Compositions containing 2,3,3,3-tetrafluoropropene and oxidation products

Abstract

Disclosed are compositions comprising HFO-1234yf, an inhibitor, and an oxidation product derived from the inhibitor. Such compositions are useful as heat transfer compositions for use in refrigeration, air conditioning, and heat pump systems, among other applications.

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) This application claims priority to U.S. Provisional Patent Application No. 63 / 158,103, filed March 8, 2021, the disclosure of which is incorporated herein by reference in its entirety.

[0002] FIELD OF THEINVENTION The present invention relates to compositions comprising 2,3,3,3-tetrafluoropropene and an inhibitor. [Background technology]

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

[0004] There is a need for alternative refrigerants with low GWP, low toxicity, low or non-flammability, reasonable cost and excellent refrigeration performance. Fluoroolefins meet these criteria. In addition, desirable properties of refrigerants include ease of detection in case of leaks, performance such as efficiency and capacity in refrigeration applications, solubility in lubricants used in such applications, and compatibility with components used in such applications.

[0005] 2,3,3,3-Tetrafluoropropene (HFO-1234yf, R-1234yf, or 1234yf) is an example of a fluoroolefin with low global warming potential (GWP) and is a replacement for high GWP hydrofluorocarbons and / or ozone-depleting hydrochlorofluorocarbons in many applications such as refrigeration, air conditioning, heating and cooling, power cycles, etc. Improved properties of compositions containing 1234yf are desirable.

[0006] Description of Related Art 1234yf is a stable molecule when used in heat transfer applications such as refrigeration and air conditioning. However, 1234yf can oligomerize or homopolymerize in the presence of radical initiators such as air, which may be unintentionally introduced.

[0007] WO 2019 / 213004 discloses compositions containing fluoroolefins and certain inhibitors to increase the stability of the fluoroolefins during packaging and storage, and during use in refrigeration or air conditioning systems. Terpenes, such as limonene, α-terpinene, and α-pinene, are disclosed to be effective in preventing polymerization reactions, as determined by visual inspection of 1234yf samples treated with the listed terpenes. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] U.S. Provisional Patent Application No. 63 / 158,103 [Patent Document 2] International Publication No. 2019 / 213004 Summary of the Invention [Means for solving the problem]

[0009] The present disclosure provides a composition comprising 2,3,3,3-tetrafluoropropene, a terpene inhibitor, and one or more oxidation products, the oxidation products being oxidation products of the terpene inhibitor. The terpene inhibitor may be selected from one or more of limonene, α-terpinene, α-pinene, and β-pinene.

[0010] The oxidation product may be an oxidation product of limonene selected from at least one of carvone, carveol (Z- and E-), and limonene oxide (Z- and E-), as shown below.

[0011] [ka]

[0012] When the inhibitor comprises limonene, the composition may further comprise one or more of the following alpha-terpenes: cymene, 1-octanol, gamma-terpinene, terpinolene, and beta-terpinene.

[0013] The oxidation product can be an oxidation product of alpha-terpinene selected from at least one of 3-isopropyl-6-methyl-7-oxabicyclo[4.1.0]hept-2-ene, 6-isopropyl-3-methyl-7-oxabicyclo[4.1.0]hept-2-ene, 1-isopropyl-4-methyl-cyclohex-2-ene-1,4-diol, E-3-isopropyl-6-methylhepta-2,6-dienal, p-cymene, and propane, all of which are as shown below except for propane.

[0014] [ka]

[0015] When the inhibitor comprises alpha-terpinene, the composition may further comprise one or more of camphene, isocamphene, terpinolene, menthomenthene, phellandrene, sabinene, beta-terpinene, 1,4-cineole, carbomenthene oxide, d-limonene, 1,8-cineole, gamma-terpinene.

[0016] The oxidation product may be an oxidation product of α-pinene, where the oxidation product is α-pinene oxide, as shown below.

[0017] [ka]

[0018] When the inhibitor includes α-pinene, the composition may further include one or more of 5-methyl-4-nonene, α-thujene, tricyclene (1,7,7-trimethyltricyclo[2.2.1.02,6]heptane), α-fenkene, camphene, cymene, d-limonene, α-camphorenal.

[0019] The oxidation product may be an oxidation product of β-pinene selected from at least one of pinocarveol and myrtenol, as shown below.

[0020] [ka]

[0021] When the inhibitor comprises β-pinene, the composition may further comprise one or more of α-pinene, α-fenkene, camphene, verbenene, myrcene, phellandrene, camphane, cymene, and 2-menthene.

[0022] The oxidation products may include oxidation products of two or more terpene inhibitors.

[0023] The composition may be HCC-40, CFC-12, HFC-23, HFC-134a, HFC-143a, HFC-152a, HCFC-225ca, HCFC-225cb, HCFC-244bb, HFC-245cb, HFC-254eb, HFC-263fb, HFO-1123, HFO-1243zf, HFO-1225ye (E- and / or Z-isomers), HFO-1225zc, It may further comprise additional compounds selected from at least one of HFO-1234ze (E- and / or Z-isomer), 3,3,3-trifluoro-1-propyne, HCFO-1233xf, HCFO-1122, HCO-1140, HCFO-1131 (E- and / or Z-isomer), HCFO-1131a, HCFC-124, HCFC-124a, and HCFC-142b.

[0024] The composition may further comprise an additional compound selected from at least one of CHF(CF3)CH2CH=CF(CF3), CHF(CF3)CH=CHCHF(CF3), CF(CF3)=CHCH2CF(CF3)CH2CHF(CF3), CF3C(=O)CH3, formaldehyde, acetaldehyde, trioxane, and trifluoroacetic acid.

[0025] The composition may further comprise an additional compound selected from at least one of Z-HFO-1336mzz, E-HFO-1336mzz, HFO-1327mz, HCFO-1122, HCFO-1122a, HFO-1123, E-HFO-1233zd, Z-HFO-1224yd, E-HFO-1132, Z-HFO-1132, HFO-1132a, HCFO-1112, HFO-1234zc, HFO-1234ye, and HFO-1234yc.

[0026] These additional compounds can be obtained from commercial suppliers or prepared by known methods. The additional compounds can be added in any desired amount. Alternatively, some of the additional compounds can be produced simultaneously in the process of producing the composition comprising 2,3,3,3-tetrafluoropropene and one or more oligomers. In that case, the total amount of the one or more additional compounds can be desirably controlled by the purification process.

[0027] The compositions disclosed herein may be useful as heat transfer compositions, aerosol propellants, foaming agents, blowing agents, solvents, cleaning agents, dispersion media, displacement drying agents, buffing agents, polymerization media, blowing agents for polyolefins and polyurethanes, gas dielectrics, fire extinguishing agents, and fire suppression agents in liquid or gas form.

[0028] In particular, the compositions disclosed herein are useful in applications as heat transfer compositions. Such applications include use as refrigerant compositions. The refrigerant compositions may further include lubricants such as polyol esters (POE), polyalkylene glycols (PAG), polyvinyl ethers (PVE) and synthetic hydrocarbon oils. The compositions disclosed herein may improve the performance of heat transfer compositions with lubricants in such applications.

[0029] Surprisingly, it has been found herein that the addition of oxidation products of terpene stabilizers improves the performance of the resulting composition as a refrigerant or heat transfer composition. The presence of the oxidation products listed above improves the solubility of 1234yf in lubricants. In certain instances, p-cymene provides antioxidant properties to the disclosed compositions. Propane is a telogen that can terminate polymer chain growth. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0030] composition Tetrafluoropropene The tetrafluoropropene component of the composition is 2,3,3,3-tetrafluoropropene (1234yf), which is commercially available or can be produced by a variety of known methods. Suitable sources of 1234yf have a purity (concentration of 1234yf relative to other components) of at least 99.95% by weight, or at least 99.9% by weight, or at least 99.8% by weight, or at least 99.5% by weight, or at least 99% by weight.

[0031] Inhibitors The compositions disclosed herein include a terpene inhibitor. Specific examples of inhibitor compounds can be selected from limonene, alpha-terpinene, alpha-pinene, and beta-pinene.

[0032] Additional inhibitors may be present, which may include one or more of α-tocopherol, butylated hydroxytoluene, 4-methoxyphenol, and benzene-1,4-diol. In one embodiment, the inhibitor includes α-terpinene. In one embodiment, the inhibitor includes limonene. In one embodiment, the inhibitor includes α-pinene. In one embodiment, the inhibitor includes β-pinene.

[0033] In one embodiment, the composition comprises limonene or alpha-terpinene, optionally containing antioxidants, which have a unique aroma even at a few ppm level. This pleasant odor can be utilized in heat transfer applications, for example for leak detection of the composition. This is particularly useful for early detection of refrigerant leaks in home or mobile air conditioners, since paraprofessional electronic leak detectors are often not available everywhere.

[0034] While any suitable amount of terpene inhibitors can be used, effective amounts of terpene inhibitors include 0.001% to 10%, 0.01% to 5%, 0.3% to 4%, 0.3% to 1% by weight based on the total weight of the composition, hi one embodiment, an effective amount includes 10 to 2000 ppm, or 10 to 1000 ppm, or 10 to 500 ppm of at least one terpene inhibitor.

[0035] When additional inhibitors are present, the total amount of inhibitors (including the terpene inhibitor and the additional inhibitor) may be in the range of 0.001% to 10% by weight, 0.01% to 5% by weight, 0.3% to 4% by weight, or 0.3% to 1% by weight, based on the total weight of the composition.

[0036] Oxidation Products The compositions disclosed herein include one or more oxidation products of the terpene inhibitor.The oxidation products can be selected from one or more of carvone, carveol, limonene oxide, 3-isopropyl-6-methyl-7-oxabicyclo[4.1.0]hept-2-ene, 6-isopropyl-3-methyl-7-oxabicyclo[4.1.0]hept-2-ene, 1-isopropyl-4-methyl-cyclohex-2-ene-1,4-diol, E-3-isopropyl-6-methylhepta-2,6-dienal, p-cymene, propane, α-pinene oxide, pinocarveol and myrtenol.

[0037] When the inhibitor is limonene, the oxidation product may be at least one of carvone, carveol, and limonene oxide, as shown above. In one embodiment, when the inhibitor is limonene, the oxidation product is limonene oxide. In one embodiment, when the inhibitor is limonene, the oxidation product is carvone. In one embodiment, when the inhibitor is limonene, the oxidation product is carveol. In one embodiment, when the inhibitor is limonene, the oxidation product is two or more of limonene oxide, carvone, and carveol.

[0038] When the inhibitor is α-terpinene, the oxidation product is at least one of 3-isopropyl-6-methyl-7-oxabicyclo[4.1.0]hept-2-ene, 6-isopropyl-3-methyl-7-oxabicyclo[4.1.0]hept-2-ene, 1-isopropyl-4-methyl-cyclohex-2-ene-1,4-diol, E-3-isopropyl-6-methylhepta-2,6-dienal, p-cymene, and propane, all of which are as exemplified above except for propane. In one embodiment, when the inhibitor is α-terpinene, the oxidation product is 3-isopropyl-6-methyl-7-oxabicyclo[4.1.0]hept-2-ene. In one embodiment, when the inhibitor is α-terpinene, the oxidation product is 6-isopropyl-3-methyl-7-oxabicyclo[4.1.0]hept-2-ene. In one embodiment, when the inhibitor is alpha-terpinene, the oxidation product is 1-isopropyl-4-methyl-cyclohex-2-ene-1,4-diol. In one embodiment, when the inhibitor is alpha-terpinene, the oxidation product comprises E-3-isopropyl-6-methylhepta-2,6-dienal. In one embodiment, when the inhibitor is alpha-terpinene, the oxidation product comprises p-cymene. In one embodiment, when the inhibitor is alpha-terpinene, the oxidation product comprises propane. In one embodiment, when the inhibitor is alpha-terpinene, the oxidation products include a combination of two or more of 3-isopropyl-6-methyl-7-oxabicyclo[4.1.0]hept-2-ene, 6-isopropyl-3-methyl-7-oxabicyclo[4.1.0]hept-2-ene, 1-isopropyl-4-methyl-cyclohex-2-ene-1,4-diol, E-3-isopropyl-6-methylhepta-2,6-dienal, p-cymene, and propane.

[0039] When the inhibitor is α-pinene, the oxidation products include α-pinene oxide as described above.

[0040] When the inhibitor is β-pinene, the oxidation product comprises at least one of pinocarveol and myrtenol, as shown above. In one embodiment, when the inhibitor is β-pinene, the oxidation product comprises pinocarveol. In one embodiment, when the inhibitor is β-pinene, the oxidation product comprises myrtenol. In one embodiment, when the inhibitor is β-pinene, the oxidation product comprises pinocarveol and myrtenol.

[0041] While any suitable amount of oxidation product can be used, effective amounts of oxidation product include from 0.0001% to 10%, from 0.01% to 5%, from 0.3% to 4%, from 0.3% to 1% by weight based on the total weight of the composition, in one embodiment, an effective amount includes from 10 to 2000 ppm, or from 10 to 1000 ppm, or from 10 to 500 ppm of at least one oxidation product.

[0042] When two or more oxidation products are present, the total amount of oxidation products may be in the range of 0.0001 wt.% to 10 wt.%, 0.01 wt.% to 5 wt.%, 0.3 wt.% to 4 wt.%, 0.3 wt.% to 1 wt.%, based on the total weight of the composition.

[0043] Additional Compounds The composition may further comprise one or more additional compounds. The additional compounds may provide some other benefits, such as improved refrigerant performance or improved compatibility with additives such as lubricants. Improved refrigerant performance may include higher capacity or better efficiency.

[0044] Additional compounds include HCC-40, CFC-12, HFC-23, HFC-134a, HFC-143a, HFC-152a, HCFC-225ca, HCFC-225cb, HCFC-244bb, HFC-245cb, HFC-254eb, HFC-263fb, HFO-1123, HFO-1243zf, HFO-1225ye (E- and / or Z-isomers), ), HFO-1225zc, HFO-1234ze (E- and / or Z-isomers), 3,3,3-trifluoro-1-propyne, HCFO-1233xf, HCFO-1122, HCO-1140, HCFO-1131 (E- and / or Z-isomers), HCFO-1131a, HCFC-124, HCFC-124a and HCFC-142b. These and other additional compounds are listed in Table 1.

[0045] The additional compound may be selected from at least one of CHF(CF3)CH2CH=CF(CF3), CHF(CF3)CH=CHCHF(CF3), CF(CF3)=CHCH2CF(CF3)CH2CHF(CF3), CF3C(=O)CH3, formaldehyde, acetaldehyde, trioxane, and trifluoroacetic acid. Some of these compounds are listed in Table 1.

[0046] The composition may further comprise additional compounds selected from at least one of Z-HFO-1336mzz, E-HFO-1336mzz, HFO-1327mz, HCFO-1122, HCFO-1122a, HFO-1123, E-HFO-1233zd, Z-HFO-1224yd, E-HFO-1132, Z-HFO-1132, HFO-1132a, HCFO-1112, HFO-1234zc, HFO-1234ye, and HFO-1234yc. These compounds are listed in Table 1.

[0047] [Table 1]

[0048] [Table 2]

[0049] The additional compounds desirably maintain the Global Warming Potential (GWP) of the composition below 1500, or below 750, or below 150. The additional compounds may reduce the GWP of the composition to below 4, which is the GWP of 1234yf. For example, certain hydrofluoroolefins (HFOs) have a GWP of less than 4, such as HFO-1243zf, which has a GWP of less than 1.

[0050] In one embodiment of the present disclosure, the additional compound may be selected from one or more of HFO-1243zf, HFC-134a, HCFO-1122, HFC-254eb, HCFC-124, and HFC-23. In one embodiment, the additional compound is a combination of HFO-1243zf, HFC-134a, and HFC-143a. In one embodiment, the additional compound is a combination of HFO-1243zf, HFC-134a, HFC-143a, HCFO-1122, and HFC-254eb.

[0051] In one embodiment of the present disclosure, the additional compound may be selected from one or more of HFC-152a, HFO-1234ze(E), HCFO-1131a, HCO-1140, CFC-12, HFC-244bb, and HCFO-1233xf. In one embodiment, the additional compound is a combination of HFC-152a and HFO-1234ze(E). In one embodiment, the additional compound is a combination of HFC-152a, HFO-1234ze(E), HCFO-1131a, HCO-1140, HFC-244bb, and HCFO-1233xf.

[0052] In one embodiment of the disclosure, the additional compound may be selected from one or more of HFO-1225ye(Z), HC-40, HFO-1123, and HFC-263fb. In one embodiment, the additional compound is selected from a combination of HFO-1225ye(Z), HFO-1123, and HFC-263fb.

[0053] In one embodiment, the additional compounds are minor components of the composition. In such an embodiment, the amount of the additional compounds may be greater than 0% and less than 1% by weight. The total amount of the additional compounds present may be greater than 0.1 ppm and less than 0.5% by weight of the total weight of the composition. The total amount of the additional compounds present may be greater than 1 ppm and less than 0.1% by weight of the total weight of the composition. The total amount of the additional compounds present may be greater than 10 ppm, or greater than 100 ppm, or greater than 1000 ppm. The total amount of the additional compounds may be less than 1% by weight, or less than 0.5% by weight, or less than 0.1% by weight. In one embodiment, the total amount of the additional compounds is less than 1% by weight, such that the amount of 1234yf is at least 99%, or the total amount of the additional compounds is less than 0.5% and the amount of 1234yf is at least 99.5%.

[0054] Antioxidants One embodiment of the present invention relates to a composition further comprising at least one antioxidant. Although any suitable oxidizing agent can be used, examples of suitable oxidizing agents include at least one member selected from the group consisting of butylated hydroxytoluene, butylated hydroxyanisole, tertiary butylhydroquinone, gallates, 2-phenyl-2-propanol, 1-(2,4,5-trihydroxyphenyl)-1-butanone, bisphenolmethane derivatives, 2,2'-methylenebis(4-methyl-6-t-butylphenol), and combinations thereof, among others.

[0055] Preparation of the Composition The present disclosure provides a composition comprising 1234yf, a terpene inhibitor, and one or more oxidation products, where the oxidation product is an oxidation product of a terpene inhibitor, and the terpene inhibitor can be selected from one or more of limonene, α-terpinene, α-pinene, and β-pinene.

[0056] The composition can be prepared by contacting a composition comprising 1234yf and a terpene inhibitor selected from one or more of limonene, α-terpinene, α-pinene, and β-pinene with an oxygen source for a contact time and at a contact temperature. Optionally, one or more additional compounds may be present during the contacting step. Examples of oxygen sources that can be used to prepare the compositions disclosed herein include oxygen (100%) and oxygen-containing gases such as air. Alternatively, the oxygen source can be a peroxide compound, such as fluoroolefin polyperoxides, peroxides, hydroperoxides, persulfates, percarbonates, perborates, and hydropersulfates. An example of a hydroperoxide is cumene hydroperoxide. A readily available oxygen source is air.

[0057] In preparing the composition, the oxygen source has an oxygen (O2) concentration of at least 0.01% by weight oxygen, or at least 21% by weight oxygen, or pure (100% by weight) oxygen. The contact time is at least 3 days, or at least 14 days. The contact temperature is in the range of -25 to 150°C. One skilled in the art will appreciate that the oxygen concentration, contact time, and contact temperature are interdependent; that is, as one of the oxygen concentration, contact time, and / or contact temperature increases, the other two decrease.

[0058] Air is the preferred oxygen source due to its availability and cost. The oxygen source may remain present in the composition after the composition is prepared in an amount from greater than 0% by weight up to 3000 ppm.

[0059] Similarly, an antioxidant may be present in the composition containing 1234yf and, optionally, one or more additional compounds prior to the contacting step described above. An antioxidant may also be added after the contacting step described above.

[0060] Alternatively, a composition comprising 2,3,3,3-tetrafluoropropene, a terpene inhibitor, and one or more oxidation products (wherein the oxidation products are oxidation products of the terpene inhibitor), and optionally one or more additional refrigerant compounds, and optionally an antioxidant, can be prepared by combining 1234yf with a terpene inhibitor selected from one or more of limonene, α-terpinene, α-pinene, and β-pinene, and an oxidation product of the selected terpene inhibitor, and optionally one or more additional compounds and optionally an antioxidant, since each of these, i.e., 1234yf, the terpene inhibitor and the oxidation product, and the additional refrigerant compounds and antioxidants, are known compounds that are commercially available or can be prepared according to known methods.

[0061] Purpose The compositions disclosed herein have a variety of utilities including, inter alia, as foaming agents, aerosol propellants, sterilants, or working fluids including heat transfer media, such as heat transfer fluids and refrigerants for use in refrigeration systems, refrigerators, air conditioning systems, heat pumps, chillers, etc. The compositions are particularly suitable for use in mobile air conditioning and heating systems, and as components for making refrigerant blends for use in stationary refrigeration, air conditioning and heat pump systems.

[0062] A blowing agent is a volatile composition that causes a polymer matrix to expand and form a cellular structure.

[0063] An aerosol propellant is a volatile composition of one or more components that exerts a pressure greater than one atmosphere to expel the material from its container.

[0064] A sterilant is a volatile germicidal fluid or blend containing a volatile germicidal fluid that destroys biologically active materials and the like.

[0065] Heat Transfer Applications 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 transport heat from a heat source to a heat sink.

[0066] The present disclosure further relates to a process for heat transfer from a heat source to a heat sink, wherein the composition disclosed herein serves as a heat transfer fluid. The method for heat transfer comprises transporting a composition comprising 2,3,3,3-tetrafluoropropene, a terpene inhibitor, and one or more oxidation products from a heat source to a heat sink, wherein the oxidation products are oxidation products of the terpene inhibitor.

[0067] A heat source is defined as any space, location, object, or body from which it is desirable to add, transfer, move, or remove heat. In one embodiment, the heat source is the body to be cooled. In one embodiment, the heat source is the body to be heated.

[0068] In some embodiments, the heat transfer composition may remain constant throughout the transfer process (i.e., it does not evaporate or condense), hi other embodiments, the heat transfer composition may also be used in vapor cooling processes.

[0069] A heat sink may be defined as any space, place, object, or body that can absorb heat. A vapor compression refrigeration system is one example of such a heat sink.

[0070] The object to be cooled may be any spatial location or object requiring refrigeration or cooling (the spatial location or object may be open or closed). In stationary applications, the object may be inside a structure such as a residential or commercial structure requiring air conditioning, industrial water cooling equipment, or storage locations such as supermarket refrigerator or freezer cases, transport refrigerated containers, or other storage locations for perishable goods such as food or medicines. In mobile applications, the object may be incorporated into a transportation unit for road, rail, ship, or air, such as the passenger compartment of a vehicle requiring air conditioning.

[0071] Certain refrigeration systems operate independently of any mobile carrier and are known as "intermodal" systems. Such intermodal systems include "containers" (intermodal ocean / land transport) and "swap bodies" (intermodal road and rail transport).

[0072] The objects to be heated may be any space, location, or object requiring heat. They may be within any residential or commercial structure requiring heating in a manner similar to the objects to be cooled. Additionally, mobile units such as those described for cooling may be similar to those requiring heating. Certain transport units require heating to prevent the materials being transported from solidifying within the transport container.

[0073] A heat transfer system is a system (or device) used to generate a heating or cooling effect in a specific space. The heat transfer system can be a mobile system or a stationary system. According to the present disclosure, a heat transfer system is provided, comprising a composition comprising 2,3,3,3-tetrafluoropropene, a terpene inhibitor, and one or more oxidation products, wherein the oxidation products are oxidation products of the terpene inhibitor. In one embodiment, the heat transfer system is a stationary system selected from a refrigeration, air conditioning, or heat pump device. In one embodiment, the heat transfer system is a mobile system that is a mobile air conditioning system.

[0074] A refrigerant is defined herein as a heat transfer fluid that undergoes a phase change from liquid to gas and back to liquid during the cycle used to transfer heat. Provided herein is a refrigerant comprising 2,3,3,3-tetrafluoropropene, a terpene inhibitor and one or more oxidation products, wherein the oxidation products are the oxidation products of the terpene inhibitor. In one embodiment, the refrigerant composition further comprises a lubricant. In one embodiment, the refrigerant comprises one or more additive refrigerants (defined below).

[0075] The present disclosure further relates to a method for producing heat comprising evaporating a refrigerant comprising 2,3,3,3-tetrafluoropropene, a terpene inhibitor, and one or more oxidation products that are oxidation products of the terpene inhibitor, and then condensing the composition in the vicinity of a body to be heated. In one embodiment of the method, the refrigerant further comprises a lubricant.

[0076] The disclosure further provides a method for producing cooling comprising condensing a refrigerant comprising 2,3,3,3-tetrafluoropropene, a terpene inhibitor, and one or more oxidation products of the terpene inhibitor, and then evaporating the composition in the vicinity of a body to be cooled. In one embodiment of the method, the refrigerant further comprises a lubricant.

[0077] The present disclosure further provides a method for producing heating or cooling in a refrigeration, air conditioning or heat pump device, the method comprising introducing a refrigerant into the device having (a) a centrifugal compressor, (b) a multi-stage centrifugal compressor or (c) a single slab / single pass heat exchanger, the refrigerant or the heat transfer fluid composition comprising a composition comprising 2,3,3,3-tetrafluoropropene, a terpene inhibitor and one or more oxidation products that are oxidation products of the terpene inhibitor. In one embodiment of this method, the refrigerant further comprises a lubricant.

[0078] Lubricants The lubricant component of the refrigerant composition can 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 the 1990 ASHRAE Handbook, Refrigeration Systems and Applications, Chapter 8, entitled "Lubricants in Refrigeration Systems", pages 8.1-8.21, which is incorporated herein by reference. These lubricants include mineral oils and synthetic oils.

[0079] Mineral oils include paraffins (i.e., saturated hydrocarbons with straight and branched carbon chains), naphthenes (i.e., cyclic or ring-structured saturated hydrocarbons, which may be paraffins), and aromatics (i.e., unsaturated cyclic hydrocarbons containing one or more rings characterized by alternating double bonds).

[0080] Synthetic oils include alkylaryls (ie, linear and branched alkylalkylbenzenes), synthetic paraffins and naphthenes, silicones, and poly-alpha-olefins.

[0081] Lubricant components may also include those designed for use with hydrofluorocarbon refrigerants and that are miscible with the compositions disclosed herein under the operating conditions of compression refrigeration and air conditioning equipment. Such lubricants and their properties are discussed in "Synthetic Lubricants and High-Performance Fluids", edited by RLShubkin and 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 (Dow Chemicals, Midland, Michigan) and polyvinyl ethers (PVEs).

[0082] Lubricants for the applications disclosed herein are selected by considering the requirements of a given compressor and the environment to which the lubricant will be exposed. In one specific embodiment, the refrigerant composition described above is combined with a PAG lubricant for use in an air conditioning (A / C) system for a vehicle having an internal combustion engine. In another specific embodiment, the refrigerant composition described above is combined with a POE lubricant for use in an A / C system for a vehicle having an electric or hybrid electric drivetrain.

[0083] Additive Refrigerant In another embodiment, the refrigerant composition comprises 2,3,3,3-tetrafluoropropene, a terpene inhibitor, and one or more oxidation products, the oxidation products being oxidation products of the terpene inhibitor and one or more additive refrigerants. In one embodiment, the additive refrigerant comprises a hydrofluorocarbon. Examples of suitable hydrofluorocarbons include difluoromethane (HFC-32), pentafluoroethane (HFC-125), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1-difluoroethane (HFC-152a), 1,1,1,3,3,3-hexafluoropropane (HFC-236fa), and 1,1,1,2,2,3,3,3-heptafluoropropane (HFC-227ea). The refrigerant composition may comprise 2,3,3,3-tetrafluoropropene, a terpene inhibitor, one or more oxidation products being oxidation products of the terpene inhibitor, one or more additive refrigerants, and a lubricant.

[0084] In one particular embodiment, the additive refrigerant comprises HFO-1234ze. In another embodiment, the additive refrigerant comprises carbon dioxide.

[0085] The amount of added refrigerant can range from 10 to 90% by weight, 25 to 75% by weight, 30 to 60% by weight, or 30 to 50% by weight.

[0086] Refrigerant Additives Additives that can improve refrigerant and A / C life and compressor durability are desirable. In one aspect of the present invention, the refrigerant compositions of the present invention are used to introduce lubricants and other additives into the A / C system, such as a) acid scavengers and b) flame suppressants.

[0087] Acid Scavenger The acid scavenger may include a siloxane, an activated aromatic compound, or a combination of both. Serrano et al. (see paragraph 38 of US 2011 / 0272624 A1) disclose that the siloxane may be any molecule with siloxy functionality. The siloxane may include an alkyl siloxane, an aryl siloxane, or a siloxane containing a mixture of aryl and alkyl substituents. For example, the siloxane may be an alkyl siloxane, such as a dialkyl siloxane or a polydialkyl siloxane. Preferred siloxanes include groups with an oxygen atom bonded to two silicon atoms, i.e., the structure: SiOSi. Preferred siloxanes include siloxanes with one or more of a methyl group, an ethyl group, a propyl group, or a butyl group.

[0088] In one aspect of the invention, the siloxane is an alkyl siloxane containing from about 1 to about 12 carbon atoms, such as hexamethyldisiloxane. The siloxane may also be a polymer, such as a polydialkylsiloxane, in which the alkyl groups are methyl, ethyl, propyl, butyl, or any combination thereof. Suitable polydialkylsiloxanes have a molecular weight of from about 100 to about 10,000. Highly preferred siloxanes include hexamethyldisiloxane, polydimethylsiloxane, and combinations thereof. The siloxane may consist essentially of polydimethylsiloxane, hexamethyldisiloxane, or combinations thereof.

[0089] The activated aromatic compound may be any aromatic molecule, or mixture thereof, that is activated for Friedel-Crafts addition reactions. An activated aromatic molecule for Friedel-Crafts addition reactions is defined as any aromatic molecule that can undergo addition reactions with mineral acids. In particular, it is any aromatic molecule that can undergo addition reactions with mineral acids either in the application environment (AC system) or during the thermal stabilization test of ASHRAE 97:2007 "Sealed Glass Tube Method to Test the Chemical Stability of Materials for Use within Refrigerant Systems".

[0090] The acid scavenger (e.g., activated aromatic compound, siloxane, or both) may 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. The acid scavenger is preferably present at a concentration of greater than about 0.0050 wt%, more preferably greater than about 0.05 wt%, even more preferably greater than about 0.1 wt% (e.g., greater than about 0.5 wt%) based on the total weight of the refrigerant composition. The acid scavenger is preferably present at a concentration of less than about 3 wt%, more preferably less than about 2.5 wt%, and most preferably less than about 2 wt% (e.g., less than about 1.8 wt%) based on the total weight of the refrigerant composition.

[0091] Flame suppressant Preferred flame suppressants include those described in Canadian Patent Application Publication No. 2557873(A1) entitled "Refrigerant compositions containing fluorine substituted olefins," incorporated herein by reference, including with fluorinated products such as HFC-125 and / or Krytox® lubricants, and those described in International Publication No. 2009018117(A1) entitled "Refrigerant compositions comprising fluoroolefins and uses thereof," incorporated herein by reference.

[0092] Preparation of refrigerant composition The refrigerant compositions of the present invention can be prepared by any convenient method for combining the desired amounts of the individual components. A preferred method is to weigh the desired amounts of the components and then combine the components in a suitable vessel. Agitation may be used if desired.

[0093] Some Selected Embodiments Embodiment 1. In one embodiment, a composition is provided that includes 2,3,3,3-tetrafluoropropene, a terpene inhibitor, and one or more oxidation products, where the oxidation product is an oxidation product of the terpene inhibitor. Embodiment 2. In one embodiment, a composition is provided that includes 2,3,3,3-tetrafluoropropene, a terpene inhibitor that is limonene, and one or more oxidation products, the oxidation products including one or more of carvone, carveol (Z- and E-), and limonene oxide (Z- and E-). Embodiment 3. In one embodiment, a composition is provided that includes 2,3,3,3-tetrafluoropropene, a terpene inhibitor that is limonene, and one or more oxidation products, where the oxidizing composition includes carvone. Embodiment 4. In one embodiment, a composition is provided comprising 2,3,3,3-tetrafluoropropene, a terpene inhibitor that is limonene, and one or more oxidation products, wherein the oxidation products include carveol (Z- and E-). Embodiment 5. In one embodiment, a composition is provided that includes 2,3,3,3-tetrafluoropropene, a terpene inhibitor that is limonene, and one or more oxidation products, the oxidation products including limonene oxides (Z- and E-). Embodiment 6. In one embodiment, there is provided a composition comprising 2,3,3,3-tetrafluoropropene, a terpene inhibitor that is α-terpinene, and one or more oxidation products, the oxidation products comprising one or more of 3-isopropyl-6-methyl-7-oxabicyclo[4.1.0]hept-2-ene, 6-isopropyl-3-methyl-7-oxabicyclo[4.1.0]hept-2-ene, 1-isopropyl-4-methyl-cyclohex-2-ene-1,4-diol, E-3-isopropyl-6-methylhepta-2,6-dienal, p-cymene, and propane. Embodiment 7. In one embodiment, a composition is provided that includes 2,3,3,3-tetrafluoropropene, a terpene inhibitor that is α-terpinene, and one or more oxidation products, where the oxidation product includes 3-isopropyl-6-methyl-7-oxabicyclo[4.1.0]hept-2-ene. Embodiment 8. In one embodiment, a composition is provided that includes 2,3,3,3-tetrafluoropropene, a terpene inhibitor that is α-terpinene, and one or more oxidation products, where the oxidation product includes 6-isopropyl-3-methyl-7-oxabicyclo[4.1.0]hept-2-ene. Embodiment 9. In one embodiment, a composition is provided that includes 2,3,3,3-tetrafluoropropene, a terpene inhibitor that is α-terpinene, and one or more oxidation products, where the oxidation product includes 1-isopropyl-4-methyl-cyclohex-2-ene-1,4-diol. Embodiment 10. In one embodiment, a composition is provided that includes 2,3,3,3-tetrafluoropropene, a terpene inhibitor that is α-terpinene, and one or more oxidation products, where the oxidation product includes E-3-isopropyl-6-methylhepta-2,6-dienal. Embodiment 11. In one embodiment, a composition is provided that includes 2,3,3,3-tetrafluoropropene, a terpene inhibitor that is α-terpinene, and one or more oxidation products, where the oxidation product includes p-cymene. Embodiment 12. In one embodiment, a composition is provided that includes 2,3,3,3-tetrafluoropropene, a terpene inhibitor that is alpha-terpinene, and one or more oxidation products, where the oxidation product includes propane. Embodiment 13. In one embodiment, a composition is provided that includes 2,3,3,3-tetrafluoropropene, a terpene inhibitor that is α-pinene, and one or more oxidation products, where the oxidation product includes α-pinene oxide. Embodiment 14. In one embodiment, a composition is provided comprising 2,3,3,3-tetrafluoropropene, a terpene inhibitor that is β-pinene, and one or more oxidation products, wherein the oxidation products include one or more of pinocarveol and myrtenol. Embodiment 15. In one embodiment, a composition is provided comprising 2,3,3,3-tetrafluoropropene, a terpene inhibitor that is β-pinene, and one or more oxidation products, wherein the oxidation product comprises pinocarveol. Embodiment 16. In one embodiment, a composition is provided that includes 2,3,3,3-tetrafluoropropene, a terpene inhibitor that is β-pinene, and one or more oxidation products, where the oxidation product includes myrtenol. Embodiment 17. In one embodiment, a refrigerant is provided comprising the composition of embodiment 3 and a lubricant. Embodiment 18. In one embodiment, a refrigerant is provided comprising the composition of embodiment 4 and a lubricant. Embodiment 19. In one embodiment, a refrigerant is provided comprising the composition of embodiment 5 and a lubricant. Embodiment 20. In one embodiment, a refrigerant is provided comprising the composition of embodiment 7 and a lubricant. Embodiment 21. In one embodiment, a refrigerant is provided comprising the composition of embodiment 8 and a lubricant. Embodiment 22. In one embodiment, a refrigerant is provided comprising the composition of embodiment 9 and a lubricant. Embodiment 23. In one embodiment, a refrigerant is provided comprising the composition of embodiment 10 and a lubricant. Embodiment 24. In one embodiment, a refrigerant is provided comprising the composition of embodiment 11 and a lubricant. Embodiment 25. In one embodiment, a refrigerant is provided comprising the composition of embodiment 12 and a lubricant. Embodiment 26. In one embodiment, a refrigerant is provided comprising the composition of embodiment 13 and a lubricant. Embodiment 27. In one embodiment, a refrigerant is provided comprising the composition of embodiment 15 and a lubricant. Embodiment 28. In one embodiment, a refrigerant is provided comprising the composition of embodiment 16 and a lubricant. Embodiment 29. In one embodiment, there is provided a process for heat transfer comprising transporting the composition of any of embodiments 3, 4, 5, 7, 8, 9, 10, 11, 12, 13, 15, or 16 from a heat source to a heat sink. Embodiment 30. In one embodiment, there is provided a method for producing cooling comprising condensing a refrigerant according to any of embodiments 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27 or 28, and then evaporating the refrigerant in the vicinity of an object to be cooled. Embodiment 31. In one embodiment, a method for producing heating is provided comprising evaporating a refrigerant as described in any of embodiments 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, or 28, and then condensing the refrigerant in the vicinity of a body to be heated. Embodiment 32. In one embodiment, a method is provided for producing heating or cooling in a refrigeration, air conditioning, or heat pump apparatus, the method comprising introducing a refrigerant into the apparatus having (a) a centrifugal compressor, (b) a multi-stage centrifugal compressor, or (c) a single slab / single pass heat exchanger, wherein the refrigerant is a refrigerant as described in any of embodiments 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, or 28. In one embodiment, HCC-40, CFC-12, HFC-23, HFC-134a, HFC-143a, HFC-152a, HCFC-225ca, HCFC-225cb, HCFC-244bb, HFC-245cb, HFC-254eb, HFC-263fb, HFO-1123, HFO-1243zf, HFO-1225ye (E- and / or Z-isomers), HFO-1225zc, HFO-123 17. The composition of any of the preceding embodiments, further comprising an additional compound selected from at least one of 4ze (E- and / or Z-isomer), 3,3,3-trifluoro-1-propyne, HCFO-1233xf, HCFO-1122, HCO-1140, HCFO-1131 (E- and / or Z-isomer), HCFO-1131a, HCFC-124, HCFC-124a, and HCFC-142b. Embodiment 34. In one embodiment, there is provided a composition according to any one of embodiments 1 to 16, further comprising an additional compound selected from at least one of CHF(CF3)CH2CH=CF(CF3), CHF(CF3)CH=CHCHF(CF3), CF(CF3)=CHCH2CF(CF3)CH2CHF(CF3), CF3C(=O)CH3, formaldehyde, acetaldehyde, trioxane, and trifluoroacetic acid. Embodiment 35. In one embodiment, there is provided a composition according to any one of embodiments 1-16, further comprising an additional compound selected from at least one of Z-HFO-1336mzz, E-HFO-1336mzz, HFO-1327mz, HCFO-1122, HCFO-1122a, HFO-1123, E-HFO-1233zd, Z-HFO-1224yd, E-HFO-1132, Z-HFO-1132, HFO-1132a, HCFO-1112, HFO-1234zc, HFO-1234ye, and HFO-1234yc. In one embodiment, HCC-40, CFC-12, HFC-23, HFC-134a, HFC-143a, HFC-152a, HCFC-225ca, HCFC-225cb, HCFC-244bb, HFC-245cb, HFC-254eb, HFC-263fb, HFO-1123, HFO-1243zf, HFO-1225ye (E- and / or Z-isomers), HFO-1225zc, HFO-1234 29. The composition of any of embodiments 17-28, further comprising an additional compound selected from at least one of: ze (E- and / or Z-isomer), 3,3,3-trifluoro-1-propyne, HCFO-1233xf, HCFO-1122, HCO-1140, HCFO-1131 (E- and / or Z-isomer), HCFO-1131a, HCFC-124, HCFC-124a, and HCFC-142b. Embodiment 37. In one embodiment, there is provided a composition according to any of embodiments 17-28, further comprising an additional compound selected from at least one of CHF(CF3)CH2CH=CF(CF3), CHF(CF3)CH=CHCHF(CF3), CF(CF3)=CHCH2CF(CF3)CH2CHF(CF3), CF3C(=O)CH3, formaldehyde, acetaldehyde, trioxane, and trifluoroacetic acid. Embodiment 38. In one embodiment, there is provided a composition according to any one of embodiments 17-28, further comprising an additional compound selected from at least one of Z-HFO-1336mzz, E-HFO-1336mzz, HFO-1327mz, HCFO-1122, HCFO-1122a, HFO-1123, E-HFO-1233zd, Z-HFO-1224yd, E-HFO-1132, Z-HFO-1132, HFO-1132a, HCFO-1112, HFO-1234zc, HFO-1234ye, and HFO-1234yc. EXAMPLES

[0094] Example 1 A 60 g sample of 2,3,3,3-tetrafluoropropene having a purity of 99.5% by weight, containing HFO-1234zf, HFO-1243ze(E) and HFC-152a, was added to a 500 mL cylinder containing 200 ppm of a terpene inhibitor and 12,000 ppm of air. The cylinder was left at room temperature from about -5°C to about 35°C for 6 months. The product in the cylinder was tested and found to be a composition free of polymer and further containing limonene and its oxidation products, as measured by gas chromatography (less than 200 ppm).

Claims

1. A composition comprising 2,3,3,3-tetrafluoropropene, a terpene inhibitor, and one or more oxidation products, wherein the terpene inhibitor is limonene or α-terpinene or α-pinene or β-pinene, and the oxidation product is an oxidation product of the terpene inhibitor; when the terpene inhibitor is limonene, the oxidation product is at least one of carvone, carveol, 3-isopropyl-6-methyl-7-oxabicyclo[4.1.0]hept-2-ene, 6-isopropyl-3-methyl-7-oxabicyclo[4.1.0]hept-2-ene, 1-isopropyl-4-methyl-cyclohex-2-ene-1,4-diol, E-3-isopropyl-6-methylhepta-2,6-dienal, p-cymene, pinocarveol, myrtenol, and propane; when the terpene inhibitor is alpha-terpinene, the oxidation product is at least one of 3-isopropyl-6-methyl-7-oxabicyclo[4.1.0]hept-2-ene, 6-isopropyl-3-methyl-7-oxabicyclo[4.1.0]hept-2-ene, 1-isopropyl-4-methyl-cyclohex-2-ene-1,4-diol, E-3-isopropyl-6-methylhepta-2,6-dienal, p-cymene, and propane; when the terpene inhibitor is α-pinene, the oxidation product is α-pinene oxide; When the terpene inhibitor is β-pinene, the oxidation product is at least one of pinocarveol and myrtenol.

2. The composition is selected from the group consisting of HCC-40, CFC-12, HFC-23, HFC-134a, HFC-143a, HFC-152a, HCFC-225ca, HCFC-225cb, HCFC-244bb, HFC-245cb, HFC-254eb, HFC-263fb, HFO-1123, HFO-1243zf, HFO-1225ye (E- and / or Z-isomers), HFO-1225zc, HFO- 12. The composition of claim 1, further comprising an additional compound selected from at least one of HCFO-1234ze (E- and / or Z-isomer), 3,3,3-trifluoro-1-propyne, HCFO-1233xf, HCFO-1122, HCO-1140, HCFO-1131 (E- and / or Z-isomer), HCFO-1131a, HCFC-124, HCFC-124a, and HCFC-142b.

3. 3. The composition of claim 2, wherein the composition further comprises an additional compound selected from at least one of CHF(CF3)CH2CH=CF(CF3), CHF(CF3)CH=CHCHF(CF3), CF(CF3)=CHCH2CF(CF3)CH2CHF(CF3), CF3C(=O)CH3, formaldehyde, acetaldehyde, trioxane, and trifluoroacetic acid.

4. The composition of any one of claims 1 to 3, wherein the terpene inhibitor is present in the composition in an amount of at least 0.001% by weight (10 ppm).

5. A composition described in any one of claims 1 to 3, wherein the terpene inhibitor is present in the composition in an amount of at least 0.01% by weight (100 ppm).

6. The composition described in claim 2, wherein the total amount of additional compounds is greater than 0% by weight and less than 1% by weight.

7. 3. The composition of claim 2, wherein the total amount of additional compounds present is greater than 0.1 ppm and less than 0.5 wt. % of the total weight of the composition.

8. The composition described in claim 1, wherein the terpene inhibitor comprises limonene.

9. The composition of claim 8, wherein the oxidation product is at least one of carvone, carveol, and p-cymene.

10. The composition of claim 8, further comprising one or more of alpha-terpene, cymene, 1-octanol, gamma-terpinene, terpinolene and beta-terpinene.

11. 2. The composition of claim 1, wherein the terpene inhibitor comprises alpha-terpinene.

12. 2. The composition of claim 1, wherein the terpene inhibitor comprises alpha-pinene.

13. 2. The composition of claim 1, wherein the terpene inhibitor comprises β-pinene.

14. A refrigerant composition comprising the composition of claim 1 and a lubricant.

15. 13. A process for heat transfer comprising transporting a composition comprising the composition of claim 1 from a heat source to a heat sink.

16. A method for producing cooling comprising condensing a refrigerant and then evaporating the composition in the vicinity of an object to be cooled, wherein the refrigerant is a refrigerant composition as described in claim 14.

17. A method for producing heating comprising evaporating a refrigerant and then condensing the composition in the vicinity of an object to be heated, wherein the refrigerant is a refrigerant composition as described in claim 14.

18. 15. A method for producing heating or cooling in a refrigeration, air conditioning or heat pump system, the method comprising introducing a refrigerant into the system having: (a) a centrifugal compressor; (b) a multi-stage centrifugal compressor; or (c) a single slab / single pass heat exchanger, the refrigerant being the refrigerant composition of claim 14.

19. 13. A heat transfer system comprising the composition of claim 1, wherein the heat transfer system is a stationary system selected from a refrigeration, air conditioning or heat pump device, or the heat transfer system is a mobile system, wherein the heat transfer system is a mobile air conditioning system.