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

Abstract

The present invention relates to compositions comprising at least one fluoroolefin and an effective amount of at least one inhibitor. The stabilized compositions are useful in cooling devices, such as refrigeration, air conditioning, coolers and heat pumps, and in applications as blowing agents, solvents, aerosol propellants, fire extinguishing agents and sanitizers.

Description

[0001] This application is a divisional application of Chinese Patent Application No. 201980028947.4, entitled "Stabilized Fluoroolefin Compositions and Methods for Production, Storage and Use Thereof". Background Technology 1. Technical Field :

[0003] This invention broadly relates to stabilized compositions comprising at least one fluoroolefin and at least one inhibitor, the inhibitor comprising at least one member selected from the group consisting of: limonene, α-terpinene, α-tocopherol, butylated hydroxytoluene, 4-methoxyphenol, and phenyl-1,4-diol.

[0004] 2. Related Technologies :

[0005] New environmental regulations for refrigerants have forced the refrigeration and air conditioning industry to search for new refrigerants with low global warming potential (GWP).

[0006] We are seeking alternative refrigerants that have low GWP, are non-toxic, non-flammable, reasonably priced, and have excellent refrigeration performance.

[0007] 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 stabilizing compositions are disclosed in JP 2009298918; US 6,969,701; US ​​8,133,407; US2006 / 0022166; US2006 / 0043330; US2008 / 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.

[0008] 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 compositions containing fluoroolefins that have reduced (if not eliminated) potential for oligomerization or homopolymerization. Summary of the Invention

[0009] This invention improves the ability of hydrofluoroolefin-containing compositions to withstand abnormal 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. Oligomerization or homopolymerization can be accelerated by relatively high temperatures. Depending on the concentration and type of initiator (e.g., contaminants), such reactions can also occur under ambient conditions. The inhibitor can act as a free radical inhibitor and does not affect the refrigeration performance or compatibility of the composition with refrigerant oils and portions. The stabilized composition can be used in cooling systems and as an alternative to existing refrigerants with higher global warming potential.

[0010] To avoid the potential instability of fluoroolefins, it has been found that adding certain inhibitor compounds (i.e., hydrocarbons containing at least one of cyclic monoterpenes; lipophilic organic compounds, including tocopherols such as α-tocopherol; phenols; aromatic organic compounds having at least one chemical moiety C6H4(OH), including benzene-1,4-diol) to compositions containing fluoroolefins will increase their stability during packaging, storage, and use in refrigeration or air conditioning system applications. 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 inventive inhibitor composition comprises a liquid at temperatures of about -100°C to about 220°C, about -90°C to about 200°C, and in some cases about -80°C to about 185°C.

[0011] In one specific embodiment, the present invention relates to compositions containing fluoroolefins, said compositions comprising inhibitors that interact or react with O2 and fluoroolefin polyperoxides, thereby inhibiting or eliminating 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:

[0012]

[0013] 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.

[0014] 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.

[0015] One embodiment of the present invention relates to a composition comprising:

[0016] a. at least one fluoroolefin; and

[0017] b. An effective amount of at least one inhibitor, said at least one inhibitor comprising: a hydrocarbon comprising a cyclic monoterpene; a lipophilic organic compound comprising tocopherol, said tocopherol including α-tocopherol; phenols having the chemical formula C6H4(OH)

[0018] Aromatic organic compounds, including phenyl-1,4-diol

[0019] One embodiment of the invention relates to any of the aforementioned 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.

[0020] One specific implementation involves using the aforementioned antioxidant in conjunction with an inhibitor, said inhibitor comprising at least one of limonene and α-terpinene.

[0021] Another embodiment of the invention relates to a method for stabilizing a 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.

[0022] Another embodiment of the invention relates to a method for reducing oligomerization or homopolymerization of compositions containing at least one fluoroolefin, said oligomerization or homopolymerization being caused by the presence of unintentional or undesirable contaminants in at least one of conduits, pipelines and other systems for processing compositions containing fluoroolefins; packaging (containers); and refrigeration, air conditioning or heat pump systems, said method comprising adding an inhibitor containing at least one hydrocarbon, said at least one hydrocarbon comprising a cyclic monoterpene, to said system, container and at least one of the compositions containing at least one fluoroolefin; a lipophilic organic compound comprising tocopherol, said tocopherol comprising α-tocopherol; phenols, aromatic organic compounds having the chemical formula C6H4(OH), including benzene-1,4-diol, and mixtures thereof.

[0023] Another embodiment of the invention relates to a composition containing fluoroolefins within a container, wherein the fluoroolefins have reduced oligomerization or homopolymerization potential compared to a composition not containing the inhibitory composition of the invention.

[0024] One embodiment of the present invention relates to a 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.

[0025] Another embodiment of the invention relates to any of the aforementioned compositions, wherein the composition comprises less than about 0.03% by weight of an oligomer, homopolymer or other polymeric product.

[0026] Another embodiment of the invention relates to any of the foregoing compositions and further comprises at least one member selected from the group consisting of: air, oxygen, hydroperoxide, cumene and fluoroolefins, peroxides, hydroperoxides, persulfates, percarbonates, perborates and hydropersulfates.

[0027] Another embodiment of the invention relates to any of the aforementioned 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.

[0028] Another embodiment of the invention relates to any of the foregoing and further comprises at least one lubricant.

[0029] Another embodiment of the invention relates to any of the foregoing compositions, wherein the fluoroolefin comprises at least one member of HFO-1234yf and HFO-1234ze.

[0030] Another embodiment of the invention relates to any of the aforementioned 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.

[0031] Another embodiment of the invention relates to any of the foregoing 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.

[0032] Another embodiment of the invention relates to any of the aforementioned 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.

[0033] Another embodiment of the invention relates to any of the aforementioned compositions, wherein the inhibitor is present in an amount of about 30 ppm to about 3,000 ppm.

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

[0035] Another embodiment of the invention relates to any of the aforementioned compositions, wherein the inhibitor comprises at least one of limonene and α-terpinene.

[0036] Another embodiment of the invention relates to any of the aforementioned compositions, wherein the inhibitor comprises a liquid at a temperature of about -80°C to 180°C.

[0037] Another embodiment of the invention relates to any of the aforementioned compositions, and optionally further comprises at least one antioxidant.

[0038] Another embodiment of the invention relates to any of the aforementioned 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.

[0039] Another embodiment of the invention relates to any of the aforementioned compositions, wherein the members comprise HFO-1234ze, HFO-1225yeZ and 3,3,3-trifluoropropyne.

[0040] Another embodiment of the invention relates to any of the foregoing compositions, wherein the compositions are substantially free of at least one of ammonia and CF3I.

[0041] Another embodiment of the invention relates to any of the aforementioned compositions, wherein the composition is substantially composed of HFO-1234yf and limonene and does not contain ammonia or CF3I.

[0042] Another embodiment of the invention relates to any of the aforementioned compositions, wherein the composition is substantially composed of HFO-1234yf, 3,3,3-trifluoropropyne and limonene.

[0043] One embodiment of the present invention relates to a method for reducing the formation of oligomers and homopolymers, comprising contacting a 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.

[0044] Another embodiment of the invention relates to any of the foregoing methods, wherein the composition has been exposed prior to the contact to at least one member selected from the group consisting of: air, oxygen, cumene hydroperoxide and fluoroolefin peroxides, peroxides, hydroperoxides, persulfates / esters, percarbonates / esters, perborates / esters and hydrogen persulfates / esters.

[0045] Another embodiment of the present invention relates to any of the foregoing methods, wherein the foregoing composition is used for heating or cooling.

[0046] Another embodiment of the invention relates to a container having a refrigerant comprising any of the aforementioned compositions.

[0047] 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. Detailed Implementation

[0048] This invention provides a stabilizing composition comprising at least one fluoroolefin and an effective amount of at least one inhibitor. "Stabilized" means a composition comprising an effective amount of at least one inhibitor compound, which inhibits (if not eliminates) the interaction of the fluoroolefin with another compound and the formation of a dimer, oligomer, homopolymer, or polymer. 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 cases 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, pipelines, and other systems used to process 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.

[0049] In one embodiment of the invention, the inventive 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.

[0050] In another embodiment of the invention, the inventive composition is substantially free of certain conventional inhibitory compounds, including sesquiterpenes such as at least one member selected from the group consisting of farmyrol, 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] -

[0051] And mixtures thereof. "Substantially free" means that the inventive 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.

[0052] The inventive compositions have a variety of uses, including as working fluids comprising foaming agents, solvents, aerosol propellants, fire extinguishing agents, sterilizing agents, or heat transfer media (such as heat transfer fluids and refrigerants used in refrigeration systems, refrigerators, air conditioning systems, heat pumps, coolers, etc.), and so on. 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.

[0053] A foaming agent is a volatile composition that causes a polymer matrix to expand to form a honeycomb structure.

[0054] The solvent is a fluid that removes dirt from a substrate, deposits material onto a substrate, or carries material.

[0055] Aerosol propellants are volatile compositions of one or more components that can be subjected to pressure greater than one atmosphere to expel material from a container.

[0056] Fire extinguishing agents are volatile compositions that extinguish or suppress flames.

[0057] Disinfectants are volatile bactericidal fluids that destroy bioactive materials or blends containing volatile bactericidal fluids.

[0058] A heat transfer medium (also referred to herein as a heat transfer fluid, heat transfer composition, or heat transfer fluid composition) is a working fluid used to carry heat from a heat source to a radiator.

[0059] The refrigerant is a compound or mixture of compounds that is used as a heat transfer fluid in a cycle, wherein the fluid undergoes a phase change from liquid to gas and back to liquid.

[0060] 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).

[0061] 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.

[0062] 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..." occupies an intermediate position between "comprising" and "consisting of...".

[0063] 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 such description should be interpreted as also including inventions using terms such as “substantially composed of” or “composed of”.

[0064] 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.

[0065] As used herein, the term fluoroolefin describes compounds comprising carbon atoms, fluorine atoms, and optionally hydrogen atoms. In one embodiment, the fluoroolefin used in the compositions of the present invention comprises compounds having 2 to 12 carbon atoms. In another embodiment, the fluoroolefin comprises compounds having 3 to 10 carbon atoms, and in yet another embodiment, the fluoroolefin comprises compounds having 3 to 7 carbon atoms. Representative fluoroolefins include, but are not limited to, all compounds listed in Tables 1, 2, and 3.

[0066] 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 the groups include, but are not limited to, CF3, C2F5, CF2CF2CF3, CF(CF3)2, CF2CF2CF2CF3, CF(CF3)CF2CF3, CF2CF(CF3)2, C(CF3)3, CF2CF2CF2CF2CF3, CF2CF2CF(CF3)2, C(CF3)2C2F5, CF2CF2CF2CF2CF2CF3, CF(CF3)CF2CF2C2F5, and C(CF3)2CF2C2F5. In one embodiment, the 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.

[0067] Table 1

[0068]

[0069]

[0070]

[0071] 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 2 It 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.

[0072] The contact between perfluoroalkyl iodides and perfluoroalkyl trihydroolefins can be carried out by mixing 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... Nickel-copper alloy, Nickel-based alloys and Containers made of nickel-chromium alloy.

[0073] 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).

[0074] 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).

[0075] 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.

[0076] 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.

[0077] 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 depends 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.

[0078] 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.

[0079] 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.

[0080] 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).

[0081] Alternatively, dehydroiodide reaction can be carried out in the absence of a solvent by adding trihydroiodine perfluoroalkane to a solid or liquid alkaline substance.

[0082] 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.

[0083] The compounds of Formula I can be recovered from the dehydroiodide reaction mixture by phase separation after the addition of water, by distillation, or by a combination thereof.

[0084] 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.

[0085] Table 2

[0086] Cyclic fluoroolefins structure Chemical name FC-C1316cc <![CDATA[cyclo-CF2CF2CF=CF-]]> 1,2,3,3,4,4-Hexafluorocyclobutene HFC-C1334cc <![CDATA[cyclo-CF2CF2CH=CH-]]> 3,3,4,4-Tetrafluorocyclobutene HFC-C1436 <![CDATA[cyclo-CF2CF2CF2CH=CH-]]> 3,3,4,4,5,5,-Hexafluorocyclopentene FC-C1418y <![CDATA[cyclo-CF2CF=CFCF2CF2-]]> 1,2,3,3,4,4,5,5-Octaflavole FC-C151-10y <![CDATA[cyclo-CF2CF=CFCF2CF2CF2-]]> 1,2,3,3,4,4,5,5,6,6-Decafluorocyclohexene

[0087] The 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.

[0088] In another embodiment, fluoroolefins may include those compounds listed in Table 3.

[0089] Table 3

[0090]

[0091]

[0092]

[0093]

[0094] The compounds listed in Tables 2 and 3 are commercially available or can be prepared by methods known in the art or described herein.

[0095] 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.

[0096] 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 about 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 about 200 °C under autogenous pressure for about 8 hours.

[0097] 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).

[0098] 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.

[0099] 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.

[0100] 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.

[0101] 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.

[0102] 1,1,1,3,4-pentafluoro-2-butene can be prepared by dehydrofluorination of 1,1,1,3,3,4,4-hexafluorobutane (CF3CH2CF2CH2F) using solid KOH.

[0103] 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.

[0104] 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.

[0105] 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.

[0106] 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).

[0107] 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).

[0108] 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.

[0109] 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.

[0110] 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.

[0111] 2,3,3,3-Tetrafluoro-1-propene can be prepared by converting at least one of HCFC-244bb or HFC-245eb into HFO-1234yf.

[0112] 1,3,3,3-Tetrafluoro-1-propene can be prepared into HFO-1234ze from HFC-245fa.

[0113] 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.

[0114] 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.

[0115] In another specific embodiment, the fluoroolefin component may comprise the compositions disclosed in U.S. Patents 8,147,709 and 8,877,086, which are incorporated herein by reference.

[0116] 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.

[0117] 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 compositions comprising at least one of HCFO-1233zd and HCFO-1224yd.

[0118] Any suitable effective amount of inhibitor may be used in the aforementioned 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 may be considered as the amount of inhibitor that, when mixed with a composition containing at least one fluoroolefin, 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, R402A, R402). Refrigerants such as B, 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 have similar performance and cooling capacity, depending on what refrigerants have been used as working fluids in similar systems in the past.

[0119] 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.

[0120] One embodiment of the invention relates to any of the foregoing 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 foregoing antioxidant with at least one inhibitor comprising α-terpinene and limonene. An example of a specific embodiment relates to the use of the foregoing antioxidant with an inhibitor comprising at least one of α-terpinene and limonene.

[0121] 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.

[0122] 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).

[0123] 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.

[0124] In another embodiment, the additional compound comprises a hydrocarbon containing heteroatoms, such as dimethyl ether (DME, CH3OCH3). DME is commercially available.

[0125] 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.

[0126] 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.

[0127] 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.

[0128] 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. Further fluoroolefin 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.

[0129] 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.

[0130] 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.

[0131] 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.

[0132] 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 blended with carbon dioxide.

[0133] In one embodiment, the aforementioned composition of the present invention may further comprise at least one lubricant. The lubricants of the present invention include those suitable for use with refrigeration or air conditioning equipment. Among these lubricants are those conventionally used in compression refrigeration equipment utilizing chlorofluorocarbon refrigerants. Such lubricants and their properties are discussed in 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 the present invention may include those commonly known as "mineral oils" in the field of compression refrigeration lubrication. Mineral oils include paraffins (i.e., saturated hydrocarbons with straight and branched carbon chains), 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 the present 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 100N (a paraffinic mineral oil sold by BVA Oils), available under the trademark of Crompton Co. 3GS and 5GS commercially available cycloalkanes mineral oil, which can be trademarked 372LT is a cycloalkanes mineral oil purchased from Pennzoil and can be trademarked. RO-30 is a cycloalkanes mineral oil obtained commercially from Calumet Lubricants and can be branded. 75. 150 and 500 linear alkylbenzenes obtained commercially from Shrieve Chemicals and branched alkylbenzenes sold by Nippon Oil as HAB 22.

[0134] 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," R.L. Shubkin, editor, Marcel Dekker, 1993. Such lubricants include, but are not limited to, polyol esters (POEs) such as… 100 (Castrol, United Kingdom), polyalkylene glycols (PAGs) such as RL-488A from Dow (Dow Chemical, Midland, Michigan), and polyvinyl ether (PVE).

[0135] 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.

[0136] 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.

[0137] 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.

[0138] 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.

[0139] The paragraph

[0039] from Serrano et al. is incorporated by reference, noting that in one aspect of the invention, the siloxane is an alkylsiloxane comprising about 1 to about 12 carbon atoms, such as hexamethyldisiloxane. The siloxane may 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.

[0140] 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.

[0141] Paragraph

[0045] from Serrano et al., incorporated herein by reference, describes an acid scavenger (e.g., an activated aromatic compound, a siloxane, or both) that 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.

[0142] Additional 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 ether, alkyl glycidyl ether, alkylene glycol glycidyl ether, cyclohexene oxide, oxooxide, 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).

[0143] Preferred additives include those described in U.S. Patent Nos. 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., Antara LP-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. Other examples of additives that may be used are given in U.S. Patent 5,976,399 (Schnur, 5:12-6:51, which is incorporated herein by reference).

[0144] 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 (RA 2017), "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.

[0145] 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.

[0146] Preferred flame retardants include those described and incorporated herein by reference in patent application “Compositions containing fluorine-substituted olefins” (CA 2557873 A1), together with fluorinated products such as HFC-125 and / or described and incorporated herein by reference in patent application “Compositions comprising fluoroolefins and uses thereof” (WO2009018117A1). Lubricant.

[0147] The compositions of the present invention can be prepared by any convenient method of mixing the desired amounts of the individual components. A preferred method is to weigh the desired amounts of the components and then mix them in a suitable container. Stirring may be used if necessary.

[0148] The present invention also relates to a method for generating cooling, the method comprising condensing a composition comprising at least one fluoroolefin and an effective amount of an inhibitor, and subsequently evaporating the composition near the subject to be cooled.

[0149] 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).

[0150] The present invention also relates to a method for generating heat, the method comprising condensing a composition containing at least one fluoroolefin and an effective amount of an inhibitor near an object to be heated, and thereafter evaporating the composition, the inhibitor containing at least one of limonene and α-terpinene.

[0151] 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.

[0152] Another embodiment of the present invention relates to an air conditioning or refrigeration device comprising the aforementioned composition.

[0153] Another embodiment of the invention relates to storing the aforementioned 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.

[0154] Containers for storing the aforementioned compositions can be constructed of any suitable material and design capable of sealing the 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.

[0155] While any suitable method may be used to stabilize fluorocarbon compositions, examples of such methods include blending the aforementioned inhibitor with the aforementioned fluoroolefin composition, purging lines, and containers having a material containing the inhibitor (e.g., an inhibitor with a nitrogen support or the stabilizing composition of the present invention), as well as other suitable methods.

[0156] The following examples are provided to illustrate certain embodiments of the invention and should not limit the scope of the appended claims.

[0157] Example 1

[0158] A mixture of HFO-1234yf (30 g, with a purity of at least 99.5% by weight*) and an initiator (and no inhibitor) was heated in a 210 mL shaking tube at the temperatures and time periods given in Table 4. Polymer formation in the shaking tube was examined visually and by detecting the yf polymer peak using IR according to standard methods. Polymer formation can also be detected using standard NMR methods.

[0159] *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 properties of the mixture or the initiator.

[0160] Table 4

[0161]

[0162]

[0163] Example 2

[0164] 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. TM Inhibitors of XP-10 refrigerant (R513a) and commercially available lubricants. Examples 7-12 evaluated inhibitors with Opteon. TM Inhibitors of XP-40 refrigerant (R449a) and commercially available lubricants. Examples 13-18 evaluated inhibitors with 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 inspection of polymer formation in the oscillating tube were performed using IR. Data reported below are in ppm by weight.

[0165] Table 5

[0166]

[0167] 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 composition comprising at least one fluoroolefin including HFO-1234yf and at least one inhibitor, wherein the composition comprises less than 0.03% by weight of an oligomer, homopolymer or other polymer derived from said HFO-1234yf; The composition further comprises at least one component selected from air, oxygen, and cumene hydroperoxide; in, The inhibitor comprises at least one component selected from limonene and α-terpinene; and The inhibitor is present in amounts ranging from 30 ppm to 3,000 ppm.

2. The composition according to claim 1, wherein the composition further comprises at least one lubricant.

3. The composition according to claim 1 or 2, wherein the composition is substantially free of at least one of ammonia and CF3I.

4. A method for reducing the formation of oligomers and homopolymers derived from HFO-1234yf, the method comprising contacting a composition comprising at least one fluoroolefin including HFO-1234yf with an inhibitor of 30 ppm to 3,000 ppm to reduce homopolymer formation, said inhibitor comprising at least one component selected from limonene and α-terpinene. in, The composition has been exposed to at least one component selected from air, oxygen, and cumene peroxide.

5. A method for heating or cooling using the composition according to any one of claims 1-3.

6. A container having a refrigerant, said refrigerant comprising the composition according to any one of claims 1-3.

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