention relates to any of the above compositions, further comprising at least one antioxidant, an air component, a tracer, a lubricant, and moisture.While any suitable antioxidant may 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.

[0021] In one embodiment of the present invention, ortho-xylene, meta-xylene, para-xylene, alpha (α)-methylstyrene, 2-methyl-alpha-methylstyrene (α,2-dimethylstyrene), 3-methyl-alpha-methylstyrene (α,3-dimethylstyrene), and 4-methyl-alpha-methylstyrene (α,4) dimethylstyrene), optionally with any of the aforementioned antioxidants, are combined with HFO-1234yf refrigerants and refrigerant blends. The inhibitor-antioxidant stabilized HFO-1234yf refrigerants and refrigerant blends may also include one or more leak detection components that are particularly beneficial for early refrigerant leak detection in home or mobile air conditioners, since paraprofessional electronic leak detectors are often not available everywhere.

[0022] In one embodiment of the invention, an oligomeric inhibitor comprising one of the C3-C4 hydrocarbons, xylene, alpha (α)-methylstyrene, 2-methyl-alpha-methylstyrene (α,2-dimethylstyrene), 3-methyl-alpha-methylstyrene (α,3-dimethylstyrene), and 4-methyl-alpha-methylstyrene (α,4) dimethylstyrene), and any of the aforementioned antioxidants, with and without a lubricant, is combined with an HFO-1234yf refrigerant or HFO-1234yf refrigerant blend.

[0023] One embodiment of the present invention is a composition comprising: a. at least one C3 fluoroolefin; b. an effective amount of at least one inhibitor, including ortho-para-, meta-xylene, pinene, limonene, and mixtures of two or more; c. optionally, at least one of an antioxidant, a tracer, a compatibilizer, and a lubricant.

[0024] Another embodiment of the invention is a composition comprising: a. at least one C3 fluoroolefin; b. an effective amount of at least one inhibitor, including ortho-para-, meta-xylene, alpha (α)-methylstyrene, 2-methyl-alpha-methylstyrene (α,2-dimethylstyrene), 3-methyl-alpha-methylstyrene (α,3-dimethylstyrene), and 4-methyl-alpha-methylstyrene (α,4) dimethylstyrene), and mixtures of two or more; c. optionally, at least one of an antioxidant, a tracer, a compatibilizer, and a lubricant.

[0025] Another embodiment of the invention is a composition comprising: (i) at least about 99.5 weight percent HFO-1234yf; (ii) an effective stabilizing amount of up to about 0.5 weight percent of at least one oligomerization inhibitor, including xylene, alpha (α)-methylstyrene, 2-methyl-alpha-methylstyrene (α,2-dimethylstyrene), 3-methyl-alpha-methylstyrene (α,3-dimethylstyrene), and 4-methyl-alpha-methylstyrene (α,4-dimethylstyrene), C3-C4 hydrocarbons, and mixtures of two or more; (iii) up to about 0.5 weight percent HFO-1234ze.

[0026] Another embodiment of the invention is a composition comprising: (i) at least about 99.5 weight percent HFO-1234ze; (ii) an effective stabilizing amount of up to about 0.5 weight percent of at least one oligomerization inhibitor comprising one or more of xylene, alpha (α)-methylstyrene, 2-methyl-alpha-methylstyrene (α,2-dimethylstyrene), 3-methyl-alpha-methylstyrene (α,3-dimethylstyrene), and 4-methyl-alpha-methylstyrene (α,4-dimethylstyrene), C3-C4 hydrocarbons, and mixtures of two or more; (iii) up to about 0.5 weight percent HFO-1234yf.

[0027] In another particular embodiment, the oligomerization inhibitor comprises up to about 0.5 weight percent of at least one of propane, cyclopropane, propylene, butane, butene, isobutane, isobutene, meta-, ortho-, and para-xylene, alpha (α)-methylstyrene, 2-methyl-alpha-methylstyrene (α,2-dimethylstyrene), 3-methyl-alpha-methylstyrene (α,3-dimethylstyrene), and 4-methyl-alpha-methylstyrene (α,4-dimethylstyrene), 1 to 99 weight percent of 1234yf and 1 to 99 weight percent of trans-HFC-1234ze; about 0.5 weight percent up to about 25.5 weight percent 1234yf and about 10 weight percent trans-1234ze; 10 weight percent HFC-1234yf and 90 weight percent trans-HFC-1234ze, 20 weight percent HFC-1234yf and 80 weight percent trans-HFC-1234ze; 40 weight percent HFC-1234yf and 60 weight percent trans-HFC-1234ze; 60 weight percent HFC-1234yf and 40 weight percent trans-HFC-1234ze; 80 weight percent HFC-1234yf and 20 weight percent trans-HFC-1234ze, 90 weight percent HFC-1234yf and 10 weight percent trans-HFC-1234ze, or It is added to a composition containing 99 weight percent HFC-1234yf and 1 weight percent trans-HFC-1234ze.

[0028] Another embodiment of the present invention relates to a method for stabilizing a composition to reduce or eliminate oligomerization comprising adding an effective amount of at least one inhibitor including, but not limited to, one of meta-, ortho-, or para-xylene, alpha (α)-methylstyrene, 2-methyl-alpha-methylstyrene (α,2-dimethylstyrene), 3-methyl-alpha-methylstyrene (α,3-dimethylstyrene), and 4-methyl-alpha-methylstyrene (α,4-dimethylstyrene), propane, cyclopropane, propylene, butane, butene, isobutane, isobutene, and a mixture of two or more of a composition comprising at least one C3 fluoroolefin.

[0029] 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 inadvertent or undesirable contaminants retransmitted in at least one of conduits, lines, and other systems, packaging (containers), and refrigeration, air conditioning, or heat pump systems used to handle the fluoroolefin-containing composition, the method comprising adding an inhibitor comprising at least one propane, propylene, butane, butene, isobutane, isobutene, meta-, ortho-, para-xylene, and mixtures thereof, and mixtures thereof, to at least one of the systems, containers, and compositions comprising at least one C3 fluoroolefin.

[0030] A further embodiment of the present invention relates to a fluoroolefin-containing composition in a vessel or tank, wherein the fluoroolefin has a reduced likelihood of oligomerizing or homopolymerizing compared to a composition not including the inhibitor composition of the present invention.

[0031] 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 oligomers, homopolymers, or other polymeric products derived from the fluoroolefin.

[0032] 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.

[0033] 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, and fluoroolefin polyperoxides, peroxides, hydroperoxides, persulfates, percarbonates, perborates, and hydropersulfates.

[0034] Another embodiment of the invention relates to any of the aforementioned fluoroolefin compositions, wherein the inhibitor comprises at least one member selected from the group consisting essentially of one of propane, cyclopropane, propylene, butane, butene, isobutane, isobutene, meta-, ortho-, or para-xylene, alpha (α)-methylstyrene, 2-methyl-alpha-methylstyrene (α,2-dimethylstyrene), 3-methyl-alpha-methylstyrene (α,3-dimethylstyrene), and 4-methyl-alpha-methylstyrene (α,4-dimethylstyrene).

[0035] Another embodiment of the present invention is directed to any of the aforementioned compositions further comprising at least one lubricant.

[0036] Another embodiment of the invention relates to any of the aforementioned compositions comprising 1234yf, at least one of the inhibitors listed or identified above, and at least one or more of the following gases: air (N2 / O2 78 / 21 ratio), air (N2 / O2 > 78 / 21 ratio), O2, N2, Ar, CO2, CH4, He.

[0037] Another embodiment of the invention relates to any of the preceding compositions wherein the fluoroolefin comprises at least one component of HFO-1234yf and HFO-1234ze, or an HFO-1234yf+HFO-1234z blend.

[0038] 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.

[0039] Another embodiment of the invention is directed to any of the preceding compositions and at least one of HFO-1243zf, HCO-1140, HFO-1125zc, HFO-1234ze, trifluoropropyne, HFC-225ca, HFC-225cb, HFC-227ea, HFC-152a.

[0040] 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.

[0041] Another embodiment of the invention relates to any of the aforementioned compositions, at least one of HFO-1243zf, HFO-1140, 1125zc, HFO-1234ze, trifluoropropyne, HFC-225ca, HFC-225cb, HFC-227ea, and HFC-152a.

[0042] Another embodiment of the invention relates to at least one of HFO-1234ze, HFO-1243zf, HFO-Z-1336mzz, HFO-E-1336mzz, HFO-1327mz, HCFO-1122, HCFO-1122a, HFO-1123, HCFO-1233zd, HCFO-1224yd, HFO-E-1132, HFO-Z-1132, HFO-1132a, CFO-1112, HFO-E-1225ye, HFO-Z-1225ye, HFO-1234zc, HFO-1234ye, HFO-1234yc, HFO-1225zc, and HFC-152a.

[0043] 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.

[0044] Another embodiment of the present invention relates to any of the aforementioned compositions, wherein the oligomerization / homopolymerization inhibitor is present in an amount from about 30 to about 1,000 ppm, from about 30 ppm to about 2,000 ppm, and from about 30 to 3,000 ppm, and ranges therebetween.

[0045] Another embodiment of the present invention is a process for preparing an oligomerization / homopolymerization inhibitor having one component selected from at least one of C2 to C5 hydrocarbons and another component selected from d-limonene, l-limonene, β-pinene, α-pinene, α-terpinene, β-terpinene, γ-terpinene, and δ-terpinene, including but not limited to up to 0.1 weight percent of: d-limonene / propane, l-limonene / propane, β-pinene / propane, α-pinene / propane, α-terpinene / propane, β-terpinene / propane, γ-terpinene / propane, γ-terpinene / propane, d-terpinene / propane, β-terpinene / propane, α-terpinene / propane, β ...γ-terpinene / propane, d-terpinene / propane, β-terpinene / propane, α-terpinene / propane, β-terpinene / propane, γ-terpinene / propane, β-terpinene / propane, γ-terpinene / propane, β-terpinene / propane, β-terpinene / propane, γ- propane, and δ-terpinene / propane, d-limonene / cyclopropane, l-limonene / cyclopropane, β-pinene / cyclopropane, α-pinene / cyclopropane, α-terpinene / cyclopropane, β-terpinene / cyclopropane, γ-terpinene / cyclopropane, and δ-terpinene / cyclopropane, d-limonene / butane, l-limonene / butane, β-pinene / butane, α-pinene / propane, α-terpinene / butane, β-terpinene / butane, γ-terpinene / butane, and δ-terpinene / butane and mixtures of two or more selected from the group consisting of d-limonene / isobutane, l-limonene / isobutane, beta-pinene / isobutane, alpha-pinene / isobutane, alpha-terpinene / isobutane, beta-terpinene / isobutane, gamma-terpinene / isobutane, and delta-terpinene / isobutane, d-limonene / butene, l-limonene / butene, beta-pinene / butene, alpha-pinene / butene, alpha-terpinene / butene, beta-terpinene / butene, gamma-terpinene / butene, or delta-terpinene / butene, and %, but greater than 0, for example, 0.001 wt%, 0.005 wt%, 0.01 wt%, 0.015 wt%, 0.02 wt%, 0.03 wt%, 0.04 wt%, 0.05 wt% (500 ppm), 0.06 wt%, 0.07 wt%, 0.08 wt%, 0.09 wt%, 0.1 wt% (1000 ppm), 0.2 wt%, 0.3 wt% (3000 ppm), 0.4 wt%, and 0.5 wt%, and all values ​​therebetween, but not present in an amount that prevents the formation of oligomers, homopolymers, or other polymer products from being present in an amount that is less than about 0.03% by weight or less, or providing a composition free of oligomers, homopolymers, or other polymeric products.

[0046] 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).

[0047] Another embodiment of the invention relates to any of the aforementioned compositions, wherein the inhibitor comprises at least one of meta-, ortho-, para-xylene, propane, cyclopropane, propylene, butane, butene, and isobutene, alpha (α)-methylstyrene, 2-methyl-alpha-methylstyrene (α,2-dimethylstyrene), 3-methyl-alpha-methylstyrene (α,3-dimethylstyrene), and 4-methyl-alpha-methylstyrene (α,4-dimethylstyrene), and mixtures thereof.

[0048] Another embodiment of the invention relates to any of the preceding compositions, wherein the inhibitor comprises a liquid at the dispensing temperature of the refrigerant, e.g., below 100°C.

[0049] Another embodiment of the present invention relates to any of the aforementioned compositions, optionally further comprising at least one antioxidant.

[0050] 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.

[0051] Another embodiment of the invention relates to any of the aforementioned compositions, wherein the components include HFO-1234ze, HFO-1225yeZ, and 3,3,3-trifluoropropyne.

[0052] 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.

[0053] Another embodiment of the invention relates to any of the aforementioned compositions, wherein the composition consists essentially of HFO-1234yf and at least one of meta-, ortho-, para-xylene, propane, cyclopropane, propylene, butane, butene, isobutane, isobutene, and mixtures of two or more.

[0054] 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 at least one of meta-, ortho-, para-xylene, one of alpha (α)-methylstyrene, 2-methyl-alpha-methylstyrene (α,2-dimethylstyrene), 3-methyl-alpha-methylstyrene (α,3-dimethylstyrene), and 4-methyl-alpha-methylstyrene (α,4-dimethylstyrene), propane, cyclopropane, propylene, butane, butene, isobutane, and isobutene.

[0055] 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.

[0056] Another embodiment of the invention relates to any of the aforementioned methods using any of the aforementioned compositions for heating or cooling.

[0057] Another embodiment of the invention relates to a container containing a refrigerant comprising any of the aforementioned compositions.

[0058] The embodiments of the present invention may be used alone or in combination with each other, and different embodiments thereof may be combined and form part of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0059] The present invention provides a stabilized composition comprising at least one fluoroolefin and an effective amount of at least one inhibitor. By "stabilized" it is meant to refer to a composition comprising 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 compounds that may cause such interactions include air, oxygen, cumene hydroperoxide, and oxidizing agents such as fluoroolefin polyperoxides, peroxides, hydroperoxides, persulfates, percarbonates, perborates, 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 embodiments, 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 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 act as radical initiators, thereby causing fluoroolefins to oligomerize, homopolymerize, or form other polymeric products.

[0060] 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 hydrofluoroolefins. 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 even about 0 ppm of such products as measured by IR or NMR.

[0061] In another embodiment of the present invention, the composition of the present invention is provided with certain conventional inhibitor compounds, including at least one member selected from the group consisting of phenols, phosphorus-containing compounds, thiophosphates, butylated triphenyl phosphorothioates, organophosphates, or phosphites, sesquiterpene compounds such as famesol, famesene; ionic liquids, e.g., [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.

[0062] The compositions of the present invention have a variety of utilities, including, inter alia, as foam foams, 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 present 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.

[0063] 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.

[0064] 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.

[0065] 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).

[0066] The transitional phrase "consisting of" excludes any element, step, or ingredient not specified. When in a claim, such a phrase closes the claim to including 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 other than immediately following the preamble, the phrase is intended to limit only the elements set forth in that clause and does not exclude other elements from the claim as a whole.

[0067] The transitional phrase "consisting essentially of" is used to define compositions, methods, and methods that include materials, steps, mechanisms, components, or elements in addition to those literally disclosed, provided that these additionally included materials, steps, mechanisms, components, or elements do not materially affect the basic and novel characteristics of the claimed invention, particularly the mechanism 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."

[0068] 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 that use the terms "consisting essentially of" or "consisting of" (unless otherwise expressly stated).

[0069] 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.

[0070] 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.

[0071] 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 2Exemplary groups include, but are not limited to, CF3, C2F5, 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.

[0072] [Table 2-1]

[0073] [Table 2-2]

[0074] 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).

[0075] 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.

[0076] 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.

[0077] 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, 261-270 (1974).

[0078] 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.

[0079] 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.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] 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).

[0084] 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.

[0085] 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.

[0086] 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.

[0087] 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 3.

[0088] [Table 3]

[0089] The compositions of the invention may include a single compound of formula I or formula II, such as one of the compounds in Table 2 or Table 3, or may include a combination of compounds of formula I or formula II.

[0090] In another embodiment, the fluoroolefin may include the compounds listed in Table 4.

[0091] [Table 4-1]

[0092] [Table 4-2]

[0093] [Table 4-3]

[0094] [Table 4-4]

[0095] The compounds listed in Tables 3 and 4 are either commercially available or can be prepared by processes known in the art or as described herein.

[0096] 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 entirety of which is incorporated herein by reference.

[0097] 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.

[0098] 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 200-300° 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).

[0099] 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.

[0100] 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.

[0101] 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.

[0102] 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.

[0103] 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.

[0104] 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.

[0105] 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.

[0106] 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.

[0107] 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.

[0108] 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).

[0109] 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.

[0110] 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.

[0111] 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.

[0112] 2,3,3,3-tetrafluoro-1-propene can be prepared by converting at least one of HCFC-244bb or HFC-245eb to HFO-1234yf.

[0113] 1,3,3,3-Tetrafluoro-1-propene can be prepared from HFO-1234ze by HFC-245fa.

[0114] Many of the compounds of Formula I, Formula II, Table 2, Table 3, and Table 4 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.

[0115] In one specific embodiment, the fluoroolefin component of the compositions of the invention includes HFO-1234yf and / or HFO-1234ze. In another specific embodiment, the fluoroolefin includes 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 includes at least 99.5% by weight of 1234yf or 1234ze and less than 0.5% by weight and greater than 0.0001% by weight, less than 0.3, and in some cases less than 0.2% by weight of other fluoroolefins.

[0116] In another specific embodiment, the fluoroolefin component may include compositions disclosed in US Pat. Nos. 8,147,709 and 8,877,086, each of which is incorporated herein by reference in its entirety.

[0117] In another specific embodiment, the fluoroolefin component comprises greater than about 99.5% by weight 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, and in some cases from about 5 to about 50 ppm. The amount of HFO1243zf 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. 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.

[0118] 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, 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.

[0119] 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.

[0120] Any suitable effective amount of inhibitor can be used in the aforementioned compositions 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, as compared to a composition without the inhibitor. For cooling devices, such effective amounts of inhibitors can be determined by testing under the conditions of standard test ASHRAE 97-2007 (RA2017). In certain embodiments of the present invention, the effective amount is determined by the amount of inhibitor that, when combined with a composition comprising at least one fluoroolefin, allows the cooling device utilizing the composition comprising at least one fluoroolefin to use 1,1,1,2-tetrafluoroethane (R-134a) or other standard refrigerants (R-12, R-22, R-502, R-507A, R-508, R401A, R402, R403, R404, R405, R406, R407, R408, R409, R410, R411, R412, R413, R414, R415, R416, R417, R418, R419, R420, R421, R422, R423, R424, R425, R426, R427, R428, R429, R430, R431, R432, R433, R434, R435, R436, R437, R438, R439, R440, R441, R442, R443, R444, R445, R446, R447, R448, R449, R450, R451, R45 In the present invention, the amount of inhibitor can be said to be an amount that can provide the same level of refrigeration performance and cooling capacity as when a composition containing a refrigerant containing an amine compound (R-01B, R402A, R402B, R408, R-410A, R-404A, R407C, 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) is used as the working fluid.

[0121] The present invention employs an effective amount of at least one of the aforementioned oligomerization / homopolymerization inhibitors. Any suitable effective amount can be used, including from about 0.001 weight percent to about 0.5 weight percent (5000 ppm), from about 0.01 weight percent to about 0.5 weight percent, from 0.01 weight percent (100 ppm) to about 0.4 weight percent, from 0.01 weight percent to about 0.3 weight percent, from about 0.01 weight percent to about 0.2 weight percent, from 0.01 weight percent to about 0.1 weight percent (1000 ppm), and all ranges and values ​​therebetween, based on the total weight of the refrigerant composition. In one embodiment, an effective amount comprises at least one oligomerization / homopolymerization inhibitor comprising at least one of meta-, ortho-, para-xylene, propane, cyclopropane, propylene, butane, butene, isobutane, isobutene, and mixtures thereof, from about 10 to about 2,000 ppm by weight, from about 10 to about 1,000 ppm, in some cases from about 10 to about 500 ppm, from about 100 to 500 ppm, from about 100 ppm to about 2000 ppm, and all ranges therebetween.

[0122] In another embodiment, the inhibitor additive (alternatively, "inhibitor" or "additive") added to a composition containing at least HFO-124yf comprises a pair of inhibitors selected from C2-C5 hydrocarbons including at least one of ethane, propane, and at least one of limonene or pinene, and the inhibitor is present in an amount up to about 0.5 wt%, less than 0.5 wt% but greater than 0, e.g., 0.001 wt%, 0.005 wt%, 0.01 wt%, 0.015 wt%, 0.02 wt%, 0.03 wt%, 0.04 wt%, 0.06 wt%, 0.08 wt%, 0.09 wt%, 0.10 wt%, 0.11 wt%, 0.12 wt%, 0.13 wt%, 0.14 wt%, 0.15 wt%, 0.16 wt%, 0.17 wt%, 0.18 wt%, 0.19 wt%, 0.20 wt%, 0.21 wt%, 0.22 wt%, 0.23 wt%, 0.24 wt%, 0.25 wt%, 0.26 wt%, 0.27 wt%, 0.28 wt%, 0.29 wt%, 0.30 wt%, 0.31 wt%, 0.32 wt%, 0.33 wt%, 0.34 wt%, 0.35 wt%, 0.36 wt%, 0.37 wt%, 0.38 wt%, 0.39 wt%, 0.40 wt%, 0.41 wt%, 0.42 wt%, 0.43 wt%, 0.44 wt%, 0.45 wt%, 0.46 wt%, 0.47 wt%, 0.48 wt%, %, 0.05% (500 ppm), 0.06%, 0.07%, 0.08%, 0.09%, 0.1% (1000 ppm), 0.2%, 0.3% (3000 ppm), 0.4%, and 0.5% by weight, and all values ​​therebetween, but in an amount sufficient to keep the formation of oligomers, homopolymers, or other polymer products to less than about 0.03% by weight, or to provide a composition that is free of oligomers, homopolymers, or other polymer products.

[0123] Another embodiment of the invention is a mixture of about 0.5 to about 99.5 weight percent HFO-1234yf, about 20 to about 90 weight percent HFO-1234yf, about 20 to about 65 weight percent HFO-1234yrom, about 20 to about 40 weight percent HFO-1234yf; about 28 to about 32 weight percent HFO-1234yf; about 30 to about 32 weight percent HFO-1234yf; about 0.5 HFO-1234ze, about 99.5 weight percent HFO-1234ze, and HFC-32, HFC-134, and HFC-136. and up to 0.1 weight percent of an inhibitor pair selected from limonene / ethane, limonene / propane, limonene / butane, limonene / cyclopropane, limonene / isobutane, pinene / ethane, pinene / propane, pinene / butane, pinene / cyclopropane, pinene / isobutane, and terpinene / ethane, terpinene / propane, terpinene / butane, terpinene / cyclopropane terpinene / butane.

[0124] One embodiment of the present invention relates to any of the aforementioned compositions, further comprising at least one antioxidant. While any suitable oxidizing agent can be used, examples of suitable oxidizing agents 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, 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 2000 ppm, and in some cases from about 0.05 to about 1000 ppm. A specific example embodiment relates to the use of the aforementioned antioxidants with at least one inhibitor comprising at least one of meta-, ortho-, para-xylene, propane, cyclopropane, propylene, butane, butene, isobutane, and isobutene. One specific embodiment example relates to the use of the aforementioned antioxidants in conjunction with an inhibitor comprising at least one of meta-, ortho-, and para-xylene.

[0125] 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%, and in some cases from about 10 to about 50%.

[0126] 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).

[0127] In another embodiment, the additional compounds include linear, branched, and cyclic hydrocarbons, i.e., non-aromatic, at levels less than 0.5% by weight. Hydrocarbons of the present invention include compounds having only carbon and hydrogen. In particular, compounds having 2-7 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.

[0128] In another embodiment, the additional compound comprises a hydrocarbon containing a heteroatom, such as dimethyl ether (DME, CH3OCH3). DME is commercially available.

[0129] 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.

[0130] 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.

[0131] In another embodiment, the aforementioned 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 aforementioned 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.

[0132] 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.

[0133] 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.

[0134] 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 25 to about 75, from about 30 to about 60, and in some cases from about 30 to about 50. In a specific embodiment, the aforementioned amount of hydrofluorocarbon is blended with at least one of HFO-1234yf and HFO-1234ze.

[0135] 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-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.

[0136] 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, titled "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 as "mineral oils" in the field of compression refrigeration lubrication. Mineral oils include paraffins (i.e., saturated hydrocarbons with 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 as "synthetic oils" in the field of compression refrigeration lubrication. 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.

[0137] 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", RLShubkin, editor, 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).

[0138] 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, from about 1 to about 20, and in some cases from about 1 to about 3. 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.

[0139] In one embodiment of the present invention, in addition to the inhibitors of the present invention, the composition may desirably include at least one additive capable of improving 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.

[0140] 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.

[0141] 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), 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 of the formula IV: R1[Si(R2R3)4O] nThe siloxane may be of the formula Si(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, in which R1, R2, R3, R4, R5, or any combination thereof, are methyl, ethyl, propyl, or butyl groups, or any combination thereof.Exemplary siloxanes that may be used include hexamethyldisiloxane, polydimethylsiloxane, polymethylphenylsiloxane, dodecamethylpentasiloxane, decamethylcyclopentasiloxane, decamethyltetrasiloxane, octamethyltrisiloxane, or any combination thereof.

[0142] Serrano et al., incorporated by reference, specifically mentions that in one aspect of the invention, the siloxane is an alkyl siloxane containing from about 1 to about 12 carbon atoms, such as 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.

[0143] 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, it is 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, -NR2, -OH, -O-, -NHCOCH3, -NHCOR, -OCH3, -OR, -CH3, -C2H5, -R, or -C6H5, where R is a hydrocarbon (preferably a hydrocarbon containing from about 1 to about 100 carbon atoms). An activated aromatic molecule may be an alcohol or an ether in which an oxygen atom (i.e., the oxygen atom of an alcohol or ether group) is directly bonded to an aromatic group. An activated aromatic molecule may be an amine in which a nitrogen atom (i.e., the nitrogen atom of an amine group) is directly bonded to an aromatic group. By way of example, an activated aromatic molecule may be of the formula ArXR nwhere 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., CH group), R can be H or a carbon-containing group, when n=2, the R groups can be the same or different. For example, R can be H (i.e., hydrogen), Ar, an alkyl group, or any combination thereof. 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 highly preferred aromatic molecule activated for Friedel-Crafts addition reaction is diphenyl oxide.

[0144] From Serrano et al., paragraph

[0045] , 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. 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.

[0145] 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 by reference herein in its entirety) and by Singh et al. (U.S. Patent Application Serial No. 11 / 250,219, published as U.S. Patent Application No. 20060116310, paragraphs 34-42, which are expressly incorporated by reference herein in their entirety), 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.

[0146] Preferred additives include those described in U.S. Patent Nos. 5,152,926 and 4,755,316, each of which is incorporated herein by reference in its 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 in its entirety).

[0147] 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.

[0148] 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.

[0149] Preferred flame suppressants include those described in patent application "Compositions containing fluorine substituted olefins" Canadian Patent Application No. 2557873(A1), which is incorporated by reference along with fluorinated products such as HFC-125 and / or Krytox® lubricants, and in patent application "Compositions comprising fluoroolefins and uses thereof" WO 2009018117(A1), which is also incorporated by reference in its entirety.

[0150] 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.

[0151] 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.

[0152] The body to be cooled may be any space, location, or object requiring refrigeration or air conditioning. In stationary applications, the body may be the interior of a structure, i.e., a residential or commercial structure, or a storage location for perishable items such as food or medicine. In portable refrigeration applications, the body 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) and "swap bodies" (road and rail intermodal).

[0153] The present invention further relates to a process for producing heating comprising condensing, near a body to be heated, a composition comprising at least one fluoroolefin and an effective amount of an inhibitor comprising at least one of meta-, ortho-, and para-xylene, and then evaporating the composition.

[0154] The object to be heated may be any space, location, or object that requires heat. They may be located inside either a residential or commercial structure in a similar manner to the body 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 material being transported from solidifying within the transport container.

[0155] Another embodiment of the present invention relates to an air conditioning or refrigeration device comprising the aforementioned composition.

[0156] 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.

[0157] 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, filled cylinders, and secondary filled cylinders. The container can be constructed from any suitable material such as carbon steel, manganese steel, chromium-molybdenum steel, especially low alloy steel, stainless steel, and possibly aluminum alloys. The container can be equipped with a perforated top or valve suitable for dispensing flammable materials.

[0158] 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.

[0159] The following examples are provided to illustrate certain embodiments of the invention and are not intended to limit the scope of the appended claims.

[0160] Example 1 30 g of HFO-1234yf having a purity of at least 99.5% by weight *and initiator (with and without inhibitor) were heated in a 210 mL shake tube at the temperature and time shown in Table 3. The shake tube is inspected for polymer formation visually and by detecting the yf polymer peak using IR according to conventional methods. Polymer can also be detected by using conventional NMR methods.

[0161] * The HFO-1234yf contained 99.7 wt. % HFO-1234yf, 1,000 ppm HFO-1234ze, 50 ppm HFO-1225yeZ, 20 ppm 1234zf, 3 ppm trifluoropropyne, and the remainder contained compounds that did not affect the refrigerant performance of the mixture.

[0162] [Table 5]

[0163] Example 2 30 g of HFO-1234yf having a purity of at least 99.5 wt. %, with and without inhibitor, was heated in a 210 mL shaker tube at the temperature and time shown in Table 6. When inhibitor is present, 3 wt. % lubricant is included. The shaker tube is inspected for polymer formation visually and by detecting the yf polymer peak using IR according to conventional methods. Polymer can also be detected by using conventional NMR methods.

[0164] [Table 6] EXAMPLES

[0165] A refrigerant blend 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) is heated in a 210 mL shaker tube at the temperatures and times shown in Tables 6-9. When an inhibitor is present, 3 wt. % of the lubricant is included.

[0166] Examples 1-6 evaluate inhibitors containing Opteon™ XP-10 refrigerant (R513a) and a commercial lubricant. XP10 refrigerant contains 56% by weight HFO-1234yf and 44% by weight HFC-134a.

[0167] [Table 7]

[0168] POE32-3MAF and ND-11 are commercially available POE lubricants. ND-12 is a commercially available PAG lubricant. After heating, the shaker tubes are visually inspected for polymer formation and analyzed by NMR. N / D indicates that no polymer was found.

[0169] Table HFO-blend cooling and heating performance data comparison The cooling and heating performance of mixtures containing HFO1234yf are measured and compared to each other. Measurements included pressure in the evaporator (Evap) and condenser (Cond), compressor discharge temperature (Disch T), and average temperature gradient of the evaporator and condenser (Avg Temp Glide). Relative energy efficiency (COP), and volumetric capacity (Cap). The data were based on the following conditions:

[0170] [Table 8]

[0171] [Table 9]

[0172] [Table 10]

[0173] [Table 11]

[0174] [Table 12]

[0175] [Table 13]

[0176] [Table 14]

[0177] [Table 15]

[0178] 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, a. HFO-1234yf, b. an effective amount of at least one oligomerization / homopolymerization inhibitor, and i. The following gases: air (N2 / O2 78 / 21 ratio), air (N ２ / O2>78 / 21 ratio), O2, N2, Ar, CO ２ , C.H. ４ , He; ii. 1243zf, 1140, 1125zc, 1234ze, trifluoropropyne, 225ca, 225cb, 227ea, 152a, and iii. at least one of the following components: 1234ze, 1243zf, Z-1336mzz, E-1336mzz, 1327mz, 1122, 1122a, 1123, 1233zd, 1224yd, E-1132, Z-1132, 1132a, 1112, E-1225ye, Z-1225ye, 1234zc, 1234ye, 1234yc, 1225zc, and 152a; One of the Including, The composition is substantially free of oligomers, homopolymers, or other polymeric products derived from the fluoroolefin.

2. 1. A composition comprising: (i) at least HFO-1234yf and HFO-1234ze, (ii) at least one C １ and / or C ２ a hydrofluorocarbon and optionally carbon dioxide; (iii) one of xylene, alpha (α)-methylstyrene, 2-methyl-alpha-methylstyrene (α,2-dimethylstyrene), 3-methyl-alpha-methylstyrene (α,3-dimethylstyrene), and 4-methyl-alpha-methylstyrene (α,4-dimethylstyrene); ３ ~C ４ an effective stabilizing amount of at least one oligomerization / homopolymerization inhibitor comprising one or more of the following: (iv) optionally at least one additional HFO, HFO, HCFO, HFC, HCC, HCFC, nitrogen, and air component different from (ii); A composition comprising:

3. 10. The composition of claim 1, 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.

4. 4. The composition of claim 3, wherein the inhibitor comprises limonene, pinene, meta-, ortho-, and para-xylene, alpha (α)-methylstyrene, 2-methyl-alpha-methylstyrene (α,2-dimethylstyrene), 3-methyl-alpha-methylstyrene (α,3-dimethylstyrene), and 4-methyl-alpha-methylstyrene (α,4-dimethylstyrene), propane, cyclopropane, propylene, butane, butene, isobutene, and mixtures of two or more.

5. 5. The composition of claim 3 or 4, further comprising at least one lubricant.

6. The composition of claim 3, wherein the fluoroolefin comprises at least one component of HFO-1234yf and HFO-1234ze.

7. 7. The composition of claim 6 further comprising at least one member selected from the group consisting of HFC-32, HFC-125, HFC-134a, HFC-134, HFC-152a, 236fa, HFC-227ea, and carbon dioxide.

8. 8. The composition of claim 6 or 7, further comprising 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-244bb, and HFC-245cb.

9. 8. The composition of claim 6 or 7, further comprising at least one member selected from the group consisting of HCC-40, HCFC-22, CFC-115, HCFC-124, HCFC-1122, and CFC-1113.

10. The composition of claim 4, wherein the oligomeric inhibitor is present in an amount of about 30 to about 5,000 ppm.

11. 5. The composition of claim 4 further comprising at least one antioxidant component selected from the group consisting of butylated hydroxytoluene, butylated hydroxyanisole, tertiary butylhydroquinone, gallate, 2-phenyl-2-propanol, 1-(2,4,5-trihydroxyphenyl)-1-butone, phenol, bisphenolmethane derivatives, and 2,2'-methylenebis(4-methyl-6-t-butylphenol).

12. The composition of claim 6, wherein the oligomeric inhibitor comprises at least one of meta-, ortho-, and para-xylene.

13. The composition of claim 1 , wherein the inhibitor comprises a liquid.

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

15. 7. The composition of claim 6, further comprising at least one member selected from the group consisting of HFO-1225yeZ, HFO-1243zf, HFO-1234ze, HFC-236ea, HFC-245fa, and 3,3,3-trifluoropropyne.

16. The composition of claim 15, wherein the components include HFO-1234ze, HFO-1225yeZ, and 3,3,3-trifluoropropyne.

17. The composition comprises ammonia and CF ３ The composition of claim 1 , which is substantially free of at least one of I.

18. 10. The composition of claim 1, wherein the composition consists essentially of HFO-1234yf and at least one of meta-, ortho-, and para-xylene.

19. The composition of claim 15, wherein the composition consists essentially of HFO-1234yf, 3,3,3-trifluoropropyne, and at least one of meta-, ortho-, and para-xylene.

20. A composition comprising at least one fluoroolefin is prepared by mixing an amount of ３ ~C ４ 1. A method for reducing the formation of oligomers and homopolymers comprising contacting a hydrocarbon with at least one member selected from the group consisting of: limonene, pinene, xylene, and methylstyrene.

21. 21. The method of claim 20, 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 said contacting.

22. 3. A method for heating or cooling using the composition of claim 1 or claim 2.

23. A container comprising a refrigerant comprising the composition of any one of claims 1 to 4.

24. 1. A stabilized HFO-1234yf and 1234ze blend comprising one of meta-, ortho-, or para-xylene, one of alpha (α)-methylstyrene, 2-methyl-alpha-methylstyrene (α,2-dimethylstyrene), 3-methyl-alpha-methylstyrene (α,3-dimethylstyrene), and 4-methyl-alpha-methylstyrene (α,4) dimethylstyrene), propane, cyclopropane, propylene, butane, butene, isobutane, isobutene, in an amount effective to inhibit oligomerization of HFO-1234yf without affecting the performance or compatibility of the stabilized blend, even when combined with refrigerant oils and other conventional additives.

25. about 20 to about 40 weight percent HFO-1234yf, or about 28 to about 32 weight percent HFO-1234yf, or about 30 to about 32 weight percent HFO-1234yf, or about 62 to about 65 weight percent HFO-1234yf, or 25. The blend of claim 24 comprising from about 76 to about 80 weight percent HFO-1234yf.

26. 25. The blend of claim 23 or 24, comprising up to 0.5% by weight of meta-, ortho-, or para-xylene, alpha (α)-methylstyrene, 2-methyl-alpha-methylstyrene (α,2-dimethylstyrene), 3-methyl-alpha-methylstyrene (α,3-dimethylstyrene), and 4-methyl-alpha-methylstyrene (α,4) dimethylstyrene), propane, cyclopropane, propylene, butane, butene, isobutane, isobutene, and mixtures of two or more oligomeric inhibitors.

27. 26. The blend of claim 25, comprising 0.01 to 0.3 weight percent of an oligomeric inhibitor comprising one of meta-xylene, alpha (α)-methylstyrene, 2-methyl-alpha-methylstyrene (α,2-dimethylstyrene), 3-methyl-alpha-methylstyrene (α,3-dimethylstyrene), and 4-methyl-alpha-methylstyrene (α,4-dimethylstyrene), propane, or cyclopropane.

28. 1. A composition comprising: (i) about 99.5 weight percent HFO-1234yf or HFO-1234ze; (ii) at least one additional refrigerant component including HFO, HFO, HCFO, HFC, HCFC, nitrogen, and carbon dioxide; (iii) limonene, pinene, xylene, alpha (α)-methylstyrene, 2-methyl-alpha-methylstyrene (α,2-dimethylstyrene), 3-methyl-alpha-methylstyrene (α,3-dimethylstyrene), and 4-methyl-alpha-methylstyrene (α,4-dimethylstyrene), C ３ ~C ４ an effective stabilizing amount of at least one oligomerization inhibitor comprising one or more of the following: A composition comprising:

29. The inhibitor is: (1) C ２ ~C ５ 21. The composition of claim 1, 3, 4, 5, 6, 7, or 20, comprising a pair of inhibitors selected from (1) at least one of the following hydrocarbons: (a) d-limonene, l-limonene, β-pinene, α-pinene, α-terpinene, β-terpinene, γ-terpinene, and δ-terpinene.

30. The inhibitor is selected from the group consisting of d-limonene / propane, l-limonene / propane, beta-pinene / propane, alpha-pinene / propane, alpha-terpinene / propane, beta-terpinene / propane, gamma-terpinene / propane, and delta-terpinene / propane, d-limonene / cyclopropane, l-limonene / cyclopropane, beta-pinene / cyclopropane, alpha-pinene / cyclopropane, alpha-terpinene / cyclopropane, beta-terpinene / cyclopropane, gamma-terpinene / cyclopropane, and delta-terpinene / cyclopropane, d-limonene / butane, l-limonene / butane, beta-pinene / butane, alpha-pinene / propane, 5. The blend of claim 1 or 4, comprising a pair of inhibitors selected from bread, alpha-terpinene / butane, beta-terpinene / butane, gamma-terpinene / butane, and delta-terpinene / butane, d-limonene / isobutane, l-limonene / isobutane, beta-pinene / isobutane, alpha-pinene / isobutane, alpha-terpinene / isobutane, beta-terpinene / isobutane, gamma-terpinene / isobutane, and delta-terpinene / isobutane, d-limonene / butene, l-limonene / butene, beta-pinene / butene, alpha-pinene / butene, alpha-terpinene / butene, alpha-terpinene / butene, gamma-terpinene / butene, or delta-terpinene / butene.

31. 21. The method of claim 20, wherein the fluoroolefin comprises HFO-1234yf and the inhibitor comprises a pair of inhibitors selected from propane and limonene, and propane and pinene.

32. d-limonene / propane, l-limonene / propane, β-pinene / propane, α-pinene / propane, α-terpinene / propane, β-terpinene / propane, γ-terpinene / propane, and δ-terpinene / propane, d-limonene / cyclopropane, l-limonene / cyclopropane, β-pinene / cyclopropane, α-pinene / cyclopropane, α-terpinene / cyclopropane, β-terpinene / cyclopropane, γ-terpinene / cyclopropane, and δ-terpinene / cyclopropane, d-limonene / butane, l-limonene / butane, β-pinene / butane, α-pinene / propane, α-terpinene / butane, β-terpinene / cyclopropane, 4. The composition according to claim 1, comprising a pair of inhibitors selected from pinene / butane, gamma-terpinene / butane and delta-terpinene / butane, d-limonene / isobutane, l-limonene / isobutane, beta-pinene / isobutane, alpha-pinene / isobutane, alpha-terpinene / isobutane, beta-terpinene / isobutane, gamma-terpinene / isobutane and delta-terpinene / isobutane, d-limonene / butene, l-limonene / butene, beta-pinene / butene, alpha-pinene / butene, alpha-terpinene / butene, beta-terpinene / butene, gamma-terpinene / butene or delta-terpinene / butene in an amount of up to 0.5% by weight.

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