Stabilized fluoroolefin compositions

Abstract

A composition comprising at least one fluoroolefin and 10 to 3,000 ppm of at least one inhibitor selected from the group consisting of limonene and α-terpinene, wherein the composition contains less than 1 wt.% oligomeric, homopolymeric, or other polymeric products derived from the fluoroolefin, and wherein the fluoroolefin comprises HFO-1234yf.

Description

BACKGROUND OF THE INVENTION 1. Field of the invention.

[0001] The present invention generally relates to stabilized compositions comprising at least one fluoroolefin and at least one inhibitor comprising at least one member selected from the group consisting of limonene, α-terpinene, α-tocopherol, butylated hydroxytoluene, 4-methoxyphenol and benzene-1,4-diol. 2. Description of the related art.

[0002] New environmental regulations on refrigerants have forced the refrigeration and air conditioning industry to search for new refrigerants with low global warming potential (THP).

[0003] The aim is to find alternative refrigerants that have low THP, no toxicity, no flammability, a reasonable price and excellent cooling or refrigeration performance.

[0004] Fluoroolefins, alone or in blends, have been proposed as refrigerants. These products have been extensively tested for chemical stability and compatibility with materials typically used in air conditioning or refrigeration systems (see: "1234yf - A Low GWP 15 Refrigerant For MAC, Honeywell / DuPont Joint Collaboration" presentation for JAMA / JARIA, October 3, 2007), and have been shown to be stable under typical operating conditions. However, it has been observed that certain fluoroolefins may exhibit degradation and / or produce unwanted byproducts under abnormal conditions such as extreme temperatures or contact with other compounds in a contaminated system (e.g., with excessive oxygen, oxidizing chemicals, or free radical-generating compounds, among various contaminants) that might be unexpected for a particular use and / or application.Such decomposition can occur when fluoroolefins are used as refrigerants or heat transfer fluids. This decomposition can occur through a variety of mechanisms. Examples of stabilized 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; US 8097181; and US 8075796; the disclosures of which are hereby incorporated by reference.

[0005] Under certain abnormal conditions and in the presence of undesirable contaminants that could act as initiators, fluoroolefins may form oligomers or homopolymers in the presence of certain contaminants that may be present. Accordingly, there is a need in the field for stabilized fluoroolefin-containing compositions that exhibit reduced, if not eliminated, oligomerization or homopolymerization potential. SUMMARY OF THE INVENTION

[0006] The present invention can improve the ability of a hydrofluoroolefin-containing composition to withstand abnormal conditions and also solves potential problems associated with initiators (e.g., contaminants) that cause oligomerization or homopolymerization of a fluoroolefin (e.g., tetrafluoropropene) by adding at least one inhibitor to a fluoroolefin-containing composition. By "inhibitor," according to the present invention, is meant at least one compound that reduces, if not prevents, the conversion of hydrofluoroolefins into 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 nature of the initiator (e.g., contaminant).The inhibitor can act as a radical scavenger without compromising the cooling performance or the compatibility of the composition with refrigerant oil and refrigerant components. The stabilized compositions can be useful in refrigeration systems and as replacements for existing refrigerants with higher global warming potential.

[0007] To avoid potential instability of fluoroolefins, it has been found that the addition of certain inhibitor compounds, namely hydrocarbons comprising 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 of C6H4(OH), including benzene-1,4-diol, to fluoroolefin-containing compositions increases 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 inhibitor composition of the invention comprises a liquid at a temperature of about -100 to about 220°C, about -90 to about 200°C, and in some cases about -80 to about 185°C.

[0008] In a particular embodiment, the invention relates to fluoroolefin-containing compositions comprising an inhibitor capable of interacting or reacting with O2 and fluoroolefin polyperoxides and, in turn, inhibiting or preventing the reaction of such compounds with a hydrofluoroolefin. Examples of such an inhibitor include at least one of limonene and α-terpinene. Limonene and α-terpinene have the following structures:

[0009] In one embodiment of the invention, the inhibitor comprises α-terpinene. Without wishing to be bound by any theory or explanation, it is believed that α-terpinene can form an aromatic ring upon oxidation due to the presence of the conjugated double bond in its structure.

[0010] In one embodiment of the invention, limonene or α-terpinene, optionally with an antioxidant, exhibits a distinct odor even at concentrations of a few ppm. This pleasant odor can be used to detect refrigerant leaks in fluoroolefin-based refrigerants and blends (e.g., consisting of at least one of the substances 1234yf, 1234ze, and combinations thereof). This is particularly useful for the early detection of refrigerant leaks in a household air conditioner or a mobile air conditioner, since paraprofessional electronic leak detectors are often unavailable at both locations.

[0011] One embodiment of the invention relates to a composition comprising: a. at least one fluoroolefin; and b. an effective amount of at least one inhibitor comprising: hydrocarbons, including cyclic monoterpene; lipophilic organic compounds, including tocopherol, including α-tocopherol; phenols, aromatic organic compounds having the chemical formula C6H4(OH), including benzene-1,4-diol

[0012] One embodiment of the invention relates to one of the above compositions and further comprises at least one antioxidant. Although any suitable oxidizing agent may be used, examples of suitable oxidizing agents include at least one member selected from the group consisting of butylated hydroxytoluene, butylated hydroxyanisole, tert-butylhydroquinone, gallate, 2-phenyl-2-propanol, 1-(2,4,5-trihydroxyphenyl)-1-butane, bisphenolmethane derivatives, 2,2'-methylenebis(4-methyl-6-t-butylphenol), and other phenols, as well as combinations thereof.

[0013] A particular embodiment relates to the use of the above antioxidants with an inhibitor comprising at least one of limonene and α-terpinene.

[0014] 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, wherein the inhibitor is a hydrocarbon comprising at least one member selected from the group consisting of cyclic monoterpene; lipophilic organic compounds, including tocopherol, including α-tocopherol; phenols and aromatic organic compounds having the chemical formula C6H4(OH) including benzene-1,4-diol and mixtures thereof to the composition comprising at least one fluoroolefin.

[0015] Another embodiment of the invention relates to a method for reducing oligomerization or homopolymerization of a composition comprising at least one fluoroolefin caused by the presence of an unwanted or undesired contaminant present in at least one of pipes, conduits and other systems used to handle the fluoroolefin-containing compositions; packaging (containers) and a cooling orA refrigeration, air conditioning, or heat pump system, the method comprising adding an inhibitor comprising at least one of hydrocarbons comprising cyclic monoterpene; lipophilic organic compounds including tocopherol, including α-tocopherol; phenols, aromatic organic compounds having the chemical formula C6H4(OH) including benzene-1,4-diol, and mixtures thereof, to at least one of the system, the container, and the composition comprising at least one fluoroolefin.

[0016] A further embodiment of the invention relates to a fluoroolefin-containing composition in a container, wherein the fluoroolefin has a lower oligomerization or homopolymerization potential compared to compositions without the inhibitor composition according to the invention.

[0017] One embodiment of the invention relates to a composition comprising at least one fluoroolefin and an effective amount of at least one inhibitor, and wherein the composition is substantially free of oligomeric, homopolymeric, or other polymeric products derived from the fluoroolefin.

[0018] Another embodiment of the invention relates to any of the above compositions, wherein the composition comprises less than about 0.03 wt.% oligomeric, homopolymeric or other polymeric products.

[0019] Another embodiment of the invention relates to any of the above compositions and further comprises at least one element selected from the group consisting of air, oxygen, cumene hydroperoxide and fluoroolefin polyperoxides, peroxides, hydroperoxides, persulfates, percarbonates, perborates and hydropersulfates.

[0020] Another embodiment of the invention relates to one of the above compositions, wherein the inhibitor comprises at least one member selected from the group consisting of limonene, α-terpinene, α-tocopherol, butylated hydroxytoluene, 4-methoxyphenol, benzene-1,4-diol.

[0021] Another embodiment of the invention relates to one of the above, which further comprises at least one lubricant.

[0022] Another embodiment of the invention relates to any of the above 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 above compositions and further comprises at least one element 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 above 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 above 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 above compositions wherein the inhibitor is present in an amount of about 30 to about 3,000 ppm.

[0027] Another embodiment of the invention relates to any of the above compositions and further comprises at least one member selected from the group consisting of butylated hydroxytoluene, butylated hydroxyanisole, tert-butylhydroquinone, gallate, 2-phenyl-2-propanol, 1-(2,4,5-trihydroxyphenyl)-1-butanone, phenols, bisphenolmethane derivatives and 2,2'-methylenebis(4-methyl-6-t-butylphenol).

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

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

[0030] Another embodiment of the invention relates to one of the above compositions and optionally additionally comprises at least one antioxidant.

[0031] Another embodiment of the invention relates to one of the above 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 one of the above compositions, wherein the element comprises HFO-1234ze, HFO-1225yeZ and 3,3,3-trifluoropropyne.

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

[0034] Another embodiment of the invention relates to one of the above compositions, wherein the composition consists essentially of HFO-1234yf and limonene and does not contain ammonia or CF3I.

[0035] Another embodiment of the invention relates to one of the above compositions, wherein the composition consists essentially of HFO-1234yf, 3,3,3-trifluoropropyne and limonene.

[0036] One embodiment of the invention relates to a method for reducing the formation of oligomers and homopolymers, which comprises contacting a composition containing at least one fluoroolefin with an amount of at least one member selected from the group consisting of limonene, α-terpinene, α-tocopherol, butylated hydroxytoluene, 4-methoxyphenol and benzene-1,4-diol, which is effective to reduce the formation of oligomers or homopolymers.

[0037] Another embodiment of the invention relates to any of the above methods, wherein the composition has been exposed prior to contacting to at least one member selected from the group consisting of air, oxygen, cumene hydroperoxide, and fluoroolefin polyperoxides, peroxides, hydroperoxides, persulfates, percarbonates, perborates, and hydropersulfates.

[0038] Another embodiment of the invention relates to one of the above methods in which one of the above compositions is used for heating or cooling.

[0039] Another embodiment of the invention relates to a container with a refrigerant comprising one of the above compositions.

[0040] The embodiments of the invention may be used alone or in combination with each other, and different embodiments may be combined and form part of the invention. DETAILED DESCRIPTION OF THE INVENTION

[0041] The present invention provides a stabilized composition comprising at least one fluoroolefin and an effective amount of at least one inhibitor. By "stabilized" is meant a composition containing an effective amount of at least one inhibitor compound that inhibits or even prevents the interaction of a fluoroolefin with another compound and the formation of dimers, oligomers, homopolymers, or polymer products. Examples of compounds that can cause such interactions are oxidizing agents such as air, oxygen, cumene hydroperoxide, and fluoroolefin polyperoxides, peroxides, hydroperoxides, persulfates, percarbonates, perborates, hydropersulfates, and other initiators. Initiator compounds can be present in an amount of about 10 to about 15,000 ppm by weight, about 1,000 to about 10,000 ppm, and in some cases, about 1,000 to about 3,000 ppm, and in some embodiments, 30 to 2,000 ppm.000 ppm. Such initiator compounds may be present as contaminants in at least one of lines, pipes, and other systems used to handle the fluoroolefin-containing compositions; packaging (containers); and a refrigeration, air conditioning, or heat pump system. Without wishing to be bound by any theory or explanation, it is believed that certain contaminants may act as free radical initiators, thereby causing oligomerization or homopolymerization of the fluoroolefin or the formation of other polymer products.

[0042] In one embodiment of the invention, the compositions of the invention are substantially free of oligomeric, homopolymeric, or other polymeric products derived from a hydrofluoroolefin. By "substantially free" is meant that the composition contains less than about 1 wt. %, less than about 0.07 wt. %, less than about 0.03 wt. %, and in some cases, about 0 ppm of such products, as measured by IR or NMR.

[0043] In another embodiment of the invention, the compositions of the invention are substantially free of certain conventional inhibitor compounds, including sesquiterpene compounds, such as at least one member selected from the group consisting of farnesol, farnesene; ionic liquids such as an ionic liquid containing an anion 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 fluorinated anions, wherein the fluorinated anion is 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. By substantially free, it is meant that the compositions of the invention contain 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.

[0044] The compositions of the invention can be used in a variety of applications, including as working fluids, including propellants, solvents, aerosol propellants, fire extinguishing agents, sterilizing agents, or heat transfer media (such as heat transfer fluids and refrigerants for use in refrigeration systems, refrigerators, air conditioning systems, heat pumps, chillers, and the like). The compounds of the invention are particularly suitable for use in mobile air conditioning systems and as a component for preparing a refrigerant mixture for use in stationary heat transfer systems.

[0045] A blowing agent is a volatile compound that expands a polymer matrix to form a cellular structure.

[0046] A solvent is a fluid that removes dirt from a substrate or deposits a material on a substrate or carries a material.

[0047] An aerosol propellant is a volatile composition of one or more components that exerts a pressure above one atmosphere to expel a material from a container.

[0048] A fire extinguishing agent is a volatile compound that extinguishes or suppresses a flame.

[0049] A sterilant is a volatile biocidal fluid or a mixture containing a volatile biocidal fluid that destroys a biologically active material or the like.

[0050] A heat transfer medium (also referred to herein as heat transfer fluid, heat transfer composition, or heat transfer fluid composition) is a working fluid used to transfer heat from a heat source to a heat sink.

[0051] A refrigerant is a compound or mixture of compounds that acts as a heat transfer fluid in a cycle in which the fluid undergoes a phase change from a liquid to a gas and back again.

[0052] As used herein, the terms "comprise," "comprising," "include," "including," "having," "comprising," or any other variation thereof, are intended to cover non-exclusive inclusion. For example, a composition, process, method, article, or device that includes a list of elements is not necessarily limited to only those elements, but may include other elements not expressly listed or inherent in such composition, process, method, article, or device. Further, unless expressly stated to the contrary, "or" refers to an inclusive or, not an exclusive or.For example, a condition A or B is satisfied by one of the following: A is true (or present) and B is false (or absent), A is false (or absent) and B is true (or present), and both A and B are true (or present).

[0053] The transitional phrase "consisting of" excludes any unspecified element, step, or component. If this were the case in a claim, the claim would be limited to the inclusion of materials other than those recited, except for impurities normally associated with them. If the phrase "consisting of" appears in a clause of the body of the claim, rather than immediately following the preamble, it limits only the element specified in that clause; other elements are not excluded from the claim as a whole.

[0054] The transitional phrase "consisting essentially of" is used to define a composition or process that includes materials, steps, features, components, or elements in addition to those literally disclosed, provided that these additional included materials, steps, features, components, or elements substantially affect the fundamental and novel characteristic(s) of the claimed invention, particularly the mode of operation to achieve the desired result of each of the processes of the present invention. The term "consisting essentially of" strikes a balance between "comprising" and "consisting of."

[0055] Where applicants have defined an invention or part thereof using an open term such as "comprising", it should be readily understood that (unless otherwise stated) the description should be construed to include such an invention even where the terms "consisting essentially of" or "consisting of" are used.

[0056] In addition, the use of "a" or "an" is used to describe the elements and components described herein. This is done solely for convenience and to provide a general idea of the scope of the invention. This description should be read as including one or at least one, and the singular includes the plural unless it is clearly intended otherwise.

[0057] The term fluoroolefin, as used herein, describes compounds comprising carbon atoms, fluorine atoms, and optionally hydrogen atoms. In one embodiment, the fluoroolefins used in the compositions of the present invention comprise compounds having 2 to 12 carbon atoms. In another embodiment, the fluoroolefins comprise compounds having 3 to 10 carbon atoms, and in yet another embodiment, the fluoroolefins comprise compounds having 3 to 7 carbon atoms. Representative fluoroolefins include compounds as listed in Table 1, Table 2, and Table 3.

[0058] One embodiment of the present invention relates to fluoroolefins of the formula E- or ZR 1 CH=CHR 2 (Formula I), where R 1 and R 2 are independently C1 to C6 perfluoroalkyl groups. Examples of R 1 and R 2include, 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, CF2CF2CF2CF2CF2CF2CF3, CF(CF3)CF2CF2C2F5, and C(CF3)2CF2C2F5. In one embodiment, the fluoroolefins of Formula I have at least about 4 carbon atoms in the molecule. In another embodiment, the fluoroolefins of Formula I have at least about 5 carbon atoms in the molecule. Exemplary non-limiting compounds of Formula I are listed in Table 1. TABLE 1 Code Structure Chemical name F11E CF3CH=CHCF3 1,1,1,4,4,4-Hexafluorobut-2-ene F12E CF3CH=CHC2F5 1,1,1,4,4,5,5,5-Octafluoropent-2-ene F13E CF3CH=CHCF2C2F5 1,1,1,4,4,5,5,6,6,6-decafluorohex-2-ene F13iE CF3CH=CHCF(CF3)2 1,1,1,4,5,5,5-heptafluoro-4-(trifluoromethyl)pent-2-ene F22E C2F5CH=CHC2F5 1,1,1,2,2,5,5,6,6,6-decafluorohex-3-ene F14E CF3CH=CH(CF2)3CF3 1,1,1,4,4,5,5,6,6,7,7,7-dodecafluorohept-2-ene F14iE CF3CH=CHCF2CF-(CF3)2 1,1,1,4,4,5,6,6,6-Nonafluoro-5-(trifluoromethyl)hex-2-ene F14sE CF3CH=CHCF(CF3)-C2F5 1,1,1,4,5,5,6,6,6-Nonafluoro-4-(trifluoromethyl)hex-2-ene F14tE CF3CH=CHC(CF3)3 1,1,1,5,5,5-Hexafluoro-4,4-bis(trifluoromethyl)pent-2-ene F23E C2F5CH=CHCF2C2F5 1,1,1,2,2,5,5,6,6,7,7,7-dodecafluorohept-3-ene F23iE C2F5CH=CHCF(CF3)2 1,1,1,2,2,5,6,6,6-Nonafluoro-5-(trifluoromethyl)hex-3-ene F15E CF3CH=CH(CF2)4CF3 1,1,1,4,4,5,5,6,6,7,7,8,8,8-tetradecafluorooct-2-ene F15iE CF3CH=CH-CF2CF2CF(CF3)2 1,1,1,4,4,5,5,6,7,7,7-undecafluoro-6-(trifluoromethyl)hept-2-ene F15tE CF3CH=CH-C(CF3)2C2F5 1,1,1,5,5,6,6,6-Octafluoro-4,4-bis(trifluoromethyl)hex-2-ene F24E C2F5CH=CH(CF2)3CF3 1,1,1,2,2,5,5,6,6,7,7,8,8,8-Tetradecafluoroct-3-en F24iE C2F5CH=CHCF2CF-(CF3)2 1,1,1,2,2,5,5,6,7,7,7-Undecafluor-6-(trifluormethyl)hept-3-en F24sE C2F5CH=CHCF(CF3)-C2F5 1,1,1,2,2,5,6,6,7,7,7-Undecafluor-5-(trifluormethyl)hept-3-en F24tE C2F5CH=CHC(CF3)3 1,1,1,2,2,6,6,6-Octafluor-5,5-bis(trifluormethyl)hex-3-en F33E C2F5CF2CH=CH-CF2C2F5 1,1,1,2,2,3,3,6,6,7,7,8,8,8-Tetradecafluoroct-4-en F3i3iE (CF3)2CFCH=CH-CF(CF3)2 1,1,1,2,5,6,6,6-Octafluor-2,5-bis(trifluormethyl)hex-3-en F33iE C2F5CF2CH=CH-CF(CF3)2 1,1,1,2,5,5,6,6,7,7,7-Undecafluor-2-(trifluormethyl)hept-3-en F16E CF3CH=CH(CF2)5CF3 1,1,1,4,4,5,5,6,6,7,7,8,8,9,9,9-Hexadecafluornon-2-en F16sE CF3CH=CHCF(CF3)(CF2)2C2F5 1,1,1,4,5,5,6,6,7,7,8,8,8-Tridecafluor-4-(trifluormethyl)hept-2-en F 16tE CF3CH=CHC(CF3)2CF2C2F5 1,1,1,6,6,6-Octafluor-4,4-bis(trifluormethyl)hept-2-en F25E C2F5CH=CH(CF2)4CF3 1,1,1,2,2,5,5,6,6,7,7,8,8,9,9,9-Hexadecafluornon-3-en F25iE C2F5CH=CH-CF2CF2CF(CF3)2 1,1,1,2,2,5,5,6,6,7,8,8,8-Tridecafluor-7-(trifluormethyl)oct-3-en F25tE C2F5CH=CH-C(CF3)2C2F5 1,1,1,2,2,6,6,7,7,7-Decafluor-5,5-bis(trifluormethyl)hept-3-en F34E C2F5CF2CH=CH-(CF2)3CF3 1,1,1,2,2,3,3,6,6,7,7,8,8,9,9,9-Hexadecafluornon-4-en F34iE C2F5CF2CH=CH-CF2CF(CF3)2 1,1,1,2,2,3,3,6,6,7,8,8,8-Tridecafluor-7-(trifluormethyl)oct-4-en F34sE C2F5CF2CH=CH-CF(CF3)C2F5 1,1,1,2,2,3,3,6,7,7,8,8,8-Tridecafluor-6-(trifluormethyl)oct-4-en F34tE C2F5CF2CH=CH-C(CF3)3 1,1,1,5,5,6,6,7,7,7-Decafluor-2,2-bis(trifluormethyl)hept-3-en F3i4E (CF3)2CFCH=CH-(CF2)3CF3 1,1,1,2,5,5,6,6,7,7,8,8,8-Tridecafluor-2(trifluormethyl)oct-3-en F3i4iE (CF3)2CFCH=CH-CF2CF(CF3)2 1,1,1,2,5,5,6,7,7,7-Decafluor-2,6-bis(trifluormethyl)hept-3-en F3i4sE (CF3)2CFCH=CH-CF(CF3)C2F5 1,1,1,2,5,6,6,7,7,7-Decafluor-2,5-bis(trifluormethyl)hept-3-en F3i4tE (CF3)2CFCH=CH-C(CF3)3 1,1,1,2,6,6,6-Heptafluor-2,5,5-tris(trifluormethyl)hex-3-en F26E C2F5CH=CH(CF2)5CF3 1,1,1,2,2,5,5,6,6,7,7,8,8,9,9,10,10,10-Octadecafluordec-3-en F26sE C2F5CH=CHCF(CF3)(CF2)2C2F 5 1,1,1,2,2,5,6,6,7,7,8,8,9,9,9-Pentadecafluor-5-(trifluormethyl)non-3-en F26tE C2F5CH=CHC(CF3)2CF2C2F5 1,1,1,2,2,6,6,7,7,8,8,8-Dodecafluor-5,5-bis(trifluormethyl)oct-3-en F35E C2F5CF2CH=CH-(CF2)4CF3 1,1,1,2,2,3,3,6,6,7,7,8,8,9,9,10,10,10-Octadecafluordec-4-en F35iE C2F5CF2CH=CH-CF2CF2CF(CF3)2 1,1,1,2,2,3,3,6,6,7,7,8,9,9,9-Pentadecafluor-8-(trifluormethyl)non-4-en F35tE C2F5CF2CH=CH-C(CF3)2C2F5 1,1,1,2,2,3,3,7,7,8,8,8-Dodecafluor-6,6-bis(trifluormethyl)oct-4-en F3i5E (CF3)2CFCH=CH-(CF2)4CF3 1,1,1,2,5,5,6,6,7,7,8,8,9,9,9-Pentadecafluor-2-(trifluormethyl)non-3-en F3i5iE (CF3)2CFCH=CH-CF2CF2CF(CF3)2 1,1,1,2,5,5,6,6,7,8,8,8-Dodecafluor-2,7-bis(trifluormethyl)oct-3-en F3i5tE (CF3)2CFCH=CH-C(CF3)2C2F5 1,1,1,2,6,6,7,7,7-Nonafluor-2,5,5-tris(trifluormethyl)hept-3-en F44E CF3(CF2)3CH=CH-(CF2)3CF3 1,1,1,2,2,3,3,4,4,7,7,8,8,9,9,10,10,10-Octadecafluordec-5-en F44iE CF3(CF2)3CH=CH-CF2CF(CF3)2 1,1,1,2,3,3,6,6,7,7,8,8,9,9,9-Pentadecafluor-2-(trifluormethyl)non-4-en F44sE CF3(CF2)3CH=CH-CF(CF3)C2F5 1,1,1,2,2,3,6,6,7,7,8,8,9,9,9-Pentadecafluor-3-(trifluormethyl)non-4-en F44tE CF3(CF2)3CH=CH-C(CF3)3 1,1,1,5,5,6,6,7,7,8,8,8-Dodecafluor-2,2,-bis(trifluormethyl)oct-3-en F4i4iE (CF3)2CFCF2CH=CH-CF2CF(CF3)2 1,1,1,2,3,3,6,6,7,8,8,8-Dodecafluor-2,7-bis(trifluormethyl)oct-4-en F4i4sE (CF3)2CFCF2CH=CH-CF(CF3)C2F5 1,1,1,2,3,3,6,7,7,8,8,8-Dodecafluor-2,6-bis(trifluormethyl)oct-4-en F4i4tE (CF3)2CFCF2CH=CH- C(CF3)3 1,1,1,5,5,6,7,7,7-Nonafluor-2,2,6-tris(trifluormethyl)hept-3-en F4s4sE C2F5CF(CF3)CH=CH-CF(CF3)C2F5 1,1,1,2,2,3,6,7,7,8,8,8-Dodecafluor-3,6-bis(trifluormethyl)oct-4-en F4s4tE C2F5CF(CF3)CH=CH- C(CF3)3 1,1,1,5,6,6,7,7,7-Nonafluor-2,2,5-tris(trifluormethyl)hept-3-en F4t4tE (CF3)3CCH=CH-C(CF3)3 1,1,1,6,6,6-Hexafluor-2,2,5,5-tetrakis(trifluormethyl)hex-3-en

[0059] Compounds of formula I can be prepared by reacting a perfluoroalkyl iodide of formula R 1 I with a perfluoroalkyltrihydroolefin of the formula R 2 CH=CH2 to form a trihydroiodoperfluoroalkane of the formula R 1 CH2CHIR 2 This trihydroiodoperfluoroalkane can then be dehydroiodinated to form R 1 CH=CHR2 Alternatively, the olefin R 1 CH=CHR 2 by dehydroiodination of a trihydroiodoperfluoroalkane of the formula R 1 CHICH2R 2 are prepared, again formed by reacting a perfluoroalkyl iodide of the formula R 2 I with a perfluoroalkyltrihydroolefin of the formula R 1 CH=CH2 is formed.

[0060] Contacting a perfluoroalkyl iodide with a perfluoroalkyl trihydroolefin can be accomplished in batch mode by combining the reactants in a suitable reaction vessel capable of operating at reaction temperature under the autogenous pressure of the reactants and products. Suitable reaction vessels include those constructed from stainless steels, particularly austenitic steels, and well-known high-nickel alloys such as Monel® nickel-copper alloys, Hastelloy® nickel-based alloys, and Inconel® nickel-chromium alloys.

[0061] Alternatively, the reaction can be carried out in semi-batch mode, in which the perfluoroalkyl trihydroolefin reactant is added to the perfluoroalkyl iodide reactant by means of a suitable addition device, such as a pump, at the reaction temperature.

[0062] The ratio of perfluoroalkyl iodide to perfluoroalkyl trihydroolefin should be between about 1:1 and about 4:1, preferably between about 1.5:1 and 2.5:1. Ratios less than 1.5:1 tend to result in large amounts of the 2:1 adduct, as reported by Jeanneaux et al. in Journal of Fluorine Chemistry, Vol. 4, pages 261-270 (1974).

[0063] Preferred temperatures for contacting the perfluoroalkyl iodide with the perfluoroalkyl trihydroolefin are preferably in the range of about 150°C to 300°C, preferably from about 170°C to about 250°C, and most preferably from about 180°C to about 230°C. Suitable contact times for the reaction of the perfluoroalkyl iodide with the perfluoroalkyl trihydroolefin are about 0.5 hours to 18 hours, preferably about 4 to about 12 hours.

[0064] The trihydroiodoperfluoroalkane produced by the reaction of the perfluoroalkyl iodo with the perfluoroalkyl trihydroolefin can be used directly in the dehydroiodination step or can preferably be recovered and purified by distillation before the dehydroiodination step.

[0065] The dehydroiodination step is carried out by contacting the trihydroiodoperfluoroalkane with a basic substance. Suitable basic substances include, for example, alkali metal hydroxides (e.g., sodium hydroxide or potassium hydroxide), alkali metal oxides (e.g., sodium oxide), alkaline earth metal hydroxides (e.g., calcium hydroxide), alkaline earth metal oxides (e.g., calcium oxide), alkali metal alkoxides (e.g., sodium methoxide or sodium ethoxide), aqueous ammonia, sodium amide, or mixtures of basic substances such as soda lime. Preferred basic substances are sodium hydroxide and potassium hydroxide. Contacting the trihydroiodoperfluoroalkane with a basic 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. Suitable solvents for the dehydroiodination step include one or more polar organic solvents such as alcohols (e.g.,Methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and tertiary butanol), nitriles (e.g., acetonitrile, propionitrile, butyronitrile, benzonitrile, or adiponitrile), dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, or sulfolane. The choice of solvent may depend on the boiling point of the product and the ease with which traces of the solvent can be separated from the product during purification. Typically, ethanol or isopropanol are good solvents for the reaction.

[0066] Typically, the trihydroiodination reaction can be carried out by adding one of the reactants (either the basic substance or the trihydroiodoperfluoroalkane) to the other reactant in a suitable reaction vessel. The reaction vessel can be made of glass, ceramic, or metal and is preferably agitated by an impeller or stirring mechanism.

[0067] Suitable temperatures for the dehydroiodination reaction are from about 10 °C to about 100 °C, preferably from about 20 °C to about 70 °C. The dehydroiodination reaction can be carried out at ambient pressure or at reduced or elevated pressure. Dehydroiodination reactions in which the compound of formula I is distilled from the reaction vessel as it is formed are noteworthy.

[0068] Alternatively, the dehydroiodination reaction can be carried out by contacting an aqueous solution of the basic substance with a solution of the trihydroiodoperfluoroalkane in one or more organic solvents of lower polarity, such as an alkane (e.g. hexane, heptane or octane), an aromatic hydrocarbon (e.g. toluene), a halogenated hydrocarbon (e.g. methylene chloride, chloroform, carbon tetrachloride or perchloroethylene) or an ether (e.g. diethyl ether, methyl tert-butyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, dimethoxyethane, diglyme or tetraglyme), in the presence of a phase transfer catalyst. Suitable phase transfer catalysts include quaternary ammonium halides (e.g. tetrabutylammonium bromide, tetrabutylammonium hydrogen sulfate, triethylbenzylammonium chloride, dodecyltrimethylammonium chloride and tricaprylylmethylammonium 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).

[0069] Alternatively, the dehydroiodination reaction can be carried out in the absence of solvent by adding the trihydroiodoperfluoroalkane to a solid or liquid basic substance.

[0070] Suitable reaction times for dehydroiodination reactions range from about 15 minutes to about six hours or more, depending on the solubility of the reactants. Typically, the dehydroiodination reaction proceeds rapidly, taking about 30 minutes to about three hours to complete.

[0071] The compound of formula I can be obtained from the dehydroiodination reaction mixture by phase separation after addition of water, by distillation or by a combination thereof.

[0072] In a further embodiment of the present invention, fluoroolefins include cyclic fluoroolefins (cyclo-[CX=CY(CZW) n -] (Formula II), wherein X, Y, Z, and W are independently selected from H and F, and n is an integer from 2 to 5. In one embodiment, the fluoroolefins of Formula II have at least about 3 carbon atoms in the molecule. In another embodiment, the fluoroolefins of Formula II have at least about 4 carbon atoms in the molecule. In yet another embodiment, the fluoroolefins of Formula II have at least about 5 carbon atoms in the molecule. Representative cyclic fluoroolefins of Formula II are listed in Table 2. TABLE 2 Cyclische Fluorolefine Struktur Chemischer Name FC-C1316 cc Cyclo-CF2CF2CF=CF- 1,2,3,3,4,4-Hexafluorcyclobuten HFC-C1334 cc Cyclo-CF2CF2CH=CH- 3,3,4,4-Tetrafluorcyclobuten HFC-C1436 Cyclo-CF2CF2CF2CH=CH- 3,3,4,4,5,5-Hexafluorcyclopenten FC-C1418y Cyclo-CF2CF=CFCF2CF2- 1,2,3,3,4,4,5,5-Octafluorcyclopenten FC-C151-10y Cyclo-CF2CF=CFCF2CF2CF2- 1,2,3,3,4,4,5,5,6,6-Decafluorcyclohexen

[0073] 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.

[0074] In another embodiment, fluoroolefins may include the compounds listed in Table 3. TABLE 3 Name Struktur Chemischer Name HFO-1225ye CF3CF=CHF 1,2,3,3,3-Pentafluor-1-propen HFO-1225zc CF3CH=CF2 1,1,3,3,3-Pentafluor-1-propen HFO-1225yc CHF2CF=CF2 1,1,2,3,3-Pentafluor-1-propen HFO-1234ye CHF2CF=CHF 1,2,3,3-Tetrafluor-1-propen HFO-1234yf CF3CF=CH2 2,3,3,3-Tetrafluor-1-propen HFO-1234ze CF3CH=CHF 1,3,3,3-Tetrafluor-1-propen HFO-1234yc CH2FCF=CF2 1,1,2,3-Tetrafluor-1-propen HFO-1234zc CHF2CH=CF2 1,1,3,3-Tetrafluor-1-propen HFO-1243yf CHF2CF=CH2 2,3,3-Trifluor-1-propen HFO-1243zf CF3CH=CH2 3,3,3-Trifluor-1-propen HFO-1243yc CH3CF=CF2 1,1,2-Trifluor-1-propen HFO-1243zc CH2FCH=CF2 1,1,3-Trifluor-1-propen HFO-1243ye CH2FCF=CHF 1,2,3-Trifluor-1-propen HFO-1243ze CHF2CH=CHF 1,3,3-Trifluor-1-propen FC-1318my CF3CF=CFCF3 1,1,1,2,3,4,4,4-Octafluor-2-buten FC-1318cy CF3CF2CF=CF2 1,1,2,3,3,4,4,4-Octafluor-1-buten HFO-1327my CF3CF=CHCF3 1,1,1,2,4,4,4-Heptafluor-2-buten HFO-1327ye CHF=CFCF2CF3 1,2,3,3,4,4,4-Heptafluor-1-buten HFO-1327py CHF2CF=CFCF3 1,1,1,2,3,4,4-Heptafluor-2-buten HFO-1327et (CF3)2C=CHF 1,3,3,3-Tetrafluor-2-(trifluormethyl)-1-propen HFO-1327cz CF2=CHCF2CF3 1,1,3,3,4,4,4-Heptafluor-1-buten HFO-1327cye CF2=CFCHFCF3 1,1,2,3,4,4,4-Heptafluor-1-buten HFO-1327cyc CF2=CFCF2CHF2 1,1,2,3,3,4,4-Heptafluor-1-buten HFO-1336yf CF3CF2CF=CH2 2,3,3,4,4,4-Hexafluor-1-buten HFO-1336ze CHF=CHCF2CF3 1,3,3,4,4,4-Hexafluor-1-buten HFO-1336eye CHF=CFCHFCF3 1,2,3,4,4,4-Hexafluor-1-buten HFO-1336eyc CHF=CFCF2CHF2 1,2,3,3,4,4-Hexafluor-1-buten HFO-1336pyy CHF2CF=CFCHF2 1,1,2,3,4,4-Hexafluor-2-buten HFO-1336qy CH2FCF=CFCF3 1,1,1,2,3,4-Hexafluor-2-buten HFO-1336pz CHF2CH=CFCF3 1,1,1,2,4,4-Hexafluor-2-buten HFO-1336mzy CF3CH=CFCHF2 1,1,1,3,4,4-Hexafluor-2-buten HFO-1336qc CF2=CFCF2CH2F 1,1,2,3,3,4-Hexafluor-1-buten HFO-1336pe CF2=CFCHFCHF2 1,1,2,3,4,4-Hexafluor-1-buten HFO-1336ft CH2=C(CF3)2 3,3,3-Trifluor-2-(trifluormethyl)-1-propen HFO-1345qz CH2FCH=CFCF3 1,1,1,2,4-Pentafluor-2-buten HFO-1345mzy CF3CH=CFCH2F 1,1,1,3,4-Pentafluor-2-buten HFO-1345fz CF3CF2CH=CH2 3,3,4,4,4-Pentafluor-1-buten HFO-1345mzz CHF2CH=CHCF3 1,1,1,4,4-Pentafluor-2-buten HFO-1345sy CH3CF=CFCF3 1,1,1,2,3-Pentafluor-2-buten HFO-1345fyc CH2=CFCF2CHF2 2,3,3,4,4-Pentafluor-1-buten HFO-1345pyz CHF2CF=CHCHF2 1,1,2,4,4-Pentafluor-2-buten HFO-1345cyc CH3CF2CF=CF2 1,1,2,3,3-Pentafluor-1-buten HFO-1345pyy CH2FCF=CFCHF2 1,1,2,3,4-Pentafluor-2-buten HFO-1345eyc CH2FCF2CF=CF2 1,2,3,3,4-Pentafluor-1-buten HFO-1345ctm CF2=C(CF3)(CH3) 1,1,3,3,3-Pentafluor-2-methyl-1-propen HFO-1345ftp CH2=C(CHF2)(CF3) 2-(Difluormethyl)-3,3,3 -trifluor-1-propen HFO1345fye CH2=CFCHFCF3 2,3,4,4,4-Pentafluor-1-buten HFO-1345eyf CHF=CFCH2CF3 1,2,4,4,4-Pentafluor-1-buten HFO-1345eze CHF=CHCHFCF3 1,3,4,4,4-Pentafluor-1-buten HFO-1345ezc CHF=CHCF2CHF2 1,3,3,4,4-Pentafluor-1-buten HFO-1345eye CHF=CFCHFCHF2 1,2,3,4,4-Pentafluor-1-buten HFO-1354fzc CH2=CHCF2CHF2 3,3,4,4-Tetrafluor-1-buten HFO-1354ctp CF2=C(CHF2)(CH3) 1,1,3,3-Tetrafluor-2-methyl-1-propen HFO-1354etm CHF=C(CF3)(CH3) 1,3,3,3-Tetrafluor-2-methyl-1-propen HFO-1354tfp CH2=C(CHF2)2 2-(Difluormethyl)-3,3-difluor-1-propen HFO-1354my CF3CF=CHCH3 1,1,1,2-Tetrafluor-2-buten HFO-1354mzy CH3CF=CHCF3 1,1,1,3-Tetrafluor-2-buten FC-141-10myy CF3CF=CFCF2CF3 1,1,1,2,3,4,4,5,5,5-Decafluor-2-penten FC-141-10cy CF2=CFCF2CF2CF3 1,1,2,3,3,4,4,5,5,5-Decafluor-1-penten HFO-1429mzt (CF3)2C=CHCF3 1,1,1,4,4,4-Hexafluor-2-(trifluormethyl)-2-buten HFO-1429myz CF3CF=CHCF2CF3 1,1,1,2,4,4,5,5,5-Nonafluor-2-penten HFO-1429mzy CF3CH=CFCF2CF3 1,1,1,3,4,4,5,5,5-Nonafluor-2-penten HFO-1429eyc CHF=CFCF2CF2CF3 1,2,3,3,4,4,5,5,5-Nonafluor-1-penten HFO-1429czc CF2=CHCF2CF2CF3 1,1,3,3,4,4,5,5,5-Nonafluor-1-penten HFO-1429cycc CF2=CFCF2CF2CHF2 1,1,2,3,3,4,4,5,5-Nonafluor-1-penten HFO-1429pyy CHF2CF=CFCF2CF3 1,1,2,3,4,4,5,5,5-Nonafluor-2-penten HFO-1429myyc CF3CF=CFCF2CHF2 1,1,1,2,3,4,4,5,5-Nonafluor-2-penten HFO-1429myye CF3CF=CFCHFCF3 1,1,1,2,3,4,5,5,5-Nonafluor-2-penten HFO-1429eyym CHF=CFCF(CF3)2 1,2,3,4,4,4-Hexafluor-3-(trifluormethyl)-1-buten HFO-1429cyzm CF2=CFCH(CF3)2 1,1,2,4,4,4-Hexafluor-3-(trifluormethyl)-1-buten HFO-1429mzt CF3CH=C(CF3)2 1,1,1,4,4,4-Hexafluor-2-(trifluormethyl)-2-buten HFO-1429czym CF2=CHCF(CF3)2 1,1,3,4,4,4-Hexafluor-3-(trifluormethyl)-1-buten HFO-1438fy CH2=CFCF2CF2CF3 2,3,3,4,4,5,5,5-Octafluor-1-penten HFO-1438eycc CHF=CFCF2CF2CHF2 1,2,3,3,4,4,5,5-Octafluor-1-penten HFO-1438ftmc CH2=C(CF3)CF2CF3 3,3,4,4,4-Pentafluor-2-(trifluormethyl)-1-buten HFO-1438czzm CF2=CHCH(CF3)2 1,1,4,4,4-Pentafluor-3-(trifluormethyl)-1-buten HFO-1438ezym CHF=CHCF(CF3)2 1,3,4,4,4-Pentafluor-3-(trifluormethyl)-1-buten HFO-1438ctmf CF2=C(CF3)CH2CF3 1,1,4,4,4-Pentafluor-2-(trifluormethyl)-1-buten HFO-1447fzy (CF3)2CFCH=CH2 3,4,4,4-Tetrafluor-3-(trifluormethyl)-1-buten HFO-1447fz CF3CF2CF2CH=CH2 3,3,4,4,5,5,5-Heptafluor-1-penten HFO-1447fycc CH2=CFCF2CF2CHF2 2,3,3,4,4,5,5-Heptafluor-1-penten HFO-1447czcf CF2=CHCF2CH2CF3 1,1,3,3,5,5,5-Heptafluor-1-penten HFO-1447mytm CF3CF=C(CF3)(CH3) 1,1,1,2,4,4,4-Heptafluor-3-methyl-2-buten HFO-1447fyz CH2=CFCH(CF3)2 2,4,4,4-Tetrafluor-3-(trifluormethyl)-1-buten HFO-1447ezz CHF=CHCH(CF3)2 1,4,4,4-Tetrafluor-3-(trifluormethyl)-1-buten HFO-1447qzt CH2FCH=C(CF3)2 1,4,4,4-Tetrafluor-2-(trifluormethyl)-2-buten HFO-1447syt CH3CF=C(CF3)2 2,4,4,4-Tetrafluoro-2-(trifluoromethyl)-2-butene HFO-1456szt (CF3)2C=CHCH3 3-(Trifluoromethyl)-4,4,4-trifluoro-2-butene HFO-1456szy CF3CF2CF=CHCH3 3,4,4,5,5,5-Hexafluoro-2-pentene HFO-1456mstz CF3C(CH3)=CHCF3 1,1,1,4,4,4-Hexafluoro-2-methyl-2-butene HFO-1456fzce CH2=CHCF2CHFCF3 3,3,4,5,5,5-Hexafluoro-1-pentene HFO-1456ftmf CH2=C(CF3)CH2CF3 4,4,4-Trifluoro-2-(trifluoromethyl)-1-butene FC-151-12c CF3(CF2)3CF=CF2 1,1,2,3,3,4,4,5,5,6,6,6-Dodecafluoro-1-hexene (or perfluoro-1-hexene) FC-151-12mcy CF3CF2CF=CFCF2CF3 1,1,1,2,2,3,4,5,5,6,6,6-Dodecafluoro-3-hexene (or perfluoro-3-hexene) FC-151-12 mmdd (CF3)2C=C(CF3)2 1,1,1,4,4,4-Hexafluoro-2,3-bis(trifluoromethyl)-2-butene FC-151-12 mmzz (CF3)2CFCF=CFCF3 1,1,1,2,3,4,5,5,5-Nonafluoro-4-(trifluoromethyl)-2-pentene HFO-152-11 mmtz (CF3)2C=CHC2F5 1,1,1,4,4,5,5,5-Octafluoro-2-(trifluoromethyl)-2-pentene HFO-152-11 mmyyz (CF3)2CFCF=CHCF3 1,1,1,3,4,5,5,5-Octafluoro-4-(trifluoromethyl)-2-pentene PFBE (or HFO-1549fz) CF3CF2CF2CF2C1-1=CH2 3,3,4,4,5,5,6,6,6-Nonafluor-1-hexen (oder Perfluorbutylethylen) HFO-1549fztmm CH2=CHC(CF3)3 4,4,4-Trifluor-3,3-bis(trifluormethyl)-1-buten HFO-1549 mmtts (CF3)2C=C(CH3)(CF3) 1,1,1,4,4,4-Hexafluor-3-methyl-2-(trifluormethyl)-2-buten HFO-1549fycz CH2=CFCF2CH(CF3)2 2,3,3,5,5,5-Hexaf l uor-4-(trifluormethyl)-1-penten HFO-1549myts CF3CF=C(CH3)CF2CF3 1,1,1,2,4,4,5,5,5-Nonafluor-3-methyl-2-penten HFO-1549mzzz CF3CH=CHCH(CF3)2 1,1,1,5,5,5-Hexafluor-4-(trifluormethyl)-2-penten HFO-1558szy CF3CF2CF2CF=CHCH3 3,4,4,5,5,6,6,6-Octafluor-2-hexen HFO-1558fzccc CH2=CHCF2CF2CF2CHF 2 3,3,4,4,5,5,6,6-Octafluor-2-hexen HFO-1558 mmtzc (CF3)2C=CHCF2CH3 1,1,1,4,4-Pentafluor-2-(trifluormethyl)-2-penten HFO-1558ftmf CH2=C(CF3)CH2C2F5 4,4,5,5,5-Pentaf l uor-2-(trifluormethyl)-1-penten HFO-1567fts CF3CF2CF2C(CH3)=CH2 3,3,4,4,5,5,5-Heptafluor-2-methyl-1-penten HFO-1567szz CF3CF2CF2CH=CHCH3 4,4,5,5,6,6,6-Heptafluor-2-hexen HFO-1567fzfc CH2=CHCH2CF2C2F5 4,4,5,5,6,6,6-Heptafluor-1-hexen HFO-1567sfyy CF3CF2CF=CFC2H5 1,1,1,2,2,3,4-Heptafluor-3-hexen HFO-1567fzfy CH2=CHCH2CF(CF3)2 4,5,5,5-Tetrafluor-4-(trifluormethyl)-1-penten HFO-1567myzzm CF3CF=CHCH(CF3)(CH3 ) 1,1,1,2,5,5,5-Heptafluoro-4-methyl-2-pentene HFO-1567 mmtyf (CF3)2C=CFC2H5 1,1,1,3-Tetrafluoro-2-(trifluoromethyl)-2-pentene FC-161-14myy CF3CF=CFCF2CF2C2F5 1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene FC-161-14mcyy CF3CF2CF=CFCF2C2F5 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene HFO-162-13mzy CF3CH=CFCF2CF2C2F5 1,1,1,3,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene HFO162-13myz CF3CF=CHCF2CF2C2F5 1,1,1,2,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene HFO-162-13mczy CF3CF2CH=CFCF2C2F5 1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene HFO-162-13mcyz CF3CF2CF=CHCF2C2F5 1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3-heptene PEVE CF2=CFOCF2CF3 Pentafluoroethyl trifluorovinyl ether PMVE CF2=CFOCF3 Trifluoromethyl trifluorovinyl ether

[0075] The compounds listed in Table 2 and Table 3 are commercially available or can be prepared by methods known in the art or described herein.

[0076] 1,1,1,4,4-Pentafluoro-2-butene can be prepared from 1,1,1,2,4,4-hexafluorobutane (CHF2CH2CHFCF3) by dehydrofluorination over solid KOH in the vapor phase at room temperature. The synthesis of 1,1,1,2,4,4-hexafluorobutane is described in US Pat. No. 6,066,768, which is hereby incorporated by reference.

[0077] 1,1,1,4,4,4-Hexafluoro-2-butene can be prepared from 1,1,1,4,4,4-hexafluoro-2-iodobutane (CF3CHICH2CF3) by reaction with KOH using a phase-transfer catalyst at about 60 °C. The synthesis of 1,1,1,4,4,4-hexafluoro-2-iodobutane can be carried out by the reaction of perfluoromethyl iodide (CF3I) and 3,3,3-trifluoropropene (CF3CH=CH2) at about 200 °C under autogenous pressure for about 8 hours.

[0078] 3,4,4,5,5,5-Hexafluoro-2-pentene can be prepared by dehydrofluorination of 1,1,1,2,2,3,3-heptafluoropentane (CF3CF2CF2CH2CH3) with solid KOH or over a carbon catalyst at 200-300 °C. 1,1,1,2,2,3,3-Heptafluoropentane can be prepared by hydrogenation of 3,3,4,4,5,5,5-heptafluoro-1-pentene (CF3CF2CF2CH=CH2).

[0079] 1,1,1,2,3,4-Hexafluoro-2-butene can be prepared by dehydrofluorination of 1,1,1,2,3,3,4-heptafluorobutane (CH2FCF2CHFCF3) with solid KOH.

[0080] 1,1,1,2,4,4-Hexafluoro-2-butene can be prepared by dehydrofluorination of 1,1,1,2,2,4,4-heptafluorobutane (CHF2CH2CF2CF3) with solid KOH.

[0081] 1,1,1,3,4,4-Hexafluoro2-butene can be prepared by dehydrofluorination of 1,1,1,3,3,4,4-heptafluorobutane (CF3CH2CF2CHF2) with solid KOH.

[0082] 1,1,1,2,4-Pentafluoro-2-butene can be prepared by dehydrofluorination of 1,1,1,2,2,3-hexafluorobutane (CH2FCH2CF2CF3) with solid KOH.

[0083] 1,1,1,3,4-Pentafluoro-2-butene can be prepared by dehydrofluorination of 1,1,1,3,3,4-hexafluorobutane (CF3CH2CF2CH2F) using solid KOH.

[0084] 1,1,1,3-Tetrafluoro-2-butene can be prepared by reacting 1,1,1,3,3-pentafluorobutane (CF3CH2CF2CH3) with aqueous KOH at 120 °C.

[0085] 1,1,1,4,4,5,5,5-Octafluoro-2-pentene can be prepared from (CF3CHICH2CF2CF3) by reaction with KOH using a phase-transfer catalyst at about 60 °C. The synthesis of 4-iodo-1,1,1,2,2,5,5,5-octafluoropentane can be carried out by reacting perfluoroethyl iodide (CF3CF2I) and 3,3,3-trifluoropropene at about 200 °C under autogenous pressure for about 8 hours.

[0086] 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 reaction with KOH using a phase-transfer catalyst at about 60 °C. The synthesis of 1,1,1,2,2,5,5,6,6,6-decafluoro-3-iodohexane can be carried out by reacting perfluoroethyl iodide (CF3CF2I) and 3,3,4,4,4-pentafluoro-1-butene (CF3CF2CH=CH2) at about 200 °C under autogenous pressure for about 8 hours.

[0087] 1,1,1,4,5,5,5-Heptafluoro-4-(trifluoromethyl)-2-pentene can be prepared by dehydrofluorination of 1,1,1,2,5,5,5-heptafluoro-4-iodo-2-(trifluoromethyl)pentane (CF3CHICH2CF(CF3)2) with KOH in isopropanol. CF3CHICH2CF(CF3)2 is produced from the reaction of (CF3)2CF1 with CF3CH=CH2 at high temperatures, such as 200 °C.

[0088] 1,1,1,4,4,5,5,6,6,6-Decafluoro-2-hexene can be prepared by the reaction of 1,1,1,4,4,4-hexafluoro-2-butene (CF3CH=CHCF3) with tetrafluoroethylene (CF2=CF2) and antimony pentafluoride (SbF5).

[0089] 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 elevated temperature.

[0090] 2,3,3,4,4,5,5,5-Ocatafluoro-1-pentene can be prepared by dehydrofluorination of 2,2,3,3,4,4,5,5,5-nonafluoropentane over solid KOH.

[0091] 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 elevated temperature.

[0092] 2,3,3,3-Tetrafluoro-1-propene can be produced by converting at least one of HCFC-244bb or HFC-245eb to HFO-1234yf.

[0093] 1,3,3,3-Tetrafluoro-1-propene can be converted into HFO-1234ze by HFC-245fa.

[0094] Many of the compounds of Formula I, Formula II, Table 1, Table 2, and Table 3 exist as different configurational isomers or stereoisomers. Unless the specific isomer is indicated, the present invention is intended to include all individual configurational isomers, individual stereoisomers, or any combination thereof. For example, F11E is intended to represent the E-isomer, Z-isomer, or any combination or mixture of both isomers in any ratio. As another example, HFO-1225ye is intended to represent the E-isomer, Z-isomer, or any combination or mixture of both isomers in any ratio.

[0095] In a particular embodiment, the fluoroolefin component of the composition of the invention comprises HFO-1234yf and / or HFO-1234ze. In another particular embodiment, the fluoroolefin comprises HFO-1234yf and / or HFO-1234ze with a purity of greater than 99% by weight, greater than 99.5% by weight, and in some cases, greater than 99.5 to 99.98 percent. In another particular embodiment, the fluoroolefin comprises at least 99.5% by weight of 1234yf or 1234ze and less than 0.5% and more than 0.0001% by weight of the other fluoroolefin, less than 0.3%, and in some cases, less than 0.2%.

[0096] In another particular embodiment, the fluoroolefin component may comprise the compositions disclosed in U.S. Patent Nos. 8,147,709 and 8,877,086, hereby incorporated by reference.

[0097] In another particular embodiment, the fluoroolefin component comprises greater than about 99.5 wt. % 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 isomers) can range from greater than 0 to about 200 wt. ppm, about 1 to about 150 ppm, and in some cases, about 5 to about 50 ppm. The amount of HFO-1243zf may range from about 0.1 to about 250 ppm, from about 10 to about 200 ppm, and in some cases from about 15 to about 150 ppm. The amount of HFO-1234ze (E-isomer) may range from about 1 to about 1,500 ppm, from about 5 to about 1,000 ppm, and in some cases from about 50 to 500 ppm. The amount of HFC-236ea may range from about 1 to about 50 ppm, from about 5 to about 25 ppm, and in some cases from about 10 to about 20 ppm.The amount of HFC-245fa, HFC-245eb, and / or HFC-245cb may range from about 0 to about 20, about 1 to about 15, and in some cases from about 5 to about 10 ppm. The amount of 3,3,3-trifluoropropyne may range from about 0 to about 500 ppm, about 1 to about 300 ppm, and in some cases from about 5 to about 100 ppm.

[0098] In another embodiment, the fluoroolefin component comprises HFO-1234yf and at least one further 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 a particular embodiment, the fluoroolefin component comprises HFO-1234yf and greater than zero and less than about 1 wt. %, less than about 0.5 wt. %, and in some cases less than 0.25 wt. % of additional compounds. In another embodiment, the inhibitor of the present invention can be used with at least one of HCFO-1233zd and HCFO-1224yd, as well as compositions of mixtures comprising at least one of HCFO-1233zd and HCFO-1224yd.

[0099] Any suitable effective amount of inhibitor may be used in the above compositions comprising at least one fluoroolefin. As described herein, the term "effective amount" refers to an amount of the inhibitor of the present invention that, when added to a composition containing at least one fluoroolefin, results in a composition in which the fluoroolefin does not interact with an initiator and / or decompose, such that, for example, when used in a refrigeration device, there is as great a performance degradation as the composition without the inhibitor. For refrigeration devices, such effective amounts of inhibitor can be determined by testing under the conditions of the ASHRAE 97-2007 (RA 2017) standard test.In a particular embodiment of the present invention, an effective amount can be referred to as the amount of inhibitor which, in combination with a composition comprising at least one fluoroolefin, enables a refrigeration device using the composition comprising at least one fluoroolefin to achieve the same cooling performance and cooling capacity as if a composition comprising 1,1,1,2-tetrafluoroethane (R-134a) or another standard refrigerant (R-12, R-22, R-502, R-507A, R-508, R401A, R401B, R402A, R402B, R408, R-410A, R-404A, R407C, R-413A, R-417A, R-422A, R-422B, R-422C, R-422D, R-423, R-114, R-11, R-113, R-123, R-124, R236fa or R-245fa), depending on which refrigerant was used in a similar system in the past when the working fluid would be used.

[0100] The present invention utilizes effective amounts of at least one of the above inhibitors. Although any suitable effective amount may be utilized, effective amounts include from about 0.001 weight percent to about 10 weight percent, from about 0.01 weight percent to about 5 weight percent, from about 0.3 weight percent to about 4 weight percent, from about 0.3 weight percent to about 1 weight percent, based on the total weight of the compositions comprising at least one of the fluoroolefin-containing compositions described herein. In one embodiment, an effective amount comprises from about 10 to about 2,000 ppm by weight, from about 10 to about 1,000 ppm, and in some cases from about 10 to about 500 ppm, of at least one initiator.

[0101] One embodiment of the invention relates to any of the above compositions and further comprises at least one antioxidant. Although any suitable oxidizing agent may be used, examples of suitable oxidizing agents include at least one member selected from the group consisting of butylated hydroxytoluene, butylated hydroxyanisole, tert-butylhydroquinone, gallate, 2-phenyl-2-propanol, 1-(2,4,5-trihydroxyphenyl)-1-butanone, phenols, bisphenolmethane derivatives, 2,2'-methylenebis(4-methyl-6-t-butylphenol), and combinations thereof. The amount of antioxidant may range from about 0.01 to about 5,000 ppm by weight, about 0.03 to about 2,000 ppm, and in some cases, about 0.05 to about 1,000 ppm. An example of a particular embodiment relates to the use of the above antioxidant with at least one inhibitor comprising α-terpinene and limonene.

[0102] An example of a particular embodiment relates to the use of the above antioxidant with an inhibitor comprising at least one of α-terpinene and limonene.

[0103] In one embodiment, the above compositions of the present invention may further comprise at least one additional compound selected from the group consisting of fluoroolefins (as described above), hydrofluorocarbons, hydrocarbons, dimethyl ether, CF3I, ammonia, carbon dioxide (CO2), and mixtures thereof, i.e., mixtures of all additional compounds listed in this paragraph. The amount of the additional compound may range from about 1 to about 90 wt.%, about 5 to about 75 wt.%, and in some cases, about 10 to about 50 wt.%.

[0104] In one embodiment, the additional compounds comprise fluorocarbons. The fluorocarbon compounds (HFCs) of the present invention comprise saturated compounds containing carbon, hydrogen, and fluorine. Particularly useful are fluorocarbons having 1-7 carbon atoms and a normal boiling point of about -90°C to about 80°C. Fluorocarbons are commercial products that are available from numerous sources or can be prepared by methods known in the art. Representative fluorocarbon compounds include fluoromethane (CH3F, HFC-41), difluoromethane (CH2F2, HFC-32), trifluoromethane (CHF3, HFC-23), pentafluoroethane (CF3CHF2, HFC-125), 1,1,2,2-tetrafluoroethane (CHF2CHF2, HFC-134), 1,1,1,2-tetrafluoroethane (CF3CH2F, HFC-134a), 1,1,1-trifluoroethane (CF3CH3, HFC-143a), 1,1-difluoroethane (CHF2CH3, HFC-152a), fluoroethane (CH3CH2F, HFC-161), 1,1,1,2,2,3,3-heptafluoropropane (CF3CF2CHF2,HFC-227ca), 1,1,1,2,3,3,3-Heptafluorpropan (CF3CHFCF3, HFC-227ea), 1,1,2,2,3,3,-Hexafluorpropan (CHF2CF2CHF2, HFC-236ca), 1,1,1,2,2,3-Hexafluorpropan (CF3CF3CH2F, HFC-236cb), 1,1,1,2,3,3-Hexafluorpropan (CF3CHFCHF2, HFC-236ea), 1,1,1,3,3,3-Hexafluorpropan (CF3CH2CF3, HFC-236fa), 1,1,2,2,3-Pentafluorpropan (CHF2CF2CH2F, HFC-245ca), 1,1,1,2,2-Pentafluorpropan (CF3CF2CH3, HFC-245cb), 1,1,2,3,3-Pentafluorpropan (CHF2CHFCHF2, HFC-245ea), 1,1,1,2,3-Pentafluorpropan (CF3CHFCH2F, HFC-245eb), 1,1,1,3,3-Pentafluorpropan (CF3CH2CHF2, HFC-245fa), 1,2,2,3-Tetrafluorpropan (CH2FCF2CH2F, HFC-254ca), 1,1,2,2-Tetrafluorpropan (CHF2CF2CH3, HFC-254cb), 1,1,2,3-Tetrafluorpropan (CHF2CHFCH2F, HFC-254ea), 1,1,1,2-Tetrafluorpropan (CF3CHFCH3, HFC-254eb), 1,1,3,3-Tetrafluorpropan (CHF2CH2CHF2, HFC-254fa), 1,1,1,3-Tetrafluorpropan (CF3CH2CH2F, HFC-254fb), 1,1,1-Trifluorpropan (CF3CH2CH3, HFC-263fb), 2,2-Difluorpropan (CH3CF2CH3, HFC-272ca), 1,2-Difluorpropan (CH2FCHFCH3, HFC-272ea), 1,3-Difluorpropan (CH2FCH2CH2F, HFC-272fa), 1,1-Difluorpropan (CHF2CH2CH3, HFC-272fb), 2-Fluorpropan (CH3CHFCH3, HFC-281ea), 1-Fluorpropan (CH2FCH2CH3, HFC-281fa), 1,1,2,2,3,3,4,4-Octafluorbutan (CHF2CF2CF2CHF2, HFC-338pcc), 1,1,1,2,2,4,4,4-Octafluorbutan (CF3CH2CF2CF3, HFC-338mf), 1,1,1,3,3-Pentafluorbutan (CF3CH2CHF2, HFC-365mfc), 1,1,1,2,3,4,4,5,5,5-Decafluorpentan (CF3CHFCHFCF2CF3, HFC-43-10mee) und 1,1,1,2,2,3,4,5,5,6,6,7,7,7-Tetradecafluorheptan (CF3CF2CHFCHFCF2CF2CF3, HFC-63-14mee).,

[0105] In another embodiment, the additional compounds comprise hydrocarbons. The hydrocarbons of the present invention include compounds having only carbon and hydrogen. Particularly useful are compounds having 3-7 carbon atoms. 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.

[0106] In another embodiment, additional compounds include hydrocarbons containing heteroatoms, such as dimethyl ether (DME, CH3OCH3). DME is commercially available.

[0107] In another embodiment, additional compounds include iodotrifluoromethane (CF3I), which is commercially available from various sources or can be prepared by methods known in the art.

[0108] In another embodiment, additional compounds include carbon dioxide (CO2), which is commercially available from various sources or can be produced by methods known in the art.

[0109] In another embodiment, the above compositions of the present invention are substantially free of additional compounds, and more particularly, substantially free of at least one of dimethyl ether, CF3I, ammonia, and carbon dioxide. In a preferred aspect of this embodiment, the above compositions are substantially free of CF3I. By "substantially free of additional compounds" is meant that the compositions, as well as the inhibitor, contain less than about 10%, usually less than about 5%, and in some cases, 0% of the additional compounds.

[0110] Of particular note are fluoroolefin compositions comprising HFO-1234yf and / or HFO-1234ze and other compounds including: HFO-1225ye and HFC-32; HFO-1225ye and HFC-134a, HFO-1225ye, HFC-134a and HFC-32; HFO-1225ye and HFO-1234yf; HFO-1225ye, HFC-32; HFO-1225ye, HFO-1225ye and HFC-125. Further fluoroolefin compositions comprise a mixture of at least one of HFO-1234yf and HFO-1234ze and i) 134a, 32 and 125; ii) 134a; iii) 227ea; iv) 236fa; and v) 134.

[0111] In other embodiments of the invention, the fluoroolefin comprises at least about 99% by mass of HFO-1234yf and greater 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.

[0112] In other embodiments of the invention, the fluoroolefin comprises at least about 99 mass % HFO-1234ze and greater than 0 but less than 1 mass % at least one member selected from the group consisting of HFO-1234yf, HFC-245fa, HFC-236fa, HFO-1234ye, and combinations thereof.

[0113] In other embodiments of the invention, the fluoroolefin comprises one or more of the above fluoroolefins blended with at least one fluorocarbon. Examples of suitable fluorocarbons include at least one member selected from the group consisting of HFC-32, HFC-125, HFC-134a, HFC-152a, HFC-236fa, and HFC-227ea. The amount of fluorocarbon can range from about 25 to about 75, from about 30 to about 60, and in some cases from about 30 to about 50. In a particular embodiment, the above-mentioned amounts of fluorocarbon are blended with at least one of HFO-1234yf and HFO-1234ze.

[0114] If desired, the blended composition may further contain at least one additional element selected from the group consisting of HCC-40, HCFC-22, CFC-115, HCFC-124, HCFC-1122, and CFC-1113. The amount of the additional element may be greater than 0 to about 5 wt.%, about 0 to about 2 wt.%, and in some cases, about 0 to about 0.5 wt.%. In a particular embodiment, the above-mentioned amounts of additional elements are blended with at least one of HFO-1234yf and HFO-1234ze. In another particular embodiment, the above amounts of additional elements are blended with at least one of HFO-1234yf and HFO-1234ze and at least one hydrofluorocarbon selected from the group consisting of HFC-32, HFC-125, HFC-134a, HFC-152a, HFC-236fa and HFC-227ea, and in some cases combined with carbon dioxide.

[0115] In one embodiment, the above compositions of the present invention may further comprise at least one lubricant. Lubricants of the present invention include those suitable for use with refrigeration or air conditioning devices. Among these lubricants are those conventionally used in compression refrigeration devices utilizing chlorofluorocarbon refrigerants. Such lubricants and their properties are discussed in the 1990 ASHRAE Handbook, Refrigeration Systems and Applications, Chapter 8, entitled "Lubricants in Refrigeration Systems," pages 8.1 to 8.21, hereby incorporated by reference. Lubricants of the present invention may comprise those commonly known in the compression refrigeration lubrication art as "mineral oils." Mineral oils include paraffins (i.e., saturated hydrocarbons having straight and branched carbon chains), naphthenes (i.e.saturated hydrocarbons with a cyclic or ring structure, which may be paraffins) and aromatics (i.e., unsaturated cyclic hydrocarbons containing one or more rings characterized by alternating double bonds). Lubricants of the present invention further include those commonly known in the compression lubrication art as "synthetic oils." Synthetic oils include alkylaryls (i.e., linear and branched alkylbenzenes), synthetic paraffins and naphthenes, silicones, and poly-alpha-olefins. Representative conventional lubricants of the present invention are the commercially available BVM 100 N (paraffinic mineral oil, marketed by BVA Oils), naphthenic mineral oil, commercially available under the trademark Suniso® 3GS and Suniso® 5GS from Crompton Co., naphthenic mineral oil, commercially available from Pennzoil under the trademark Sontex® 372LT, naphthenic mineral oil, commercially available from Calumet Lubricants under the trademark Calumet® RO-30, linear alkylbenzenes, commercially available from Shrieve Chemicals under the trademarks Zerol® 75, Zerol® 150 and Zerol® 500 and branched alkylbenzene, marketed by Nippon Oil as HAB 22.

[0116] In another embodiment, lubricants of the present invention include those designed for use with fluorocarbon refrigerants and miscible with refrigerants of the present invention under compression refrigeration or refrigeration and air conditioning operating conditions. Such lubricants and their properties are discussed in "Synthetic Lubricants and High-Performance Fluids," R.L. Shubkin, Ed., Marcel Dekker, 1993. Such lubricants include, but are not limited to, polyol esters (POEs) such as Castrol® 100 (Castrol, UK), polyalkylene glycols (PAGs) such as RL 488A from Dow (Dow Chemical, Midland, Michigan), and polyvinyl ethers (PVEs).

[0117] Lubricants of the present invention are selected taking into account the requirements of a given compressor and the environment to which the lubricant will be exposed. The amount of lubricant may range from about 1 to about 50, about 1 to about 20, and in some cases, about 1 to about 3. In a particular embodiment, the above compositions are combined with a PAG lubricant for use in an automotive air conditioning system with an internal combustion engine. In another particular embodiment, the above compositions are combined with a POE lubricant for use in an automotive air conditioning system with an electric or hybrid-electric powertrain.

[0118] In one embodiment of the invention, the composition may comprise, in addition to the inhibitor of the invention, at least one additive capable of improving the service life of the refrigerant and the air conditioning system, with compressor durability also being desirable. In one aspect of the invention, the above compositions comprise at least one element selected from the group consisting of acid scavengers, performance enhancers, and flame retardants.

[0119] Additives that can improve the service life of the refrigerant and the air conditioning system, as well as the durability of the compressor, are desirable. In one aspect of the invention, the refrigerant-containing composition of the invention is used to introduce lubricants and other additives such as a) acid scavengers, b) performance enhancers, and c) flame retardants into the air conditioning system.

[0120] An acid scavenger can be a siloxane, an activated aromatic compound, or a combination of both. Serrano et al. (paragraph 38 of US 2011 / 0272624 A1), which is hereby incorporated by reference, discloses that the siloxane can be any molecule having a siloxy functionality. The siloxane can be an alkylsiloxane, an arylsiloxane, or a siloxane having mixtures of aryl and alkyl substituents. For example, the siloxane can be an alkylsiloxane, including a dialkylsiloxane or a polydialkylsiloxane. Preferred siloxanes contain one oxygen atom bonded to two silicon atoms, i.e., a group having the structure: SiOSi. For example, the siloxane can be a siloxane of formula IV: R1 [Si(R2R3)4O]nSi(R2R3)R4, where n is 1 or more. Siloxanes of formula IV have n which is preferably 2 or more, more preferably 3 or more (e.g. 4 or more).Siloxanes of formula IV have n that is preferably 30 or less, more preferably 12 or less, and most preferably 7 or less. Preferably, the R4 group is an aryl group or an alkyl group. Preferably, the R2 groups are aryl groups or alkyl groups, or mixtures thereof. Preferably, the R3 groups are aryl groups or alkyl groups, or mixtures thereof. Preferably, the R4 group is an aryl group or an alkyl group. Preferably, R1, R2, R3, R4, or any combination thereof is not hydrogen. The R2 groups in a molecule may be the same or different. Preferably, the R2 groups in a molecule are the same. The R2 groups in a molecule may be the same or different from the R3 groups. Preferably, the R2 groups and R3 groups in a molecule are the same.Preferred siloxanes include siloxanes of formula IV, wherein R1, R2, R3, R4, R5, or any combination thereof is methyl, ethyl, propyl, or butyl, or any combination thereof. Examples of useful siloxanes include hexamethyldisiloxane, polydimethylsiloxane, polymethylphenylsiloxane, dodecamethylpentasiloxane, decamethylcyclopentasiloxane, decamethyltetrasiloxane, octamethyltrisiloxane, or any combination thereof.

[0121] In paragraph

[0039] of Serrano et al., incorporated by reference, it is noted that in one aspect of the invention, the siloxane is an alkylsiloxane having from 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 from about 100 to about 10,000. Particularly preferred siloxanes include hexamethyldisiloxane, polydimethylsiloxane, and combinations thereof. The siloxane may consist essentially of polydimethylsiloxane, hexamethyldisiloxane, or a combination thereof.

[0122] The activated aromatic compound can be any aromatic molecule that is activated for a Friedel-Crafts addition reaction, or mixtures thereof. An aromatic molecule that is activated for a Friedel-Crafts addition reaction is defined as any aromatic molecule capable of an addition reaction with mineral acids. In particular, these are aromatic molecules with the ability to undergo addition reactions with mineral acids either in the application environment (air conditioning system) or during thermal stability testing ASHRAE 97: 2007 “Sealed Glass Tube Method to Test the Chemical Stability of Materials for Use within Refrigerant Systems”. Such molecules or compounds are typically activated by substitution of a hydrogen atom or a hydrogen atom.Hydrogen atoms of the aromatic ring are replaced by 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 1 to 100 carbon atoms). The activated aromatic molecule may be an alcohol or an ether wherein the oxygen atom (i.e., the oxygen atom of the alcohol or ether group) is directly bonded to an aromatic group. The activated aromatic molecule may be an amine wherein the nitrogen atom (i.e., the nitrogen atom of the amine group) is directly bonded to an aromatic group. For example, the activated aromatic molecule may have the formula ArXRn, where X is O (i.e., oxygen) or N (i.e., nitrogen); n:1 when X:O; n:2 when X:N; Ar is an aromatic group (i.e., 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 a refrigerant composition 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 for a Friedel-Crafts addition reaction is diphenyl oxide.

[0123] Incorporated by reference from Serrano et al., paragraph

[0045] . The acid scavenger (e.g., the activated aromatic compound, the siloxane, or both) can be present at any concentration that results in a relatively low total acid number, a relatively low total halide concentration, a relatively low total organic acid concentration, or any combination thereof. Preferably, the acid scavenger is present at a concentration of greater than about 0.0050 wt. %, more preferably greater than about 0.05 wt. %, and even more preferably greater than about 0.1 wt. % (e.g., greater than about 0.5 wt. %), based on the total weight of the refrigerant composition. The acid scavenger is preferably present at a concentration of less than about 3 wt. %, more preferably less than about 2.5 wt. %, and most preferably greater than about 2 wt. % (e.g., less than about 1.8 wt. %), based on the total weight of the refrigerant composition.

[0124] Additional examples of acid scavengers that may be included in the refrigerant composition and are preferably excluded from the refrigerant composition include those described by Kaneko (U.S. Patent Application Ser. No. 11 / 575,256, published as U.S. Patent Publication 2007 / 0290164, paragraph 42, hereby expressly incorporated by reference), such as one or more of: phenyl glycidyl ethers, alkyl glycidyl ethers, alkylene glycol glycidyl ethers, cyclohexene oxides, olefin oxides, or epoxy compounds such as epoxidized soybean oil, and those described by Singh et al. (U.S. Patent Application Ser. No. 11 / 250,219, published as 20060116310, paragraphs 34-42, hereby expressly incorporated by reference).

[0125] Preferred additives include those described in U.S. Pat. Nos. 5,152,926; 4,755,316, which are hereby incorporated by reference. In particular, the preferred extreme pressure additives comprise mixtures of (A) tolyltriazole or substituted derivatives thereof, (B) an amine (e.g., Jeffamine M-600), and (C) a third component which is (i) an ethoxylated phosphate ester (e.g., Antara LP-700 type), or (ii) a phosphate alcohol (e.g., ZELEC 3337 type), or (iii) a zinc dialkyldithiophosphate (e.g., Lubrizol 5139, 5604, 5178, or 5186 type), or (iv) a mercaptobenzothiazole, or (v) a 2,5-dimercapto-1,3,4-triadiazole derivative (e.g., Curvan 826), or a mixture thereof. Additional examples of useful additives are given in U.S. Pat. No. 5,976,399 (Schnur, 5:12-6:51, hereby incorporated by reference).

[0126] The acid number is measured according to ASTM D664-01 in units of mg KOH / g. The total halide concentration, the fluorine ion concentration, and the total organic acid concentration are measured by ion chromatography. The chemical stability of the refrigerant system is measured according to ASHRAE 97:2007 (RA 2017) "Sealed Glass Tube Method to Test the Chemical Stability of Materials for Use within Refrigerant Systems." The viscosity of the lubricant is tested at 40°C according to ASTM D-7042.

[0127] Mouli et al. (WO 2008 / 027595 and WO 2009 / 042847) teach the use of alkylsilanes as stabilizers in refrigerant compositions containing fluoroolefins. Phosphates, phosphites, epoxides, and phenolic additives are also used in certain refrigerant compositions. These are described, for example, by Kaneko (US Patent Application Serial No. 11 / 575,256, published as US Publication 2007 / 0290164) and Singh et al. (US Patent Application Serial No. 11 / 250,219, published as US Publication 2006 / 0116310). All of the aforementioned applications are expressly incorporated herein by reference.

[0128] Preferred flame retardants include those described in patent application "Compositions containing fluorine substituted olefins CA 2557873 A1" and incorporated by reference, along with fluorinated products such as HFC-125 and / or Krytox® lubricants, also incorporated by reference and described in patent application "Compositions comprising fluoroolefins and uses thereof WO2009018117A1".

[0129] The compositions of the present invention can be prepared by any convenient method to combine the desired amounts of the individual components. A preferred method is to weigh the desired amounts of components and then combine the components in an appropriate container. Stirring may be used if desired.

[0130] The present invention further relates to a method for producing cooling comprising condensing a composition comprising at least one fluoroolefin and an effective amount of inhibitor, and thereafter evaporating the composition in the vicinity of a body to be cooled.

[0131] A body to be cooled can be any space, place, or object that requires cooling or air conditioning. In stationary applications, the body can be the interior of a structure, i.e., a residential or commercial structure, or a storage location for perishable goods such as food or pharmaceuticals. For mobile refrigeration applications, the body can be incorporated into a transport unit for road, rail, sea, or air. Certain refrigeration systems operate independently with respect to each moving carrier, and these are known as "intermodal" systems. Such intermodal systems include "containers" (combined sea / land transport) and "swap bodies" (combined road / rail transport).

[0132] The present invention further relates to a method for generating heat comprising condensing the composition of the invention comprising at least one fluoroolefin and an effective amount of an inhibitor comprising at least one of limonene and α-terpinene in the vicinity of a body to be heated, and thereafter evaporating the composition.

[0133] An object to be heated can be any space, place, or object that requires heat. Similar to the object to be cooled, this can be the interior of structures, either residential or commercial. Furthermore, mobile units described for cooling may be similar to those that require heating. Certain transport units require heating to prevent the material being transported from solidifying inside the transport container.

[0134] Another embodiment of the invention relates to an air conditioning or cooling or refrigerating device comprising the above compositions according to the invention.

[0135] Another embodiment of the invention relates to storage of the above compositions in gaseous and / or liquid phase within a tightly sealed container, wherein the oxygen and / or water concentration in the gaseous and / or liquid phase is in the range of 3 vol ppm to below 3,000 vol ppm at a temperature of 25°C, 5 vol ppm to below 1,000 vol ppm and, in some cases, 5 vol ppm to below 500 vol ppm.

[0136] The container for storing the above compositions can be constructed of any suitable material and structure capable of tightly containing the compositions therein while maintaining gaseous and liquid phases. Examples of suitable containers include pressure-resistant containers such as a tank, a filling cylinder, and a secondary filling cylinder. The container can be constructed of any suitable material, such as carbon steel, manganese steel, chromium-molybdenum steel, among other low-alloy steels, stainless steel, and, in some cases, an aluminum alloy. The container can include a pierceable lid or valves suitable for dispensing flammable substances.

[0137] While any suitable method for stabilizing fluorocarbon-containing compositions may be employed, examples of such methods include mixing the above inhibitors with the above fluoroolefin composition, purging lines and containers with a material comprising the inhibitor (e.g., an inhibitor with a nitrogen carrier or the stabilized composition of the present invention), among other suitable methods.

[0138] The following examples are provided to illustrate certain embodiments of the invention and are not intended to limit the scope of the appended claims. EXAMPLE 1

[0139] A mixture of HFO-1234yf (30 g with a purity of at least 99.5 wt%*) and initiator (and no inhibitor) was heated in a 210 mL shake tube at the temperature and for the time specified in Table 4. The shake tube was visually inspected for polymer formation and analyzed by IR according to conventional methods by detecting yf polymer peaks. Polymers can also be detected using conventional NMR techniques.

[0140] *The HFO-1234yf consisted of 99.7 wt% HFO-1234yf, 1000 ppm HFO-1234ze, 150 ppm HFO-1225yeZ, 3 ppm trifluoropropyne; the remainder comprised of compounds that did not affect the performance of the blend or initiator. TABLE 4 Examples Inhibitor Concentration (ppm) initiator Time T (°C) Polymer (wt%) Control-1 None Air (3300 ppm) 2 weeks 75 0,003 1 d-Limonen 50 ppm Air (3300 ppm) 2 weeks 75 N / D 2 d-Limonen 100 ppm Air (3300 ppm) 2 weeks 75 N / D 3 α-Terpinen 100 ppm Air (3300 ppm) 2 weeks 75 N / D Control-2 None Air (10,000 ppm) 2 weeks 100 2,8 4 d-Limonen 500 ppm Air (10,000 ppm) 2 weeks 100 <1 5 d-Limonen 1000 ppm Air (10,000 ppm) 2 weeks 100 <1 6 α-Terpinen 1000 ppm Air (10,000 ppm) 2 weeks 100 <1 Control-3 None Cumene hydroperoxide (1700 ppm) 3 days 50 0,07 7 d-Limonen 100 ppm Cumene hydroperoxide (1700 ppm) 3 days 50 N / D 8 α-Terpinen 100 ppm Cumene hydroperoxide (1700 ppm) 3 days 50 N / D Control-4 None Air (3300 ppm) 2 weeks 50 0,05 9 d-Limonen 100 ppm Air (3300 ppm) 2 weeks 150 <0,003 10 d-Limonen 200 ppm Air (3300 ppm) 2 weeks 150 N / D 11 α-Terpinen 200 ppm Air (3300 ppm) 2 weeks 150 N / D Control-5 None Air (6600 ppm) 2 weeks 150 1,34 12 d-Limonen 100 ppm Air (6600 ppm) 2 weeks 100 <0,003 13 d-Limonen 200 ppm Air (6600 ppm) 2 weeks 100 N / D 14 α-Terpinen 200 ppm Air (6600 ppm) 2 weeks 100 N / D 15 α-Terpinene + butylated hydroxytoluene 200 ppm Air (6600 ppm) 2 weeks 100 N / D 16 d-Limonene + butylated hydroxytoluene 200 ppm Air (6600 ppm) 2 weeks 100 N / D Control-6 None Air (6600 ppm) 2 weeks 101 0,003 Control-7 None Air (10,000 ppm) 2 weeks 40 0,01 17 d-Limonen 200 Air (6600 ppm) 2 weeks 40 N / D 18 d-Limonen 200 Air (10,000 ppm) 2 weeks 40 N / D 19 α-Terpinen 200 Air (6600 ppm) 2 weeks 40 N / D 20 α-Terpinen 200 Air (10,000 ppm) 2 weeks 40 N / D 21 α-Terpinene + butylated hydroxytoluene 200 Air (6600 ppm) 2 weeks 40 N / D 22 d-Limonene + butylated hydroxytoluene 200 Air (10,000 ppm) 2 weeks 40 N / D EXAMPLE 2

[0141] A refrigerant mixture consisting of a mixture of HFO-1234yf (30 g with the composition of Example 1), at least one other compound, and an initiator (and no inhibitor) was heated in a 210 ml shake tube at the temperature and for the time specified in Table 5. In Examples 1-6, an inhibitor is evaluated using the refrigerant Opteon™ XP-10 (R513a) and a commercially available lubricant. In Examples 7-12, an inhibitor is evaluated using the refrigerant Opteon™ XP-40 (R449a) and a commercially available lubricant. In Examples 13-18, an inhibitor is evaluated using HFO-1234yf and a commercially available lubricant. Refrigerant XP10 comprises 56 wt% HFO-1234yf and 44 wt% HFC-134a, and refrigerant XP40 comprises 24.3 wt% R32, 24.7 wt% R125, 25.3 wt% 1234yf, and 25.7 wt% 134a. Refrigerants XP10 and XP40 are commercially available from The Chemours Company.The shake tube was checked for polymer formation both visually and by IR. The data presented below are ppm by weight. TABLE 5 Examples Inhibitor Concentration (ppm) lubricant initiator Time T (°C) Polymer (wt%) control None Air (2000 ppm) 2 weeks 135 0,003 1 d-Limonen 100 POE32-3MAF Air (2000 ppm) 2 weeks 135 N / D 2 α-Terpinen 100 POE32-3MAF Air (2000 ppm) 2 weeks 135 N / D 3 d-Limonen 100 ND-11 Air (2000 ppm) 2 weeks 135 N / D 4 α-Terpinen 100 ND-11 Air (2000 ppm) 2 weeks 135 N / D 5 d-Limonen 100 ND-12 Air (2000 ppm) 2 weeks 135 N / D 6 α-Terpinen 100 ND-12 Air (2000 ppm) 2 weeks 135 N / D control None Air (1000 ppm) 2 weeks 135 0,003 7 d-Limonen 50 POE32-3MAF Air (1000 ppm) 2 weeks 135 N / D 8 α-Terpinen 50 POE32-3MAF Air (1000 ppm) 2 weeks 135 N / D 9 d-Limonen 50 ND-11 Air (1000 ppm) 2 weeks 135 N / D 10 α-Terpinen 50 ND-11 Air (1000 ppm) 2 weeks 135 N / D 11 d-Limonen 50 ND-12 Air (1000 ppm) 2 weeks 135 N / D 12 α-Terpinen 50 ND-12 Air (1000 ppm) 2 weeks 135 N / D control None 2 weeks 100 2,8 13 d-Limonen 100 POE32-3MAF Air (10,000) 2 weeks 100 N / D 14 α-Terpinen 100 POE32-3MAF Air (10,000) 2 weeks 100 N / D 15 d-Limonen 100 ND-11 Air (10,000) 2 weeks 100 N / D 16 α-Terpinen 100 ND-11 Air (10,000) 2 weeks 100 N / D 17 d-Limonen 100 ND-12 Air (10,000) 2 weeks 100 N / D 18 α-Terpinen 100 ND-12 Air (10,000) 2 weeks 100 N / D

[0142] Although certain aspects, embodiments, and principles have been described above, it should be understood that this description is merely exemplary and does not serve as a limitation on the scope of the invention or the appended claims. The above various aspects, embodiments, and principles may be used alone or in combination with one another. QUOTES CONTAINED IN THE DESCRIPTION

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[0096] US 2011 / 0272624 A1

[0120] US 11 / 250,219 [0124, 0127] US 20060116310

[0124] US- Pat. Nr. 5,152,926

[0125] US 4,755,316

[0125] US- Pat. Nr. 5,976,399

[0125] WO 2008 / 027595

[0127] WO 2009 / 042847

[0127] US 11 / 575,256

[0127] US 2007 / 0290164

[0127] CA 2557873 A1

[0128] WO 2009018117A1

[0128] Cited non-patent literature

[0000] Eanneaux et al. in Journal of Fluorine Chemistry, Vol. 4, pages 261-270 (1974

[0062]

Claims

[1] A composition comprising at least one fluoroolefin and 10 to 3,000 ppm of at least one inhibitor selected from the group consisting of limonene and α-terpinene, wherein the composition contains less than 1 wt.% oligomeric, homopolymeric, or other polymeric products derived from the fluoroolefin, and wherein the fluoroolefin comprises HFO-1234yf. [2] The composition of claim 1, wherein the at least one inhibitor is present in an amount of 10 to 2,000 ppm, preferably 30 to 1,000 ppm, more preferably 50 to 1,000 ppm. [3] The composition of claim 1, wherein the at least one inhibitor is present in an amount of 30 to 3,000 ppm. [4] The composition according to any one of claims 1 to 3, further comprising at least one member selected from the group consisting of HFC-134a, HFO-1225ye, HFO-1234ze, HFC-245cb and HFC-245eb [5] The composition of any one of claims 1 to 4, further comprising HFC-245eb. [6] The composition of any one of claims 1 to 5, further comprising HFO-1225ye(Z). [7] A composition according to any one of claims 1 to 6, further comprising HFO-1234ze(E). [8] The composition according to any one of claims 1 to 3, wherein the composition further comprises at least one member selected from the group consisting of HFC-134a, HFO-1225ye(Z), HFO-1234ze(E), HFC-245cb and HFC-245eb. [9] The composition of any one of claims 1 to 8, further comprising at least one member selected from the group consisting of HCC-40, HCFC-22, CFC-115, HCFC-124, HCFC-1122 and CFC-1113. [10] The composition of any one of claims 1 to 3, wherein the fluoroolefin comprises more than 99.5 wt.% HFO-1234yf and one or more members selected from the group consisting of HFO-1225ye, HFO-1234ze, HFC-245eb, HFC-245cb, and mixtures thereof. [11] The composition of claim 10, wherein the amount of HFO-1225ye (E / Z isomers) is in a range of more than 0 to 200 ppm by weight, the amount of HFO-1234ze (E isomer) is in a range of 1 to 1,500 ppm, and the amount of HFC-245eb and / or HFC-245cb is in a range of 0 to 20 ppm. [12] Composition according to any one of claims 1 to 11, wherein the composition comprises less than 0.07% by weight, preferably less than 0.03% by weight, of oligomeric, homopolymeric or other polymeric products. [13] The composition of any one of claims 1 to 12, further comprising at least one member selected from the group consisting of air, oxygen, cumene hydroperoxide and fluoroolefin polyperoxides, peroxides, hydroperoxides, persulfates, percarbonates, perborates and hydropersulfates. [14] Composition according to any one of claims 1 to 13, further comprising at least one lubricant. [15] A container with a refrigerant comprising the composition according to any one of claims 1 to 14.