Stabilized fluoroolefin products, and methods for producing, storing, and using the same.

Abstract

To provide replacement refrigerants that have low GWP, no toxicity, nonflammability, reasonable cost and excellent refrigeration performance.SOLUTION: The present invention provides a refrigerant blend comprising: at least one fluoroolefin component; 25 to 75 wt.% of at least one hydrofluorocarbon selected from the group consisting of HFC-32, HFC-125, HFC-134a, HFC-152a, 236fa, and HFC-227ea; at least one lubricant; and an inhibitor, wherein the fluoroolefin comprises HFO-1234yf having a purity of greater than 99.7 wt.%; the inhibitor comprises at least one of d-limonene and α-terpinene; and the inhibitor is present in an effective amount to inhibit interaction of the fluoroolefin with other compounds to form dimers, oligomers, homopolymers, or polymeric products.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] (Cross-reference of related applications) This application claims the benefits of International Application PCT / 2019 / 02977, filed on 30 April 2019. The disclosures of International Application PCT / 2019 / 02977 are incorporated herein by reference.

[0002] (Field of Invention) The present invention broadly relates to a stabilized refrigerant composition comprising at least one fluoroolefin, at least one lubricant, and at least one inhibitor comprising at least one component selected from the group consisting of limonene, α-terpinene, α-tocopherol, butylated hydroxytoluene, 4-methoxyphenol, and benzene-1,4-diol, wherein the inhibitor is present in the liquid phase fluoroolefin and the lubricant. [Background technology]

[0003] New environmental regulations on refrigerants are forcing the refrigeration and air conditioning industries to seek out new refrigerants with lower global warming potential (GWP).

[0004] There is a need for alternative refrigerants that are low GWP, non-toxic, non-flammable, reasonably priced, and offer excellent refrigeration performance.

[0005] Fluoroolefins have been proposed as refrigerants, either alone or in mixtures. These products have been extensively tested for chemical stability and compatibility with materials typically used in air conditioning or refrigeration systems (see "1234yf-A Low GWP Refrigerant For MAC, Honeywell / DuPont Joint Collaboration," published in JAMA / JARIA, October 3, 2007), and have been shown to be stable under typical operating conditions. However, certain fluoroolefins have been observed to degrade and / or produce unwanted byproducts under unusual conditions, such as extreme temperatures or contact with other compounds in a contaminated system (including various contaminants, such as excess oxygen, oxidizing chemicals, or radical-generating compounds), which can occur unexpectedly in certain uses and / or applications. Such degradation can occur when fluoroolefins are used as refrigerants or heat transfer fluids. This degradation can occur by any number of different mechanisms. Examples of stabilized refrigerant compositions are disclosed in Japanese Patent Application Publication No. 2009-298918, U.S. Patent Nos. 6,969,701, 8,133,407, U.S. Patent Application Publication Nos. 2006 / 0022166, 2006 / 0043330, 2008 / 0157022, and International Publication No. 2007 / 126760, as well as European Patent No. 2057245, U.S. Patent Nos. 8101094, 8535555, 8097181, and 8075796, which are incorporated herein by reference. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2009-298918 [Patent Document 2] U.S. Patent No. 6,969,701 [Patent Document 3] U.S. Patent No. 8,133,407 [Patent Document 4] U.S. Patent Application Publication No. 2006 / 0022166

Patent Document 5

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Patent Document 7

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Patent Document 9

Patent Document 10

Patent Document 11

Patent Document 12

Non-Patent Document

[0007]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0008] Under certain abnormal conditions and in the presence of undesirable contaminants that can function as initiators of reaction, fluoroolefins may oligomerize or homopolymerize in the presence of certain contaminants that may be present. Therefore, in this technical field, there is a need for a stabilized fluoroolefin-containing refrigerant composition in which the possibility of oligomerization or homopolymerization is reduced, if not eliminated.

Means for Solving the Problems

[0009] The present invention can solve problems related to polymerization initiation by providing at least one inhibitor present in liquid fluoroolefins and lubricants. In particular, the present invention can improve the ability of a hydrofluoroolefin-containing refrigerant composition to withstand abnormal conditions by adding at least one inhibitor to the fluoroolefin-containing refrigerant composition, and also solves potential problems related to reaction initiators (e.g., contaminants) that oligomerize or homopolymerize fluoroolefins (e.g., tetrafluoropropene). "Inhibitor" means at least one compound according to the present invention that reduces, if not eliminates, the conversion of hydrofluoroolefins to oligomers or polymers. While oligomerization or homopolymerization reactions can be accelerated by relatively high temperatures, such reactions can also occur under ambient conditions depending on the concentration and type of reaction initiator (e.g., contaminants). The inhibitor can function as a radical inhibitor without affecting the refrigeration performance of the refrigerant composition or its compatibility with refrigerant oil and components. The stabilized refrigerant composition may be useful in cooling systems and as a replacement for existing refrigerants with higher global warming potentials.

[0010] To avoid the potential instability of fluoroolefins, it has been found that adding specific inhibitor compounds to fluoroolefin-containing refrigerant compositions, namely hydrocarbons containing at least one cyclic monoterpene, lipophilic organic compounds containing tocopherols such as α-tocopherol, phenols, and aromatic organic compounds having at least one chemical moiety C6H4(OH), including benzene-1,4-diol, improves the stability during packaging, storage, and use in refrigeration or air conditioning system applications. Specific examples of inhibitor compounds include at least one component selected from the group consisting of limomene, α-terpinene, α-tocopherol, butylated hydroxytoluene, 4-methoxyphenol, and benzene-1,4-diol. In one embodiment of the present invention, the inhibitor composition of the present invention comprises a liquid at temperatures of about -100 to about 220°C, about -90 to about 200°C, and optionally about -80 to about 185°C.

[0011] In one specific embodiment, the present invention relates to a fluoroolefin-containing refrigerant composition comprising an inhibitor that interacts with or reacts with O2 and fluoroolefin polyperoxides, and subsequently inhibits or prevents the reaction between such compounds and hydrofluoroolefins. Examples of such inhibitors include at least one of limonene and α-terpinene. Limonene and α-terpinene have the following structures:

[0012] [ka]

[0013] In one embodiment of the present invention, the inhibitor contains α-terpinene. Although not bound by theory or explanation, it is thought that the presence of a conjugated double bond in its structure allows α-terpinene to form an aromatic ring upon oxidation.

[0014] In one embodiment of the present invention, limonene or α-terpinene, optionally containing an antioxidant, has a distinctive aroma even at levels of a few ppm. This pleasant scent can be used to detect refrigerant leaks in refrigerants and blends based on hydrofluoroolefins (e.g., including at least one of 1234yf, 1234ze, and combinations thereof). This is particularly useful for early detection of refrigerant leaks in residential or portable air conditioning systems, as paraprofessional electronic leak detectors are often unavailable in all locations.

[0015] One embodiment of the present invention is a. At least one fluoroolefin, b. At least one lubricant, c. A refrigerant composition comprising an effective amount of at least one inhibitor, the inhibitor comprising a hydrocarbon containing a cyclic monoterpene, a lipophilic organic compound containing α-tocopherol, a phenol, and an aromatic organic compound having the chemical formula C6H4(OH), comprising benzene-1,4-diol, wherein the inhibitor is present in a liquid fluoroolefin and a lubricant.

[0016] One embodiment of the present invention relates to any of the aforementioned refrigerant compositions, further comprising at least one antioxidant. Any suitable oxidizing agent can be used, but examples of suitable oxidizing agents include at least one component selected from the group consisting of butylated hydroxytoluene, butylated hydroxyanisole, tertiary butylhydroquinone, gallate, 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 many other phenols.

[0017] One specific embodiment relates to using the aforementioned antioxidant together with an inhibitor comprising at least one of limonene and α-terpinene.

[0018] Another embodiment of the present invention relates to a method for stabilizing a refrigerant composition comprising at least one fluoroolefin, the method comprising adding to the composition comprising at least one fluoroolefin in an effective amount of at least one inhibitor, which is a hydrocarbon comprising at least one component selected from the group consisting of cyclic monoterpenes, lipophilic organic compounds including α-tocopherol, phenols, aromatic organic compounds having the chemical formula C6H4(OH) including benzene-1,4-diol, and mixtures thereof.

[0019] Another embodiment of the present invention relates to a method for reducing oligomerization or homopolymerization of a refrigerant composition containing at least one fluoroolefin, caused by the presence of accidental or undesirable contaminants in at least one of the following: conduits, lines, and other systems used to handle the fluoroolefin-containing refrigerant composition; packaging (containers); and refrigeration, air conditioning, or heat pump systems, comprising adding an inhibitor to at least one of the following systems, containers, and compositions containing at least one fluoroolefin: an inhibitor comprising a cyclic monoterpene, a lipophilic organic compound containing tocopherol including α-tocopherol, a phenol, an aromatic organic compound having the chemical formula C6H4(OH) including benzene-1,4-diol, and a mixture thereof.

[0020] A further embodiment of the present invention relates to a fluoroolefin-containing refrigerant composition for use in a container, wherein the possibility of oligomerization or homopolymerization of the fluoroolefin is reduced compared to a composition that does not contain the inhibitor composition of the present invention.

[0021] One embodiment of the present invention relates to a refrigerant composition comprising at least one fluoroolefin and an effective amount of at least one inhibitor, wherein the composition is substantially free of oligomers, homopolymers, or other polymer products derived from the fluoroolefin.

[0022] Another embodiment of the present invention relates to any of the aforementioned refrigerant compositions comprising less than about 0.03% by weight of oligomers, homopolymers, or other polymer products.

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

[0024] Another embodiment of the present invention relates to any of the aforementioned refrigerant compositions, wherein the inhibitor comprises at least one component selected from the group consisting of limomene, α-terpinene, α-tocopherol, butylated hydroxytoluene, 4-methoxyphenol, and benzene-1,4-diol.

[0025] Another embodiment of the present invention relates to any of the aforementioned refrigerant compositions, wherein the fluoroolefin comprises at least one component from HFO-1234yf and HFO-1234ze.

[0026] Another embodiment of the present invention relates to any of the aforementioned refrigerant 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.

[0027] Another embodiment of the present invention relates to any of the aforementioned refrigerant compositions, further comprising at least one component 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.

[0028] Another embodiment of the present invention relates to any of the aforementioned refrigerant 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.

[0029] Another embodiment of the present invention relates to any of the aforementioned refrigerant compositions, wherein the inhibitor is present in an amount of about 30 to about 3,000 ppm.

[0030] Another embodiment of the present invention relates to any of the aforementioned refrigerant compositions, further comprising at least one component 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).

[0031] Another embodiment of the present invention relates to any of the aforementioned refrigerant compositions, wherein the inhibitor comprises at least one of limonene and α-terpinene.

[0032] Another embodiment of the present invention relates to any of the aforementioned refrigerant compositions, wherein the inhibitor is a liquid at a temperature of about -80 to 180°C.

[0033] Another embodiment of the present invention relates to any of the aforementioned refrigerant compositions, further optionally comprising at least one antioxidant.

[0034] Another embodiment of the present invention relates to any of the aforementioned refrigerant 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.

[0035] Another embodiment of the present invention relates to any of the aforementioned refrigerant compositions, wherein the components include HFO-1234ze, HFO-1225yeZ, and 3,3,3-trifluoropropyne.

[0036] Another embodiment of the present invention relates to any of the aforementioned refrigerant compositions, wherein the composition substantially contains at least one of ammonia and CF3I.

[0037] Another embodiment of the present invention relates to any of the aforementioned refrigerant compositions, wherein the composition essentially consists of HFO-1234yf and limonene and does not contain ammonia or CF3I.

[0038] Another embodiment of the present invention relates to any of the aforementioned refrigerant compositions, wherein the composition essentially consists of HFO-1234yf, 3,3,3-trifluoropropyne, and limonene.

[0039] One embodiment of the present invention relates to a method for reducing the formation of oligomers and homopolymers, comprising contacting a refrigerant composition comprising at least one fluoroolefin with at least one component selected from the group consisting of limomene, α-terpinene, α-tocopherol, butylated hydroxytoluene, 4-methoxyphenol, and benzene-1,4-diol in an amount effective in reducing the formation of oligomers or homopolymers.

[0040] Another embodiment of the present invention relates to any of the above methods, wherein the refrigerant composition is exposed prior to contact to air, oxygen, cumene hydroperoxide, and at least one component selected from the group consisting of fluoroolefin polyperoxides, peroxides, hydroperoxides, persulfates, percarbonates, perborates, and hydropersulfates.

[0041] Another embodiment of the present invention relates to any of the methods described above, using any of the aforementioned refrigerant compositions for heating or cooling.

[0042] Another embodiment of the present invention relates to a container containing a refrigerant comprising any of the refrigerant compositions described above.

[0043] The embodiments of the present invention can be used individually or in combination with each other, and different embodiments can be combined to form a part of the present invention. [Brief explanation of the drawing]

[0044] [Figure 1] This is a graph showing the NRTL fit to the experimental VLE for R-1234yf / lubricant. [Figure 2] This is a graphical representation of the NRTL fit for experimental VLE of R-1234yf / d-limonene. [Figure 3] This is a graph showing an enlarged view of the R-1234yf-rich domain of R-1234yf / d-limonene, which exhibits a negative deviation from Raoult's Law. [Figure 4] This is a graphical representation of the NRTL fit using the calculated d-limonene / POE32-3MAF VLE data. [Figure 5] This is a graph displaying the ternary VLLE calculation for R-1234yf / 1000ppm d-limonene / POE32-3MAF. [Modes for carrying out the invention]

[0045] The present invention provides a stabilized refrigerant composition comprising at least one fluoroolefin, at least one lubricant, and at least one inhibitor in an effective amount, wherein the inhibitor is present in the liquid fluoroolefin and the lubricant. “Stabilized” means a composition comprising at least one inhibitor compound in an effective amount that inhibits, if not eliminates, the interaction of the fluoroolefin with another compound to form dimers, oligomers, homopolymers, or polymer products. Examples of such compounds that can cause such interactions include, among many reaction initiators, air, oxygen, cumene hydroperoxide, and oxidizing agents such as fluoroolefin polyperoxides, peroxides, hydroperoxides, persulfates, percarbonates, perborates, and hydropersulfates. The reaction initiator compound may be present in amounts of about 10 to about 15,000 ppm, about 1,000 to about 10,000 ppm, possibly about 1,000 to about 3,000 ppm, and in some embodiments, 30 to 2,000 ppm by weight. Such reaction initiator compounds may be present as contaminants in conduits, lines, and other systems, packaging (containers), and at least one of the following systems used to process fluoroolefin-containing refrigerant compositions: refrigeration, air conditioning, or heat pump systems. While not bound by theory or explanation, certain contaminants are thought to function as radical reaction initiators, thereby causing oligomerization, homopolymerization, or formation of other polymer products of fluoroolefins.

[0046] In one embodiment of the present invention, the refrigerant composition of the present invention is substantially free of oligomers, homopolymers, or other polymer products derived from hydrofluoroolefins. "Substantially free" means that the composition contains less than about 1% by weight, less than about 0.07% by weight, less than about 0.03% by weight, and possibly about 0 ppm of such products, as measured by IR or NMR.

[0047] In another embodiment of the present invention, the refrigerant composition of the present invention comprises a sesquiterpene compound such as at least one component selected from the group consisting of famesol and farnesene; [CH3CO2] - , [HSO4] - , [CH3OSO3] - , [C2H5OSO3] - , [AlCl4] - , [CO3] 2- , [HCO3] - , [NO2] - , [NO3] - , [SO4] 2- , [PO4] 3- , [HPO4] 2- , [H2PO4] - , [HSO3], and specific fluorinated anions, [BF4] - , [PF6] - , [SbF6] - , [CF3SO3] - , [HCF2CF2SO3] - , [CF3HFCCF2SO3] - , [HCClFCF2SO3] - , [(CF3SO2)2N] - , [(CF3CF2SO2)2N] - , [(CF3SO2)3C] - , [CF3CO2] - , [CF3OCFHCF2SO3] - , [CF3CF2OCFHCF2SO3] - , [CF3CFHOCF2CF2SO3] - , [CF2HCF2OCF2CF2SO3] - , [CF2ICF2OCF2CF2SO3] - , [CF3CF2OCF2CF2SO3] - , [(CF2HCF2SO2)2N] - , [(CF3CFHCF2SO2)2N] -The refrigerant composition of the present invention is substantially free of certain conventional inhibitor compounds, including ionic liquids such as ionic liquids containing anions selected from the group consisting of fluorinated anions and mixtures thereof. Substantially free means that the refrigerant composition of the present invention contains less than about 500 ppm, typically less than about 250 ppm, possibly about 100 ppm, and possibly about 0 ppm of such conventional inhibitors.

[0048] The refrigerant compositions of the present invention have various utilities, particularly including heat transfer media (heat transfer fluids and refrigerants for use in refrigeration systems, refrigerators, air conditioning systems, heat pumps, coolers, etc.). The compounds of the present invention are particularly suitable as components for preparing refrigerant blends for use in portable air conditioning systems and for use in stationary heat transfer systems.

[0049] The 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 transfer heat from a heat source to a heat sink.

[0050] A refrigerant is a compound or mixture of compounds that functions as a heat transfer fluid in a cycle in which the fluid undergoes a phase change from liquid to gas (or vapor) and then returns to its original state. Inhibitors are present in at least the liquid fluoroolefin-containing phase of the refrigerant, as well as in the lubricant component of the refrigerant. In one embodiment, about 10 to about 80% by weight, about 25 to about 75% by weight, and optionally about 45 to about 60% by weight of inhibitors are present in the liquid fluoroolefin phase, with the remainder mainly present in the lubricant phase. In one embodiment, the gas phase is substantially free of inhibitors. "Substantially free" means that the amount of inhibitor in the vapor fluoroolefin phase is less than about 10 ppm, optionally less than about 5, and typically less than about 2 ppm. In one embodiment, the refrigerant comprises a gas phase containing at least one fluoroolefin, and a liquid phase containing at least one fluoroolefin, at least one lubricant, and at least one inhibitor, and optionally the gas phase is substantially free of inhibitors.

[0051] When used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having,” or any other variations thereof are intended to encompass non-exclusive inclusion. For example, a composition, process, method, article, or apparatus containing the elements listed is not necessarily limited to those elements alone, but may include other elements not expressly listed, or other elements associated with such composition, process, method, article, or apparatus. Furthermore, unless expressly stated otherwise, “or” means an inclusive “or” and not an exclusive “or.” For example, condition A or B is satisfied by any one of the following: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); and both A and B are true (or exist).

[0052] The transitional phrase "consisting of" excludes any unspecified elements, processes, or components. In the context of claims, with the exception of impurities normally associated with materials, such phrase excludes the inclusion of materials other than those enumerated from the claims. If the phrase "consisting of" appears in a clause of the claim rather than immediately following the preamble, it limits the elements to those specified in that clause only, and does not exclude other elements from the claims as a whole.

[0053] The transitional phrase "essentially from" is used to define compositions and methods that include materials, processes, features, components, or elements in addition to those literally disclosed, provided that these additionally included materials, processes, features, components, or elements substantially influence the basic and novel features(s) of the claimed invention, particularly the modes of action for achieving any of the desired results of the processes of the invention. The term "essentially from" occupies an intermediate position between "includes" and "consists of."

[0054] If applicants define an invention or part thereof using non-limiting terms such as "includes," it should be easily understood that (unless otherwise specified) such descriptions should be interpreted to also include inventions that use terms such as "essentially consist of" or "consist of."

[0055] Furthermore, the use of "a" or "an" is used to describe the elements and components described herein. This is done solely for convenience and to give a general sense of the scope of the invention. This description should be interpreted as including one or at least one, and the singular form also includes the plural form unless it is evident that it has a different meaning.

[0056] As used herein, the term fluoroolefin refers to a compound comprising carbon atoms, fluorine atoms, and optionally hydrogen atoms. In one embodiment, the fluoroolefin used in the refrigerant composition of the present invention comprises compounds having 2 to 12 carbon atoms. In another embodiment, the fluoroolefin comprises compounds having 3 to 10 carbon atoms, and in yet another embodiment, the fluoroolefin comprises compounds having 3 to 7 carbon atoms. Representative fluoroolefins include, but are not limited to, all compounds listed in Tables 1, 2, and 3.

[0057] One embodiment of the present invention relates to the formula E- or ZR 1 CH=CHR 2 (Formula I) (wherein, R 1 and R 2 R provides a fluoroolefin having a C1-C6 perfluoroalkyl group independently. 1 Base and R 2Examples of the base 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 four carbon atoms in the molecule. In another embodiment, the fluoroolefin of formula I has at least about five carbon atoms in the molecule. Exemplary, non-limiting compounds of formula I are shown in Table 1.

[0058] [Table 1-1]

[0059] [Table 1-2]

[0060] The compound of formula I is, formula R 1 I perfluoroalkyl iodide formula R 2 When contacted with a CH=CH2 perfluoroalkyltrihydroolefin, formula R 1 ICH2CHIR 2 It can be prepared by forming a trihydroiodoperfluoroalkane. Then, this trihydroiodoperfluoroalkane is dehydroiodized, R 1 CH=CHR 2 It can form olefin R. 1 CH=CHR 2 Next is equation R 2 I perfluoroalkyl iodide formula R 1 Formula R is formed by reacting CH=CH2 perfluoroalkyltrihydroolefin. 1 ICHICH2R 2It can also be prepared by deiodizing and hydrogenating the trihydroiodoperfluoroalkane.

[0061] The contact between perfluoroalkyl iodide and perfluoroalkyl trihydroolefin may be carried out in batch mode by combining the reactants in a suitable reaction vessel that can be operated under the self-pressure of the reactants and products at the reaction temperature. Suitable reaction vessels may be made from stainless steel (especially austenitic) and well-known high-nickel alloys, such as Monel® nickel-copper alloy, Hastelloy® nickel-based alloy, and Inconel® nickel-chromium alloy.

[0062] Alternatively, the reaction may be carried out in a semi-batch mode, in which the perfluoroalkyltrihydroolefin reactant is added to the perfluoroalkyl iodide reactant at the reaction temperature using a suitable addition device such as a pump.

[0063] 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 result in a large amount of 2:1 adducts, as reported in Jeanneaux, et al. in Journal of Fluorine Chemistry, Vol. 4, pages 261-270 (1974).

[0064] The preferred temperature for contacting the perfluoroalkyl iodide with the perfluoroalkyl trihydroolefin is preferably in the range of about 150°C to 300°C, preferably about 170°C to 250°C, and most preferably about 180°C to 230°C. The preferred contact time for the reaction between the perfluoroalkyl iodide and the perfluoroalkyl trihydroolefin is about 0.5 hours to 18 hours, preferably about 4 hours to 12 hours.

[0065] The trihydroiodoperfluoroalkane prepared by the reaction of a perfluoroalkyl iodide with a perfluoroalkyltrihydroolefin may be used directly in the deiodization step, or, preferably, may be recovered and purified by distillation before the deiodization step.

[0066] The deiodization 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 solutions, sodium amides, or mixtures of basic substances such as soda lime. Preferred basic substances are sodium hydroxide and potassium hydroxide. The contact between the trihydroiodoperfluoroalkane and the basic substance may preferably be carried out in a liquid phase in the presence of a solvent capable of dissolving at least a portion of both reactants. Suitable solvents for the deiodization 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), dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, or sulfolane. The choice of solvent may depend on the boiling point and the ease of separating trace amounts of solvent from the product during purification. Typically, ethanol or isopropanol are good solvents for this reaction.

[0067] Typically, the deiodization reaction can be carried out by adding one of the reactants (either a basic substance or a trihydroiodoperfluoroalkane) to the other reactants in a suitable reaction vessel. The reaction may be made of glass, ceramic, or metal, and is preferably stirred with an impeller or stirring mechanism.

[0068] The optimal temperature for the deiodide reaction is approximately 10°C to 100°C, preferably approximately 20°C to 70°C. The deiodide reaction may be carried out at ambient pressure, reduced pressure, or high pressure. Attention should be paid to the deiodide reaction, in which the compound of formula I is formed by distillation from the reaction vessel.

[0069] Alternatively, the deiodization reaction may be carried out by contacting an aqueous solution of the basic substance with a solution of the trihydroiodoperfluoroalkane in one or more less polar organic solvents such as alkanes (e.g., hexane, heptane, or octane), aromatic hydrocarbons (e.g., toluene), halogenated hydrocarbons (e.g., methylene chloride, chloroform, carbon tetrachloride, or perchloroethylene), or ethers (e.g., diethyl ether, methyl tert-butyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, dimethoxyethane, diglyme, or tetralyme), in the presence of a phase transfer catalyst. Suitable phase transfer catalysts include quaternary ammonium halides (e.g., tetrabutylammonium bromide, tetrabutylammonium hydrosulfate, triethylbenzylammonium chloride, dodecyltrimethylammonium chloride, and tricaprylylammonium 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).

[0070] Alternatively, the deiodide hydrogenation reaction may be carried out in the absence of a solvent by adding a trihydroiodoperfluoroalkane to a solid or liquid basic substance.

[0071] The appropriate reaction time for deiodide reactions is approximately 15 minutes to 6 hours or longer, depending on the solubility of the reactants. Typically, deiodide reactions are rapid and require approximately 30 minutes to 3 hours to complete.

[0072] The compound of formula I can be recovered from the deiodide hydrolysis reaction mixture by phase separation after the addition of water, by distillation, or a combination thereof.

[0073] In another embodiment of the present invention, the fluoroolefin is a cyclic fluoroolefin (cyclo-[CX=CY(CZW) n -] (Formula II) (wherein X, Y, Z, and W are independently selected from H and F, and n is an integer between 2 and 5). In one embodiment, the fluoroolefin of Formula II has at least about 3 carbon atoms in the molecule. In another embodiment, the fluoroolefin of Formula II has at least about 4 carbon atoms in the molecule. In yet another embodiment, the fluoroolefin of Formula II has at least about 5 carbon atoms in the molecule. Representative cyclic fluoroolefins of Formula II are listed in Table 2.

[0074] [Table 2]

[0075] The refrigerant composition of the present invention may contain a single compound of formula I or formula II, for example, one of the compounds in Table 1 or Table 2, or it may contain a combination of compounds of formula I or formula II.

[0076] In another embodiment, the fluoroolefin may include the compounds listed in Table 3.

[0077] [Table 3-1]

[0078] [Table 3-2]

[0079] [Table 3-3]

[0080] [Table 3-4]

[0081] The compounds listed in Tables 2 and 3 are commercially available or can be prepared by processes known in the art or as described herein.

[0082] 1,1,1,4,4-Pentafluoro-2-butene can be prepared from 1,1,1,2,4,4-hexafluorobutane (CHF2CH2CHFCF3) by dehydrofluoridation 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.

[0083] 1,1,1,4,4,4-Hexafluoro-2-butene can be prepared from 1,1,1,4,4,4-Hexafluoro-2-iodobutane (CF3CHICH2CF3) by reacting with KOH using a phase-transfer catalyst at approximately 60°C. The synthesis of 1,1,1,4,4,4-Hexafluoro-2-iodobutane can be carried out by reacting perfluoromethyl iodide (CF3I) and 3,3,3-trifluoropropene (CF3CH=CH2) at approximately 200°C under self-pressure for approximately 8 hours.

[0084] 3,4,4,5,5,5-Hexafluoro-2-pentene can be prepared by dehydrofluoridating 1,1,1,2,2,3,3-heptafluoropentane (CF3CF2CF2CH2CH3) using solid KOH or a carbon catalyst at 200-300°C. 1,1,1,2,2,3,3-Heptafluoropentane can be prepared by hydrogenating 3,3,4,4,5,5,5-heptafluoro-1-pentene (CF3CF2CF2CH=CH2).

[0085] 1,1,1,2,3,4-Hexafluoro-2-butene can be prepared by dehydrofluoridating 1,1,1,2,3,3,4-heptafluorobutane (CH2FCF2CHFCF3) using solid KOH.

[0086] 1,1,1,2,4,4-Hexafluoro-2-butene can be prepared by dehydrofluoridating 1,1,1,2,2,4,4-heptafluorobutane (CHF2CH2CF2CF3) using solid KOH.

[0087] 1,1,1,3,4,4-Hexafluoro2-butene can be prepared by dehydrofluoridating 1,1,1,3,3,4,4-heptafluorobutane (CF3CH2CF2CHF2) using solid KOH.

[0088] 1,1,1,2,4-Pentafluoro-2-butene can be prepared by dehydrofluoridating 1,1,1,2,2,3-hexafluorobutane (CH2FCH2CF2CF3) using solid KOH.

[0089] 1,1,1,3,4-Pentafluoro-2-butene can be prepared by dehydrofluoridating 1,1,1,3,3,4-hexafluorobutane (CF3CH2CF2CH2F) using solid KOH.

[0090] 1,1,1,3-tetrafluoro-2-butene can be prepared by reacting 1,1,1,3,3-pentafluorobutane (CF3CH2CF2CH3) with an aqueous KOH solution at 120°C.

[0091] 1,1,1,4,4,5,5,5-Octafluoro-2-pentene can be prepared from (CF3CHICH2CF2CF3) by reacting with KOH using a phase-transfer catalyst at approximately 60°C. The synthesis of 4-iodo-1,1,1,2,2,5,5,5-octafluoropentane can be carried out by reacting perfluoroethyl iodide (CF3CF2I) and 3,3,3-trifluoropropene at approximately 200°C under self-pressure for approximately 8 hours.

[0092] 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 reacting with KOH using a phase-transfer catalyst at approximately 60°C. The synthesis of 1,1,1,2,2,5,5,6,6,6-Decafluoro-3-iodohexane can be carried out by reacting perfluoroethyl iodide (CF3CF2I) and 3,3,4,4,4-pentafluoro-1-butene (CF3CF2CH=CH2) at approximately 200°C under self-pressure for approximately 8 hours.

[0093] 1,1,1,4,5,5,5-heptafluoro-4-(trifluoromethyl)-2-pentene can be prepared by dehydrofluoridating 1,1,1,2,5,5,5-heptafluoro-4-iodo-2-(trifluoromethyl)-pentane (CF3CHICH2CF(CF3)2) with KOH in isopropanol. CF3CHICH2CF(CF3)2 is produced by reacting (CF3)2CFI with CF3CH=CH2 at high temperatures, for example, about 200°C.

[0094] 1,1,1,4,4,5,5,6,6,6-Decafluoro-2-hexene can be prepared by reacting 1,1,1,4,4,4-hexafluoro-2-butene (CF3CH=CHCF3) with tetrafluoroethylene (CF2=CF2) and antimony pentafluoride (SbF5).

[0095] 2,3,3,4,4-Pentafluoro-1-butene can be prepared by dehydrofluorinating 1,1,2,2,3,3-hexafluorobutane with alumina fluoride at high temperatures.

[0096] 2,3,3,4,4,5,5,5-Octafluoro-1-pentene can be prepared by dehydrofluoridating 2,2,3,3,4,4,5,5,5-nonafluoropentane with solid KOH.

[0097] 1,2,3,3,4,4,5,5-Octafluoro-1-pentene can be prepared by dehydrofluoridating 2,2,3,3,4,4,5,5,5-nonafluoropentane with alumina fluoride at high temperatures.

[0098] 2,3,3,3-tetrafluoro-1-propene can be prepared by converting at least one of HCFC-244bb or HFC-245eb to HFO-1234yf.

[0099] 1,3,3,3-tetrafluoro-1-propene can be prepared to HFO-1234ze by HFC-245fa.

[0100] Many of the compounds in Formulas I, II, Tables 1, 2, and 3 exist as isomers or stereoisomers with different stereoconfigurations. Where no specific isomer is specified, the present invention is intended to include all single stereoconfiguration isomers, single stereoisomers, or any combination thereof. For example, F11E means that the E isomer, the Z isomer, or any combination or mixture of both isomers in any ratio. As another example, HFO-1225ye means that the E isomer, the Z isomer, or any combination or mixture of both isomers in any ratio.

[0101] In one specific embodiment, the fluoroolefin component of the composition of the present invention comprises HFO-1234yf and / or HFO-1234ze. In another specific embodiment, the fluoroolefin comprises HFO-1234yf and / or HFO-1234ze having a purity of more than 99% by weight, more than 99.5% by weight, and optionally more than 99.5 to 99.98 percent. In yet another specific embodiment, the fluoroolefin comprises at least 99.5% by weight of 1234yf or 1234ze and other fluoroolefins in amounts less than 0.5 and more than 0.0001% by weight, less than 0.3, and optionally less than 0.2.

[0102] In another specific embodiment, the fluoroolefin component may include the refrigerant compositions disclosed in U.S. Patent Nos. 8,147,709 and 8,877,086, which are incorporated herein by reference.

[0103] In another specific embodiment, the fluoroolefin component comprises more than about 99.5% by weight of HFO-1234yf and one or more components 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) may range from greater than 0 to about 200 ppm, about 1 to about 150 ppm, and optionally about 5 to about 50 ppm by weight. The amount of HFO1243zf may range from about 0.1 to about 250 ppm, about 10 to about 200 ppm, and optionally about 15 to about 150 ppm. The amount of HFO-1234ze (E isomer) may range from approximately 1 to approximately 1,500 ppm, approximately 5 to approximately 1,000 ppm, and in some cases, approximately 50 to approximately 500 ppm. The amount of HFC-236ea may range from approximately 1 to approximately 50 ppm, approximately 5 to approximately 25 ppm, and in some cases, approximately 10 to approximately 20 ppm. The amounts of HFC-245fa, HFC-245eb and / or HFC-245cb may range from approximately 0 to approximately 20 ppm, approximately 1 to approximately 15 ppm, and in some cases, approximately 5 to approximately 10 ppm. The amount of 3,3,3-trifluoropropine may range from approximately 0 to approximately 500 ppm, approximately 1 to approximately 300 ppm, and in some cases, approximately 5 to approximately 100 ppm.

[0104] 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, CF3CF2I, 236fa, 142b, 244cc, 1223, 1132a, 2316, 1327 isomers, 1336mzzE, 1336 isomer, 1234zeZ, and 1224 isomer. In one specific embodiment, the fluoroolefin component comprises HFO-1234yf and additional compounds in amounts greater than 0 and less than about 1% by weight, less than about 0.5% by weight, and optionally less than 0.25% by weight. In a further embodiment, the inhibitor of the present invention can be used with a refrigerant composition of at least one of HCFO-1233zd and HCFO-1224yd, and a blend containing at least one of HCFO-1233zd and HCFO-1224yd.

[0105] Any suitable effective amount of inhibitor can be used in the aforementioned refrigerant compositions comprising at least one fluoroolefin. As described herein, the phrase “effective amount” means the amount of the inhibitor of the present invention, when added to a composition comprising at least one fluoroolefin, such that the fluoroolefin does not interact with the reaction initiator and / or degrades, resulting in a composition that does not significantly reduce performance when used in a cooling system, for example, compared to a composition without the inhibitor, and which is present in the liquid-phase fluoroolefin and lubricant. In the case of a cooling system, such an effective amount of inhibitor can be determined by testing under the conditions of the standard test ASHRAE 97-2007 (RA2017). In certain embodiments of the present invention, the effective amount is such that the amount of inhibitor is included as a component comprising a refrigerant composition comprising at least one fluoroolefin and a lubricant, depending on which refrigerant may have been used in similar systems in the past, such as 1,1,1,2-tetrafluoroethane (R-134a) or other standard refrigerants (R-12, R-22, R-502, R-507A, R-508, R-401A, R-401B, R-402A, R-402B, R-408, R-410A, It can be said that a cooling device utilizing a refrigerant composition containing at least one fluoroolefin and a lubricant can exhibit the same level of refrigeration performance and cooling capacity as if a composition containing 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 were used as the working fluid.

[0106] The present invention utilizes an effective amount of at least one of the aforementioned inhibitors. Any suitable effective amount can be used, but the effective amount comprises about 0.001% to about 10% by weight, about 0.01% to about 5% by weight, about 0.3% to about 4% by weight, and about 0.3% to about 1% by weight, based on the total weight of the refrigerant composition comprising the refrigerant composition containing at least one fluoroolefin as described herein. In one embodiment, the effective amount comprises about 10 to about 2,000 ppm, about 10 to about 1,000 ppm, and optionally about 10 to about 500 ppm by weight of at least one reaction initiator.

[0107] In one embodiment of the present invention, the inhibitor is distributed between two liquid phases, namely, a liquid fluoroolefin and a lubricant. The amount of inhibitor present in the liquid phase of the fluoroolefin may range from about 10 to about 80% by weight, about 25 to about 75% by weight, and possibly about 45 to about 60% by weight, with the remaining inhibitor mainly present in the lubricant phase.

[0108] One embodiment of the present invention relates to any of the aforementioned refrigerant compositions, further comprising at least one antioxidant. Any suitable oxidizing agent can be used, but examples of suitable oxidizing agents include at least one component selected from the group consisting of butylated hydroxytoluene, butylated hydroxyanisole, tertiary butylhydroquinone, gallate, 2-phenyl-2-propanol, 1-(2,4,5-trihydroxyphenyl)-1-butanone, phenol, bisphenolmethane derivatives, 2,2'-methylenebis(4-methyl-6-t-butylphenol), and combinations thereof. The amount of antioxidant may range from about 0.01 to about 5,000 ppm, about 0.03 to about 2,000 ppm, and possibly about 0.05 to about 1,000 ppm by weight. An example of a specific embodiment relates to the use of the aforementioned antioxidant together with at least one inhibitor comprising α-terpinene and limonene. One specific embodiment involves using the aforementioned antioxidant together with an inhibitor comprising at least one of α-terpinene and limonene.

[0109] In one embodiment, the aforementioned refrigerant composition of the present invention may further comprise at least one additional compound selected from the group consisting of fluoroolefins (as described herein), hydrofluorocarbons, hydrocarbons, dimethyl ethers, 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, about 5 to about 75%, and optionally about 10 to about 50%.

[0110] In one embodiment, the additional compound includes 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 a standard boiling point of about -90°C to about 80°C. Hydrofluorocarbons are commercially available from many 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), and 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-227ea), 1,1,2,2,3,3-Hexafluoropropane Olopropane (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 (CHF2CF2C H2F, 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-2 54fa), 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 (CH2FCH2CH2F, HFC-272fa), 1,1-difluoropropane Olopropane (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, HFC-338mf), 1, Examples include, but are not limited to, 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).

[0111] In another embodiment, the additional compounds include hydrocarbons. The hydrocarbons of the present invention include compounds having only carbon and hydrogen. Compounds having 3 to 7 carbon atoms are particularly useful. Hydrocarbons are commercially available through numerous chemical suppliers. 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.

[0112] In another embodiment, the additional compound includes hydrocarbons containing heteroatoms such as dimethyl ether (DME, CH3OCH3). DME is commercially available.

[0113] In another embodiment, the additional compound includes iodotrifluoromethane (CF3I), which is commercially available from various sources or can be prepared by methods known in the art.

[0114] In another embodiment, the additional compound includes carbon dioxide (CO2), which is commercially available from various sources or can be prepared by methods known in the art. Generally, any suitable additional compound can be used, as long as the amount of the additional compound does not eliminate the aforementioned distribution of the inhibitor between the liquid-phase oleolefin and the lubricant.

[0115] In another embodiment, the aforementioned refrigerant composition of the present invention is substantially free of additional compounds, and in particular substantially free of at least one of dimethyl ether, CF3I, ammonia, and carbon dioxide. In a preferred embodiment of this embodiment, the aforementioned refrigerant composition is substantially free of CF3I. "Substantially free of additional compounds" means that the refrigerant composition and inhibitor contain less than about 10%, typically less than about 5%, and possibly 0% of additional compounds.

[0116] Of particular note are refrigerant compositions comprising HFO-1234yf and / or HFO-1234ze, and additional compounds including HFO-1225ye and HFC-32; HFO-1225ye and HFC-134a; HFO-1225ye, HFC-134a, and HFC-32; HFO-1225ye and HFO-1234yf; HFO-1225ye, HFC-32; HFO-1225ye, HFO-1225ye, and HFC-125. Further refrigerant compositions include blends of HFO-1234yf and HFO-1234ze with at least one of i) 134a, 32, and 125; ii) 134a; iii) 227ea; iv) 236fa, and v) 134.

[0117] In another embodiment of the present invention, the fluoroolefin component of the refrigerant composition comprises at least about 99% by mass of HFO-1234yf and at least one component 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, in amounts greater than 0 but less than 1% by mass.

[0118] In another embodiment of the present invention, the fluoroolefin component of the refrigerant composition comprises at least about 99% by mass of HFO-1234ze and at least one component selected from the group consisting of HFO-1234yf, HFC-245fa, HFC-236fa, HFO-1234ye, and combinations thereof, in amounts greater than 0 but less than 1% by mass.

[0119] In other embodiments of the present invention, the fluoroolefin component of the refrigerant composition comprises one or more of the aforementioned fluoroolefins blended with at least one hydrofluorocarbon. Examples of suitable hydrofluorocarbons include at least one component 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, about 30 to about 60, and optionally about 30 to about 50. In one specific embodiment, the aforementioned amounts of hydrofluorocarbon are blended with at least one of HFO-1234yf and HFO-1234ze.

[0120] If desired, the blended composition may further include 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 constitute greater than 0 to about 5% by weight, about 0 to about 2% by weight, and optionally about 0 to about 0.5% by weight. In one specific embodiment, the aforementioned amounts of the additional component are blended with at least one of HFO-1234yf and HFO-1234ze. In another specific embodiment, the aforementioned amounts of the additional component are 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.

[0121] The lubricant components of the refrigerant composition may include those suitable for use with refrigeration or air conditioning systems. Among these lubricants are those conventionally used in compression refrigeration systems utilizing chlorofluorocarbon refrigerants. Such lubricants and their properties are discussed in Chapter 8, “Lubricants in Refrigeration Systems,” pp. 8.1-8.21, of the 1990 ASHRAE Handbook, Refrigeration Systems and Applications, which is incorporated herein by reference. The 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 linear and branched carbon chains), naphthenes (i.e., cyclic or cyclic saturated hydrocarbons, which may be paraffins), and aromatics (i.e., unsaturated cyclic hydrocarbons containing one or more rings characterized by alternating double bonds). The lubricants of the present invention may further include those commonly known as “synthetic oils” in the field of compression refrigeration lubrication. Synthetic oils include alkylaryls (i.e., linear and branched alkylalkylbenzenes), synthetic paraffins and naphthenes, silicones, and poly-alpha-olefins. Typical conventional lubricants of the present invention include commercially available BVM 100 N (paraffinic mineral oil sold by BVA Oils), naphthenic mineral oil sold by Crompton Co. under the trademarks Suniso® 3GS and Suniso® 5GS, naphthenic mineral oil sold by Pennzoil under the trademark Sontex® 372LT, naphthenic mineral oil sold by Calumet Lubricants under the trademark Calumet® RO-30, linear alkylbenzenes sold by Shrieve Chemicals under the trademarks Zerol® 75, Zerol® 150, and Zerol® 500, and branched alkylbenzenes sold by Nippon Oil under the trademark HAB22.

[0122] In another embodiment, the lubricant component of the refrigerant composition of the present invention may include those designed for use with hydrofluorocarbon refrigerants and that are miscible with the refrigerant and inhibitor of the present invention under the operating conditions of compressed refrigeration and air conditioning systems. Such lubricants and their properties are discussed in "Synthetic Lubricants and High-Performance Fluids," edited by RLShubkin and Marcel Dekker, 1993. Examples of such lubricants include, but are not limited to, polyol esters (POEs) such as Castrol® 100 (Castrol, United Kingdom), polyalkylene glycols (PAGs) such as RL-488A from Dow Chemical (Midland, Michigan), and polyvinyl ethers (PVEs).

[0123] The lubricant of the present invention is selected by taking into consideration the requirements of a given compressor and the environment to which the lubricant will be exposed. The amount of lubricant may range from about 1 to about 50, about 1 to about 20, and in some cases from about 1 to about 3. In one specific embodiment, the aforementioned refrigerant composition is combined with a PAG lubricant for use in an A / C system for an automobile having an internal combustion engine. In another specific embodiment, the aforementioned refrigerant composition is combined with a POE lubricant for use in an A / C system for an automobile having an electric or hybrid electric drivetrain.

[0124] The inhibitor is sufficiently miscible in the lubricant so that a portion of it is present in the lubricant. The amount of inhibitor present in the lubricant may change when the refrigerant composition is used as a working fluid or heat transfer medium.

[0125] In one embodiment of the present invention, in addition to the inhibitor of the present invention, the refrigerant composition may preferably include at least one additive that can improve the lifespan of the refrigerant and the air conditioning system, as well as the durability of the compressor. In one aspect of the present invention, the aforementioned refrigerant composition includes at least one component selected from the group consisting of acid scavengers, performance enhancers, and flame suppressants.

[0126] Additives that can improve the lifespan of the refrigerant and A / C, as well as the durability of the compressor, are desirable. In one aspect of the present invention, a refrigerant composition of the present invention is used to introduce a lubricant and other additives, such as a) an acid scavenger, b) a performance enhancer, and c) a flame suppressant into an A / C system.

[0127] The acid scavenger may include a siloxane, an activated aromatic compound, or a combination of both. Serrano et al. (paragraph 38 of U.S. Patent Application Publication 2011 / 0272624(A1)), as incorporated herein by reference, disclose that the siloxane may be any molecule having a siloxy functional group. The siloxane may include an alkylsiloxane, an arylsiloxane, or a siloxane containing a mixture of aryl and alkyl substituents. For example, the siloxane may be an alkylsiloxane, including a dialkylsiloxane or a polydialkylsiloxane. Preferred siloxanes include groups having an oxygen atom bonded to two silicon atoms, i.e., a structure:SiOSi. For example, the siloxane may be a siloxane of formula IV:R1[Si(R2R3)4O]nSi(R2R3)R4 (wherein n is 1 or greater). The siloxane of formula IV has n which is preferably 2 or more, more preferably 3 or more (for example, about 4 or more). The siloxane of formula IV has n which is preferably about 30 or less, more preferably about 12 or less, and most preferably about 7 or less. Preferably, the R4 group is an aryl group or an alkyl group. Preferably, the R2 group is an aryl group or an alkyl group, or a mixture thereof. Preferably, the R3 group is an aryl group or an alkyl group, or a mixture thereof. Preferably, the R4 group is an aryl group or an alkyl group. Preferably, R1, R2, R3, R4, or any combination thereof is not hydrogen. The R2 groups in the molecule may be the same or different. Preferably, the R2 groups in the molecule are the same. The R2 group in the molecule may be the same or different from the R3 group. Preferably, the R2 and R3 groups in the molecule are the same. Preferred siloxanes include siloxanes of formula IV in which R1, R2, R3, R4, R5, or any combination thereof is a methyl, ethyl, propyl, or butyl group, or any combination thereof. Exemplary siloxanes that may be used include hexamethyldisiloxane, polydimethylsiloxane, polymethylphenylsiloxane, dodecamethylpentasiloxane, decamethylcyclopentasiloxane, decamethyltetrasiloxane, octamethyltrisiloxane, or any combination thereof.

[0128] It should be noted, drawing on the previously cited work of Serrano et al., that in one aspect of the present invention, the siloxane is an alkylsiloxane containing 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. Preferred polydialkylsiloxanes have a molecular weight of about 100 to about 10,000. Very preferred siloxanes include hexamethyldisiloxane, polydimethylsiloxane, and combinations thereof. The siloxane may essentially consist of polydimethylsiloxane, hexamethyldisiloxane, or combinations thereof.

[0129] Activated aromatic compounds may be any aromatic molecule or mixture thereof that has been activated for a Friedel-Crafts addition reaction. An aromatic molecule activated for a Friedel-Crafts addition reaction is defined as any aromatic molecule that can undergo addition with a mineral acid. In particular, it is any aromatic molecule that can undergo addition with a mineral acid either in the application environment (AC system) or during the thermal stabilization test of ASHRAE 97:2007 "Sealed Glass Tube Method to Test the Chemical Stability of Materials for Use within Refrigerant Systems". Such molecules or compounds are typically activated by substituting a hydrogen atom of the aromatic ring with one of the following groups: NH2, NHR, NRz, ADH, AD, NHCOCH3, NHCOR, 4OCH3, OR, CH3, 4C2H5, R, or C6H5 (wherein R is a hydrocarbon, preferably a hydrocarbon containing about 1 to about 100 carbon atoms). The activated aromatic molecule may be an alcohol or ether in which an oxygen atom (i.e., the oxygen atom of the alcohol or ether group) is directly bonded to the aromatic group. The activated aromatic molecule may be an amine in which a nitrogen atom (i.e., the nitrogen atom of the amine group) is directly bonded to the aromatic group. For example, the activated aromatic molecule may have the formula ArXRn, where X is O (i.e., oxygen) or N (i.e., nitrogen), where n is 1 if X is O, and n is 2 if X is N, where Ar is an aromatic group (i.e., a C6H5 group), and R may be H or a carbon-containing group, and when n:2, the R groups may be the same or different. For example, R may be H (i.e., hydrogen), Ar, an alkyl group, or any combination thereof. Exemplary activated aromatic molecules that may be used in the refrigerant compositions taught herein include diphenyl oxide (i.e., diphenyl ether), methylphenyl ether (e.g., anisole), ethylphenyl ether, butylphenyl ether, or any combination thereof. A highly preferred aromatic molecule activated for the Friedel-Crafts addition reaction is diphenyl oxide.

[0130] From Serrano et al., previously cited by reference, acid scavengers (e.g., activated aromatic compounds, siloxanes, or both) may be present at any concentration, resulting in a relatively low total acid value, 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 more than about 0.0050% by weight, more preferably more than about 0.05% by weight, and even more preferably more than about 0.1% by weight (e.g., more than about 0.5% by weight) based on the total weight of the refrigerant composition. Preferably, the acid scavenger is present at a concentration of less than about 3% by weight, more preferably less than about 2.5% by weight, and most preferably less than about 2% by weight (e.g., less than about 1.8% by weight) based on the total weight of the refrigerant composition.

[0131] Additional examples of acid scavengers that may be included in the refrigerant composition and are preferably excluded from it include one or more of the following: phenyl glycidyl ethers, alkyl glycidyl ethers, alkylene glycol glycidyl ethers, cyclohexene oxides, otolenoxides, or epoxy compounds such as epoxidized soybean oil, as described by Kaneko (paragraph 42 of U.S. Patent Application No. 11 / 575,256, published as U.S. Patent Application Publication No. 2007 / 0290164, expressly incorporated herein by reference), as described by Singh et al. (paragraphs 34-42 of U.S. Patent Application No. 11 / 250,219, published as U.S. Patent Application Publication No. 2006 / 0116310, expressly incorporated herein by reference).

[0132] Preferred additives include those described in U.S. Patents No. 5,152,926 and No. 4,755,316, which are incorporated herein by reference. Particularly preferred extreme pressure additives include mixtures of (A) tolyltriazole or a substituted derivative thereof, (B) an amine (e.g., Jeffamine M-600), and (C)(i) an ethoxylated phosphate ester (e.g., Antara LP-700), or (ii) a phosphate alcohol (e.g., ZELEC 3337), or (iii) zinc dialkyldithiophosphate (e.g., Lubrizol 5139, 5604, 5178, or 5186), or (iv) mercaptobenzothiazole, or (v) a 2,5-dimercapto-1,3,4-triadianazole derivative (e.g., Curvan 826), or a mixture thereof. Additional examples of additives that may be used are described in U.S. Patent No. 5,976,399 (Schnur, 5:12–6:51, incorporated herein by reference).

[0133] The acid value is measured in mg KOH / g units according to ASTM D664-01. The total halide concentration, fluoride ion concentration, and total organic acid concentration are measured by ion chromatography. The chemical stability of the refrigerant system is measured according to ASHRAE 97:2007 (RA2017) "Sealed Glass Tube Method to Test the Chemical Stability of Materials for Use within Refrigerant Systems". The viscosity of the lubricating oil is tested at 40°C according to ASTM D-7042.

[0134] Mouli et al. (International Publication Nos. 2008 / 027595 and 2009 / 042847) teach the use of alkylsilanes as stabilizers in refrigerant compositions containing fluoroolefins. Phosphates, phosphates, epoxides, and phenolic additives are also 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 Publication No. 2007 / 0290164) and Singh et al. (U.S. Patent Application 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.

[0135] Preferred flame suppressants include those described in the patent application "Refrigerant compositions containing fluorine substituted olefins" (Canadian Patent No. 2557873(A1)), which is also referred to and described in the patent application "Refrigerant compositions comprising fluoroolefins and uses thereof" (International Publication No. 2009 / 018117(A1)), together with fluorinated products such as HFC-125 and / or Krytox® lubricant.

[0136] The refrigerant composition of the present invention can be prepared by any simple method for combining desired amounts of individual components. A preferred method is to measure the desired amounts of components and then mix them in a suitable container. Stirring may be used if desired.

[0137] The present invention further relates to a process for producing cooling, comprising condensing a refrigerant composition comprising at least one fluoroolefin, at least one lubricant, and an effective amount of an inhibitor, and then evaporating the composition near a body to be cooled.

[0138] The cooling unit may be any space, location, or object requiring refrigeration or air conditioning. In fixed applications, the unit may be located within a structure, i.e., inside a residential or commercial building, or in a storage location for perishable items such as food or medicine. In portable refrigeration applications, the unit may be incorporated into a transport unit for road, rail, sea, or air transport. Certain refrigeration systems operate independently of any mobile carrier and are known as “intermodal” systems. Examples of such intermodal transport systems include “containers” (sea / land intermodal transport) and “swap bodies” (road and rail intermodal transport).

[0139] The present invention further relates to a process for generating heating, comprising condensing a refrigerant composition near a body to be heated, the refrigerant composition comprising at least one fluoroolefin, at least one lubricant, and an effective amount of an inhibitor comprising at least one of limonene and α-terpinene, and then evaporating the composition.

[0140] The object to be heated may be any space, location, or object that requires heat. These may be located inside a residential or commercial structure in a manner similar to that of the body to be cooled. Furthermore, portable units, such as those described for cooling, may be similar to those requiring heating. Certain transport units require heating to prevent the transported material from solidifying within the transport container.

[0141] Another embodiment of the present invention relates to an air conditioning or refrigeration system comprising the aforementioned refrigerant composition.

[0142] Another embodiment of the present invention relates to storing the aforementioned refrigerant composition in the gas phase and / or liquid phase in a sealed container in which the oxygen and / or water concentrations in the gas phase and / or liquid phase are in the range of about 3 volume ppm to less than about 3,000 volume ppm, about 5 volume ppm to less than about 1,000 volume ppm, and optionally about 5 volume ppm to less than about 500 volume ppm at a temperature of about 25°C.

[0143] Containers for storing the aforementioned refrigerant compositions can be constructed of any suitable material and design that can seal the refrigerant composition while maintaining the gas and liquid phases. Examples of suitable containers include pressure-resistant containers such as tanks, filling cylinders, and secondary filling cylinders. Containers 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. Containers may be equipped with perforated tops or valves suitable for dispensing flammable materials.

[0144] Any suitable method can be used to prepare the refrigerant composition of the present invention, but examples of such methods include, among other preferred methods, blending the aforementioned inhibitor with the aforementioned fluoroolefin composition, purging lines and vessels with a material containing the inhibitor (e.g., an inhibitor containing a nitrogen carrier, or the stabilizing composition of the present invention), and combining it with a lubricant.

[0145] In one embodiment, the composition of the present invention is prepared by adding the inhibitor to at least one of the fluoroolefin component and the lubricant, and then combining the fluoroolefin component with the lubricant. In this case, the inhibitor is added to only one of the fluoroolefin or the lubricant, and then the fluoroolefin and the lubricant are combined, and the inhibitor is distributed so that it is present in both the fluoroolefin and the lubricant. In another embodiment, the inhibitor can be added to a composition comprising at least one fluoroolefin component and at least one lubricant.

[0146] The following examples are provided to illustrate specific embodiments of the present invention and are not intended to limit the scope of the appended claims. Example 1 demonstrates the efficacy of an inhibitor having a fluoroolefin, Example 2 demonstrates the efficacy of an inhibitor having a fluoroolefin and a lubricant, and Example 3 demonstrates the phase equilibrium and AC cycle performance of a ternary R-1234yf / d-limonene / lubricant (commercially available as POE32-3MAF) system. [Examples]

[0147] HFO-1234yf (at least 99.5% by weight purity) * A mixture of 30 g of (containing) and a reaction initiator (with and without an inhibitor) was heated in a 210 mL shaking tube at the temperatures and times shown in Table 4. The shaking tube was visually inspected for polymer formation using NMR according to conventional methods. The polymer can also be detected using conventional IR methods.

[0148] * HFO-1234yf contains 99.7% by weight of HFO-1234yf, 1,000 ppm of HFO-1234ze, 150 ppm of HFO-1225yeZ, and 3 ppm of trifluoropropine, with the remainder being compounds that do not affect the refrigeration performance or inhibitory activity of the mixture.

[0149] [Table 4] [Examples]

[0150] A refrigerant blend containing HFO-1234yf (30 g having the composition of Example 1), a mixture of at least one additional compound and a reaction initiator (but without an inhibitor) was heated in a 210 mL shaking tube at the temperatures and times shown in Table 5. Examples 1-6 evaluate inhibitors containing Opteon® XP-10 refrigerant (R513a) and a commercially available lubricant. Examples 7-12 evaluate inhibitors containing Opteon® XP-40 refrigerant (R449a) and a commercially available lubricant. Examples 13-18 evaluate inhibitors containing HFO-1234yf and a commercially available lubricant. XP10 refrigerant contains 56 wt% HFO1234yf and 44 wt% HFC-134a, while XP40 refrigerant contains 24.3 wt% R32, 24.7 wt% R125, 25.3 wt% 1234yf, and 25.7 wt% 134a. XP10 and XP40 refrigerants are commercially available from Chemors Company. The shaking tubes were visually inspected for polymer formation and by using NMR. The data reported below are in ppm by weight.

[0151] [Table 5] [Examples]

[0152] Two-phase behavior To analyze the phase behavior and d-limonene partitioning of the R-1234yf / d-limonene / lubricant (POE32-3MAF) system, the NRTL binary interaction parameters were fitted to the following binary data. 1) VLE solubility data for R-1234yf / POE32-3MAF was measured at -25 to 75°C. The NRTL binary interaction parameters fit VLE, ​​leading to a prediction of VLLE, and liquid-liquid phase separation is predicted toward the R-1234yf-rich side of the composition domain. The fit quality is excellent, with a deviation of 2.1% AARD from the data, as shown with the data in Figure 1. 2) R-1234yf / d-limonene-VLE bubble point data were measured at 50°C, and the NRTL binary interaction parameters were fitted to experimental data that met the accuracy of 2.1% AARD. In the d-limonene system region of composition space, a negative deviation from Raul's law was observed for 0 to approximately 9 mol% d-limonene, indicating that the R-1234yf / d-limonene interaction is stronger than the R-1234yf / R-1234yf and d-limonene / d-limonene interactions. This is not the expected behavior, and d-limonene activity is more locally dominant near liquid R-1234yf. These data and model fit are shown in Figure 2. The negative deviation from Raul's law is shown in Figure 3. 3) The d-limonene / POE32-3MAP was determined using computer software-based parameterization to calculate the VLE behavior. The calculated VLE is shown in Figure 4.

[0153] Three-phase behavior The experimental bubble point pressure was measured experimentally for various POE32-3MAF content using a binary mixture of R-1234yf and d-limonene at a weight basis of 1000 ppm. The LLE of this ternary system was calculated using the NRTL model. Next, as shown in Figure 5, the ternary phase behavior of the R-1234yf / d-limonene / POE32-3MAF system was calculated using binary interaction parameter data (shown in Figures 1-3) for R-1234yf / POE32-3MAF, d-limonene / POE32-3MAF, and R-1234yf / d-limonene.

[0154] Using the data and calculations shown in Figures 1-5, the phase behavior (distribution effect) and A / C performance of d-limonene in amounts less than 1,000 ppm and greater than 1,000 ppm can be determined.

[0155] The data and calculations shown in Figures 1-5 also represent the vapor-liquid equilibrium distribution of d-limonene such that the vapor becomes R-1234yf, which is substantially free of d-limonene. D-limonene remains primarily in the liquid phase in either the evaporator or the compressor oil sump, and the vapor circulating within the A / C system is substantially free of d-limonene. As a result, since d-limonene is primarily present in the liquid phase, it does not have a significant impact on the power efficiency or capacity of the A / C system.

[0156] While specific aspects, embodiments, and principles have been described above, this specification is for illustrative purposes only and should not be understood as limiting the scope of the present invention or the appended claims. The various aspects, embodiments, and principles described above can be used individually or in combination with each other.

Claims

1. At least one fluoroolefin component, A refrigerant blend comprising 25 to 75% by weight of at least one hydrofluorocarbon selected from the group consisting of HFC-32, HFC-125, HFC-134a, HFC-152a, 236fa, and HFC-227ea, at least one lubricant, and an inhibitor, The fluoroolefin comprises HFO-1234yf having a purity of at least 99.7% by weight, The inhibitor comprises at least one of d-limonene and α-terpinene, and is present in an effective amount that inhibits, if not eliminates, the interaction of the fluoroolefin with another compound to form a dimer, oligomer, homopolymer, or polymer product. The refrigerant blend comprises less than 0.03% by weight of an oligomer, homopolymer, or other polymer product derived from at least one HFO-1234yf fluoroolefin.

2. The refrigerant blend according to claim 1, wherein at least one of the d-limonene and α-terpinene is present in an amount of 10 to 500 ppm.

3. The refrigerant blend according to claim 1 or 2, wherein at least one of the d-limonene and α-terpinene is present in an amount of 50 to 100 ppm.

4. The refrigerant blend according to claim 1, wherein the inhibitor is d-limonene, present in an amount of 50 to 100 ppm.

5. The refrigerant blend according to claim 4, wherein the inhibitor is d-limonene, present in an amount of 50 ppm.

6. The refrigerant blend according to claim 4, wherein the inhibitor is d-limonene, present in an amount of 10 ppm.

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