Hydrocarbon additives for 1234yf and HFC compositions, and methods for their production, storage, and use - Patents.com

Abstract

The present disclosure relates to a composition comprising HFO-1,1,1,2-tetrafluoropropene (HFO-1234yf), at least one of HFC-32 (1,1-difluoromethane), HFC-134a (1,1,1,2-tetrafluoroethane), pentafluoroethane (HFC-125), and carbon dioxide, and at least one additive selected from one or more C3-C4 hydrocarbons, xylene, methylstyrene, and combinations thereof, which functions as a fluoroolefin oligomerization / polymerization inhibitor or chain transfer component to prevent the formation of oligomeric or polymeric by-products.

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) This application relates to and incorporates by reference the entire disclosures of the applicant's concurrently filed application number FL2040-WO01, as well as U.S. Provisional Applications Nos. 63 / 321120 and 63 / 321,118, each filed on March 18, 2022, and U.S. Applications Nos. 63 / 344,904 and 63 / 344,899, each filed on May 23, 2022 (by the same named inventors, Sheng Peng and Barbara Haviland Minor of The Chemours Company FC, LLC).

[0002] FIELD OF THEINVENTION The present invention relates to a stabilized composition mixture comprising HFO-1234yf (2223-tetrafluoropropene), at least one of C1 and / or C2 hydrofluorocarbons, optionally containing carbon dioxide, and at least one oligomerization / polymerization inhibitor or chain transfer agent selected from one or more of xylene, methylstyrene, C2-C5 hydrocarbons, and mixtures of two or more. [Background technology]

[0003] Fluoroolefins and fluoroolefin blends have been proposed as refrigerants, in part due to their low global warming potential (GWP) and low ozone depletion potential (ODP). 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, certain fluoroolefins have been observed to oligomerize or polymerize 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), and to generate unwanted by-products via oligomerization or homopolymerization. Such oligomerization or homopolymerization can occur when fluoroolefins are utilized as refrigerants or heat transfer fluids, or when fluoroolefins are stored, either alone or in admixture with other refrigerant components, in closed container systems, for example when fluoroolefins are stored in transport containers or canisters.

[0004] The formation of undesirable by-products may occur by any number of different mechanisms. Examples of stabilized compositions are disclosed in JP2009298918, U.S. Patent Nos. 6,969,701, 8,133,407, U.S. Patent Application Publication Nos. 2006 / 0022166, 2006 / 0043330, 2008 / 0157022, and WO2007 / 126760, as well as EP2057245, U.S. Patent Nos. 8,101,094, 8,535,555, 8,097,181, and 8,075,796, the entire disclosures of each of which are incorporated herein by reference. Other stabilized compositions are disclosed in related co-pending U.S. Patent Application Publication Nos. 2021 / 0108119, 2021 / 0040368, and 202110340421, each of which is incorporated by reference in its entirety into this specification.

[0005] Under certain abnormal conditions and in the presence of unwanted contaminants which may function as initiators, fluoroolefins may oligomerize or homopolymerize in the presence of certain contaminants which may be present. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] U.S. Provisional Application No. 63 / 321120 [Patent Document 2] U.S. Provisional Application No. 63 / 321,118 [Patent Document 3] U.S. Application No. 63 / 344,904 [Patent Document 4] U.S. 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 Application Publication No. 2021 / 0108119 [Patent Document 18] U.S. Patent Application Publication No. 2021 / 0040368 [Patent Document 19] U.S. Patent Application Publication No. 202110340421 [Non-patent literature]

[0007] [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]

[0008] Thus, there is a continuing need in the art for stabilized fluoroolefin-containing compositions in which the potential for oligomerization or homopolymerization is reduced, if not eliminated. [Means for solving the problem]

[0009] Disclosed herein is a refrigerant mixture comprising at least 2,3,3,3-tetrafluoropropene (HFO-1234yf), at least one of C1 and / or C2 hydrofluorocarbons, and optionally carbon dioxide, and an effective amount of up to about 0.5% by weight, based on the total weight of the refrigerant components in the composition, of a radical inhibiting additive that inhibits oligomerization / polymerization of the fluoroolefin component in the composition. The effective amount of the radical inhibiting additive inhibits oligomerization and / or polymerization of the olefin component without substantially affecting the performance or compatibility of the stabilized refrigerant composition, even when combined with refrigerant oils and other conventional additives.

[0010] Representative C1 and C2 hydrofluorocarbon compounds include, but are not limited to, difluoromethane (HFC-32 or R-32), pentafluoroethane (CF3CHF2, HFC-125, R-125), and 1,1,1,2-tetrafluoroethane (CHF3CFH2, HFC-134a, R-134a). An effective amount of a radical inhibiting additive, i.e., an oligomerization / polymerization inhibitor or chain transfer agent, such as C2-C5 hydrocarbons, xylene, methylstyrene, and up to 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, and 0.5 wt% of ethane, propane, cyclopropane, propylene, butane, isobutane, butene, isobutene, 2-methylbutane, meta-xylene, ortho-xylene, 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), optionally in combination with at least one compatibilizer to improve compatibility / miscibility with mineral oils and alkylbenzenes and lubricants including POE, PVE, and PAG, and optionally at least one solubilizer to improve solubility with UV dyes and other refrigerant additives.

[0011] Also disclosed herein is a method for reducing the formation of oligomer and homopolymer products or by-products, comprising contacting a composition comprising at least 2,3,3,3-tetrafluoropropene (HFO-1234yf) and at least one of difluoromethane (HFC-32), pentafluoroethane (HFC-125), and 1,1,1,2-tetrafluoroethane (HFC-134a), and optionally containing at least one of HFC-125 and CO2, with an effective amount of a radical inhibiting additive, such as meta-xylene, ortho-xylene, or para-xylene, or 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), to form a stable composition or composition blend, and a method for storing the stabilized fluoroolefin mixture in a storage tank or container.

[0012] Also disclosed herein is a method of 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) and at least one of difluoromethane (HFC-32), pentafluoroethane (HFC-125), and 1,1,1,2-tetrafluoroethane (HFC-134a), and optionally at least one of HFC-125 and CO2, with an effective amount of a radical inhibiting additive, such as limonene or pinene, alone or in combination with propane.

[0013] 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 62 to 65 weight percent HFO-1234yf, Also disclosed herein are compositions comprising about at least one, and up to 0.1 weight percent, of an inhibitor pair selected from limonene / ethane, limonene / propane, limonene / butane, limonene / cyclopropane, pinene / ethane, limonene / isobutane, pinene / propane, pinene / butane, pinene / cyclopropane, pinene / isobutane, and terpinene / ethane, terpinene / propane, terpinene / butane, terpinene / cyclopropane, terpinene / butane.

[0014] One component is selected from at least one of C2 to C5 hydrocarbons and the other component is selected from d-limonene, l-limonene, β-pinene, α-pinene, α-terpinene, β-terpinene, γ-terpinene, and δ-terpinene, and up to 0.1 weight percent of d-limonene / propane, l-limonene / propane, β-pinene / propane, α-pinene / propane, α-terpinene / propane, β-terpinene pinene / 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 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, γ-terpinene / isobutane, and δ-terpinene / isobutane. Also disclosed herein are oligomeric inhibitor pairs selected from mixtures of two or more including, but not limited to, butane, d-limonene / butene, l-limonene / butene, β-pinene / butene, α-pinene / butene, α-terpinene / butene, β-terpinene / butene, β-terpinene / butene, α-pinene / butane, α-terpinene / butene, γ-terpinene / butene, or δ-terpinene / butene.

[0015] Also disclosed herein is a method of using the stabilized fluoroolefin-hydrofluorocarbon mixture as a blend as a heat exchange fluid.

[0016] Also disclosed herein is a vessel filled with at least an effective amount of at least one oligomerization / polymerization inhibitor or chain transfer agent, more specifically a stabilized fluoroolefin-hydrofluorocarbon mixture comprising at least ethane, propane, cyclopropane, propylene, butane, isobutane, butene, isobutene, and mixtures thereof.

[0017] Also disclosed herein is a vessel filled with at least an effective amount of at least one oligomerization / polymerization inhibitor, more specifically, a stabilized fluoroolefin-hydrofluorocarbon mixture comprising meta-xylene, ortho-xylene, or para-xylene, and mixtures thereof. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] The present invention can improve the ability of hydrofluoroolefin-containing compositions, such as a mixture of 2,3,3,3-tetrafluoropropene and at least one of C1 and / or C2 hydrofluorocarbons, including difluoromethane, pentafluoroethane, and 1,1,2,2-tetrafluoroethane, optionally containing carbon dioxide, to withstand normal storage or abnormal conditions and avoid potential problems associated with possible initiators (e.g., contaminants such as air, Loctite, cleaning solutions containing peroxides) that oligomerize or homopolymerize fluoroolefins (e.g., tetrafluoropropene) by adding at least one inhibitor. Furthermore, the fluoroolefin composition includes a blend of at least HFO-1234yf and one or more of R-32, R-125, and R-134a.

[0019] 2,3,3,3-Tetrafluoropropene is also sometimes referred to as 2,3,3,3-tetrafluoropropene (HFO-1234yf), HFC-1234yf, R-1234yf, or 1234yf. HFO-1234yf can be made by methods known in the art, such as by dehydrofluorination of 1,1,1,2,3-pentafluoropropane (HFC-245eb) or 1,1,1,2,2-pentafluoropropane (HFC-245cb).

[0020] Difluoromethane (HFC-32 or R-32) is commercially available or can be made by methods known in the art, such as, for example, the dechlorination of methylene chloride. Similarly, pentafluoroethane and 1,1,2,2-tetrafluoroethane are commercially available or can be made by methods known in the art.

[0021] Disclosed are blends of two or more refrigerant components, such as HFO-1234yf and (1) HFC-32, (2) HFC-32 and HFC-134a, (3) HFC-32, HFC-125, HFC-134a, and carbon dioxide, as well as commercially available blends including, but not limited to, R513a, R449a, R454C, and R463A.

[0022] "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. Although the oligomerization or homopolymerization reaction can be accelerated by relatively high temperatures, such reactions can also occur under ambient conditions depending on the concentration and type of initiator (e.g., contaminants). 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 equipment (e.g., resins used in sealing). The stabilized composition can be useful in cooling / heating systems and as a replacement for existing refrigerants with higher global warming potential.

[0023] To avoid possible instability of at least 2,3,3,3-tetrafluoropropene (HFO-1234yf) fluoroolefins, it has been found that the addition of certain inhibitor compounds, namely, propane, cyclopropane, propylene, butane, isobutane, butene, and isobutene, meta-xylene, ortho-xylene, 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), to a fluoroolefin-containing composition increases its stability during packaging, storage, and use in refrigeration, air conditioning, or heat pump system applications and inhibits the formation of oligomeric and / or homopolymeric products and by-products. In one embodiment, the present invention relates to a composition comprising 2,3,3,3-HFO-1234yf and HFC-32, and an effective amount of an inhibitor capable of interacting or reacting with O2 and fluoroolefin polyperoxides and subsequently inhibiting or preventing the reaction of such compounds with hydrofluoroolefins. The 2,3,3,3-HFO-1234yf and HFC-32 composition of certain embodiments comprises about 20 to about 85 weight percent HFO-1234yf and about 80 to about 15 weight percent HFC-32, based on the total amount of HFO-1234yf and HFC-32 in the composition. In certain embodiments, the composition comprises about 20 to about 40 weight percent HFO-1234yf and about 60 to about 80 weight percent HFC-32. In other embodiments, the composition contains about 30 to about 32 weight percent HFO-1234yf and about 68 to about 70 weight percent HFC-32. In other embodiments, the composition comprises from about 77 to about 80 weight percent HFO-1234yf and from about 20 to about 23 weight percent HFC-32.

[0024] In certain embodiments, the 2,3,3,3-HFO-1234yf and HFC-32 composition comprises from about 20 to about 85 weight percent HFO-1234yf and from about 80 to about 15 weight percent HFC-32; from about 20 to about 40 weight percent HFO-1234yf; from about 60 to about 80 weight percent HFC-32; from about 30 to about 32 weight percent HFO-1234yf and from about 68 to about 70 weight percent HFC-32; from about 77 to about 80 weight percent HFO-1234yf; and from about 20 to about 23 weight percent HFC-32; each up to 0.5 weight percent , ethane, propane, cyclopropane, propylene, butane, isobutane, butene, isobutene, limonene, pinene, 2-methylbutane, meta-xylene, ortho-xylene, 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), limonene, pinene, and C3 limonene- or pinene mixtures.

[0025] Limonene has the following structure:

[0026] [ka]

[0027] Xylene and (alpha) methylstyrene (AMS) have the following chemical structures:

[0028] [Table 1-1]

[0029] [Table 1-2]

[0030] Examples of hydrocarbon inhibitors that can interact or react with O2 and fluoroolefin polyperoxides and their derivatized radical chains and subsequently inhibit or prevent the reaction of such compounds with hydrofluoroolefins include C2-C5 hydrocarbons, including ethane, propane, cyclopropane, propylene, butane, isobutane, butene, isobutene, 2-methylbutane, and mixtures of two or more, in a total amount up to 0.5% by weight.

[0031] In one embodiment, the invention relates to a composition comprising HFO-1234yf, HFC-134a, and an effective amount of an inhibitor capable of interacting or reacting with O2 and fluoroolefin polyperoxides and subsequently inhibiting or preventing the reaction of such compounds with hydrofluoroolefins. Examples of inhibitors include propane, cyclopropane, propylene, butane, isobutane, butene, isobutene, meta-xylene, ortho-xylene, para-xylene, and mixtures of two or more, in effective amounts up to 0.5% by weight of the HFO and HFC components.

[0032] In one embodiment, the invention relates to a composition comprising HFC-125, HFO-1234yf, HFC-134a, and an effective amount of an inhibitor capable of interacting or reacting with O2 and fluoroolefin polyperoxides and subsequently inhibiting or preventing the reaction of such compounds with hydrofluoroolefins. Examples of inhibitors include propane, cyclopropane, propylene, butane, isobutane, butene, isobutene, meta-xylene, ortho-xylene, para-xylene, and mixtures of two or more used in an effective amount up to 0.5% by weight of the HFO and HFC components.

[0033] In one embodiment, the present invention relates to a composition comprising HFC-125, HFC-134a, HFC-32, HFO-1234yf, CO2, and an effective amount of an inhibitor capable of interacting or reacting with O2 and fluoroolefin polyperoxides and subsequently inhibiting or preventing the reaction of such compounds with hydrofluoroolefins. Examples of inhibitors include propane, cyclopropane, propylene, butane, isobutane, butene, isobutene, meta-xylene, ortho-xylene, para-xylene, and mixtures of two or more used in an effective amount up to 0.5% by weight of the HFO and HFC components.

[0034] The inhibitor additives of the present invention can prevent polymerization by functioning as either a polymerization inhibitor or a chain transfer agent, thereby preventing oligomerization or homopolymerization of the 2,3,3,3-tetrafluoropropene (HFO-1234yf) component of the refrigerant composition, mixture, or blend. The stabilizing inhibitor additives can also be useful as compatibilizers to improve compatibility / miscibility with mineral oils and alkylbenzenes, as well as lubricants including POE, PVE, and PAG. They can also be useful as solubilizers to improve solubility with UV dyes and other refrigerant additives.

[0035] In one embodiment, the inhibitor additive (or alternatively, "inhibitor" or "additive") comprises a C2-C5 hydrocarbon including at least one of ethane, propane, cyclopropane, propylene, butane, butane, isobutene, and 2-methylbutane.

[0036] In another embodiment, the inhibitor additive (or alternatively, "inhibitor" or "additive") added to a composition containing at least HFO-124yf comprises an inhibitor pair selected from C2-C5 hydrocarbons including ethane, propane, and at least one of limonene or pinene, the inhibitor being 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%, 0.05 wt%, 0.06 wt%, 0.07 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%, 0.05% (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 maintain the formation of oligomers, homopolymers, or other polymer products at less than about 0.03% by weight, or to provide a composition that is free of oligomers, homopolymers, or other polymer products.

[0037] In another embodiment, the inhibitor additive comprises at least one of meta-xylene, ortho-xylene, para-xylene, or 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).

[0038] In another embodiment of the invention, the inhibitor comprises meta-xylene, ortho-xylene, para-xylene, and mixtures of two or more.

[0039] In one embodiment of the invention, the inhibitor comprises one or a mixture of two or more 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).

[0040] In one embodiment, the composition of the present invention comprises: At least HFO-1234yf; at least one of C1 and C2 hydrofluorocarbons, and optionally carbon dioxide; an effective stabilizing amount of at least one inhibitor comprising one or more of a C3-C4 hydrocarbon, a xylene, and combinations thereof; Optionally, the at least one additional HFO, HCFO, (ii) comprises, or consists essentially of, a different HFC, HCC, HCFC, nitrogen, and air component.

[0041] An embodiment of the present invention relates to a composition or composition blend comprising: a. at least 2,3,3,3-tetrafluoropropene (HFO-1234yf); b. One or more C2 or C3 hydrofluorocarbons; c. an effective amount of at least one oligomer / polymer inhibitor comprising propane, cyclopropane, propylene, butane, isobutane, butene isobutene, meta-xylene, ortho-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); and d. Optionally, at least one additional HFO, HCO, HFC, HCC, HCFC, nitrogen, air, and carbon dioxide (CO2) component.

[0042] An embodiment of the present invention relates to a composition or composition blend comprising: - at least 2,3,3,3-tetrafluoropropene (HFO-1234yf); - one or more C2 or C3 hydrofluorocarbons; - an effective amount of from 0.001 weight percent to 0.3 weight percent of propane, cyclopropane, propylene, butane, isobutane, butene, and isobutene, meta-xylene, ortho-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), as well as mixtures of two or more, as oligomerization inhibitors; and Optionally, at least one additional HFO, HCO, HFC, HCC, HCFC, nitrogen, air, and carbon dioxide (CO2) component.

[0043] 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 adventitious or unwanted contaminants present in at least one of conduits, transfer lines (including pipes and tubing), and other systems used to handle the fluoroolefin-containing composition; packaging (containers), and refrigeration units, air conditioning, heat pumps, or chiller systems, the method comprising adding an oligomer inhibitor, such as propane, cyclopropane, propylene, butane, isobutane, butene, isobutene, meta-xylene, ortho-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), and mixtures of two or more, to the composition being transported.

[0044] A further embodiment of the present invention relates to a composition comprising at least 2,3,3,3-tetrafluoropropene (HFO-1234yf) and at least one of HFC-32, HFC-125, HFC-134a, and carbon dioxide in a container, wherein the fluoroolefins of the composition are less likely to oligomerize or homopolymerize compared to a composition not including the inhibitor composition of the present invention.

[0045] One embodiment of the present invention relates to a composition comprising at least 2,3,3,3-tetrafluoropropene (HFO-1234yf), HFC-32, and an effective amount of at least one inhibitor, the composition being substantially free of oligomers, homopolymers, or other polymeric products derived from 2,3,3,3-tetrafluoropropene (HFO-1234yf).

[0046] Another embodiment of the invention is directed to any of the aforementioned compositions comprising greater than less than about 0.03% by weight of oligomers, homopolymers, or other polymeric products.

[0047] Another embodiment of the invention relates to any of the preceding compositions wherein the inhibitor is present in an amount up to about 0.5% by weight, less than 0.5% by weight but greater than 0, for example, 0.001%, 0.005%, 0.01%, 0.015%, 0.02%, 0.03%, 0.04%, 0.05% by weight (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 maintain formation of oligomers, homopolymers, or other polymeric products at less than about 0.03% by weight, or to provide a composition free of oligomers, homopolymers, or other polymeric products.

[0048] Another embodiment of the invention relates to any of the aforementioned additional compositions comprising at least one lubricant, hi some embodiments, the lubricant is selected from the group consisting of POE, PAG, and PVE.

[0049] In further embodiments, the stabilized 2,3,3,3-tetrafluoropropene (HFO-1234yf) and at least one of HFC-32, HFC-125, HFC-134a, and carbon dioxide compositions disclosed herein comprise at least one or more of the following gases: air (N2 / O2 78 / 21 ratio), air (N2 / O2 > 78 / 21 ratio), O2, N2, Ar, CH4, and He.

[0050] The stabilized HFO-1234yf disclosed herein, as well as at least one of HFC-32, HFC-125, HFC-134a, and carbon dioxide compositions, include at least one of the following additional components: HFO-1234ze, 1243zf, HFO-Z-1336mzz, HFO-E-1336mzz, HFO-1327mz, HFO-1122, HFO-1122a, HFO-1123, HFO-1233zd, 1224yd, E-1132, Z-1132, 1132a, CFO-1112, HFO-E-1225ye, HFO-Z-1225ye, HFO-1234zc, HFO-1234ye, HFO-1234yc, HFO-1225zc, HFC-152a.

[0051] The stabilized HFO-1234yf disclosed herein, as well as HFC-32, HFC-125. At least one of the compositions of HFC-134a and carbon dioxide includes at least one of the following additional components: 1234ze, 1243zf, HFO-Z-1336mzz, HFO-E-1336mzz, HFO-1327mz, HFO-1122, HFO-1122a, HFO-1123, HFO-1233zd, HFO-1224yd, HFO-E-1132, HFO-Z-1132, HFO-1132a, HCFO-1112, HFO-E-1225ye, HFO-Z-1225ye, HFO-1234zc, HFO-1234ye, HFO-1234yc, HFO-1225zc, HFC-152a.

[0052] The stabilized HFO-1234yf and HFC-32 compositions disclosed herein include at least one of the following additional components: HFC-125, HFC-134, HFC-134a, HFC-152a, and CO2, as well as other commercially available HFOs (such as HFO-1234zeE, HFO-1233zdE, etc.).

[0053] The stabilized HFO-1234yf disclosed herein, as well as HFC-32, HFC-125, HFC-134a, and carbon dioxide compositions contain at least one of the following additional components: 143a, 22, and 12.

[0054] The stabilized HFO-1234yf and HFC-32 compositions disclosed herein contain at least one of the following components: HFC-134a: R-114, R-114a, R-1122, R-40, R-134, R-143a, R-125.

[0055] The stabilized HFO-1234yf disclosed herein, as well as HFC-32, HFC-125, HFC-134a, and carbon dioxide compositions contain at least one of the following additional components: HFC-125, R-115, R-1113, R-40, R-23, R-143a.

[0056] The stabilized composition includes HFO-1234yf and at least one of HFC-32, HFC-125, HFC-134a, and carbon dioxide, and may include at least one or more of the following components: R-152a, R-1140, R-161.

[0057] The compositions of the invention have a variety of utilities, including, inter alia, as blowing agents, aerosol propellants, sterilants, or working fluids, including heat transfer media, such as heat transfer fluids and refrigerants for use in refrigeration systems, refrigerators, air conditioning systems, heat pumps, chillers, etc. The compounds of the invention are particularly suitable for use in portable air conditioning systems and as components for making refrigerant blends for use in stationary heat transfer systems, all of which systems include one or more fluid circulation circuits, such as refrigeration circuits.

[0058] 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.

[0059] In certain embodiments, the circulating heat transfer medium of an existing refrigerant system is removed and replaced with a stabilized refrigerant, using the stabilized composition from a bulb refrigerant reservoir containing the stabilized composition to provide a refrigerant circuit containing the stabilized composition disclosed herein.

[0060] 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.

[0061] As used herein, a refrigerant is a compound or mixture (blend) 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.

[0062] 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).

[0063] The transitional phrase "consisting of" excludes any unspecified element, step, or ingredient. 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 "consists of" appears within a clause in the body of a claim rather than immediately following the introductory paragraph, the phrase is limited to only the elements recited in that clause and does not exclude other elements from the claim as a whole.

[0064] 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."

[0065] It should be readily understood that where applicants have defined an invention or a portion thereof with open-ended terms such as "comprising," the description should be construed to also include inventions using the terms "consisting essentially of" or "consisting of" (unless otherwise expressly stated).

[0066] 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.

[0067] As used herein, the term fluoroolefin describes a compound that contains carbon atoms, fluorine atoms, and optionally hydrogen atoms. As used herein, the term chlorofluoroolefin describes a compound that contains carbon atoms, chlorine atoms, fluorine atoms, and optionally hydrogen atoms. In one embodiment, the fluoroolefin used in the composition of the present invention comprises a compound having 3 to 12 carbon atoms. In another embodiment, the fluoroolefin comprises a compound having 3 to 10 carbon atoms, and in yet another embodiment, the fluoroolefin comprises a compound having 3 to 7 carbon atoms. Representative chlorofluoroolefins and fluoroolefins include, but are not limited to, all of the compounds listed in Table 1 below.

[0068] [Table 2]

[0069] Representative HFC, HCC, HCFC components that can be used in the disclosed stabilized compositions include, but are not limited to, the compounds listed in Table 1 above.

[0070] The compounds listed in Table 1 are either commercially available or can be prepared by processes known in the art or as described herein.

[0071] 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, which is incorporated herein by reference.

[0072] 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.

[0073] 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.

[0074] In some embodiments, the compositions include specific weight ratios of HFO-1234yf and HFC-32. Difluoromethane (HFC-32 or R-32) is commercially available or can be made by methods known in the art, such as, for example, dechlorination of methylene chloride. In one embodiment, the HFC-32 component of the compositions of the invention includes HFC-32 having a purity of greater than 99% by weight, greater than 99.5% by weight, and in some cases, a purity of greater than 99.5 to 99.98 weight percent. In another specific embodiment, the HFC-32 component has a purity of greater than 99.99% by weight. In one embodiment, the HFC-32 component further comprises HFC-32 and at least one additional compound selected from the group consisting of HFC-23 (trifluoromethane), HCFC-31 (chlorofluoromethane), HFC-41 (fluoromethane), HFC-143a (1,1,1-trifluoroethane), HCFC-22 (chlorodifluoromethane), CFC-12 (dichlorodifluoromethane), HCC-40 (chloromethane), and HFC-134a (1,1,1,2-tetrafluoroethane).

[0075] In some embodiments, the compositions of the present invention comprise oligomeric / polymeric inhibitors, HFO-1234yf, and HFC-32 in a particular weight ratio. In certain embodiments, the compositions comprise about 20 to about 85 weight percent HFO-1234yf and about 80 to about 15 weight percent HFC-32, based on the total amount of HFO-1234yf and HFC-32 in the composition. In certain embodiments, the compositions comprise about 20 to about 40 weight percent HFO-1234yf and about 60 to about 80 weight percent HFC-32. In other embodiments, the compositions contain about 30 to about 32 weight percent HFO-1234yf and about 68 to about 70 weight percent HFC-32. In other embodiments, the compositions comprise about 77 to about 80 weight percent HFO-1234yf and about 20 to about 23 weight percent HFC-32.

[0076] In specific embodiments, the inhibitor-containing composition may contain: about 31% by weight HFO-1234yf and about 69% by weight HFC-32; about 65% by weight HFO-1234yf and about 35% by weight HFC-32; or About 78.5% by weight HFO-1234yf and about 21.5% by weight HFC-32.

[0077] In specific embodiments, the composition may contain one of the following: a. about 20 to about 40 weight percent HFO-1234yf; b. about 28 to about 32 weight percent HFO-1234yf; c. about 30 to about 32 weight percent HFO-1234yf; d. about 62 to about 65 weight percent HFO-1234yf, and e. about 76 to about 80 weight percent HFO-1234yf.

[0078] In one embodiment, a stable refrigerant composition is formed by adding up to about 0.5 wt. % of at least one or more of a C3-C4 hydrocarbon and a xylene to a mixture including one of the following: a. HFO-1234yf and the balance about 14 weight percent HFC-134a; b. HFO-1234yf and the balance about 25.7 weight percent HFC-134a; c. about 55 to about 75 weight percent HFO-1234yf and about 25 weight percent to about 45 weight percent HFC-134a; d. about 56 to about 75 weight percent HFO-1234yf and about 25 weight percent to about 44 weight percent HFC-134a; e. HFO-1234yf, with the balance being about 30 weight percent HFC-125, about 14 weight percent HFC-134a, about 36 weight percent HFC-32, and about 6 weight percent CO2; f. HFO-1234yf, with the balance being about 28 to about 32 weight percent HFC-32; and g. HFO-1234yf and the balance about 68 to 72 weight percent HFC-32.

[0079] In one embodiment, the refrigerant is removed from the existing system and modified and replaced by transferring the stabilized refrigerant from a pressurized container filled with the stabilized composition disclosed herein. The container for storing the stabilized composition disclosed herein can be constructed of any suitable material and design that can seal the composition therein 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 may be equipped with a perforated top or valve suitable for dispensing flammable materials.

[0080] In some embodiments, the compositions include HFO-1234yf and HFC-134a in a particular weight ratio. The amount of HFC-134a can range from about 25 to about 75, from about 30 to about 60, and in some cases from about 30 to about 50.

[0081] Any suitable effective amount of inhibitor can be used in the aforementioned composition comprising at least one fluoroolefin. As described herein, the phrase "effective amount" refers to an amount of the inhibitor of the present invention that, when added to a composition comprising at least one fluoroolefin, causes oligomerization or polymerization that significantly reduces performance, for example, when used in a cooling device, compared to a composition that does not contain the inhibitor. In the case of a cooling device, such an effective amount of inhibitor can be determined by testing under the conditions of standard test ASHRAE 97-2007 (RA 2017).

[0082] In certain embodiments of the invention, an effective amount is an amount of inhibitor that, when combined with a composition comprising at least one fluoroolefin and HFC-32, reduces the amount of 1,1,1,2-tetrafluoroethane (R-134a) or other standard refrigerants (R-12, R-22, R-502, R-507A, R-508, R401A, R401B, R402A, R402B, R408, R-410A, R-401C, R-401D, R-401E, R-401F, R-401G, R-401H, R-401I, R-401N, R-401O, R-401O, R-401N ... In the present invention, the amount of fluoroolefin and HFC-32 in the composition is an amount capable of providing the same level of refrigeration performance and cooling capacity in a cooling device that uses a composition containing at least one fluoroolefin and HFC-32 as in the case where a composition containing at least one fluoroolefin and HFC-32 is used as a working fluid.

[0083] The present invention employs an effective amount of at least one of the aforementioned oligomeric / polymeric inhibitors. Any suitable effective amount may be used, but the effective amount includes about 0.001 weight percent to about 0.5 weight percent, about 0.001 weight percent to about 0.05 weight percent, about 0.001 weight percent to about 0.02 weight percent, about 0.01 weight percent to about 0.5 weight percent, 0.01 weight percent to about 0.4 weight percent, 0.01 weight percent to about 0.3 weight percent, about 0.01 weight percent to about 0.2 weight percent, 0.01 weight percent to about 0.1 weight percent, and all ranges and values ​​therebetween, based on the total weight of the refrigerant composition including at least HFO-1234yf and at least one of HFC-32, HFC-125, HFC-134a, and carbon dioxide.

[0084] In one embodiment, an effective amount of inhibitor comprises at least one initiator comprising at least one of propane, cyclopropane, propylene, butane, isobutane, butene, isobutene, meta-xylene, ortho-xylene, para-xylene, and mixtures thereof, from about 10 to about 2000 ppm by weight, from about 10 to about 1,000 ppm, in some cases from about 100 to about 1000 ppm, from about 100 to 500 ppm, from about 100 ppm to about 2000 ppm, and all ranges therebetween.

[0085] In another embodiment of the present invention, the compositions of the present invention are substantially free of certain conventional inhibitor compounds, including: phenols, phosphorus-containing compounds, thiophosphates, butylated triphenyl phosphorothionate, organophosphates, or phosphites; sesquiterpene compounds, such as at least one member selected from the group consisting of 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 specific fluorinated anion, the fluorinated anion being [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.

[0086] In one embodiment, the aforementioned stabilized compositions of the present invention may further comprise at least one additional compound selected from fluoroolefins (as previously described herein), hydrofluorocarbons, alpha ethers, ammonia, carbon dioxide (CO2), and mixtures thereof, i.e., mixtures of any of the additional compounds listed in this paragraph. The amount of the additional compound may range from about 1 to about 90% by weight, from about 5 to about 75% by weight, and in some cases from about 10 to about 50% by weight.

[0087] In a particular embodiment for use as a replacement for R-410A, the refrigerant mixture consists essentially of about 42 to about 44 weight percent difluoromethane (HFC-32) and about 58 to about 56 weight percent 2,3,3,3-tetrafluoropropene (HFO-1234yf). In one embodiment, the refrigerant composition consists essentially of about 43 to about 44 weight percent HFC-32 and about 57 to about 56 weight percent HFO-1234yf. In another embodiment, the refrigerant composition consists essentially of about 44 weight percent HFC-32 and about 56 weight percent HFO-1234yf. In another embodiment, the refrigerant composition consists of about 44 weight percent HFC-32 and about 56 weight percent HFO-1234yf.

[0088] In one embodiment, the invention is a stabilized HFO-1234yf blend comprising one of propane, cyclopropane, propylene, butane, isobutane, butene and isobutene, meta-xylene, ortho-xylene, 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) 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. The HFO-1234yf content is 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 62 to 65 weight percent HFO-1234yf, and about 76 to 80 weight percent HFO-1234yf.

[0089] In another embodiment, the invention is a stabilized HFO-1234yf blend comprising one of propane, cyclopropane, propylene, butane, isobutane, butene and isobutene, meta-xylene, ortho-xylene, 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) 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. The content of HFO-1234yf and additional HFCs is about 55 to about 75 weight percent HFO-1234yf and about 25 to 45 weight percent HFC-134a, about 56 to about 75 weight percent HFO-1234yf and about 25 to 44 weight percent HFC-134a, about 25.7 weight percent HFC-134a, about 14 weight percent HFC-134a, about 30 weight percent HFC-125, about 14 weight percent HFC-134a, about 36 weight percent HFC-32 and about 6 weight percent CO2, and about 28 to about 32 weight percent HFO-1234yf and about 68 to 72 weight percent HFC-32.

[0090] The HFO-1234yf blends disclosed herein include up to 0.5 wt.% of propane, cyclopropane, propylene, butane, isobutane, butene, and isobutene, limonene, pinene, meta-xylene, ortho-xylene, para-xylene, alpha (α)-methylstyrene, 2-methyl-alpha-methylstyrene (α,2-dimethylstyrene), 3-methyl-alpha-methylstyrene (α,3-dimethylstyrene), 4-methyl-alpha-methylstyrene (α,4-dimethylstyrene), and mixtures of two or more.

[0091] In another embodiment, the composition comprises one of the following: a. a refrigerant blend consisting essentially of HFO-1234yf, HFC-32, or HFC-134a; b. A refrigerant blend consisting essentially of HFO-1234yf and HFC-32; or c. HFO-1234yf and HFC-134a, and One or mixtures of two or more of propane, cyclopropane, propylene, butane, isobutane, butene, isobutene, meta-xylene, ortho-xylene, para-xylene, d-limonene, l-limonene, β-pinene, α-pinene, α-terpinene, β-terpinene, γ-terpinene, and δ-terpinene, and up to 0.1 percent by weight 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 / Refrigerant blends consisting essentially of at least one inhibitor selected from mixtures of two or more including, but not limited to, 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, and delta-terpinene / butene.

[0092] In another embodiment, the composition comprises: a. a refrigerant blend consisting essentially of HFO-1234yf, HFC-32, and HFC-134a; and b. At least one inhibitor selected from one of propane, cyclopropane, propylene, butane, isobutane, butene, and isobutene, meta-xylene, ortho-xylene, and para-xylene.

[0093] In another embodiment, the composition comprises: A refrigerant blend consisting essentially of HFO-1234yf, HFC-32, HFC-134a, HFC-125, and carbon dioxide. b. At least one inhibitor selected from one of propane, cyclopropane, propylene, butane, isobutane, butene, and isobutene, meta-xylene, ortho-xylene, and para-xylene.

[0094] In one embodiment, the aforementioned compositions of the present invention may further comprise at least one lubricant. Lubricants of the present invention include those suitable for use with refrigeration or air conditioning equipment. Among these lubricants are those conventionally used in compression refrigeration equipment utilizing chlorofluorocarbon refrigerants. Such lubricants and their properties are discussed in the 1990 ASHRAE Handbook, Refrigeration Systems and Applications, Chapter 8, entitled "Lubricants in Refrigeration Systems", pages 8.1-8.21, which is incorporated herein by reference. Lubricants of the present invention may include those commonly known in the field of compression refrigeration lubrication as "mineral oils". Mineral oils include paraffins (i.e., saturated hydrocarbons of linear and branched carbon chains), naphthenes (i.e., saturated hydrocarbons of cyclic or ring structures that may be paraffins), and aromatics (i.e., unsaturated cyclic hydrocarbons containing one or more rings characterized by alternating double bonds). Lubricants of the present invention further include those commonly known in the field of compression refrigeration lubrication as "synthetic oils". Synthetic oils include alkylaryls (i.e., linear and branched alkyl alkylbenzenes), synthetic paraffins and naphthenes, silicones, and poly-alpha-olefins. Representative conventional lubricants of the present invention are commercially available BVM 100 N (paraffinic mineral oil sold by BVA Oils), naphthenic mineral oils sold by Crompton Co. under the trade names Suniso® 3GS and Suniso® 5GS, naphthenic mineral oils sold by Pennzoil under the trade name Sontex® 372LT, naphthenic mineral oils sold by Calumet Lubricants under the trade name Calumet® RO-30, linear alkyl benzenes sold by Shrieve Chemicals under the trade names Zerol® 75, Zerol® 150, and Zerol® 500, and branched alkyl benzenes sold by Nippon Oil under the trade name HAB 22.

[0095] In another embodiment, the lubricants of the present invention include those designed for use with hydrofluorocarbon refrigerants and miscible with the refrigerants of the present invention under the operating conditions of compression refrigeration and air conditioning equipment. Such lubricants and their properties are discussed in "Synthetic Lubricants and High-Performance Fluids", edited by RLShubkin and Marcel Dekker, 1993. Such lubricants include, but are not limited to, polyol esters (POEs) such as Castrol® 100 (Castrol, United Kingdom), and commercially available POE32-3MAF, and ND-11; and polyalkylene glycols (PAGs) such as RL-488A from Dow (Dow Chemical, Midland, Michigan) and commercially available ND-12; and polyvinyl ethers (PVEs).

[0096] In one embodiment, the composition comprises a lubricant selected from the group consisting of polyol esters (POEs), polyalkylene glycols (PAGs), and polyvinyl ethers (PVEs).

[0097] The lubricant of the present invention is selected by considering the requirements of a given compressor and the environment to which the lubricant will be exposed. The amount of lubricant can range from about 1 to about 50% by weight, about 1 to about 20% by weight, about 1 to about 10% by weight, about 1 to about 5% by weight, and in some cases about 1 to about 3% by weight. In one specific embodiment, the aforementioned composition is combined with a PAG lubricant for use in an air conditioning 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 air conditioning system for a vehicle having an electric or hybrid electric drivetrain.

[0098] In one embodiment of the present invention, in addition to the inhibitor of the present invention, the composition may desirably include at least one additive that can improve the life and compressor durability of refrigerants and air conditioning systems. In one aspect of the present invention, the aforementioned composition includes at least one of an acid scavenger, a performance enhancer, and a flame suppressant.

[0099] 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.

[0100] The acid scavenger may include a siloxane, an activated aromatic compound, or a combination of both. Serrano et al. (U.S. Patent Application Publication No. 2011 / 0272624 A1, paragraph 38), incorporated herein by reference, disclose that the siloxane can be any molecule 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:R 1 [Si(R 2 R 3 )O]nSi(R 2 R 3 )R 4 where n is 1 or greater. Siloxanes of Formula IV preferably have n 2 or greater, more preferably 3 or greater (e.g., about 4 or greater). Siloxanes of Formula IV preferably have n 30 or less, more preferably 12 or less, and most preferably 7 or less. Preferably, R 4 The group is an aryl group or an alkyl group. 2The group is an aryl or alkyl group, or a mixture thereof. 3 The group is an aryl or alkyl group, or a mixture thereof. 4 The group is an aryl group or an alkyl group. 1 , R 2 , R 3 , R 4 , or any combination thereof is not hydrogen. 2 The groups may be the same or different. Preferably, R 2 The groups are the same. R 2 The group is R 3 The R 2 Groups and R 3 The groups R and R are the same. Preferred siloxanes include 2 , R 3 , R 4 , R 5 or any combination thereof is a methyl, ethyl, propyl, or butyl group. Exemplary siloxanes that may be used include hexamethyldisiloxane, polydimethylsiloxane, polymethylphenylsiloxane, dodecamethylpentasiloxane, decamethylcyclopentasiloxane, decamethyltetrasiloxane, octamethyltrisiloxane, or any combination thereof.

[0101] From Serrano et al., previously incorporated by reference, it is noted that in one aspect of the invention, the siloxane is an alkyl siloxane containing from about 1 to about 12 carbon atoms, e.g., hexamethyldisiloxane. The siloxane may also be a polymer, such as a polydialkylsiloxane, in which the alkyl groups are methyl, ethyl, propyl, butyl, or any combination thereof. Suitable polydialkylsiloxanes have a molecular weight of from about 100 to about 10,000. Highly preferred siloxanes include hexamethyldisiloxane, polydimethylsiloxane, and combinations thereof. The siloxane may consist essentially of polydimethylsiloxane, hexamethyldisiloxane, or combinations thereof.

[0102] 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. The 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. The 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. As an example, an activated aromatic molecule may be of the formula ArXRn where X is O (i.e., oxygen) or N (i.e., nitrogen), when X=O, n is 1, when x=N, n is 2, Ar is an aromatic group (i.e., group CH), 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 can 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.

[0103] From Serrano et al., previously incorporated by reference, the acid scavenger (e.g., activated aromatic compound, siloxane, or both) may be present at any concentration, resulting in a relatively low total acid number, a relatively low total halide concentration, a relatively low total organic acid concentration, or any combination thereof. The acid scavenger is preferably present at a concentration of greater than about 0.0050 wt%, more preferably greater than about 0.05 wt%, even more preferably greater than about 0.1 wt% (e.g., greater than about 0.5 wt%) based on the total weight of the refrigerant composition. The acid scavenger is preferably present at a concentration of less than about 3 wt%, more preferably less than about 2.5 wt%, and most preferably less than about 2 wt% (e.g., less than about 1.8 wt%) based on the total weight of the refrigerant composition.

[0104] Additional examples of acid scavengers that may be included in the refrigerant composition include those described in Kaneko (U.S. Patent Application Serial No. 11 / 575,256, published as U.S. Patent Application Publication No. 2007 / 0290164, paragraph 42, each of which is incorporated herein by reference in its 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, and those described in Singh et al. (U.S. Patent Application Serial No. 11 / 250,219, published as U.S. Patent Application Publication No. 20060116310, paragraphs 34-42, each of which is incorporated herein by reference in its entirety).

[0105] Preferred antiwear additives include those disclosed 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 a substituted derivative thereof, (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) a phosphate alcohol (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, which is incorporated herein by reference in its entirety).

[0106] 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.

[0107] 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 No. 11 / 575,256, published as U.S. Patent Application No. 2007 / 0290164) and Singh et al. (U.S. Patent Application No. 11 / 250,219, published as U.S. Patent Application No. 2006 / 0116310). All of these aforementioned applications are expressly incorporated herein by reference in their entirety.

[0108] Preferred flame suppressants include those described in patent application "Compositions containing fluorine substituted olefins" Canadian Patent Publication No. 2557873(A1), which is incorporated by reference along with fluorinated products such as HFC-125 and / or Krytox® lubricants, and those described in patent application "Compositions comprising fluoroolefins and uses thereof" International Patent Publication No. WO2009018117(A1), which is also incorporated by reference.

[0109] 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.

[0110] The present invention further relates to a process for producing cooling comprising condensing a composition comprising at least HFO-1234yf, a mixture or blend of at least one of HFC-32, HFC-134a, HFC-125, and carbon dioxide, and an inhibitor comprising effective amounts of at least propane, cyclopropane, propylene, butane, isobutane, butene and isobutene, meta-xylene, ortho-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), and mixtures of two or more, and then evaporating the composition in the vicinity of a body to be cooled.

[0111] The body to be cooled can be any space, location, or object requiring refrigeration or air conditioning. In stationary applications, the body may be inside 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 transport), and "swap bodies" (road and rail intermodal transport).

[0112] The present invention further relates to a process for generating heat comprising condensing a composition comprising at least one fluoroolefin, HFC-32 and / or HFC-134a, and an inhibitor comprising effective amounts of at least one of propane, cyclopropane, propylene, butane, isobutane, butene and isobutene, meta-xylene, ortho-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) in the vicinity of a body to be heated and then evaporating the composition.

[0113] The object to be heated may be any space, location, or object that requires heat. They may be located inside either residential or commercial structures in a similar manner to the objects to be cooled. Additionally, portable units such as those described for cooling may be similar to those requiring heating. Certain transport units require heating to prevent the materials being transported from solidifying within the transport container.

[0114] Another embodiment of the present invention relates to an air conditioning, refrigeration, heat pump, or cooling system comprising at least one evaporator, at least one compressor, at least one condenser, and at least one expansion device, characterized in that the composition described above is contained therein.

[0115] 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.

[0116] 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 in some cases aluminum alloys. The container can be equipped with a perforated top or valve suitable for dispensing flammable materials.

[0117] 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.

[0118] The following examples are provided to illustrate certain embodiments of the invention and are not intended to limit the scope of the appended claims. EXAMPLES

[0119] The present disclosure is further defined in the following examples. It should be understood that these examples, although showing preferred embodiments, are provided for illustrative purposes only. From the above discussion and these examples, those skilled in the art can ascertain preferred features, and can make various changes and modifications to accommodate various applications and conditions without departing from the spirit and scope thereof.

[0120] 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 shaker tube at the temperature and time shown in Table 3. The shaker tube is visually inspected for polymer formation and by using IR according to conventional methods by detecting the yf polymer peak. Polymer can also be detected by using conventional NMR methods.

[0121] * The HFO-1234yf contained 99.7 wt. % HFO-1234yf, 1,000 ppm HFO-1234ze, 50 ppm HFO-1225yeZ, 20 ppm 1243zf, 3 ppm trifluoropropyne, and the remainder contained compounds that did not affect the refrigerant performance of the mixture.

[0122] [Table 3]

[0123] Example 2 30 g of HFO-1234yf (with and without inhibitor) having a purity of at least 99.5 wt% was heated in a 210 mL shaker tube at the temperature and time shown in Table 3. When an inhibitor is present, 3 wt% lubricant is included. The shaker tube is visually inspected for polymer formation and by using IR according to conventional methods by detecting the yf polymer peak. Polymer can also be detected by using conventional NMR methods.

[0124] [Table 4]

[0125] Examples 3 to 6 Refrigerant blends containing a mixture of HFO-1234yf (30 g having the composition of Example 1), at least one additional compound, and an initiator (and no inhibitor) were heated in 210 mL shaker tubes at the temperatures and times shown in Tables 4-7. When an inhibitor was present, 3 wt. % of the lubricant was included.

[0126] Runs 1-6 of Example 3 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.

[0127] Runs 7-12 of Example 4 evaluate an inhibitor containing Opteon™ XP-40 refrigerant (R449a) and a commercial lubricant. XP40 refrigerant contains 24.3 wt% R32, 24.7 wt% R125, 25.3 wt% 1234yf, and 25.7 wt% 134a. When the inhibitor is present, 3 wt% lubricant is included.

[0128] Runs 13-19 of Example 5 evaluate an inhibitor containing Opteon™ XL-20 refrigerant (454C) and a commercial lubricant. XL20 contains 21.5% HFC-32 and 78.5% HFO-1234yf. When the inhibitor is present, it contains 3% by weight of the lubricant.

[0129] Runs 20-26 of Example 6 evaluate an inhibitor containing Opteon™ XP-41 refrigerant (463A) and a commercial lubricant. XL41 contains 30% HFC-125, 14% HFC-134a, 36% HFC-32, 14% HFO-1234yf, and 6% CO2. When the inhibitor is present, 3% by weight of the lubricant is included.

[0130] [Table 5]

[0131] [Table 6]

[0132] [Table 7]

[0133] [Table 8]

[0134] 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.

[0135] Cooling and heating performance data comparison of HFO-1234yf and blends The cooling and heating performance of mixtures containing xylene and C3 and C4 hydrocarbon oligomer inhibitors, HFO1234yf alone, and commercial blends of Opteon® XL20, XL40, and XL41 were determined and compared to each other in Tables 9-16 below. Measurements included evaporator (Evap) and condenser (Cond), compressor discharge temperature (Disch T), and average temperature gradient (average temperature glide) (Avg Temp Glide) of the evaporator and condenser. Relative energy efficiency (COP) and volumetric capacity (Cap). The data was based on the following conditions:

[0136] [Table 9]

[0137] [Table 10-1]

[0138] [Table 10-2]

[0139] [Table 11-1]

[0140] [Table 11-2]

[0141]

Table 12-1

[0142]

Table 12-2

[0143]

Table 13-1

[0144]

Table 13-2

[0145]

Table 14-1

[0146]

Table 14-2

[0147]

Table 15-1

[0148]

Table 15-2

[0149]

Table 16-1

[0150]

Table 16-2

[0151] [Table 17-1]

[0152] [Table 17-2]

[0153] 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. (i) at least HFO-1234yf; (ii) C １ and / or C ２ at least one of a hydrofluorocarbon and optionally carbon dioxide; (iii) an effective stabilizing amount of C ２ ~C ５ at least one oligomerization inhibitor comprising one or more of a hydrocarbon, limonene, pinene, terpinene, xylene, and combinations thereof; (iv) optionally at least one additional HFO, HCFO, HFC, HCC, HCFC, nitrogen, and air component different from (ii); A composition comprising:

2. Said C ２ ~C ５ 2. The composition of claim 1, wherein the hydrocarbon inhibitors include ethane, propane, propylene, butane, butane, and isobutene in effective amounts up to about 0.5% by weight relative to (i), (ii), and (iv).

3. 10. The composition of claim 1, wherein the inhibitor comprises propane or xylene.

4. 4. The composition of claim 3, wherein the inhibitor is a xylene and includes one of meta-xylene, ortho-xylene, and para-xylene.

5. 4. The composition of claim 1 or 3, wherein the effective stabilizing amount is from greater than 0 to about 0.5% by weight, based on the weight of (i), (ii), and (iv).

6. 2. The composition of claim 1, wherein (ii) comprises at least one of HFC-32, HFC-125, HFC-134a, and carbon dioxide.

7. 2. The composition of claim 1, wherein the amount of the inhibitor is up to about 0.2% by weight, based on the weight of (i), (ii), and (iv).

8. The C of (ii) １ The composition of claim 7, wherein the hydrofluorocarbon comprises HFC-32.

9. The C of (ii) ２ The composition of claim 7, wherein the hydrofluorocarbon comprises HFC-134a.

10. The C of (ii) １ and C ２ 2. The composition of claim 1, wherein the hydrocarbon comprises at least HFC-32 and one of HFC-125, HFC-134a, and carbon dioxide.

11. 2. The composition of claim 1, wherein up to about 0.1% by weight of the inhibitor is present, based on the weight of (i), (ii), and (iv).

12. 2. The composition of claim 1, wherein up to about 0.05% by weight of the inhibitor is present, based on the weight of (i), (ii), and (iv).

13. 4. The composition of claim 1 or 3, wherein up to about 0.01% by weight of the inhibitor is present, based on the weight of (i), (ii), and (iv).

14. a. about 20 to about 40 weight percent HFO-1234yf, or b. about 28 to about 32 weight percent HFO-1234yf, or c. about 30 to about 32 weight percent HFO-1234yf, or d. about 62 to about 65 weight percent HFO-1234yf, or e. about 76 to about 80 weight percent HFO-1234yf The composition of claim 1 comprising:

15. A process for forming a stable refrigerant composition comprising up to about 0.5 wt. % of at least one C ３ ~C ４ Hydrocarbons, d-limonene, l-limonene, β-pinene, α-pinene, α-terpinene, β-terpinene, γ-terpinene, and δ-terpinene, 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, beta-pinene / butane, alpha-pinene / propane, 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, beta-terpinene / butene, gamma-terpinene / butene, and delta-terpinene / butene, a. about 55 to about 75 weight percent HFO-1234yf and about 25 to 45 weight percent HFC-134a; b. about 56 to about 75 weight percent HFO-1234yf and about 25 to 44 weight percent HFC-134a, or c. about 56 weight percent HFO-1234yf and 44 weight percent HFC-134a, optionally including a lubricant; d. about 24.3 weight percent HFC-32, about 24.7 weight percent HFC-125, about 25.3 weight percent HFO-1234yf, and about 25.7 weight percent HFC134a, optionally including a lubricant; e. about 21.5 weight percent HFC-32 and about 78.5 weight percent HFO-1234yf, optionally including a lubricant; f. 30% HFC-125, 14% HFC-134a, 36% HFC-32, 14% HFO-1234yf, and 6% CO, optionally with a lubricant; g. about 30 weight percent HFC-125, about 14 weight percent HFC-134a, about 36 weight percent HFC-32, and about 6 weight percent CO ２ ,and h. about 28 to about 32 weight percent HFO-1234yf and about 68 to 72 weight percent HFC-32 The process comprising adding to one of

16. 16. A storage-stable refrigerant comprising a pressurized container filled with the composition formed by the process of claim 15.

17. 13. A storage stable refrigerant comprising a pressurized vessel containing a refrigerant comprising the composition formed by the process of claim 12 and a lubricant.

18. 12. A storage-stable refrigerant comprising a pressurized container filled with the refrigerant composition of claim 5 or 11.

19. 13. A method for providing an oligomerization stabilized 1234yf composition to a refrigerant system, comprising the steps of removing a refrigerant from an existing system and transferring the stabilized refrigerant from one of the pressurized vessels filled with the composition of claim 1, 11, or 12.

20. A method of transferring heat comprising using the stabilized composition of claim 1.

21. A refrigerant system comprising a refrigerant circuit containing the composition of claim 1.

22. A valve refrigerant vessel containing the composition of claim 1.

23. 1. A method for stabilizing an HFO-1234yf blend comprising adding to the blend one of limonene, pinene, ethane, propane, cyclopropane, propylene, butane, isobutane, butene, isobutene, meta-xylene, ortho-xylene, 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) 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.

24. 1. A stabilized HFO-1234yf blend comprising one of ethane, propane, cyclopropane, propylene, butane, isobutane, butene and isobutene, meta-xylene, ortho-xylene, 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) 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 about 76 to about 80 weight percent HFO-1234yf; 22. The blend of claim 21 , comprising:

26. a. about 55 to about 75 weight percent HFO-1234yf and about 25 to 45 weight percent HFC-134a, or b. about 56 to about 75 weight percent HFO-1234yf and about 25 to 44 weight percent HFC-134a, or c. about 25.7 weight percent HFC-134a, or d. about 14 weight percent HFC-134a, or e. about 30 weight percent HFC-125, about 14 weight percent HFC-134a, about 36 weight percent HFC-32, and about 6 weight percent CO ２ or f. about 28 to about 32 weight percent HFO-1234yf and about 68 to 72 weight percent HFC-32; 22. The blend of claim 21 , comprising:

27. 24. The blend of claims 22 or 23 comprising up to 0.5% by weight of ethane, propane, cyclopropane, propylene, butane, isobutane, butene and isobutene, meta-xylene, ortho-xylene, or para-xylene, alpha (α)-methylstyrene, 2-methyl-alpha-methylstyrene (α,2-dimethylstyrene), 3-methyl-alpha-methylstyrene (α,3-dimethylstyrene), 4-methyl-alpha-methylstyrene (α,4-dimethylstyrene), and mixtures of two or more.

28. 24. The blend of claim 23, comprising an inhibitor pair selected from propane / -limonene and propane / pinene in an amount up to 0.5% by weight.

29. 28. The method of claim 24 or 27, comprising an inhibitor pair selected from propane / -limonene and propane / pinene in an amount of up to 0.5% by weight.

30. 16. The process of claim 15, comprising an inhibitor pair selected from propane / -limonene and propane / pinene in an amount of up to 0.5% by weight.

31. 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- 15. The composition of any one of claims 1 to 14, comprising an amount of up to 0.5 wt.% of inhibitor pairs selected from 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, beta-terpinene / butene, gamma-terpinene / butene, or delta-terpinene / butene.

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