Stabilized fluoroolefin refrigerant compositions and methods for their production, storage and use

Abstract

The present invention relates to a refrigerant composition comprising at least one fluoroolefin, at least one lubricant and an effective amount of at least one inhibitor, wherein the inhibitor is present in the fluoroolefin and the lubricant.

Description

[0001] This application is a divisional application of Chinese Patent Application No. 201980034127.6, entitled "Stabilized Fluoroolefin Refrigerant Compositions and Methods for the Production, Storage and Use of Them".

[0002] This application claims the benefit of application No. PCT / 2019 / 02977, filed on April 30, 2019. The disclosure of PCT / 2019 / 02977 is hereby incorporated by reference. Background Technology 1. Technical Field : This invention broadly relates to stabilized refrigerant compositions comprising at least one fluoroolefin, at least one lubricant, and at least one inhibitor, wherein the inhibitor comprises at least one member 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 fluoroolefin and the lubricant.

[0004] 2. Related Technologies : New environmental regulations for refrigerants have forced the refrigeration and air conditioning industry to search for new refrigerants with low global warming potential (GWP).

[0005] We are seeking alternative refrigerants that have low GWP, are non-toxic, non-flammable, reasonably priced, and have excellent refrigeration performance.

[0006] Fluoroolefins have been proposed as refrigerants, either alone or in mixtures. These products have been thoroughly tested for chemical stability and compatibility with materials commonly used in air conditioning or refrigeration systems (see “1234yf – A Low GWP Refrigerant For MAC,” Honeywell / DuPont Joint Collaboration, submitted to JAMA / JARIA October 3, 2007), and have shown stability under typical operating conditions. However, it has been observed that some fluoroolefins may exhibit degradation and / or generate unwanted byproducts (e.g., excess oxygen, oxidizing chemicals, or free radical-generating compounds, and various contaminants) under anomalous conditions that may occur unexpectedly in a particular application and / or use. Such degradation can occur when fluoroolefins are used as a refrigerant or heat transfer fluid. This degradation can occur through any number of different mechanisms. Examples of stabilized refrigerant compositions are disclosed in JP 2009298918; US 6,969,701; US ​​8,133,407; US 2006 / 0022166; US 2006 / 0043330; US 2008 / 0157022; and WO 2007 / 126760, as well as EP 2057245; US 8101094; US 8535555; US8097181; and US 8075796, the disclosures of which are hereby incorporated by reference.

[0007] Under certain abnormal conditions, and in the presence of undesirable contaminants that may act as initiators, fluoroolefins can oligomerize or homopolymerize in the presence of certain contaminants. Therefore, there is a need in the art for stabilized fluoroolefin-containing refrigerant compositions that have reduced (if not eliminated) potential for oligomerization or homopolymerization. Summary of the Invention

[0008] This invention addresses problems associated with polymerization initiation by providing at least one inhibitor present in liquid fluoroolefins, along with a lubricant. Specifically, the invention improves the ability of refrigerant compositions containing hydrofluoroolefins to withstand adverse conditions and also addresses potential problems associated with initiators (e.g., contaminants) that cause oligomerization or homopolymerization of fluoroolefins (e.g., tetrafluoropropylene) by adding at least one inhibitor to the fluoroolefin-containing composition. An "inhibitor" refers to at least one compound according to the 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 initiator (e.g., contaminant). The inhibitor can act as a free radical inhibitor and does not affect the refrigeration performance or compatibility of the refrigerant composition with refrigerant oils and portions. The stabilized refrigerant composition can be used in cooling systems and as a replacement for existing refrigerants with higher global warming potential.

[0009] To avoid the potential instability of fluoroolefins, it has been found that adding certain inhibitor compounds to refrigerant compositions containing fluoroolefins increases their stability during packaging, storage, and use in refrigeration or air conditioning systems. These inhibitor compounds include at least one hydrocarbon from the following: cyclic monoterpenes; 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). Specific examples of inhibitor compounds include at least one member 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 invention, the inhibitor composition comprises a liquid at temperatures from about -100°C to about 220°C, from about -90°C to about 200°C, and in some cases from about -80°C to about 185°C.

[0010] In one specific embodiment, the present invention relates to a refrigerant composition containing fluoroolefins, the refrigerant composition comprising an inhibitor that can interact or react with O2 and fluoroolefin peroxides, and thereby inhibit or eliminate the reaction of such compounds with hydrofluoroolefins. Examples of such inhibitors include at least one of limonene and α-terpinene. Limonene and α-terpinene have the following structures: Limonene α-terpinene In one embodiment of the invention, the inhibitor comprises α-terpinene. Without wishing to be bound by any theory or interpretation, it is believed that α-terpinene can form an aromatic ring upon oxidation due to the presence of conjugated double bonds in its structure.

[0011] In one embodiment of the invention, limonene or α-terpinene optionally possesses an antioxidant with a distinctive aroma, even at concentrations of several ppm. This pleasant odor can be used for refrigerant leak detection with refrigerants and blends based on hydrofluoroolefins (e.g., containing at least one of 1234yf, 1234ze, and combinations thereof). This is particularly advantageous for early refrigerant leak detection in household or portable air conditioners, where specialized electronic leak detectors are often unavailable at any given location.

[0012] One embodiment of the present invention relates to a refrigerant composition comprising: a. At least one fluoroolefin; b. At least one lubricant; and c. An effective amount of at least one inhibitor, said at least one inhibitor comprising: a hydrocarbon, said hydrocarbon including cyclic monoterpenes; a lipophilic organic compound, said lipophilic organic compound including tocopherol, said tocopherol including α-tocopherol; phenols, aromatic organic compounds having the chemical formula C6H4(OH), including benzene-1,4-diol; wherein said inhibitor is present in the liquid fluoroolefin and the lubricant.

[0013] One embodiment of the present invention relates to any of the aforementioned refrigerant compositions and further comprises at least one antioxidant. While any suitable oxidant may be used, examples of suitable oxidants include at least one member selected from the group consisting of: butylated hydroxytoluene, butylated hydroxyanisole, tert-butylhydroquinone, gallate / salt, 2-phenyl-2-propanol, 1-(2,4,5-trihydroxyphenyl)-1-butanone, bisphenol methane derivatives, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), and other phenols, and combinations thereof.

[0014] One specific implementation involves using the aforementioned antioxidant in conjunction with an inhibitor, said inhibitor comprising at least one of limonene and α-terpinene.

[0015] Another embodiment of the invention relates to a method for stabilizing a refrigerant composition comprising at least one fluoroolefin, the method comprising adding an effective amount of at least one inhibitor to the composition comprising at least one fluoroolefin, wherein the inhibitor is a hydrocarbon comprising at least one member selected from the group consisting of: cyclic monoterpenes; lipophilic organic compounds comprising tocopherols, including α-tocopherols; phenols; and aromatic organic compounds having the chemical formula C6H4(OH) (including benzene-1,4-diol), and mixtures thereof.

[0016] Another embodiment of the invention relates to a method for reducing oligomerization or homopolymerization of a refrigerant composition containing at least one fluoroolefin, the oligomerization or homopolymerization being caused by the presence of an unintentional or undesirable contaminant in at least one of conduits, pipelines, and other systems used for processing refrigerant compositions containing fluoroolefins; packaging (containers) and refrigeration, air conditioning, or heat pump systems, the method comprising adding an inhibitor to at least one of the systems, containers, and compositions containing at least one fluoroolefin, the inhibitor containing at least one hydrocarbon including cyclic monoterpenes; lipophilic organic compounds including tocopherols, the tocopherols including α-tocopherol; phenols, aromatic organic compounds having the chemical formula C6H4(OH) (including benzene-1,4-diol), and mixtures thereof.

[0017] Another embodiment of the invention relates to a refrigerant composition containing fluoroolefins within a container, wherein the fluoroolefins have reduced oligomerization or homopolymerization potential compared to a refrigerant composition not containing the inhibitor composition of the invention.

[0018] 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 polymers derived from the fluoroolefin.

[0019] Another embodiment of the present invention relates to any of the aforementioned refrigerant compositions, wherein the composition comprises less than about 0.03% by weight of an oligomer, homopolymer or other polymeric product.

[0020] Another embodiment of the invention relates to any of the aforementioned refrigerant compositions and further comprises at least one member selected from the group consisting of: air, oxygen, cumene hydroperoxide and fluoroolefin polyperoxides, peroxides, hydroperoxides, persulfates, percarbonates, perborates and hydropersulfates.

[0021] Another embodiment of the invention relates to any of the aforementioned refrigerant compositions, wherein the inhibitor comprises at least one member selected from the group consisting of: limonene, α-terpinene, α-tocopherol, butylated hydroxytoluene, 4-methoxyphenol, and benzene-1,4-diol.

[0022] Another embodiment of the invention relates to any of the aforementioned refrigerant compositions, wherein the fluoroolefin comprises at least one member of HFO-1234yf and HFO-1234ze.

[0023] Another embodiment of the invention relates to any of the aforementioned refrigerant compositions and further comprises at least one member selected from the group consisting of: HFC-32, HFC-125, HFC-134a, HFC-152a, HFC-227ea and carbon dioxide.

[0024] Another embodiment of the invention relates to any of the aforementioned refrigerant compositions and further comprises at least one member 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.

[0025] Another embodiment of the invention relates to any of the aforementioned refrigerant compositions and further comprises at least one member selected from the group consisting of: HCC-40, HCFC-22, CFC-115, HCFC-124, HCFC-1122 and CFC-1113.

[0026] Another embodiment of the invention relates to any of the aforementioned refrigerant compositions, wherein the inhibitor is present in an amount of about 30 ppm to about 3,000 ppm.

[0027] Another embodiment of the invention relates to any of the aforementioned refrigerant compositions and further comprises at least one member selected from the group consisting of: butylated hydroxytoluene, butylated hydroxyanisole, tert-butylhydroquinone, gallate / salt, 2-phenyl-2-propanol, 1-(2,4,5-trihydroxyphenyl)-1-butanone, phenols, bisphenol methane derivatives, and 2,2'-methylenebis(4-methyl-6-tert-butylphenol).

[0028] Another embodiment of the invention relates to any of the aforementioned refrigerant compositions, wherein the inhibitor comprises at least one of limonene and α-terpinene.

[0029] Another embodiment of the invention relates to any of the aforementioned refrigerant compositions, wherein the inhibitor comprises a liquid at a temperature of about -80°C to 180°C.

[0030] Another embodiment of the invention relates to any of the aforementioned refrigerant compositions, and optionally further comprises at least one antioxidant.

[0031] Another embodiment of the invention relates to any of the aforementioned refrigerant compositions and further comprises at least one member selected from the group consisting of: HFO-1225yeZ, HFO-1243zf, HFO-1234ze, HFC-236ea, HFC-245fa and 3,3,3-trifluoropropyne.

[0032] Another embodiment of the invention relates to any of the aforementioned refrigerant compositions, wherein the member comprises HFO-1234ze, HFO-1225yeZ and 3,3,3-trifluoropropyne.

[0033] Another embodiment of the invention relates to any of the aforementioned refrigerant compositions, wherein the composition is substantially free of at least one of ammonia and CF3I.

[0034] Another embodiment of the invention relates to any of the aforementioned refrigerant compositions, wherein the composition is substantially composed of HFO-1234yf and limonene and does not contain ammonia or CF3I.

[0035] Another embodiment of the invention relates to any of the aforementioned refrigerant compositions, wherein the composition is substantially composed of HFO-1234yf, 3,3,3-trifluoropropyne and limonene.

[0036] 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 member selected from the group consisting of: limonene, α-terpinene, α-tocopherol, butylated hydroxytoluene, 4-methoxyphenol, and phenyl-1,4-diol.

[0037] Another embodiment of the invention relates to any of the foregoing methods, wherein the refrigerant composition has been exposed prior to the contact to at least one member selected from the group consisting of: air, oxygen, cumene hydroperoxide and fluoroolefins, peroxides, hydroperoxides, persulfates / esters, percarbonates / esters, perborates / esters and hydrogen persulfates / esters.

[0038] Another embodiment of the present invention relates to any of the foregoing methods, wherein the method employs any of the foregoing refrigerant compositions for heating or cooling.

[0039] Another embodiment of the invention relates to a container having a refrigerant comprising any of the aforementioned refrigerant compositions.

[0040] The embodiments of the present invention can be used alone or in combination with each other, and different embodiments can be combined to form a part of the present invention. Attached Figure Description

[0041] Figure 1 A graphical representation of the NRTL fit for the experimental VLE of R-1234yf / lubricant.

[0042] Figure 2 A graphical representation of the NRTL fit for the experimental VLE of R-1234yf / dextrin.

[0043] Figure 3 A graphical representation of an enlarged view of the R-1234yf-rich domain of R-1234yf / dextrin, showing a negative deviation from Raoult's Law.

[0044] Figure 4 A graphical representation of the NRTL fit using calculated dextrorotatory limonene / POE32-3MAF VLE data.

[0045] Figure 5 Graphical representation of the ternary VLLE calculated for R-1234yf / 1000ppm dextrorotatory limonene / POE32-3MAF. Detailed Implementation

[0046] This invention provides a stabilized refrigerant composition comprising at least one fluoroolefin, at least one lubricant, and an effective amount of at least one inhibitor, wherein the inhibitor is present in the liquid fluoroolefin and the lubricant. "Stabilized" means a composition comprising an effective amount of at least one inhibitor compound that inhibits (if not eliminates) the interaction of the fluoroolefin with another compound and the formation of dimers, oligomers, homopolymers, or polymers. Examples of such compounds that can cause such interactions include oxidants such as air, oxygen, cumene hydroperoxide, and fluoroolefin peroxides, peroxides, hydroperoxides, persulfates / esters, percarbonates / esters, perborates / esters, hydrogen perborates / esters, and other initiators. The initiator compound may be present in amounts from about 10 ppm to about 15,000 ppm, from about 1,000 ppm to about 10,000 ppm by weight, and in some embodiments from about 1,000 ppm to about 3,000 ppm, and in some embodiments in amounts from 30 ppm to 2,000 ppm. Such initiator compounds can be present as contaminants in at least one of the conduits, lines, and other systems used to handle refrigerant compositions containing fluoroolefins; packaging (containers); and refrigeration, air conditioning, or heat pump systems. Without being bound by any theory or interpretation, it is believed that certain contaminants can act as free radical initiators, leading to oligomerization, homopolymerization, or the formation of other polymers of fluoroolefins.

[0047] In one embodiment of the invention, the refrigerant composition is substantially free of oligomers, homopolymers, or other polymers derived from hydrofluoroolefins. "Substantially free" means that, when measured by IR or NMR, 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.

[0048] In another embodiment of the invention, the inventive refrigerant composition is substantially free of certain conventional inhibitory compounds, including sesquiterpenes such as at least one member selected from the group consisting of farmyrol and farmyne; and ionic liquids such as ionic liquids containing anions selected from the group consisting of [CH3CO2]. - [HSO4] - [CH3OSO3] - [C2H5OSO3] - [AlCl4] - [CO3] 2- [HCO3] - [NO2] - [NO3] - [SO4] 2- [PO4] 3- [HPO4] 2- [H2PO4] - [HSO3] and certain fluoride anions, wherein the fluoride anions are selected from the group consisting of: [BF4] - [PF6] - [SbF6] - [CF3SO3] - [HCF2CF2SO3] - [CF3HFCCF2SO3] - [HCClFCF2SO3] - [(CF3SO2)2N] - [(CF3CF2SO2)2N] - [(CF3SO2)3C] - [CF3CO2] - [CF3OCFHCF2SO3] - [CF3CF2OCFHCF2SO3] - [CF3CFHOCF2CF2SO3] - [CF2HCF2OCF2CF2SO3] - [CF2ICF2OCF2CF2SO3]- [CF3CF2OCF2CF2SO3] - [(CF2HCF2SO2)2N] - [(CF3CFHCF2SO2)2N] - And mixtures thereof. "Effectively free of" means that the inventive refrigerant composition contains less than about 500 ppm, typically less than about 250 ppm, in some cases about 100 ppm, and in some cases about 0 ppm of such conventional inhibitors.

[0049] The inventive refrigerant compositions have various applications as heat transfer media (such as heat transfer fluids and refrigerants in refrigeration systems, refrigerators, air conditioning systems, heat pumps, coolers, etc.). The inventive compounds are particularly suitable for mobile air conditioning systems and are used as components in the preparation of refrigerant blends for stationary heat transfer systems.

[0050] 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 radiator.

[0051] The refrigerant is a compound or mixture of compounds used as a heat transfer fluid in a cycle, wherein the fluid undergoes a phase change from liquid to gas (or vapor) and back to liquid. Inhibitors are present in the liquid phase of the refrigerant containing at least a fluoroolefin and 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 in some cases, about 45% to about 60% by weight of inhibitors are present in the liquid fluoroolefin phase, with the remainder primarily present in the lubricant phase. In one embodiment, the gas phase is substantially free of inhibitors. “Substantially free” means that the amount of inhibitors in the vapor fluoroolefin phase is less than about 10 ppm, in some cases less than about 5 ppm, 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 in some cases, the gas phase is substantially free of inhibitors.

[0052] As used herein, the terms “comprising,” “including,” “having,” or any other variations thereof are intended to cover non-exclusive inclusion. For example, a composition, process, method, article of manufacture, or apparatus that includes a list of elements is not necessarily limited to those elements, but may include other elements not expressly listed or inherent to such composition, process, method, article of manufacture, or apparatus. Furthermore, unless expressly stated otherwise, “or” means inclusive or not exclusive. For example, condition A or B satisfies one of the following conditions: 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).

[0053] The transitional phrase "composed of..." does not include any unspecified elements, steps, or components. If in a claim, it will not include protection for materials other than those described, except for impurities typically associated with them. When the phrase "composed of..." appears in a clause of the body of a claim, rather than immediately following the preamble, it only limits the elements described in that clause; other elements are not excluded from the entire claim.

[0054] The transitional phrase "consistently of..." is used to define a composition or method that includes, in addition to those disclosed in the literature, materials, steps, features, components, or elements, provided that these additionally included materials, steps, features, components, or elements substantially affect one or more essential and novel features of the invention protected by the claims, particularly the mode of action that achieves any desired result in the method of the invention. The term "consistently of..." falls between "comprising" and "consisting of...".

[0055] Where the applicant has defined the invention or a part thereof using open-ended terms such as “comprising”, it should be readily understood (unless otherwise stated) that the description should be interpreted as also including inventions using terms such as “substantially composed of” or “composed of”.

[0056] Furthermore, the terms "an" or "a" are used to describe the elements and components described herein. This is for convenience only and to give a general meaning to the scope of the invention. This description should be understood to include one or at least one, and the singular includes the plural, unless it is obvious that it means otherwise.

[0057] As used herein, the term fluoroolefin describes a compound comprising a carbon atom, a fluorine atom, and optionally a hydrogen atom. In one embodiment, the fluoroolefin used in the refrigerant composition of the present invention comprises a compound having 2 to 12 carbon atoms. In another embodiment, the fluoroolefin comprises a compound having 3 to 10 carbon atoms, and in yet another embodiment, the fluoroolefin comprises a compound having 3 to 7 carbon atoms. Representative fluoroolefins include, but are not limited to, all compounds listed in Tables 1, 2, and 3.

[0058] One embodiment of the present invention provides a form having E- or ZR 1 CH=CHR 2 Fluoroolefins of formula I, wherein R 1 and R 2 Independently a C1 to C6 perfluoroalkyl group. R 1 and R 2 Examples of functional groups include, but are not limited to, CF3 and C2F. 5、 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 fluoroalkene of formula I has at least about 4 carbon atoms in the molecule. In another embodiment, the fluoroalkene of formula I has at least about 5 carbon atoms in the molecule. Exemplary non-limiting compounds of formula I are present in Table 1.

[0059] Table 1

[0060] Compounds of formula I can be made by causing formula R 1 I's perfluoroalkyl iodine and formula R 2 CH=CH2 perfluoroalkyl trihydroolefin contacts to form formula R 1 CH2CHIR 2 It is prepared from trihydroiodine perfluoroalkane. This trihydroiodine perfluoroalkane can be dehydroiodinated to form R. 1 CH=CHR 2 Alternatively, olefin R 1 CH=CHR 2 It can be obtained through formula R 1 CHICH2R 2It is prepared by dehydroiodination of trihydroiodinated perfluoroalkane, wherein the trihydroiodinated perfluoroalkane is then prepared by making R... 2 I's perfluoroalkyl iodine and formula R 1 It is formed by the reaction of CH=CH2 with perfluoroalkyl trihydroolefins.

[0061] The contact between perfluoroalkyl iodides and perfluoroalkyl trihydroolefins can be carried out by combining the reactants in a suitable reaction vessel capable of operating at the reaction temperature under the autogenous pressure of the reactants and products. Suitable reaction vessels include those made of stainless steel (especially austenitic type) and well-known high-nickel alloys (such as Monel). ® Nickel-copper alloy, Hastelloy ® Nickel-based alloys and Inconel ® Containers made of nickel-chromium alloy.

[0062] Alternatively, the reaction can be carried out in a semi-batch mode, wherein the perfluoroalkyl trihydroolefin reactant is added to the perfluoroalkyl iodine reactant using a suitable addition device (such as a pump at the reaction temperature).

[0063] The ratio of perfluoroalkyl iodine to perfluoroalkyl trihydroolefin should be between about 1:1 and about 4:1, preferably about 1.5:1 to 2.5:1. Ratios less than 1.5:1 tend to result in a large number of 2:1 adducts, as described by Jeanneaux et al. in "..." Journal of Fluorine Chemistry As reported in Volume 4, pp. 261-270 (1974).

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

[0065] Trihydroiodine perfluoroalkane prepared by the reaction of perfluoroalkyl iodine with perfluoroalkyl trihydroolefin can be used directly in the dehydroiodination step, or preferably recovered and purified by distillation before the dehydroiodination step.

[0066] The deiodide removal step is carried out by contacting the trihydroiodine perfluoroalkane with an alkaline substance. Suitable alkaline 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), ammonia, sodium amide, or mixtures of alkaline substances such as soda lime. Preferred alkaline substances are sodium hydroxide and potassium hydroxide. The contact between the trihydroiodine perfluoroalkane and the alkaline substance can be carried out in the liquid phase, preferably in the presence of a solvent capable of dissolving at least a portion of both reactants. Solvents suitable for the deiodide removal step include one or more polar organic solvents, such as alcohols (e.g., methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and tert-butanol), nitriles (e.g., acetonitrile, propionitrile, butyronitrile, benzyl nitrile, or adiponitrile), dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, or sulfolane. The choice of solvent may depend on the boiling point of the product and the ease with which trace amounts of solvent can be separated from the product during purification. Generally, ethanol or isopropanol are good solvents for the reaction.

[0067] Typically, the dehydroiodide reaction is carried out by adding one of the reactants (a basic substance or a trihydroiodine perfluoroalkane) to another reactant in a suitable reaction vessel. The reaction can be made of glass, ceramic, or metal, and is preferably stirred by an impeller or a stirring mechanism.

[0068] The suitable temperature for the dehydroiodide reaction is from about 10°C to about 100°C, preferably from about 20°C to about 70°C. The dehydroiodide reaction can be carried out under ambient pressure or under reduced or increased pressure. It is noteworthy that the dehydroiodide reaction in which the compound of formula I is distilled from the reaction vessel during its formation is a significant part of the reaction.

[0069] Alternatively, in the presence of a phase transfer catalyst, the dehydroiodide reaction can be carried out by contacting an aqueous solution of the basic substance with a solution of a trihydroiodic perfluoroalkanes in one or more organic solvents of lower polarity (e.g., hexane, heptane, or octane), an aromatic hydrocarbon (e.g., toluene), a halogenated hydrocarbon (e.g., dichloromethane, chloroform, carbon tetrachloride, or perchloroethylene), or an ether (e.g., diethyl ether, methyl tert-butyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, dimethoxyethane, diethylene glycol dimethyl ether, or tetraethylene glycol dimethyl ether). Suitable phase transfer catalysts include quaternary ammonium halides (e.g., tetrabutylammonium bromide, tetrabutylammonium hydrogen sulfate, triethylbenzylammonium chloride, dodecyltrimethylammonium chloride, and trioctylmethylammonium 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, dehydroiodide reaction can be carried out in the absence of a solvent by adding trihydroiodine perfluoroalkane to a solid or liquid alkaline substance.

[0071] The suitable reaction time for the dehydroiodide reaction is from about 15 minutes to about six hours or longer, depending on the solubility of the reactants. The dehydroiodide reaction is usually relatively fast and takes about 30 minutes to about three hours to complete.

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

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

[0074] Table 2

[0075] The refrigerant compositions 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 may comprise a combination of compounds of formula I or formula II.

[0076] In another embodiment, fluoroolefins may include those compounds listed in Table 3.

[0077] Table 3

[0078] The compounds listed in Tables 2 and 3 are commercially available or can be prepared by methods known in the art or described herein.

[0079] 1,1,1,4,4-Pentafluoro-2-butene can be prepared from 1,1,1,2,4,4-hexafluorobutane (CHF2CH2CHFCF3) by dehydrofluorination in the gas phase over solid KOH at room temperature. The synthesis of 1,1,1,2,4,4-hexafluorobutane is described in US 6,066,768, which is incorporated herein by reference.

[0080] 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 it with KOH at approximately 60 °C using a phase transfer catalyst. The synthesis of 1,1,1,4,4,4-hexafluoro-2-iodobutane can be carried out by reacting perfluoromethyl iodine (CF3I) and 3,3,3-trifluoropropene (CF3CH=CH2) at approximately 200 °C under autogenous pressure for approximately 8 hours.

[0081] 3,4,4,5,5,5-Hexafluoro-2-pentene can be prepared by dehydrofluorination of 1,1,1,2,2,3,3-heptafluoropentane (CF3CF2CF2CH2CH3) at 200-300 °C using solid KOH or over a carbon catalyst. 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).

[0082] 1,1,1,2,3,4-hexafluoro-2-butene can be prepared by dehydrofluorinating 1,1,1,2,3,4-heptafluorobutane (CH2FCF2CHFCF3) with solid KOH.

[0083] 1,1,1,2,4,4-Hexafluoro-2-butene can be prepared by dehydrofluorinating 1,1,1,2,2,4,4-heptafluorobutane (CHF2CH2CF2CF3) with solid KOH.

[0084] 1,1,1,3,4,4-Hexafluoro-2-butene can be prepared by dehydrofluorinating 1,1,1,3,3,4,4-heptafluorobutane (CF3CH2CF2CHF2) with solid KOH.

[0085] 1,1,1,2,4-pentafluoro-2-butene can be prepared by dehydrofluorinating 1,1,1,2,2,3,4-hexafluorobutane (CH2FCH2CF2CF3) with solid KOH.

[0086] 1,1,1,3,4-pentafluoro-2-butene can be prepared by dehydrofluorinating 1,1,1,3,3,4,4-hexafluorobutane (CF3CH2CF2CH2F) with solid KOH.

[0087] 1,1,1,3-Tetrafluoro-2-butene can be prepared by reacting 1,1,1,3,3-pentafluorobutane (CF3CH2CF2CH3) with an aqueous solution of KOH at 120 °C.

[0088] 1,1,1,4,4,5,5,5-octafluoro-2-pentene can be prepared from (CF3CHICH2CF2CF3) by reacting it with KOH at approximately 60 °C using a phase transfer catalyst. 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 autogenous pressure for approximately 8 hours.

[0089] 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 at about 60 °C using a phase transfer catalyst. 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 autogenous pressure for about 8 hours.

[0090] 1,1,1,4,5,5,5-Hepenofluoro-4-(trifluoromethyl)-2-pentene can be prepared by the dehydrofluorination reaction of 1,1,1,2,5,5,5-Hepenofluoro-4-iodo-2-(trifluoromethyl)-pentane (CF3CHICH2CF(CF3)2) with KOH in isopropanol. CF3CHICH2CF(CF3)2 is prepared by the reaction of (CF3)2CFI with CF3CH=CH2 at high temperatures (such as about 200°C).

[0091] 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).

[0092] 2,3,3,4,4-Pentafluoro-1-butene can be prepared by dehydrofluorination of 1,1,2,2,3,3-hexafluorobutane over fluorinated alumina at high temperature.

[0093] 2,3,3,4,4,5,5,5-octafluoro-1-pentene can be prepared by dehydrofluorination of 2,2,3,3,4,4,5,5,5-nonafluoropentane over solid KOH.

[0094] 1,2,3,3,4,4,5,5-octafluoro-1-pentene can be prepared by dehydrofluorination of 2,2,3,3,4,4,5,5,5-nonafluoropentane over fluorinated alumina at high temperature.

[0095] 2,3,3,3-Tetrafluoro-1-propene can be prepared by converting at least one of HCFC-244bb or HFC-245eb into HFO-1234yf.

[0096] 1,3,3,3-Tetrafluoro-1-propene can be prepared into HFO-1234ze from HFC-245fa.

[0097] Many of the compounds in Formula I, Formula II, Tables 1, 2, and 3 exist as different configurational isomers or stereoisomers. When a specific isomer is not specified, this invention is intended to include all isomers of a single configuration, a single stereoisomer, or any combination thereof. For example, F11E is intended to represent any combination or mixture of E-isomers, Z-isomers, or two isomers in any ratio. Similarly, HFO-1225ye is intended to represent any combination or mixture of E-isomers, Z-isomers, or two isomers in any ratio.

[0098] In one embodiment, the fluoroolefin component of the inventive composition comprises HFO-1234yf and / or HFO-1234ze. In another embodiment, the fluoroolefin comprises HFO-1234yf and / or HFO-1234ze having a purity greater than 99.5% by weight, and in some cases greater than 99.5% to 99.98% by weight. In yet another embodiment, the fluoroolefin comprises at least 99.5% by weight of 1234yf or 1234ze, and less than 0.5% by weight and greater than 0.0001% by weight, less than 0.3% by weight, and in some cases less than 0.2% by weight of other fluoroolefins.

[0099] In another specific embodiment, the fluoroolefin component may comprise the refrigerant compositions disclosed in U.S. Patents 8,147,709 and 8,877,086, which are incorporated herein by reference.

[0100] In another specific embodiment, the fluoroolefin component comprises greater than about 99.5% by weight of HFO-1234yf and one or more members selected from the group consisting of: HFO-1225ye, HFO-1243zf, HFO-1234ze, HFC-236ea, HFC-244bb, HFC-245fa, HFC-245eb, HFC-245cb, 3,3,3-trifluoropropyne, and mixtures thereof. The amount of HFO-1225ye (E / Z isomer) may range from greater than 0 ppm to about 200 ppm, from about 1 ppm to about 150 ppm, and in some cases from about 5 ppm to about 50 ppm. The amount of HFO1243zf may range from about 0.1 ppm to about 250 ppm, from about 10 ppm to about 200 ppm, and in some cases from about 15 ppm to about 150 ppm. The amount of HFO-1234ze (E isomer) can range from about 1 ppm to about 1,500 ppm, from about 5 ppm to about 1,000 ppm, and in some cases from about 50 ppm to 500 ppm. The amount of HFC-236ea can range from about 1 ppm to about 50 ppm, from about 5 ppm to about 25 ppm, and in some cases from about 10 ppm to about 20 ppm. The amount of HFC-245fa, HFC-245eb and / or HFC-245cb can range from about 0 ppm to about 20 ppm, from about 1 ppm to about 15 ppm, and in some cases from about 5 ppm to about 10 ppm. The amount of 3,3,3-trifluoropropyne can range from about 0 ppm to about 500 ppm, from about 1 ppm to about 300 ppm, and in some cases from about 5 ppm to about 100 ppm.

[0101] 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 isomer, 1336mzzE, 1336 isomer, 1234zeZ, and 1224 isomer. In one specific embodiment, the fluoroolefin component comprises HFO-1234yf and additional compounds greater than zero and less than about 1% by weight, less than about 0.5% by weight, and in some cases less than 0.25% by weight. In another embodiment, the inventive inhibitor can be used with at least one of HCFO-1233zd and HCFO-1224yd, and a refrigerant composition comprising at least one of HCFO-1233zd and HCFO-1224yd.

[0102] Any suitable effective amount of inhibitor can be used in the aforementioned refrigerant compositions containing at least one fluoroolefin. As described herein, the phrase "effective amount" refers to a certain amount of inhibitor of the present invention that, when added to a composition containing at least one fluoroolefin, causes the fluoroolefin to not interact with the initiator, and / or, for example, degrades to produce a significant performance reduction when used in a cooling device compared to a composition without an inhibitor. For cooling devices, such effective amount of inhibitor can be determined by testing under standard testing conditions ASHRAE 97-2007 (RA 2017). In one embodiment of the invention, effective amount can be considered as the amount of inhibitor that, when included as a component of a refrigerant composition containing at least one fluoroolefin and a lubricant, allows the cooling device to utilize the composition containing at least one fluoroolefin to behave as if the composition contained 1,1,1,2-tetrafluoroethane (R-134a), or other standard refrigerants (R-12, R-22, R-502, R-507A, R-508, R401A, R401B, R402...). The refrigeration performance and cooling capacity of refrigerants such as 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 are at the same level, depending on what refrigerants have been used as working fluids in similar systems in the past.

[0103] The present invention employs an effective amount of at least one of the aforementioned inhibitors. While any suitable effective amount may be used, the effective amount comprises, based on the total weight of a composition comprising at least one fluoroolefin containing the composition described herein, about 0.001 wt% to about 10 wt%, about 0.01 wt% to about 5 wt%, about 0.3 wt% to about 4 wt%, and about 0.3 wt% to about 1 wt%. In one embodiment, the effective amount comprises, by weight, at least one initiator of about 10 ppm to about 2,000 ppm, about 10 ppm to about 1,000 ppm, and in some cases about 10 ppm to about 500 ppm.

[0104] In one embodiment of the invention, the inhibitor is distributed between two liquid phases: the liquid fluoroolefin and the lubricant. The amount of inhibitor present in the liquid phase of the fluoroolefin can range from about 10% by weight to about 80% by weight, from about 25% by weight to about 75% by weight, and in some cases, from about 45% by weight to about 60% by weight, with the remainder of the inhibitor primarily present in the lubricant phase.

[0105] One embodiment of the invention relates to any of the aforementioned refrigerant compositions and further comprises at least one antioxidant. While any suitable oxidant may be used, examples of suitable oxidants include at least one member selected from the group consisting of: butylated hydroxytoluene, butylated hydroxyanisole, tert-butylhydroquinone, gallate / salt, 2-phenyl-2-propanol, 1-(2,4,5-trihydroxyphenyl)-1-butanone, phenols, bisphenol methane derivatives, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), and combinations thereof. The amount of antioxidant may range from about 0.01 ppm to about 5,000 ppm by weight, from about 0.03 ppm to about 2,000 ppm, and in some cases from about 0.05 ppm to about 1,000 ppm. An example of a specific embodiment relates to the use of the aforementioned antioxidant with at least one inhibitor comprising α-terpinene and limonene. An example of a specific embodiment relates to the use of the aforementioned antioxidant with an inhibitor comprising at least one of α-terpinene and limonene.

[0106] In one embodiment, the aforementioned 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, meaning a mixture of any of the additional compounds listed in this paragraph. The amount of the additional compound may range from about 1% by weight to about 90% by weight, from about 5% by weight to about 75% by weight, and in some cases from about 10% by weight to about 50% by weight.

[0107] In one embodiment, the additional compound comprises a hydrofluorocarbon. The hydrofluorocarbon (HFC) compounds of the present invention comprise saturated compounds containing carbon, hydrogen, and fluorine. Particularly available are hydrofluorocarbons having 1 to 7 carbon atoms and a normal boiling point of about -90°C to about 80°C. The hydrofluorocarbons are commercially available products from various sources or can be prepared by methods known in the art. Representative hydrofluorocarbons include, but are not limited to, 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), and fluoroethane (CH3C). H2F, 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-Octafluoropropane (CHF 2CF2CF2CHF2, HFC-338pcc), 1,1,1,2,2,4,4,4-octafluoropropane (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-tetrafluoroheptane (CF3CF2CHFCHFCF2CF2CF3, HFC-63-14mee).

[0108] In another embodiment, the additional compound comprises a hydrocarbon. The hydrocarbons of the present invention include compounds having only carbon and hydrogen atoms. Compounds having 3 to 7 carbon atoms are particularly available. Hydrocarbons are commercially available from 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.

[0109] In another embodiment, the additional compound comprises a hydrocarbon containing heteroatoms, such as dimethyl ether (DME, CH3OCH3). DME is commercially available.

[0110] In another embodiment, the additional compound includes trifluoroiodimethane (CF3I), which is commercially available from various sources or can be prepared by methods known in the art.

[0111] 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 may be used, provided that the amount of the additional compound does not preclude the partitioning of the aforementioned inhibitor between the liquid-phase fluoroolefin and the lubricant.

[0112] In another embodiment, the aforementioned compositions of the present invention are substantially free of additional compounds, and specifically, substantially free of at least one of dimethyl ether, CF3I, ammonia, and carbon dioxide. In a preferred aspect of this embodiment, the aforementioned compositions are substantially free of CF3I. "Substantially free of additional compounds" means that the compositions and inhibitors contain less than about 10%, typically less than about 5%, and in some cases 0% of additional compounds.

[0113] Of particular note are fluoroolefin compositions comprising HFO-1234yf and / or HFO-1234ze and additional compounds 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 and HFC-32; HFO-1225ye, HFO-1225ye and HFC-125. Additional refrigerant compositions comprise at least one of HFO-1234yf and HFO-1234ze, and blends of i) 134a, 32 and 125; ii) 134a; iii) 227ea; iv) 236fa; and v) 134.

[0114] In other embodiments of the invention, the fluoroolefin comprises at least about 99% by mass of HFO-1234yf and more than 0 but less than 1% by mass of at least one member selected from the group consisting of: HFC-134a, HFO-1243zf, HFO-1225ye, HFO-1234ze, 3,3,3-trifluoro-1-propyne, HCFO-1233xf, HFC-245cb, and combinations thereof.

[0115] In other embodiments of the invention, the fluoroolefin comprises at least about 99% by mass of HFO-1234ze and more than 0 but less than 1% by mass of at least one member selected from the group consisting of HFO-1234yf, HFC-245fa, HFC-236fa, HFO-1234ye, and combinations thereof.

[0116] In other embodiments of the invention, the fluoroolefin comprises one or more of the aforementioned fluoroolefins blended with at least one hydrofluorocarbon. Examples of suitable hydrofluorocarbons include at least one member selected from the group consisting of HFC-32, HFC-125, HFC-134a, HFC-152a, 236fa, and HFC-227ea. The amount of hydrofluorocarbon can range from about 25 ppm to about 75 ppm, from about 30 ppm to about 60 ppm, and in some cases from about 30 ppm to about 50 ppm. In one specific embodiment, the aforementioned amount of hydrofluorocarbon is blended with at least one of HFO-1234yf and HFO-1234ze.

[0117] If desired, the blend composition may further comprise at least one additional member selected from the group consisting of HCC-40, HCFC-22, CFC-115, HCFC-124, HCFC-1122, and CFC-1113. The amount of the additional member may be greater than 0% by weight to about 5% by weight, about 0% by weight to about 2% by weight, and in some cases about 0% by weight to about 0.5% by weight. In one specific embodiment, the aforementioned amount of the additional member is blended with at least one of HFO-1234yf and HFO-1234ze. In another specific embodiment, the aforementioned amount of the additional member 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 in some cases combined with carbon dioxide.

[0118] The lubricants of this invention include those suitable for use with refrigeration or air conditioning equipment. Among these lubricants are those conventionally used in compression refrigeration equipment utilizing chlorofluorocarbon (CFC) refrigerants. Such lubricants and their properties are discussed in Chapter 8, entitled "Lubricants in Refrigeration Systems," of the 1990 ASHRAE manual *Refrigeration Systems and Applications*, pages 8.1 to 8.21, which are incorporated herein by reference. The lubricants of this invention may include those commonly known as "mineral oils" in the field of compression refrigeration lubrication. Mineral oils include paraffins (i.e., saturated hydrocarbons with straight and branched carbon chains), cycloalkanes (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 this invention also include those commonly known as "synthetic oils" in the field of compression refrigeration lubrication. Synthetic oils contain alkyl aryl groups (i.e., straight-chain and branched alkylalkylbenzenes), synthetic alkanes and cycloalkanes, organosilicones, and poly-α-olefins. A representative conventional lubricant of this invention is commercially available BVM 100 N (a paraffinic mineral oil sold by BVA Oils), available under the trademark of Crompton Co. from Suniso. ® 3GS and Suniso ® 5GS commercially available cycloalkane mineral oil, can be branded as Sontex ® 372LT is a cycloalkanes mineral oil purchased from Pennzoil, and can be marketed under the trademark Calumet. ® RO-30 is a cycloalkanes mineral oil obtained from Calumet Lubricants, and can be marketed under the brand name Zerol. ® 75. Zerol ® 150 and Zerol ® 500 linear alkylbenzenes obtained commercially from Shrieve Chemicals and branched alkylbenzenes sold by Nippon Oil as HAB 22.

[0119] In another embodiment, the lubricants of the present invention include those designed for use with hydrofluorocarbon refrigerants and miscible with the refrigerants of the present invention under compression refrigeration and air conditioning equipment operating conditions. Such lubricants and their properties are discussed in "Synthetic Lubricants and High-Performance Fluids," RL Shubkin, editor, Marcel Dekker, 1993. Such lubricants include, but are not limited to, polyol esters (POEs) such as Castrol. ® 100 (Castrol, United Kingdom), polyalkylene glycols (PAGs) such as RL-488A from Dow (Dow Chemical, Midland, Michigan), and polyvinyl ether (PVE).

[0120] The lubricant of the present invention is selected by taking into account the given compressor requirements and the environment in which the lubricant will be exposed. The amount of lubricant can range from about 1 ppm to about 50 ppm, from about 1 ppm to about 20 ppm, and in some cases from about 1 ppm to about 3 ppm. In one specific embodiment, the foregoing composition is combined with a PAG lubricant for use in an A / C system of a motor vehicle having an internal combustion engine. In another specific embodiment, the foregoing composition is combined with a POE lubricant for use in an A / C system of a motor vehicle having an electric or hybrid electric drive system.

[0121] Inhibitors are miscible enough in lubricants that a portion of the inhibitor is present within 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.

[0122] In one embodiment of the invention, in addition to the inventive inhibitor, the composition may contain at least one additive that improves the lifespan of the refrigerant and air conditioning system and the required compressor durability. In one aspect of the invention, the aforementioned composition contains at least one member selected from the group consisting of acid scavengers, performance enhancers, and flame retardants.

[0123] Additives that can improve refrigerant and A / C life and compressor durability are desirable. In one aspect of the invention, the refrigerant-containing composition of the invention is used to introduce lubricants into A / C systems as well as other additives, such as a) acid scavengers, b) performance enhancers, and c) flame retardants.

[0124] Acid scavengers may comprise siloxanes, activated aromatic compounds, or combinations thereof. Serrano et al. (paragraph 38 of US2011 / 0272624 A1, which is incorporated herein by reference) disclose that siloxanes may be any molecule having silanoxy functionality. Siloxanes may include alkylsiloxanes, arylsiloxanes, or siloxanes comprising a mixture of aryl and alkyl substituents. For example, a siloxane may be an alkylsiloxane, including dialkylsiloxanes or polydialkylsiloxanes. Preferred siloxanes comprise oxygen atoms bonded to two silicon atoms, i.e., groups having the structure SiOSi. For example, a siloxane may be a siloxane of formula IV: R1[Si(R2R3)4O]nSi(R2R3)R4, where n is 1 or greater. The n of a siloxane of formula IV is preferably 2 or greater, more preferably 3 or greater (e.g., about 4 or greater). The n of the siloxane of formula IV 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 or alkyl group. Preferably, the R2 group is an aryl or alkyl group or a mixture thereof. Preferably, the R3 group is an aryl or alkyl group or a mixture thereof. Preferably, the R4 group is an aryl or alkyl group. Preferably, R1, R2, R3, R4, or any combination thereof are not hydrogen. The R2 group in the molecule can be the same or different. Preferably, the R2 group in the molecule is the same. The R2 group in the molecule can be the same or different from the R3 group. Preferably, the R2 group and R3 group in the molecule are the same. Preferred siloxanes include siloxanes of formula IV, wherein R1, R2, R3, R4, R5, or any combination thereof are methyl, ethyl, propyl, or butyl groups, or any combination thereof. Exemplary siloxanes that may be used include hexamethyldisiloxane, polydimethylsiloxane, polymethylphenylsiloxane, dodecylpentasiloxane, decamethylcyclopentasiloxane, decamethyltetrasiloxane, octamethyltrisiloxane, or any combination thereof.

[0125] The paragraph from Serrano et al. is incorporated herein by reference, noting that in one aspect of the invention, the siloxane is an alkylsiloxane containing about 1 to about 12 carbon atoms, such as hexamethyldisiloxane. The siloxane can also be a polymer, such as polydialkylsiloxane, wherein 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 substantially of polydimethylsiloxane, hexamethyldisiloxane, or combinations thereof.

[0126] Activated aromatic compounds can be any aromatic molecule activated by Friedel-Crafts addition reactions, or mixtures thereof. An aromatic molecule activated by Friedel-Crafts addition reactions is defined as any aromatic molecule capable of undergoing an addition reaction with an inorganic acid. This is particularly true for aromatic molecules capable of undergoing an addition reaction with an inorganic acid during application environments (AC systems) or the thermal stability test as described in ASHRAE 97:2007, "Sealed glass tube method for testing the chemical stability of materials used in refrigerant systems." These molecules or compounds are typically activated by substituting a hydrogen atom of the aromatic ring with one of the following groups: NH2, NHR, NR2, ADH, AD, NHCOCH3, NHCOR, 4OCH3, OR, CH3, 4C2H5, R, or C6H5, where R is a hydrocarbon (preferably a hydrocarbon containing about 1 to about 100 carbon atoms). Activated aromatic molecules can be alcohols or ethers, where the oxygen atom (i.e., the oxygen atom of the alcohol or ether group) is directly bonded to the aromatic group. The activated aromatic molecule can be an amine, wherein the nitrogen atom (i.e., the nitrogen atom of the amine group) is directly bonded to the aromatic group. For example, the activated aromatic molecule can have the formula ArXRn, where X is O (i.e., oxygen) or N (i.e., nitrogen); n: 1 when X: O; n: 2 when X: N; Ar is an aromatic group (i.e., a group, C6H5); R can be H or a carbon-containing group; and when n: 2, the R groups can be the same or different. For example, R can be H (i.e., hydrogen), Ar, an alkyl group, or any combination thereof. Exemplary activated aromatic molecules that can be used in 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 highly preferred aromatic molecule activated by Friedel-Crafts addition reactions is diphenyl ether.

[0127] From Serrano et al., incorporated 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 greater than about 0.0050% by weight, more preferably greater than about 0.05% by weight, and even more preferably greater than about 0.1% by weight (e.g., greater than about 0.5% by weight) based on the total weight of the refrigerant composition. The acid scavenger is preferably present at a concentration less than about 3% by weight, more preferably less than about 2.5% by weight, and most preferably greater than about 2% by weight (e.g., less than about 1.8% by weight) based on the total weight of the refrigerant composition.

[0128] Other examples of acid scavengers that may be included in and preferably excluded from a refrigerant composition include those described by Kaneko (U.S. Patent Application Serial No. 11 / 575,256, published as U.S. Patent Publication 2007 / 0290164, paragraph 42, expressly incorporated herein by reference), such as phenyl glycidyl ethers, alkyl glycidyl ethers, alkylene glycol glycidyl ethers, cyclohexene oxides, oxooxides, or epoxides such as epoxidized soybean oil, and one or more of those described by Singh et al. (U.S. Patent Application Serial No. 11 / 250,219, published as 20060116310, paragraphs 34-42, expressly incorporated herein by reference).

[0129] Preferred additives include those described in U.S. Patents 5,152,926; 4,755,316, which are incorporated herein by reference. In particular, preferred extreme pressure additives comprise mixtures of: (A) toluenetriazole 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., AntaraLP-700), or (ii) a phosphoethanol (e.g., ZELEC 3337), or (iii) zinc dialkyl dithiophosphate (e.g., Lubrizol 5139, 5604, 5178, or 5186), or (iv) mercaptobenzothiazole, or (v) a 2,5-dimercapto-1,3,4-thiadiazole derivative (e.g., Curvan 826), or mixtures thereof. Additional examples of additives that may be used are given in U.S. Patent No. 5,976,399 (Schnur, 5:12-6:51, which is incorporated herein by reference).

[0130] Acid value was measured in mg KOH / g according to ASTM D664-01. Total halide ion concentration, fluoride ion concentration, and total organic acid concentration were measured by ion chromatography. The chemical stability of the refrigerant system was 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 lubricant was tested at 40°C according to ASTM D-7042.

[0131] Mouli et al. (WO 2008 / 027595 and WO 2009 / 042847) proposed the use of alkylsilanes as stabilizers in refrigerant compositions containing fluoroolefins. Phosphates, phosphites, epoxides, and phenolic additives have also been used in some refrigerant compositions. These are described, for example, by Kaneko (U.S. Patent Application Serial No. 11 / 575,256, published as U.S. Publication 2007 / 0290164) and Singh et al. (U.S. Patent Application Serial No. 11 / 250,219, published as U.S. Publication 2006 / 0116310). All of the foregoing applications are expressly incorporated herein by reference.

[0132] Preferred flame retardants include those described and incorporated herein by reference in patent application CA 2557873 A1, “Refrigerant compositions containing fluorine-substituted olefins”, together with fluorinated products such as HFC-125 and / or Krytox described and incorporated herein by reference in patent application WO2009018117A1, “Refrigerant compositions comprising fluoroolefins and uses thereof”. ® lubricant The refrigerant composition of the present invention can be prepared by any convenient method of combining the desired amounts of the individual components. A preferred method is to weigh the desired amounts of the components and then combine them in a suitable container. Stirring may be used if necessary.

[0133] The present invention also relates to a method for generating cooling, the method comprising condensing a refrigerant composition comprising at least one fluoroolefin, at least one lubricant and an effective amount of an inhibitor, and thereafter evaporating the composition near the subject to be cooled.

[0134] The subject to be cooled can be any space, location, or object requiring refrigeration or air conditioning. In static applications, the subject can be the interior of a structure, such as a residential or commercial building, or a storage location for perishable goods such as food or medicine. For mobile refrigeration applications, the subject can be integrated into a transport unit for road, rail, sea, or air transport. Some refrigeration systems operate independently of any moving vehicle; these are known as “combined” systems. Such combined systems include “containers” (sea / land combined transport) and “foldable containers” (road and rail combined transport).

[0135] The present invention also relates to a method for generating heat, the method comprising condensing a refrigerant composition comprising at least one fluoroolefin, at least one lubricant and an effective amount of an inhibitor near an object to be heated, and thereafter evaporating the composition, the inhibitor comprising at least one of limonene and α-terpinene.

[0136] The subject to be heated can be any space, location, or object requiring heating. These can be the interior of a residential or commercial structure, in a manner similar to that of a subject to be cooled. Furthermore, the moving unit described for refrigeration can be similar to those requiring heating. Some transport units require heating to prevent the material being transported from solidifying within the transport container.

[0137] Another embodiment of the present invention relates to an air conditioner or refrigeration device comprising the aforementioned refrigerant composition.

[0138] Another embodiment of the invention relates to storing the aforementioned refrigerant composition in a sealed container in a gaseous and / or liquid phase, wherein at a temperature of about 25°C, the concentration of oxygen and / or water in the gaseous and / or liquid phase is in the range of about 3 volume ppm to at least about 3,000 volume ppm, about 5 volume ppm to at least about 1,000 volume ppm, and in some cases about 5 volume ppm to at least about 500 volume ppm.

[0139] Containers for storing the aforementioned refrigerant compositions can be constructed of any suitable material and design capable of sealing the refrigerant composition within while maintaining both gaseous and liquid phases. Examples of suitable containers include pressure vessels, such as tanks, filling cylinders, and second filling cylinders. Containers can be constructed of any suitable material such as carbon steel, manganese steel, chromium-molybdenum steel, and other low-alloy steels, stainless steel, and in some cases, aluminum alloys. Containers may include a puncture-resistant top or valve suitable for dispensing flammable substances.

[0140] While any suitable method may be used to prepare the refrigerant compositions of the present invention, examples of such methods include blending the aforementioned inhibitor with the aforementioned fluoroolefin composition, purging pipelines and containers having materials containing the inhibitor (e.g., inhibitors with nitrogen supports or the stabilizing compositions of the present invention), and combining with lubricants, as well as other suitable methods.

[0141] In one embodiment, the composition of the 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. If only one of the fluoroolefin or the lubricant is added and then the fluoroolefin and the lubricant are combined, the inhibitor will be distributed such that the inhibitor becomes present in both the fluoroolefin and the lubricant. In another embodiment, the inhibitor may be added to a composition comprising at least one fluoroolefin component and at least one lubricant.

[0142] The following examples are provided to illustrate certain embodiments of the invention and should not limit the scope of the appended claims. Example 1 illustrates the effect of the inhibitor with fluoroolefins, Example 2 illustrates the effect of the inhibitor with fluoroolefins and lubricants, and Example 3 illustrates the phase balance and AC cycle performance with a ternary R-1234yf / d-limonene / lubricant (commercially available from POE32-3MAF).

[0143] Example 1 HFO-1234yf (30g, with a purity of at least 99.5% by weight) was used. A mixture of the initiator and the initiator (and no inhibitor) was heated in a 210 mL shaking tube at the temperatures and time periods given in Table 4. The polymer formation in the shaking tube was visually inspected and examined by NMR according to standard methods. The polymer could also be detected using standard IR methods.

[0144] HFO-1234yf contains 99.7% by weight of HFO-1234yf, 1,000 ppm of HFO-1234ze, 150 pp of HFO-1225yeZ, 3 ppm of trifluoropropyne, and the remainder contains compounds that do not affect the refrigeration performance of the mixture or the activity of the inhibitors.

[0145] Table 4

[0146] Example 2 In a 210 mL shaking tube, a refrigerant blend containing HFO-1234yf (30 g, having the composition of Example 1), at least one additional compound, and an initiator (and no inhibitor) was heated at the temperatures given in Table 5 for the time periods given in Table 5. Examples 1-6 evaluated the effects of Opteon. ™ Inhibitors of XP-10 refrigerant (R513a) and commercially available lubricants. Examples 7-12 evaluated inhibitors with Opteon. ™Inhibitors of XP-40 refrigerant (R449a) and commercially available lubricants. Examples 13-18 evaluated inhibitors containing HFO-1234yf and commercially available lubricants. XP10 refrigerant contained 56 wt% HFO1234yf and 44 wt% HFC-134a, and XP40 refrigerant contained 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 The Chemours Company. Visual inspection and NMR were performed to examine polymer formation in the oscillating tubes. Data reported below are in ppm by weight.

[0147] Table 5

[0148] Example 3 Binary phase properties To analyze the phase characteristics and dextrorotatory limonene partitioning of the R-1234yf / dextrin / lubricant (POE32-3MAF) system, the NRTL binary interaction parameters were fitted into the following binary data: 1) Measured solubility data of R-1234yf / POE32-3MAF–VLE from -25℃ to 75℃. The NRTL binary interaction parameters were fitted to the VLE to obtain a prediction of the VLLE, where liquid-liquid phase splitting was predicted towards the R-1234yf-rich side of the compositional domain. The fitting quality was excellent, and the deviation of AARD from the data was only 2.1%, and with… Figure 1 The data is shown in the figure.

[0149] 2) R-1234yf / dextrin – VLE bubble point data were measured at 50 °C, and NRTL binary interaction parameters were fitted to the experimental data to an accuracy of 2.1% AARD. In the dextrorotatory limonene-line region of compositional space, a negative deviation from Raoult's law was observed between 0 and 9 mol% dextrorotatory limonene, indicating that the R-1234yf / dextrin interaction is stronger than the R-1234yf / R-1234yf and dextrorotatory limonene / dextrin interactions. This is not the expected property and makes the dextrorotatory limonene activity more locally prevalent near liquid R-1234yf. These data and model fits are shown in… Figure 2 The negative deviation from Raoult's law is shown in... Figure 3 middle.

[0150] 3) D-Limonene / POE32-3MAP – Determined using parameterization based on computer software to calculate VLE properties. The calculated VLE is shown in... Figure 4 middle.

[0151] Ternary phase properties The experimental bubble point pressures were measured using a binary mixture of R-1234yf containing 1000 ppm (by weight) of d-limonene at various POE32-3MAF contents. The LLE of this ternary system was calculated using the NRTL model. Binary interaction parameters for R-1234yf / POE32-3MAF, d-limonene / POE32-3MAF, and R-1234yf / d-limonene were then used (shown in...). Figure 1-3 (The following text appears to be a separate, unrelated sentence fragment: "to calculate the ternary phase characteristics of the R-1234yf / dextral limonene / POE32-3MAF system, such as...") Figure 5 As shown in the image.

[0152] For amounts less than and greater than 1,000 ppm, the following can be used: Figures 1 to 5 The data and calculations shown are used to determine the phase characteristics (partition effect) and A / C properties of dextrorotatory limonene.

[0153] Figures 1 to 5 The data and calculations shown also illustrate the gas-liquid equilibrium distribution of d-limonene, such that the vapor will be essentially d-limonene-free R-1234yf, and the d-limonene will remain primarily in the liquid phase of the evaporator or compressor reservoir, where the vapor circulating in the A / C system is essentially d-limonene-free. Therefore, d-limonene will not have a significant impact on the power efficiency or capacity of the A / C system because it will be predominantly present in the liquid phase.

[0154] While certain aspects, embodiments, and principles have been described above, it should be understood that this description is exemplary only and not intended to limit the 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. A refrigerant composition comprising: HFO-1234yf, Limonene, which reduces or eliminates the conversion of HFO-1234yf into oligomers or polymers, and Based on the total weight of the refrigerant composition, less than 0.03% by weight of oligomers, homopolymers or other polymers derived from the HFO-1234yf.

2. The refrigerant composition according to claim 1, wherein, Based on the total weight of the refrigerant composition, the limonene content is 10-500 ppm, or 30-2,000 ppm, or 30-3,000 ppm.

3. The refrigerant composition according to claim 1 or 2, wherein, The limonene reduces or eliminates the conversion of HFO-1234yf to oligomers or polymers caused by the initiator, wherein the initiator is selected from one or more of air, oxygen, cumene hydroperoxide, fluoroolefin peroxide, peroxide, hydroperoxide, persulfate / ester, percarbonate / ester, perborate / ester, and persulfate / ester.

4. The refrigerant composition according to claim 3, wherein, The weight ratio of limonene to the initiator is 1:1.5 to 1:100, or 1:2 to 1:100, or 1:3 to 1:100, or 1:20 to 1:

100.

5. The refrigerant composition according to any one of the preceding claims, wherein, The limonene in question is d-limonene.

6. The refrigerant composition according to claim 5, wherein, The vapor phase of HFO-1234yf does not contain d-limonene.

7. The refrigerant composition according to claim 6, wherein, The composition contains a lubricant, and the lubricant includes polyol esters, polyvinyl ethers, and polyalkylene glycols.

8. The refrigerant composition according to any one of the preceding claims, wherein, The composition consists of HFO-1234yf and limonene.

9. A working fluid composition comprising the refrigerant composition according to claim 9 and a lubricant.

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