Stabilized fluoroolefin compositions and method thereof for production, storage and usage

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 to Related Applications) This application claims the benefit of International Application No. PCT / 2019 / 02977, filed on April 30, 2019. The disclosure of International Application No. PCT / 2019 / 02977 is incorporated herein by reference.

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

Background Art

[0003] Due to new environmental regulations on refrigerants, the refrigeration and air - conditioning industries have to search for new refrigerants with a low global warming potential (GWP).

[0004] Alternative refrigerants with low GWP, non - toxicity, non - flammability, reasonable cost, and excellent refrigeration performance are required.

[0005] Fluoroolefins have been proposed as refrigerants, either alone or in mixtures. These products have been extensively tested for their 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", presentation to JAMA / JARIA, October 3, 2007), and have been shown to be stable under typical operating conditions. However, certain fluoroolefins have been observed to exhibit degradation and / or produce unwanted by - products under abnormal conditions such as extreme temperatures or contact with other compounds (among various contaminants, for example, excess oxygen, oxidizing chemicals, or radical - generating compounds) in a contaminated system, 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 JP 2009 - 298918, US Patent No. 6,969,701, No. 8,133,407, US Patent Application Publication No. 2006 / 0022166, No. 2006 / 0043330, No. 2008 / 0157022, and International Publication No. 2007 / 126760, as well as European Patent No. 2057245, US Patent No. 8101094, No. 8535555, No. 8097181, and No. 8075796, the disclosures of which are incorporated herein by reference.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

Patent Document 8

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, fluorinated olefins 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 fluorinated olefin-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 a liquid fluoroolefin and at least one inhibitor present in a lubricant. 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 can also solve 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. The oligomerization or homopolymerization reaction can be accelerated by relatively high temperatures, but 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 either the refrigeration performance of the refrigerant composition or its compatibility with refrigerant oils and components. The stabilized refrigerant composition can be useful in cooling systems and as a replacement for existing refrigerants having a higher global warming potential.

[0010] To avoid possible instabilities of fluoroolefins, it has been found that the stability during packaging, storage, and use in refrigeration or air-conditioning system applications is improved by adding specific inhibitor compounds, namely hydrocarbons containing at least one of the cyclic monoterpenes, lipophilic organic compounds containing tocopherols such as α-tocopherol, phenols, and aromatic organic compounds having at least one chemical moiety C6H4(OH) containing benzene-1,4-diol, to the fluoroolefin-containing refrigerant composition. Specific examples of inhibitor compounds include at least one component selected from the group consisting of limonene, 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 contains a liquid at a temperature of about -100 to about 220 °C, about -90 to about 200 °C, and in some cases about -80 to about 185 °C.

[0011] In a specific embodiment, the present invention relates to a hydrofluorocarbon-containing refrigerant composition comprising an inhibitor that can interact or react with O2 and a fluoroolefin peroxide and then inhibit or prevent the reaction of such a compound with a hydrofluoroolefin. Examples of such inhibitors include at least one of limonene and α-terpinene. Limonene and α-terpinene have the following structures:

[0012]

Chemical formula

[0013] In one embodiment of the present invention, the inhibitor comprises α-terpinene. Without being bound by theory or explanation, it is believed that due to the presence of conjugated double bonds in its structure, α-terpinene can form an aromatic ring upon oxidation.

[0014] In one embodiment of the present invention, limonene or α-terpinene, optionally containing an antioxidant, has a unique aroma even at the ppm level. This pleasant smell can be utilized for the detection of refrigerant leaks by refrigerants and blends based on hydrofluoroolefins (e.g., including at least one of 1234yf, 1234ze, and combinations thereof). This is particularly beneficial for early detection of refrigerant leaks in household air conditioners or portable air conditioners because professional electronic leak detectors are often not available everywhere.

[0015] One embodiment of the present invention is a. at least one hydrofluoroolefin, and b. at least one lubricant, and c. A refrigerant composition comprising an inhibitor, which is at least one inhibitor in an effective amount and includes a hydrocarbon containing a cyclic monoterpene, a lipophilic organic compound containing a tocopherol including α-tocopherol, a phenol, and an aromatic organic compound having a chemical formula C6H4(OH) including benzene-1,4-diol, and relates to a refrigerant composition 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 antioxidant can be used, and examples of suitable antioxidants include, among several phenols, butylated hydroxytoluene, butylated hydroxyanisole, tertiary butylhydroquinone, gallate, 2-phenyl-2-propanol, 1-(2,4,5-trihydroxyphenyl)-1-butanone, bisphenol methane derivatives, 2,2'-methylenebis(4-methyl-6-t-butylphenol), and at least one component selected from the group consisting of combinations thereof.

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

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

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

[0020] A further embodiment of the present invention relates to a fluoroolefin-containing refrigerant composition within a container, having a reduced likelihood of oligomerization or homopolymerization of the fluoroolefin as compared to a composition that does not contain the inhibitor composition of the present invention.

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

[0023] 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 air, oxygen, cumene hydroperoxide, and fluoroolefin polyperoxides, peroxides, hydroperoxides, persulfates, percarbonates, perborates, and persulfates.

[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 limonene, 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 of 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, HFO1225ye, 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 foregoing refrigerant compositions further comprising at least one component selected from the group consisting of butylated hydroxytoluene, butylated hydroxyanisole, tertiary butyl hydroquinone, gallate, 2-phenyl-2-propanol, 1-(2,4,5-trihydroxyphenyl)-1-butanone, phenol, bisphenol methane derivatives, and 2,2'-methylenebis(4-methyl-6-t-butylphenol).

[0031] Another embodiment of the present invention relates to any of the foregoing 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 foregoing refrigerant compositions wherein the inhibitor comprises a liquid at a temperature of about -80 to 180°C.

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

[0034] Another embodiment of the present invention relates to any of the foregoing 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 foregoing refrigerant compositions wherein the components comprise HFO-1234ze, HFO-1225yeZ, and 3,3,3-trifluoropropyne.

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

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

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

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

[0040] Another embodiment of the present invention relates to any of the foregoing methods, wherein the refrigerant composition is exposed to at least one component selected from the group consisting of air, oxygen, cumene hydroperoxide, and fluoroolefin polyperoxide, peroxide, hydroperoxide, persulfate, percarbonate, perborate, and persulfate before the contact.

[0041] Another embodiment of the present invention relates to any of the foregoing methods, wherein any of the foregoing refrigerant compositions is used for heating or cooling.

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

[0043] Embodiments of the present invention can be used alone or in combination with each other, and different embodiments can be combined to form part of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0044]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Mode for Carrying Out the Invention

[0045] The present invention provides a stabilized refrigerant composition comprising at least one fluoroolefin, at least one lubricant, and an effective amount of at least one inhibitor, the inhibitor being present in the liquid fluoroolefin and lubricant. "Stabilized" means a composition containing an effective amount of at least one inhibitor compound that inhibits, if not excluding, the fluoroolefin from interacting with another compound to form a dimer, oligomer, homopolymer, or polymer product. Examples of such compounds that can cause such interactions include, among numerous reaction initiators, oxidizing agents such as air, oxygen, cumene hydroperoxide, and fluoroolefin polyperoxides, peroxides, hydroperoxides, persulfates, percarbonates, perborates, hydropersulfates. The reaction initiator compound can be present in an amount of about 10 to about 15,000 ppm, about 1,000 to about 10,000 ppm, in some cases about 1,000 to about 3,000 ppm, and in some embodiments, 30 to 2,000 ppm by weight. Such reaction initiator compounds can be present as contaminants in at least one of the conduits, lines, and other systems, packaging (containers), and refrigeration, air conditioning, or heat pump systems used to process the fluoroolefin-containing refrigerant composition. Without being bound by theory or explanation, it is believed that certain contaminants function as radical reaction initiators, thereby oligomerizing, homopolymerizing, or forming other polymer products from the fluoroolefin.

[0046] In one embodiment of the present invention, the refrigerant composition of the present invention substantially does not contain oligomers, homopolymers, or other polymer products derived from hydrofluoroolefins. "Substantially does not contain" 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 in some cases about 0 ppm of such products when 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 famesene; [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] -It substantially does not contain specific conventional inhibitor compounds including ionic liquids such as ionic liquids containing anions selected from the group consisting of fluorinated anions and mixtures thereof. "Substantially does not contain" means that the refrigerant composition of the present invention contains such a conventional inhibitor of less than about 500 ppm, typically less than about 250 ppm, in some cases about 100 ppm, and in some cases about 0 ppm.

[0048] The refrigerant composition of the present invention has various utilities including, in particular, heat transfer media (such as 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 use in portable air conditioning systems and for making refrigerant blends for use in stationary heat transfer systems.

[0049] 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 carry heat from a heat source to a heat sink.

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

[0051] As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," or any other variations thereof are intended to cover non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises elements listed therein is not necessarily limited to only those elements, but may include other elements not expressly listed or other elements associated with such composition, process, method, article, or apparatus. Further, unless expressly stated to the contrary, "or" refers to an inclusive "or" and not an exclusive "or." For example, the condition A or B is satisfied by any one of the following: namely, 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).

[0052] The transitional phrase "consisting of" excludes any unrecited element, step, or ingredient. In the context of a claim, such a phrase excludes from the claim the inclusion of materials other than those recited, except for impurities ordinarily associated with the recited materials. When the phrase "consisting of" appears in a clause within the body of a claim rather than immediately following the preamble, the phrase limits only the elements set forth in that clause and does not necessarily exclude other elements from the scope of the claim as a whole.

[0053] The transitional phrase "consisting essentially of" is used to define compositions, methods that include materials, steps, features, ingredients, or elements in addition to those literally disclosed, provided that these additional materials, steps, features, ingredients, or elements do not materially affect the basic and novel characteristics (s) of the claimed invention, particularly the mode of operation for achieving any desired result of the process of the present invention. The term "consisting essentially of" occupies a middle ground between "comprising" and "consisting of."

[0054] When the applicant defines the invention or a part thereof using non - limiting terms such as "comprising", it should be readily understood that (unless otherwise specified), the description should be construed to include inventions using the terms "consisting essentially of" or "consisting of".

[0055] Also, the use of "a" or "an" is for describing the elements and components described in this specification. This is merely for convenience and for giving the general meaning of the scope of the present invention. This description should be construed to include one or at least one, and the singular form also includes the plural form unless it is clear that the singular form has a different meaning.

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

[0057] One embodiment of the present invention is a fluoroolefin having the formula E - or Z - R 1 CH=CHR 2 (Formula I) (wherein R 1 and R 2 are independently C1 - C6 perfluoroalkyl groups). 1 The R 2Examples of the group include, but are not limited to, CF3, C2F5, CF2CF2CF3, CF(CF3)2, CF2CF2CF2CF3, CF(CF3)CF2CF3, CF2CF(CF3)2, C(CF3)3, CF2CF2CF2CF2CF3, CF2CF2CF(CF3)2, C(CF3)2C2F5, CF2CF2CF2CF2CF2CF3, CF(CF3)CF2CF2C2F5, and C(CF3)2CF2C2F5. In one embodiment, the fluoroolefin of Formula I has at least about 4 carbon atoms in the molecule. In another embodiment, the fluoroolefin of Formula I has at least about 5 carbon atoms in the molecule. Exemplary non-limiting compounds of Formula I are presented in Table 1.

[0058]

Table 1-1

[0059]

Table 1-2

[0060] The compound of Formula I is a perfluoroalkyl iodide of Formula R 1 I contacted with a perfluoroalkyltrihydroolefin of Formula R 2 CH=CH2 to form a trihydroiodoperfluoroalkane of Formula R 1 ICH2CHIR 2 and can be prepared by. This trihydroiodoperfluoroalkane is then dehydroiodinated to form R 1 CH=CHR 2 Alternatively, the olefin R 1 CH=CHR 2 is then the perfluoroalkyl iodide of Formula R 2 I reacted with a perfluoroalkyltrihydroolefin of Formula R 1 CH=CH2 to form a compound of Formula R 1 ICHICH2R 2It can also be prepared by dehydroiodination of trihydroiodoperfluoroalkane.

[0061] The contact of perfluoroalkyl iodide and perfluoroalkyl trihydroolefin can 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 include those made of stainless steel (especially austenitic), as well as 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 semi-batch mode by adding the perfluoroalkyl trihydroolefin reactant to the perfluoroalkyl iodide reactant by a suitable addition device such as a pump at the reaction temperature.

[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. At a ratio less than 1.5:1, a large amount of 2:1 adduct tends to form as reported by 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 about 250°C, and most preferably about 180°C to about 230°C. The suitable contact time for the reaction of perfluoroalkyl iodide and perfluoroalkyl trihydroolefin is about 0.5 hour to 18 hours, preferably about 4 to about 12 hours.

[0065] The trihydroiodoperfluoroalkane prepared by the reaction of a perfluoroalkyl iodide and a perfluoroalkyl trihydroolefin may be used directly in the dehydroiodination step or, preferably, may be recovered and purified by distillation prior to the dehydroiodination step.

[0066] The dehydroiodination step is carried out by contacting the trihydroiodoperfluoroalkane with a basic substance. Suitable basic substances include alkali metal hydroxides (e.g., sodium hydroxide or potassium hydroxide), alkali metal oxides (e.g., sodium oxide), alkaline earth metal hydroxides (e.g., calcium hydroxide), alkaline earth metal oxides (e.g., calcium oxide), alkali metal alkoxides (e.g., sodium methoxide or sodium ethoxide), aqueous ammonia, sodium amide, or mixtures of basic substances such as soda lime. Preferred basic substances are sodium hydroxide and potassium hydroxide. The contact of the trihydroiodoperfluoroalkane with the basic substance may preferably be carried out in the liquid phase in the presence of a solvent capable of dissolving at least a portion of both reactants. Suitable solvents for the dehydroiodination step include one or more polar organic solvents such as alcohols (e.g., methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and tertiary butanol), nitriles (e.g., acetonitrile, propionitrile, butyronitrile, benzonitrile, or adiponitrile), dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, or sulfolane. The choice of solvent may depend on the ease of separating the boiling point products and trace amounts of solvent from the product during purification. Typically, ethanol or isopropanol is a good solvent for this reaction.

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

[0068] Suitable temperatures for the dehydroiodination reaction are from about 10 °C to about 100 °C, preferably from about 20 °C to about 70 °C. The dehydroiodination reaction may be carried out at ambient pressure or under reduced or elevated pressure. Attention should be paid to the dehydroiodination reaction that is distilled from the reaction vessel when the compound of formula I is formed.

[0069] Alternatively, the dehydroiodination reaction may be carried out by contacting an aqueous solution of the basic substance with a solution of 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 tetraglyme) in the presence of a phase transfer catalyst. Suitable phase transfer catalysts include quaternary ammonium halides (e.g., tetrabutylammonium bromide, tetrabutylammonium hydrogensulfate, 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 such as crown ethers (e.g., 18-crown-6 and 15-crown-5).

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

[0071] A suitable reaction time for the dehydroiodination reaction is from about 15 minutes to about 6 hours, or more, depending on the solubility of the reactants. Typically, the dehydroiodination reaction is rapid and requires from about 30 minutes to about 3 hours to complete.

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

[0073] In another embodiment of the present invention, the fluoroolefin comprises 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 from 2 to 5). In one embodiment, the fluoroolefin of formula II has at least about 3 carbon atoms in the molecule. In another embodiment, the fluoroolefin of formula II has at least about 4 carbon atoms in the molecule. In yet another embodiment, the fluoroolefin of formula II has at least about 5 carbon atoms in the molecule. Representative cyclic fluoroolefins of formula II are listed in Table 2.

[0074]

Table 2

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

[0076] In another embodiment, the fluoroolefin may comprise 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 either 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 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.

[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 about 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 about 200 °C under self-pressure for about 8 hours.

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

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

[0086] 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.

[0087] 1,1,1,3,4,4 - Hexafluoro - 2 - butene can be prepared by dehydrofluorination of 1,1,1,3,3,4,4 - heptafluorobutane (CF3CH2CF2CHF2) using solid KOH.

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

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

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

[0093] 1,1,1,4,5,5,5-heptafluoro-4-(trifluoromethyl)-2-pentene can be prepared by dehydrofluorinating 1,1,1,2,5,5,5-heptafluoro-4-iodo-2-(trifluoromethyl)-pentane (CF3CHICH2CF(CF3)2) with KOH in isopropanol. CF3CHICH2CF(CF3)2 is prepared by reacting (CF3)2CFI with CF3CH=CH2 at a high temperature, 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 dehydrogenating 1,1,2,2,3,3 - hexafluorobutane with aluminum fluoride at high temperature.

[0096] 2,3,3,4,4,5,5,5 - Octafluoro - 1 - pentene can be prepared by dehydrogenating 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 dehydrogenating 2,2,3,3,4,4,5,5,5 - nonafluoropentane with aluminum fluoride at high temperature.

[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 from HFC - 245fa to HFO - 1234ze.

[0100] Many of the compounds of Formula I, Formula II, Table 1, Table 2, and Table 3 exist as isomers or stereoisomers of different configurations. When no specific isomer is designated, the present invention is intended to include all single-configuration isomers, single stereoisomers, or any combination thereof. For example, F11E means the E isomer, the Z isomer, or any combination or mixture of both isomers in any ratio. As another example, HFO-1225ye means the E isomer, the Z isomer, or any combination or mixture of both isomers in any ratio.

[0101] In a 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 in some cases more than 99.5 - 99.98% by weight. In another specific embodiment, the fluorolefin comprises at least 99.5% by weight of 1234yf or 1234ze and less than 0.5% and more than 0.0001% by weight, less than 0.3% by weight, and in some cases less than 0.2% by weight of other fluoroolefins.

[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 greater than about 99.5 weight % 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 isomers) can range from greater than 0 to about 200 ppm, from about 1 to about 150 ppm, and in some cases from about 5 to about 50 ppm on a weight basis. The amount of HFO1243zf can range from about 0.1 to about 250 ppm, from about 10 to about 200 ppm, and in some cases from about 15 to about 150 ppm. The amount of HFO-1234ze (E isomer) can range from about 1 to about 1,500 ppm, from about 5 to about 1,000 ppm, and in some cases from about 50 to 500 ppm. The amount of HFC-236ea can range from about 1 to about 50 ppm, from about 5 to about 25 ppm, and in some cases from about 10 to about 20 ppm. The amount of HFC-245fa, HFC-245eb, and / or HFC-245cb can range from about 0 to about 20 ppm, from about 1 to about 15 ppm, and in some cases from about 5 to about 10 ppm. The amount of 3,3,3-trifluoropropyne can range from about 0 to about 500 ppm, from about 1 to about 300 ppm, and in some cases from about 5 to about 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 isomers, 1234zeZ, and 1224 isomers. In a specific embodiment, the fluoroolefin component comprises HFO-1234yf and an additional compound greater than 0 and less than about 1 wt%, less than about 0.5 wt%, and in some cases less than 0.25 wt%. In a further embodiment, the inhibitor of the present invention can be used with at least one of HCFO-1233zd and HCFO-1224yd and a refrigerant composition of a blend comprising at least one of HCFO-1233zd and HCFO-1224yd.

[0105] Any suitable effective amount of inhibitor can be used in the refrigerant composition described above, which contains at least one fluoroolefin. As described herein, the phrase "effective amount" means that when added to a composition containing at least one fluoroolefin, the fluoroolefin does not interact with the initiator and / or deteriorates, and for example, compared to a composition without an inhibitor, a composition is obtained that does not significantly reduce performance when used in a cooling device. The amount of the inhibitor of the present invention is present in the liquid-phase fluoroolefin and the lubricant. In the case of a cooling device, such an effective amount of inhibitor can be determined by the method of testing under the conditions of the standard test ASHRAE 97-2007 (RA2017). In a particular embodiment of the present invention, the effective amount is such that when the amount of inhibitor is included as a component in a refrigerant composition containing at least one fluoroolefin and a lubricant, depending on what refrigerant might have been used in a similar system in the past, a cooling device using the 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 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-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 uses at least one of the aforementioned inhibitors in an effective amount. Any suitable effective amount can be used, and the effective amount is about 0.001 wt% to about 10 wt%, about 0.01 wt% to about 5 wt%, about 0.3 wt% to about 4 wt%, about 0.3 wt% to about 1 wt% based on the total weight of the refrigerant composition including the refrigerant composition containing at least one fluoroolefin described herein. In one embodiment, the effective amount comprises at least one initiator in an amount of about 10 to about 2,000 ppm, about 10 to about 1,000 ppm, and in some cases about 10 to about 500 ppm by weight.

[0107] In one embodiment of the present invention, the inhibitor is distributed between two liquid phases, namely, the liquid-phase fluoroolefin and the lubricant. The amount of the inhibitor present in the liquid phase of the fluoroolefin can range from about 10 to about 80 wt%, about 25 to about 75 wt%, and in some cases about 45 to about 60 wt% of the inhibitor, and the remaining inhibitor is 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 antioxidant can be used, and examples of suitable antioxidants 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, bisphenol methane derivatives, 2,2'-methylenebis(4-methyl-6-t-butylphenol), and combinations thereof. The amount of the antioxidant can range from about 0.01 to about 5,000 ppm, about 0.03 to about 2,000 ppm, and in some cases about 0.05 to about 1,000 ppm by weight. An example of a specific embodiment relates to using the aforementioned antioxidant together with at least one inhibitor including α-terpinene and limonene. An example of a specific embodiment relates to using the aforementioned antioxidant together with at least one inhibitor including at least one of α-terpinene and limonene.

[0109] In one embodiment, the aforementioned refrigerant composition of the present invention may further contain at least one additional compound selected from the group consisting of fluoroolefins (as described above in this specification), hydrofluorocarbons, hydrocarbons, dimethyl ether, CF3I, ammonia, carbon dioxide (CO2), and mixtures thereof, i.e., mixtures of any of the additional compounds listed in this paragraph. The amount of the additional compound can range from about 1 to about 90% by weight, about 5 to about 75%, and in some cases 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 from 1 to 7 carbon atoms and a normal boiling point of from 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), 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 (CHF2CF2CHF2, HFC-236ca), 1,1,1,2,2,3-hexafluoropropane (CF3CF3CH2F, HFC-236cb), 1,1,1,2,3,3-hexafluoropropane (CF3CHFCHF2, HFC-236ea), 1,1,1,3,3,3-hexafluoropropane (CF3CH2CF3, HFC-236fa), 1,1,2,2,3-pentafluoropropane (CHF2CF2CH2F, HFC-245ca), 1,1,1,2,2-pentafluoropropane (CF3CF2CH3, HFC-245cb), 1,1,2,3,3-pentafluoropropane (CHF2CHFCHF2, HFC-245ea), 1,1,1,2,3-pentafluoropropane (CF3CHFCH2F, HFC-245eb), 1,1,1,3,3-pentafluoropropane (CF3CH2CHF2, HFC-245fa), 1,2,2,3-Tetrafluoropropane (CH2FCF2CH2F, HFC-254ca), 1,1,2,2-tetrafluoropropane (CHF2CF2CH3, HFC-254cb), 1,1,2,3-tetrafluoropropane (CHF2CHFCH2F, HFC-254ea), 1,1,1,2-tetrafluoropropane (CF3CHFCH3, HFC-254eb), 1,1,3,3-tetrafluoropropane (CHF2CH2CHF2, HFC-254fa), 1,1,1,3-tetrafluoropropane (CF3CH2CH2F, HFC-254fb), 1,1,1-trifluoropropane (CF3CH2CH3, HFC-263fb), 2,2-difluoropropane (CH3CF2CH3, HFC-272ca), 1,2-difluoropropane (CH2FCHFCH3, HFC-272ea), 1,3-difluoropropane (CH2FCH2CH2F, HFC-272fa), 1,1-difluoropropane (CHF2CH2CH3, HFC-272fb), 2-fluoropropane (CH3CHFCH3, HFC-281ea), 1-fluoropropane (CH2FCH2CH3, HFC-281fa), 1,1,2,2,3,3,4,4-octafluorobutane (CHF2CF2CF2CHF2, HFC-338pcc), 1,1,1,2,2,4,4,4-octafluorobutane (CF3CH2CF2CF3, HFC-338mf), 1,1,1,3,3-pentafluorobutane (CF3CH2CHF2, HFC-365mfc), 1,1,1,2,3,4,4,5,5,5-decafluoropentane (CF3CHFCHFCF2CF3, HFC-43-10mee), and 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoroheptane (CF3CF2CHFCHFCF2CF2CF3, HFC-63-14mee) are included, but not limited thereto.,

[0111] In another embodiment, the additional compound comprises a hydrocarbon. The hydrocarbons of the present invention include compounds having only carbon and hydrogen. In particular, compounds having 3 to 7 carbon atoms are useful. Hydrocarbons are commercially available through a number of chemical 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 comprises dimethyl ether (DME), a hydrocarbon containing heteroatoms such as CH3OCH3. DME is commercially available.

[0113] In another embodiment, the additional compound comprises iodo-trifluoromethane (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 comprises 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 partitioning of the inhibitor between the liquid olefin and the lubricant.

[0115] In another embodiment, the aforementioned refrigerant composition of the present invention substantially does not contain an additional compound, and in particular, substantially does not contain at least one of dimethyl ether, CF3I, ammonia, and carbon dioxide. In a preferred aspect of this embodiment, the aforementioned refrigerant composition substantially does not contain CF3I. "Substantially does not contain an additional compound" means that the refrigerant composition and the inhibitor contain less than about 10%, usually less than about 5%, and in some cases 0% of the additional compound.

[0116] Particularly noteworthy are refrigerant compositions comprising HFO-1234yf and / or HFO-1234ze, and an additional compound comprising 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 comprise a blend 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 other embodiments of the present invention, the fluoroolefin component of the refrigerant composition comprises at least about 99% by weight 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, where the amount is greater than 0 but less than 1% by weight.

[0118] In other embodiments of the present invention, the fluoroolefin component of the refrigerant composition comprises at least about 99% by weight 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, where the amount is greater than 0 but less than 1% by weight.

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

[0120] If desired, the blended composition may further comprise at least one additional component selected from the group consisting of HCC-40, HCFC-22, CFC-115, HCFC-124, HCFC-1122, and CFC-1113. The amount of the additional component can constitute more than 0 to about 5 wt%, about 0 to about 2 wt%, and in some cases about 0 to about 0.5 wt%. In a specific embodiment, the aforementioned amount of the additional component is blended with at least one of HFO-1234yf and HFO-1234ze. In another specific embodiment, the aforementioned amount of the additional component is blended with at least one of HFO-1234yf and HFO-1234ze, and at least one hydrofluorocarbon selected from the group consisting of HFC-32, HFC-125, HFC-134a, HFC-152a, 236fa, and HFC-227ea, and optionally combined with carbon dioxide.

[0121] The lubricant components of the refrigerant composition can include those suitable for use with refrigeration or air conditioning devices. Among these lubricants, those conventionally used in compression refrigeration devices that utilize chlorofluorocarbon refrigerants. Such lubricants and their properties are discussed in the 1990 ASHRAE Handbook, Refrigeration Systems and Applications, Chapter 8, titled "Lubricants in Refrigeration Systems", pages 8.1 - 8.21, which is incorporated herein by reference. The lubricants of the present invention can include those generally known as "mineral oils" in the field of compression refrigeration lubrication. Mineral oils include paraffins (i.e., saturated hydrocarbons with straight-chain and branched carbon chains), naphthenes (i.e., cyclic or ring-structured saturated hydrocarbons, which can 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 further include those generally known as "synthetic oils" in the field of compression refrigeration lubrication. Synthetic oils include alkyl aromatics (i.e., straight-chain 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 (a paraffinic mineral oil sold by BVA Oils), naphthenic mineral oils commercially available under the trade names Suniso® 3GS and Suniso® 5GS by Crompton Co., naphthenic mineral oils commercially available from Pennzoil under the trade name Sontex® 372LT, naphthenic mineral oils commercially available from Calumet Lubricants under the trade name Calumet® RO-30, linear alkylbenzenes commercially available from Shrieve Chemicals under the trade names Zerol® 75, Zerol® 150, and Zerol® 500, and branched alkylbenzenes sold by Nippon Oil as HAB22.

[0122] In another embodiment, the lubricant component of the refrigerant composition of the present invention is designed for use with hydrofluorocarbon refrigerants and can include those that are miscible with the refrigerant and inhibitor 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 R.L. Shubkin, Marcel Dekker, 1993. Such lubricants include, but are not limited to, polyol esters (POE) such as Castrol® 100 (Castrol, United Kingdom), polyalkylene glycols (PAG) such as RL-488A manufactured by Dow (Dow Chemical, Midland, Michigan), and polyvinyl ethers (PVE).

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

[0124] The inhibitor has sufficient miscibility in the lubricant such that a portion of the inhibitor is present in the lubricant. The amount of inhibitor present in the lubricant can vary 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, it is desirable that the refrigerant composition can include at least one additive that can improve the life of the refrigerant and air conditioning system and 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 improvers, and flame suppressants.

[0126] Additives that can improve the life of the refrigerant and A / C and the durability of the compressor are desirable. In one aspect of the present invention, using the refrigerant composition of the present invention, lubricants and other additives, such as a) acid scavengers, b) performance improvers, and c) flame suppressants, are introduced into the 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 US Patent Application Publication No. 2011 / 0272624 (A1)), which is incorporated herein by reference, discloses that a siloxane can 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 an oxygen atom bonded to two silicon atoms, i.e., a group having the structure: SiOSi. For example, the siloxane may be a siloxane of formula IV: R1[Si(R2R3)4O]nSi(R2R3)R4, where n is 1 or more. The siloxane of formula IV preferably has an n that is 2 or more, more preferably 3 or more (e.g., about 4 or more). The siloxane of formula IV preferably has an n that is about 30 or less, more preferably about 12 or less, and most preferably about 7 or less. Preferably, the R4 group is an aryl group or an alkyl group. Preferably, the R2 group is an aryl group, an alkyl group, or a mixture thereof. Preferably, the R3 group is an aryl group, 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 within the molecule may be the same or different. Preferably, the R2 groups within the molecule are the same. The R2 group within the molecule may be the same as or different from the R3 group. Preferably, the R2 group and the R3 group within the molecule are the same. Preferred siloxanes include siloxanes of formula IV where R1, R2, R3, R4, R5, or any combination thereof is a methyl, ethyl, propyl, or butyl group, or any combination thereof. Exemplary siloxanes that may be used include hexamethyldisiloxane, polydimethylsiloxane, polymethylphenylsiloxane, dodecamethylpentasiloxane, decamethylcyclopentasiloxane, decamethyltetrasiloxane, octamethyltrisiloxane, or any combination thereof.

[0128] It should be noted that in one aspect of the present invention, from Serrano et al. who are cited in advance, the siloxane is an alkylsiloxane containing about 1 to about 12 carbon atoms, for example, hexamethyldisiloxane. The siloxane may also be a polymer such as a polydialkylsiloxane, where the alkyl group is methyl, ethyl, propyl, butyl, or any combination thereof. Suitable polydialkylsiloxanes have a molecular weight of about 100 to about 10,000. Highly preferred siloxanes include hexamethyldisiloxane, polydimethylsiloxane, and combinations thereof. The siloxane may consist essentially of polydimethylsiloxane, hexamethyldisiloxane, or a combination thereof.

[0129] An activated aromatic compound may be any aromatic molecule, or mixture thereof, that is activated towards a Friedel-Crafts addition reaction. An aromatic molecule activated towards 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 a molecule or compound is 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, 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 the 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 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), when X is O, n is 1, when X is N, n is 2, Ar is an aromatic group (i.e., a C6H5 group), R may be H or a carbon-containing group, and when n:2, the R groups may be the same or different. For example, R may be H (i.e., hydrogen), Ar, an alkyl group, or any combination thereof, and exemplary activated aromatic molecules that may be used in the refrigerant compositions according to the teachings herein include diphenyl oxide (i.e., diphenyl ether), methyl phenyl ether (e.g., anisole), ethyl phenyl ether, butyl phenyl ether, or any combination thereof. A very preferred mono-aromatic molecule activated towards a Friedel-Crafts addition reaction is diphenyl oxide.

[0130] From Serrano et al., incorporated herein by reference in advance, acid scavengers (e.g., activated aromatic compounds, siloxanes, or both) may be present at any concentration, such that the total acid value is relatively low, the total halide concentration is relatively low, the total organic acid concentration is relatively low, or any combination thereof. Preferably, the acid scavenger is present at a concentration of greater than about 0.0050 wt%, more preferably greater than about 0.05 wt%, even more preferably greater than about 0.1 wt% (e.g., greater than about 0.5 wt%) based on the total weight of the refrigerant composition. The acid scavenger is preferably present at a concentration of less than about 3 wt%, more preferably less than about 2.5 wt%, most preferably less than about 2 wt% (e.g., less than about 1.8 wt%) based on the total weight of the refrigerant composition.

[0131] Additional examples of acid scavengers that may be included in and are preferably excluded from the refrigerant composition include those described by Kaneko (paragraph 42 of U.S. Patent Application No. 11 / 575,256, published as U.S. Patent Application Publication No. 2007 / 0290164, incorporated herein by reference in its entirety), such as one or more of epoxy compounds such as phenyl glycidyl ether, alkyl glycidyl ether, alkylene glycol glycidyl ether, cyclohexene oxide, otolenoxides, or epoxidized soybean oil, and those 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, incorporated herein by reference in its entirety).

[0132] Preferred additives include those described in U.S. Patent Nos. 5,152,926 and 4,755,316, which are hereby incorporated by reference. In particular, 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 which is (i) an ethoxylated phosphate ester (e.g., Antara LP-700 type) or (ii) an alcohol phosphate (e.g., ZELEC 3337 type) or (iii) zinc dialkyldithiophosphate (e.g., Lubrizol 5139, 5604, 5178, or 5186 type) or (iv) mercaptobenzothiazole or (v) a 2,5-dimercapto-1,3,4-triazole 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, hereby incorporated by reference).

[0133] The acid value is measured in units of mg KOH / g 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. 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 are also used in certain refrigerant compositions. These are described, for example, by Kaneko (U.S. Patent Application Publication No. 2007 / 0290164, corresponding to U.S. Patent Application No. 11 / 575,256) and Singh et al. (U.S. Patent Application Publication No. 2006 / 0116310, corresponding to U.S. Patent Application No. 11 / 250,219). All of the above-mentioned applications are hereby expressly incorporated by reference.

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

[0136] The refrigerant composition 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 meter the desired amounts of the components and then mix the components 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 in the vicinity of a body to be cooled.

[0138] The body to be cooled may be any space, location, or object that requires refrigeration or air conditioning. In stationary applications, the body may be present in a structure, i.e., inside a residential or commercial structure, or in a storage location for perishable items such as food or pharmaceuticals. In portable refrigeration applications, the body may be incorporated into a transportation unit for road, rail, sea, or air. Certain refrigeration systems operate independently of any mobile carrier, and these are known as "intermodal" systems. Such multimodal transportation systems include "containers" (intermodal sea / land transportation), as well as "swap bodies" (intermodal road and rail transportation).

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

[0140] The object to be heated may be any space, location, or object that requires heat. These may be present inside either a residential or commercial structure in the same manner as the body to be cooled. Further, portable units as described for cooling may be the same as those that require heating. Certain transportation units require heating to prevent the materials being transported from solidifying within the transport container.

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

[0142] Another embodiment of the present invention relates to storing the aforementioned refrigerant composition in a sealed container in a gas phase and / or a liquid phase, where the oxygen and / or water concentration in the gas phase and / or the liquid phase is 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 in some cases about 5 volume ppm to less than about 500 volume ppm at a temperature of about 25°C.

[0143] The container for storing the aforementioned refrigerant composition can be constructed of any suitable material and design that can seal the refrigerant composition while maintaining a gas phase and a liquid phase. Examples of suitable containers include pressure-resistant containers 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 may be provided with a perforated top or valve suitable for dispensing flammable substances.

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

[0145] In one embodiment, the composition of the present invention is prepared by adding an inhibitor to at least one of a fluoroolefin component and a 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 such that the inhibitor is present in the fluoroolefin and the lubricant. In another embodiment, the inhibitor can be added to a composition containing 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 shows the effectiveness of an inhibitor having a fluoroolefin, Example 2 shows the effectiveness of an inhibitor having a fluoroolefin and a lubricant, and Example 3 shows the phase equilibrium and AC cycle performance of a ternary R-1234yf / d-limonene / lubricant (commercially available as POE32-3MAF) system.

Examples

[0147] A mixture of HFO-1234yf (30 g having a purity of at least 99.5% by weight * ), with 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 by 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 trifluoropropene, and the balance contains compounds that do not affect the refrigeration performance of the mixture or the activity of the inhibitor.

[0149] [Table 4] Examples

[0150] A refrigerant blend containing a mixture of 30 g of HFO-1234yf (having the composition of Example 1), at least one additional compound, and a reaction initiator (and not containing an inhibitor) was heated in a 210 mL shake 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. The XP10 refrigerant contains 56 wt% HFO1234yf and 44 wt% HFC-134a, and the XP40 refrigerant contains 24.3 wt% R32, 24.7 wt% R125, 25.3 wt% 1234yf, and 25.7 wt% 134a. The XP10 and XP40 refrigerants are commercially available from the Chemours Company. The shake tubes were visually inspected for polymer formation and by using NMR. The data reported below are in ppm on a weight basis.

[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) R-1234yf / POE32-3MAF VLE solubility data from -25 to 75 °C were measured. The NRTL binary interaction parameters were fitted to the VLE, resulting in predictions of VLLE, and liquid-liquid phase separation is predicted towards the R-1234yf-rich side of the composition domain. The fit quality is excellent with a 2.1% AARD deviation from the data and is shown with the data in Figure 1. 2) The R-1234yf / d-limonene VLE bubble point data were measured at 50 °C, and the NRTL binary interaction parameters were fitted to the experimental data to an accuracy of 2.1% AARD. In the d-limonene-based region of the composition space, negative deviations from Raoult's law were 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 the d-limonene activity becomes more locally dominant near liquid R-1234yf. These data and model fits are shown in Figure 2. The negative deviations from Raoult's law are 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 pressures were measured experimentally at various POE32-3MAF contents using a binary mixture of 1000 ppm d-limonene on a weight basis of R-1234yf. 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 the binary interaction parameter data of R-1234yf / POE32-3MAF, d-limonene / POE32-3MAF, and R-1234yf / d-limonene (shown in Figures 1 - 3).

[0154] Using the data and calculations shown in Figures 1 - 5, the phase behavior (partitioning effects) and A / C performance of d-limonene in amounts less than 1000 ppm and greater than 1000 ppm can be determined.

[0155] The data and calculations shown in FIGS. 1-5 also show the vapor-liquid equilibrium partitioning of d-limonene such that the vapor becomes substantially d-limonene-free R-1234yf, with d-limonene remaining predominantly in the liquid phase either in the evaporator or in the compressor oil sample, and the vapor circulating within the A / C system being substantially d-limonene-free. As a result, since d-limonene is present predominantly in the liquid phase, d-limonene does not have a significant impact on the power efficiency or capacity of the A / C system.

[0156] Particular aspects, embodiments, and principles have been described above, but it is understood that this specification is made for illustrative purposes only and is not intended to limit the scope of the present 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. at least one fluoroolefin component, 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, a refrigerant blend comprising: wherein the fluoroolefin comprises HFO-1234yf having a purity of more than at least 99.7% by weight, wherein the inhibitor comprises at least one of d-limonene and α-terpinene, and the inhibitor is present in an effective amount to inhibit, if not prevent, the fluoroolefin from interacting with another compound to form a dimer, oligomer, homopolymer, or polymer product, wherein the refrigerant blend comprises less than 0.03% by weight of oligomers, homopolymers, or other polymer products 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 and is present in an amount of 50 to 100 ppm.

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

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

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