Compositions comprising difluoropropene and uses thereof

Abstract

The present disclosure relates to a composition comprising HFO-1252zc, HFC-32, and HFO-1234zeE, in particular to a composition comprising HFO-1252zc and HFO-1234zeE. The compositions are useful in methods of heating and cooling, air conditioning and heat pump systems, and methods of replacing existing refrigerants.

Description

TECHNICAL FIELD

[0001] The present disclosure relates to compositions useful as refrigerants, particularly for air conditioning and heat pump systems. The compositions of the present disclosure are useful in methods of refrigeration and heat pump and methods of replacing refrigerants, as well as in air conditioning and heat pump systems. BACKGROUND

[0002] The fluorocarbon industry has been working for the past several decades to find replacements for the ozone-depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) that are being phased out by the Montreal Protocol. The solution for many applications has been the commercialization of hydrofluorocarbon (HFC) compounds for use as refrigerants, solvents, fire extinguishing agents, foam blowing agents, and propellants. These new compounds, which are currently the most widely used (such as HFC refrigerants, HFC-134a and HFC-125), have zero ozone depletion potential (ODP) and are therefore not affected by the current phase-out provisions of the Montreal Protocol. In addition to the problem of ozone depletion, global warming is another environmental issue for many of these applications. According to the United Nations IPCC Fourth Assessment Report (AR4), HFC refrigerants such as HFC-134a and HFC-125 have global warming potentials (GWPs) of 1,430 and 3,500, respectively.

[0003] This regulatory environment is continuing to evolve, with properties under consideration not limited to ODP and GWP. More specifically, there is a need for refrigerant compositions that not only meet low ODP standards and have low global warming potential, but also provide excellent performance in a variety of applications and meet the standards of the evolving regulations.

[0004] The present invention addresses certain problems associated with conventional refrigerants and provides refrigerant blends containing 1,1-difluoropropene that meet the evolving regulatory environment. SUMMARY

[0005] In order to meet the rapidly changing regulatory environment, the inventors have identified a fluoroolefin compound that provides performance associated with existing refrigerants that can continue to be used even considering the standards of the evolving regulatory environment.

[0006] Particular embodiments disclosed herein relate to fluoropropene compositions comprising 1,1-difluoropropene (also known as HFO-1252zc or R-1252zc). It is shown herein that this compound has advantageous properties for refrigerant applications, such as air conditioning and heat pumps.

[0007] In one embodiment, disclosed herein is a composition comprising HFO-1252zc, HFC-32, and HFO-1234zeE.

[0008] Also disclosed herein is a composition comprising from about 0.5 weight percent to 65 weight percent HFO-1252zc, from about 1 weight percent to 22 weight percent HFC-32, and from about 13 weight percent to 78 weight percent HFO-1234zeE, according to any of the preceding embodiments.

[0009] Also disclosed herein is a composition comprising from about 1 weight percent to 65 weight percent HFO-1252zc, from about 21 weight percent to 22 weight percent HFC-32, and from about 13 weight percent to 78 weight percent HFO-1234zeE, according to any of the preceding embodiments.

[0010] Also disclosed herein is a composition comprising from about 30 weight percent HFO-1252zc, from about 21 weight percent HFC-32, and from about 49 weight percent HFO-1234zeE, according to any of the preceding embodiments.

[0011] Also disclosed herein is a composition further comprising at least one additional compound selected from the group consisting of HCFC-22, HFC-23, HCC-30, HCFC-31, HCC-40, HFC-41, methane, HFC-125, HFC-143, HFC-143a, HFC-152a, HFC-245cb, HCFC-253dc, HFC-254fb, HCC-260fb, HCFC-261fc, HCFC-262fc, HFC-263fb, HFC-272fb, propane, HFO-374, n-butane, propadiene, 2-butene, cyclobutene, 2-methylpropene, HCFO-1122, HFO-1132, HFO-1132a, HFO-1141, ethylene, HCFO-1233xf, HFO-1234yf, HCFO-1242zf, HFO-1243zf, HCFO-1251, HCO-1260zf, HFO-1261zf, propylene, HFO-1345, HFO-1252ze, HFO-1252yf, HFO-1252zf, HFO-1252ye, and E / Z-t-BuO-CF=CH-CH3, according to any of the preceding embodiments.

[0012] Also disclosed herein is a composition further comprising at least one additional compound selected from the group consisting of HFO-1234yf, HFO-1243zf, HFC-263fb, HFO-1252ze, HFO-1252yf, HFO-1252zf, and HFO-1252ye, according to any of the preceding embodiments.

[0013] According to any of the preceding embodiments, also disclosed herein is a composition, wherein the composition further comprises 0.1 ppm to 200 ppm by weight of water; about 10 ppm to about 0.35% by volume of oxygen; and / or about 100 ppm to about 1.5% by volume of air or NAG.

[0014] According to any of the preceding embodiments, also disclosed herein is a composition, wherein the composition comprises a stabilizing agent.

[0015] According to any of the preceding embodiments, also disclosed herein is a composition, wherein the stabilizing agent is selected from the group consisting of nitromethane, ascorbic acid, terephthalic acid, azoles, phenolic compounds, cyclic monoterpenes, terpenes, phosphites, phosphates, phosphonates, thiols, and lactones.

[0016] According to any of the preceding embodiments, also disclosed herein is a composition, wherein the stabilizing agent is selected from tolyltriazole, benzotriazole, tocopherol, hydroquinone, t-butyl hydroquinone, 2,6-di-t-butyl-4-methylphenol, fluorinated epoxide, n-butyl glycidyl ether, hexanediol diglycidyl ether, allyl glycidyl ether, butyl phenyl glycidyl ether, d-limonene, a-terpinene, b-terpinene, a-pinene, b-pinene, or butylated hydroxytoluene.

[0017] According to any of the preceding embodiments, also disclosed herein is a composition, wherein the stabilizing agent is present in an amount of about 0.001 wt% to 1.0 wt% based on the weight of the refrigerant.

[0018] According to any of the preceding embodiments, also disclosed herein is a composition, wherein the composition further comprises a lubricant.

[0019] According to any of the preceding embodiments, also disclosed herein is a composition, wherein the lubricant is at least one selected from the group consisting of polyalkylene glycols, polyol esters, poly-alpha-olefins, and polyvinyl ethers.

[0020] According to any of the preceding embodiments, also disclosed herein is a composition, wherein the lubricant is a polyol ester or a polyvinyl ether.

[0021] According to any of the preceding embodiments, also disclosed herein is a composition, wherein the lubricant has at least one property selected from the group consisting of greater than 10 10an electrical resistivity of about 1.0 x 1010ohm-m to about 1.0 x 1011ohm-m; a volume resistivity of about 1.0 x 1010ohm-m to about 1.0 x 1011ohm-m; a surface tension of about 0.02 N / m to 0.04 N / m at 20 °C; a kinematic viscosity of about 20 cSt to about 500 cSt at 40 °C; a breakdown voltage of at least 25 kV; and a hydroxyl value of at most 0.1 mg KOH / g.

[0022] According to any of the preceding embodiments, also disclosed herein is a composition, wherein the composition comprises at least one tracer.

[0023] According to any of the preceding embodiments, also disclosed herein is a composition, wherein the tracer is present in an amount of about 1.0 ppm by weight to about 1000 ppm by weight.

[0024] According to any of the preceding embodiments, also disclosed herein is a composition, wherein the at least one tracer is selected from the group consisting of a hydrofluorocarbon, a hydrofluoroolefin, a hydrochlorocarbon, a hydrochloroolefin, a hydrochlorofluorocarbon, a hydrochlorofluoroolefin, a hydrochlorocarbon, a hydrochloroolefin, a chlorofluorocarbon, a chlorofluoroolefin, a hydrocarbon, a perfluorocarbon, a perfluoroolefin, and combinations thereof.

[0025] According to any of the preceding embodiments, also disclosed herein is a composition, wherein the at least one tracer is selected from the group consisting of HFC-23, HCFC-31, HFC-41, HFC-161, HFC-143a, HFC-134a, HFC-125, HFC-236fa, HFC-236ea, HFC-245cb, HFC-245fa, HFC-254eb, HFC-263fb, HFC-272ca, HFC-281ea, HFC-281fa, HFC-329p, HFC-329mmz, HFC338mf, HFC-338pcc, CFC-12, CFC-11, CFC-114, CFC-114a, HCFC-22, HCFC-123, HCFC-124, HCFC-124a, HCFC-141b, HCFC-142b, HCFC-151a, HCFC-244bb, HCC-40, HFO-1141, HCFO-1130, HCFO-1130a, HCFO-1131, HCFO-1122, HFO-1123, HFO-1234yf, HFO-1234ye, HFO-1243zf, HFO-1225ye, HFO-1225zc, PFC-116, PFC-C216, PFC-218, PFC-C318, PFC-1216, PFC-31-10mc, PFC-31-10my, and combinations thereof.

[0026] According to any of the preceding embodiments, also disclosed herein is a composition, wherein the composition is free or substantially free of Group A fluorinated substances, and wherein degradation products of the composition are free or substantially free of Group A fluorinated substances.

[0027] According to any of the preceding embodiments, also disclosed herein is a method for cooling comprising evaporating the composition in the vicinity of a body to be cooled, and then condensing said composition, wherein said cooling is provided by an air conditioner or heat pump.

[0028] According to any of the preceding embodiments, also disclosed herein is a method for heating comprising evaporating the composition, and then condensing said composition in the vicinity of a body to be heated, wherein said heating is provided by a heat pump.

[0029] According to any of the preceding embodiments, also disclosed herein is a system for cooling or heating comprising the composition. In another embodiment, the system comprises an evaporator, a compressor, a condenser, and an expansion device, each operably connected to perform a vapor compression cycle. In another embodiment, said air conditioner or heat pump is a residential, light commercial, or industrial air conditioner or heat pump. In another embodiment, the system can be a secondary loop system. DETAILED DESCRIPTION

[0030] The present invention relates to compositions containing 1,1-difluoropropene (HFO-1252zc), difluoromethane (HFC-32), and E-1,3,3,3-tetrafluoropropene (HFO-1234zeE). The compositions can be candidates to replace refrigerants such as R-454C, R-410A, or propane, with low global warming potential (GWP), improved environmental fate characteristics, and improved energy efficiency (COP).

[0031] The compositions contain HFO-1252zc, HFC-32, and HFO-1234zeE. They provide refrigerant blends with low global warming potential, improved glide compared to other proposed refrigerant blends, and improved coefficient of performance compared to existing refrigerants and other proposed replacements.

[0032] A refrigerant is defined as a heat transfer fluid that undergoes a phase change from liquid to gas and back again during a cycle for transferring heat.

[0033] A heat transfer system is a system (or device) for producing a heating or cooling effect in a particular space. The heat transfer system can be a mobile system or a stationary system.

[0034] Examples of heat transfer systems include any type of refrigeration and air conditioning system, including but not limited to stationary heat transfer systems, air conditioners, refrigerators, chillers, heat pumps, flooded evaporator heat pumps, direct expansion cooler heat pumps, coolers, flooded evaporator coolers, direct expansion coolers, walk-in coolers, portable refrigeration units, portable heat transfer systems, portable heat pumps (including heat pumps for comfort cooling and heating of passenger compartments in automobiles), portable air conditioning units (for cooling passenger compartments in automobiles), dehumidifiers, and combinations thereof. The focus of this application is air conditioning and heat pump systems.

[0035] Volumetric capacity is the amount of heat absorbed or discharged divided by the theoretical compressor displacement. The heat removed or absorbed is the refrigerant mass flow rate multiplied by the enthalpy difference across the heat exchanger. The theoretical compressor displacement is the refrigerant mass flow rate divided by the density of the gas entering the compressor (i.e., the compressor suction density). More simply, volumetric capacity is the suction density multiplied by the enthalpy difference across the heat exchanger. A higher volumetric capacity allows for the use of a smaller compressor under the same heat load. Here, cooling capacity refers to volumetric capacity in cooling mode, while heating capacity refers to volumetric capacity in heating mode.

[0036] The coefficient of performance (COP) is the heat absorbed or released divided by the energy input required to operate the cycle (approximately the compressor power). COP is specific to the operating mode of a heat pump, so COP is used for heating or COP is used for cooling. COP is directly related to the energy efficiency ratio (EER).

[0037] Subcooling refers to the temperature of a liquid dropping below its saturation point at a given pressure. The saturation point of a liquid is the temperature at which vapor completely condenses into a liquid. By cooling the liquid below its saturation temperature (or bubble point), the net cooling effect can be increased. Subcooling thus improves the cooling capacity and energy efficiency of a system. Subcooling is the amount of cooling to below the saturation temperature (in degrees Celsius).

[0038] Superheating refers to the temperature of vapor rising above its saturation point at a given pressure. The vapor saturation point is the temperature at which a liquid completely evaporates into vapor. At a given pressure, superheating continues to heat the vapor to a higher temperature. By heating the vapor above its saturation temperature (or dew point), the net refrigeration effect can be increased. Therefore, when superheating occurs in the evaporator, the system's refrigeration capacity and energy efficiency can be improved. Superheating in the suction line does not increase the net refrigeration effect and reduces efficiency and capacity. Superheat is the amount of heat generated above the saturation temperature (in degrees Celsius).

[0039] Temperature glide (sometimes simply called "glide") is the absolute value of the difference between the onset and termination temperatures of a refrigerant phase change process within the condenser of a refrigerant system, excluding any subcooling or superheating. For the evaporator, glide is the temperature difference between the dew point and the evaporator inlet. Glide can be used to describe the condensation or evaporation of near-azeotropic or non-azeotropic compositions. When referring to temperature glide in air conditioning or heat pump systems, it is common to provide an average temperature glide, which is the average of the temperature glide in the evaporator and the temperature glide in the condenser. Glide applies to blended refrigerants, i.e., refrigerants composed of at least two components.

[0040] Net cooling efficiency is the amount of heat absorbed by each kilogram of refrigerant in the evaporator to produce usable cooling.

[0041] Mass flow rate is the amount (in kilograms) of refrigerant that circulates through a refrigeration system, heat pump system, or air conditioning system within a given time period.

[0042] As used herein, the term "lubricant" means any material added to a composition or compressor (and in contact with any heat transfer composition used in any heat transfer system) that provides hydrodynamic lubrication to the compressor to help prevent parts from seizing.

[0043] The Global Warming Potential (GWP) is an indicator used to estimate the relative contribution of atmospheric emissions of a specific greenhouse gas to global warming compared to the emission of one kilogram of carbon dioxide. GWPs can be calculated over different time periods, showing the impact on the atmospheric lifetime of a given gas. GWPs over a 100-year time period are typically used as a reference value. For mixtures, a weighted average can be calculated based on the individual GWPs for each component. In this paper, the GWP values ​​are those reported in the Intergovernmental Panel on Climate Change (IPCC) Fourth Assessment Report (AR4). The GWP estimate for 1252 zc is 1.

[0044] Ozone depletion potential (ODP) refers to the amount of ozone loss caused by a substance. ODP is the ratio of the effect of a chemical on ozone to the effect of a similar mass of CFC-11 (trichlorofluoromethane). Therefore, the ODP of CFC-11 is defined as 1.0. Other CFCs and HCFCs have ODPs ranging from 0.01 to 1.0. The hydrofluorocarbons (HFCs) and hydrofluoroolefins (HFOs) described herein have zero ODP because they do not contain chlorine, bromine, or iodine compounds known to cause ozone decomposition and depletion. HFO-1252zc has zero ozone depletion potential.

[0045] 1,1-Difluoropropene (HFO-1252zc or R-1252zc) can be prepared by hydrogenating 3,3,3-trifluoropropene (HFO-1243zf) on a carbon-supported palladium catalyst to form 1,1,1-trifluoropropane (HFC-263fb), followed by dehydrofluorination of HFC-263fb on a chromium catalyst or pyrolysis at high temperature (see Agent’s Case No. FL2084, which is filed with and incorporated herein by reference).

[0046] E-1,3,3,3-Tetrafluoropropylene (HFO-1234zeE or R-1234zeE) is commercially available from Honeywell (Charlotte, North Carolina, USA). Difluoromethane (HFC-32 or R-32) is commercially available from various sources worldwide.

[0047] As used herein, the terms “comprising,” “including,” “having,” or any other variations thereof are intended to cover non-exclusive inclusion. For example, a composition, process, method, article of manufacture, or apparatus that includes a list of elements is not necessarily limited to those elements, but may include other elements not expressly listed or inherent to such composition, process, method, article of manufacture, or apparatus.

[0048] The transitional phrase "composed of..." does not include any unspecified elements, steps, or components. If included in the claims, protection will not be provided for materials other than those described, except for impurities typically associated with them. When the phrase "composed of..." appears in a clause of the body of a claim, rather than immediately following the preamble, it only limits the elements described in that clause; other elements as a whole are not excluded from the claims.

[0049] The transitional phrase "consistently composed of..." is used to define a composition, method, or apparatus that includes materials, steps, features, components, or elements in addition to those disclosed in the literature, provided that the additionally included materials, steps, features, components, or elements do not significantly affect the essential and novel characteristics of the invention protected by the claims. The term "consistently composed of..." occupies an intermediate position between "comprising" and "composed of...". Typically, the components of a refrigerant mixture and the refrigerant mixture itself may contain trace amounts (e.g., less than about 0.5% by weight in total) of impurities and / or byproducts (e.g., refrigerant components from the preparation of the refrigerant components or refrigerant components reused from other systems) that do not substantially affect the novel and essential characteristics of the refrigerant mixture.

[0050] Furthermore, the terms "an" or "a" are used to describe the elements and components described herein. This is for convenience only and to give a general meaning to the scope of the invention. This description should be understood to include one or at least one, and the singular includes the plural, unless it is obvious that it means otherwise.

[0051] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. While methods and materials similar to or equivalent to those described herein may be used in the practice or testing of embodiments of the disclosed compositions, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated herein by reference in their entirety unless specific paragraphs are cited. In case of any conflict, this specification and its included definitions shall prevail. Furthermore, materials, methods, and examples are illustrative only and are not intended to be limiting.

[0052] Refrigerant composition

[0053] In one embodiment, the composition comprises, or is substantially comprised of, HFO-1252zc, HFC-32, and HFO-1234zeE. These compositions provide low global warming potential (GWP), improved environmental fate characteristics, and improved energy efficiency (COP).

[0054] In another embodiment, the composition comprises, or is substantially comprised of, about 0.5 wt% to 65 wt% of HFO-1252zc, about 21 wt% to 22 wt% of HFC-32 and about 13 wt% to 78 wt% of HFO-1234zeE.

[0055] Flammability is a term used to refer to the ability of a composition to ignite and / or spread a flame. For refrigerants and other heat transfer compositions or working fluids, the lower flammability limit (“LFL”) is the minimum concentration of a heat transfer composition in air that, under the test conditions specified in ASTM E681, can propagate a flame through a homogeneous mixture of the composition and air. The upper flammability limit (“UFL”) is the maximum concentration of a heat transfer composition in air that, under the same test conditions, can propagate a flame through a homogeneous mixture of the composition and air.

[0056] In order for a refrigerant to be classified as low flammability (2L class) by ANSI / ASHRAE, it must: 1) exhibit flame propagation when tested at 140℉ (60℃) and 14.7psia (101.3kPa); 2) have a flame propagation rate of >0.0062lb / ft. 3 (0.10kg / m 31) LFL; 2) Heat of combustion <8169 Btu / lb (19,000 kJ / kg); and 3) Maximum combustion rate ≤3.9 in / s (10 cm / s) when tested in dry air at 73.4℉ (23.0℃) and 14.7 psia (101.3 kPa).

[0057] For a refrigerant to be classified as flammable (Class 2) by ANSI / ASHRAE, it must: 1) exhibit flame propagation when tested at 140℉ (60℃) and 14.7psia (101.3kPa); 2) have a flame propagation rate >0.0062 lb / ft. 3 (0.10kg / m 3 ) LFL; and 3) having a heat of combustion of <8169 Btu / lb (19,000 kJ / kg).

[0058] ASHRAE Standard 34 provides a method for calculating the heat of combustion of refrigerant blends using an equilibrium stoichiometric equation based on the complete combustion of one mole of refrigerant with enough oxygen for a stoichiometric reaction.

[0059] HFO-1252zc can be combined with HFC-32 and HFO-1234zeE, and provides an estimated Class 2 or 2L flammability as defined by ANSI / ASHRAE Standard 34 and ISO 817. Class 2 and 2L flammability are manageable in refrigeration systems. Specific applications may have different flammability requirements.

[0060] Compositions comprising or substantially comprising HFO-1252zc, HFC-32 and HFO-1234zeE may also contain at least one additional compound from the list in Table 1.

[0061] Table 1

[0062]

[0063]

[0064] In another embodiment, a composition comprising or substantially comprising HFO-1252zc, HFC-32, and HFO-1234zeE may further comprise at least one additional compound selected from HCFC-22, HCC-40, HFO-1234yf, HFO-1243zf, HFO-263fb, HFO-1252ze, HFO-1252yf, HFO-1252zf, and HFO-1252ye. In another embodiment, a composition comprising or substantially comprising HFO-1252zc, HFC-32, and HFO-1234zeE may further comprise at least one additional compound comprising HFO-1234yf. In another embodiment, a composition comprising or substantially comprising HFO-1252zc, HFC-32, and HFO-1234zeE may further comprise at least one additional compound comprising HFO-1243zf. In another embodiment, the composition comprising or substantially comprising HFO-1252zc, HFC-32 and HFO-1234zeE may further comprise at least one additional compound comprising HFO-263fb.

[0065] Some of the compounds present in the compositions of the present invention identified in Table 1 may exist as different configurational isomers or stereoisomers. The present invention is intended to include all single configurational isomers, single stereoisomers, or any combination or mixture thereof. For example, 1,2-difluoroethane (HFO-1132) is intended to represent any combination or mixture of cis-isomers (Z), trans-isomers (E), or any ratio of two isomers. Single or multiple isomers of the same compound may be used in any proportion.

[0066] The amount of additional compounds present in any of the aforementioned refrigerant compositions may be greater than 0 ppm and less than 5,000 ppm, and specifically may be in the range of greater than zero to about 1,000 ppm, about 5 ppm to about 500 ppm and about 1 ppm to about 100 ppm.

[0067] In one embodiment, the amount of the additional compound present in any of the aforementioned refrigerant compositions may be greater than 0% by weight and less than 1% by weight, preferably less than 0.5% by weight, or more preferably less than 0.1% by weight of the refrigerant composition.

[0068] Compositions containing HFO-1252zc, HFC-32, and HFO-1234zeE, or substantially composed of these, will behave more consistently and stably in the presence of only small amounts of water. Therefore, the composition may also contain less than 100 ppm (by weight) of water, preferably less than 20 ppm (by weight), and even more preferably less than 10 ppm (by weight).

[0069] Furthermore, compositions comprising or substantially comprising HFO-1252zc, HFC-32, and HFO-1234zeE will behave more consistently and stably in the presence of only trace amounts of oxygen or air. Therefore, the compositions claimed in this invention may also contain less than about 5% by volume of non-adsorbable gas (NAG), preferably less than 3% by volume, and more preferably less than 1.5% by volume. In addition, due to the presence of air or NAG, the compositions claimed in this invention will contain less than 1% by volume of oxygen, preferably less than 0.5% by volume, and more preferably less than 0.3% by volume.

[0070] In another embodiment, compositions comprising or substantially comprising HFO-1252zc, HFC-32, and HFO-1234zeE may contain stabilizers. Such stabilizer compounds are intended to be present in small amounts and to prevent decomposition during use or storage of the composition due to the presence of water, air, NAG, or oxygen in the system. HFO-type refrigerants may also experience thermal instability and decomposition under extreme use, handling, or storage conditions due to the presence of double bonds. Therefore, the addition of stabilizers to HFO-type refrigerants can be advantageous. Stabilizers may particularly include nitromethane, ascorbic acid, terephthalic acid, azoles such as toluenetriazole or benzotriazole, phenolic compounds such as tocopherol, hydroquinone, tert-butylhydroquinone, 2,6-di-tert-butyl-4-methylphenol, epoxides (possibly fluorinated or perfluorinated alkyl epoxides or alkenyl or aromatic epoxides) such as n-butyl glycidyl ether, hexanediol diglycidyl ether, allyl glycidyl ether, butylphenyl glycidyl ether, cyclic monoterpenes, terpenes such as d-limonene, α-terpinene, β-terpinene, γ-terpinene, α-pinene or β-pinene, phosphites, phosphates, phosphonates, thiols and lactones. Examples of suitable stabilizers are disclosed in WO2019213004, WO2020222864 and WO2020222865; the disclosure of which is incorporated herein by reference.

[0071] If the composition does contain a stabilizer, it may contain any amount of any of the stabilizers listed above, from 0.001% by weight to up to 1% by weight, preferably from about 0.001% by weight to about 0.5% by weight, more preferably from about 0.001% by weight to about 0.3% by weight.

[0072] In some embodiments, compositions comprising or substantially comprising HFO-1252zc, HFC-32, and HFO-1234ze may contain one or more tracer compounds. The tracer may include two or more tracer compounds. In some embodiments, the tracer is present in the composition at a total concentration of about 50 parts per million parts (ppm) to about 1000 ppm by weight based on the total composition. In other embodiments, the tracer is present at a total concentration of about 50 ppm to about 500 ppm. Alternatively, the tracer is present at a total concentration of about 100 ppm to about 300 ppm.

[0073] The tracer can be present in predetermined amounts in a composition comprising, or substantially comprising, HFO-1252zc, HFC-32, and HFO-1234zeE to allow detection of any dilution, contamination, or other alterations to the composition. The presence of certain compounds in the composition can indicate the method or process by which one of the components was produced. The tracer can also be added to the composition in specific amounts to identify the source of the composition. In this way, the detection of patent infringement can be achieved. The tracer can be a refrigerant compound, but present in the composition at a level unlikely to affect the performance of the refrigerant component of the composition.

[0074] The tracer compound can be a hydrofluorocarbon, a hydrofluoroolefin, a hydrochlorocarbon, a hydrochloroolefin, a hydrochlorofluorocarbon, a hydrochlorofluoroolefin, a hydrochloroolefin, a hydrochlorofluorocarbon, a hydrochloroolefin, a chlorofluorocarbon, a chlorofluoroolefin, a hydrocarbon, a perfluorocarbon, a perfluoroolefin, or a combination thereof. Examples of tracer compounds include, but are not limited to, HFC-23 (trifluoromethane), HCFC-31 (chlorofluoromethane), HFC-41 (fluoromethane), HFC-161 (fluoroethane), HFC-143a (1,1,1-trifluoroethane), HFC-134a (1,1,1,2-tetrafluoroethane), HFC-125 (pentafluoroethane), HFC-236fa (1,1,1,3,3,3-hexafluoropropane), HFC-236ea (1,1,1,2,3,3-hexafluoropropane), HFC-245cb (1,1,1,2,2-pentafluoropropane), and HFC-245fa (1,1,1,3,3-pentafluoropropane). Propane), HFC-254eb (1,1,1,2-tetrafluoropropane), HFC-263fb (1,1,1-trifluoropropane), HFC-272ca (2,2-difluoropropane), HFC-281ea (2-fluoropropane), HFC-281fa (1-fluoropropane), HFC-329p (1,1,1,2,2,3,3,4,4-nonafluorobutane), HFC-329mmz (1,1,1-trifluoro-2-methylpropane), HFC-338mf (1,1,1,2,2,4,4,4-octafluorobutane), HFC-338pcc (1,1,2,2,3,3,4,4-octafluorobutane) CFC-12 (dichlorodifluoromethane), CFC-11 (trichlorofluoromethane), CFC-114 (1,2-dichloro-1,1,2,2-tetrafluoroethane), CFC-114a (1,1,-dichloro-1,2,2,2-tetrafluoroethane), HCFC-22 (chlorodifluoromethane), HCFC-123 (1,1-dichloro-2,2,2-trifluoroethane), HCFC-124 (2-chloro-1,1,1,2-tetrafluoroethane), HCFC-124a (1-chloro-1,1,2,2-tetrafluoroethane), HCFC-141b (1,1-dichloro-1-fluoroethane), HCFC-142b (1-chloro-1,1... -difluoroethane), HCFC-151a (1-chloro-1-fluoroethane), HCFC-244bb (2-chloro-1,1,1,2-tetrafluoropropane), HCC-40 (chloromethane), HFO-1141 (ethylene fluoride), HCFO-1130 (1,2-dichloroethylene), HCFO-1130a (1,1-dichloroethylene), HCFO-1131 (1-chloro-2-fluoroethane), HCFO-1122 (2-chloro-1,1-difluoroethylene), HFO-1123 (1,1,2-trifluoroethylene), HFO-1234ye (1,2,3,3-tetrafluoropropylene), HFO-1243zf (3,3,3-Trifluoropropene), HFO-1225ye (1,2,3,3,3-pentafluoropropene), HFO-1225zc (1,1,3,3,3-pentafluoropropene), PFC-116 (hexafluoroethane), PFC-C216 (hexafluorocyclopropane), PFC-218 (octafluoropropane), PFC-C318 (octafluorocyclobutane), PFC-1216 (hexafluoroethane), PFC-31-10mc (1,1,1,2,2,3,3,4,4,4-decafluorobutane), PFC-31-10my (1,1,1,2,3,3,3-heptafluoro-2-trifluoromethylpropane), and combinations thereof.

[0075] In another embodiment of this disclosure, compositions comprising or substantially comprising HFO-1252zc, HFC-32, and HFO-1234zeE further comprise at least one lubricant. The lubricant may be selected from polyol esters, polyvinyl ethers, and polyalkylene glycols. The lubricant may also include those commonly referred to as "mineral oils" in the field of compression refrigeration lubrication. Mineral oils include alkanes (i.e., saturated hydrocarbons with straight and branched carbon chains), cycloalkanes (i.e., saturated hydrocarbons with cyclic or cyclic structures, which may be alkanes), and aromatics (i.e., unsaturated cyclic hydrocarbons containing one or more rings characterized by alternating double bonds). The lubricants of the present invention also include those commonly known as "synthetic oils" in the field of compression refrigeration lubrication. Synthetic oils comprise alkylaryl compounds (i.e., straight and branched alkylalkylbenzenes), synthetic alkanes and cycloalkanes, organosilicones, and polyalphaolefins. A representative conventional lubricant of this invention is commercially available BVM 100 N (an alkane mineral oil sold by BVA Oils), which is available from Crompton Co. under the trademark Suniso. ® 3GS and Suniso ® 5GS commercially available cycloalkane mineral oil, can be branded as Sontex ® 372LT is a cycloalkanes mineral oil purchased from Pennzoil, and can be marketed under the trademark Calumet. ® RO-30 is a cycloalkanes mineral oil obtained from Calumet Lubricants, and can be marketed under the brand name Zerol. ® 75. Zerol ® 150 and Zerol ® 500 linear alkylbenzenes obtained commercially from Shrieve Chemicals and branched alkylbenzenes sold by Nippon Oil as HAB 22.

[0076] The lubricants of this invention also include lubricants designed for use with hydrofluorocarbon refrigerants and miscible with the refrigerants of this invention under the operating conditions of compression refrigeration and air conditioning equipment. Lubricants include, but are not limited to, polyol esters (POEs) such as Castrol. ® 100 (Castrol, United Kingdom), polyalkylene glycols (PAGs) such as RL-488A from Dow Chemical, Midland, Mich., and polyvinyl ethers (PVEs) such as PVE-FVC68D.

[0077] In one specific embodiment, a composition comprising or substantially comprising HFO-1252zc, HFC-32 and HFO-1234ze is combined with a PAG lubricant or a PVE lubricant or a POE lubricant for use in an air conditioning system or a heat pump system.

[0078] In compositions comprising or substantially comprising HFO-1252zc, HFC-32, and HFO-1234zeE, the lubricant may be present in an amount less than 80% by weight of the total composition. The lubricant may also be present in an amount less than 60% by weight of the total composition. In other embodiments, the amount of lubricant may be between about 0.1% by weight and 50% by weight of the total composition. The lubricant may also be between about 0.1% by weight and 20% by weight of the total composition. The lubricant may also be between about 0.1% by weight and 5% by weight of the total composition.

[0079] In another aspect of the invention, compositions of the invention comprising or substantially comprising HFO-1252zc, HFC-32, and HFO-1234zeE are used for introducing lubricants into air conditioning or heat pump systems, and alternatively, other additives such as a) acid scavengers, b) performance enhancers, and c) flame retardants. In a preferred embodiment, the compositions of the invention comprise an acid scavenger.

[0080] Examples of acid scavengers that may be included in the compositions of the present invention include, but are not limited to, the stabilizers and / or epoxide components of stabilizers disclosed in U.S. Patent No. 8,535,555 and the acid scavengers disclosed in International Application Publication No. WO 2020 / 222864, the disclosures of which are incorporated herein by reference in their entirety.

[0081] In some embodiments, the acid scavenger may comprise one or more epoxides, one or more amines, and / or one or more hindered amines, such as, for example, but not limited to, epoxide.

[0082] Acid scavengers (e.g., activated aromatic compounds, siloxanes, or both) may be present at any concentration that results in a relatively low total acid value, a relatively low total halide concentration, a relatively low total organic acid concentration, or any combination thereof.

[0083] Preferably, the acid scavenger is present at a concentration greater than about 0.0050% by weight, more preferably greater than about 0.05% by weight, and even more preferably greater than about 0.1% by weight (e.g., greater than about 0.5% by weight) based on the total weight of the refrigerant composition. Based on the total weight of the refrigerant composition, the acid scavenger is preferably present at a concentration less than about 5% by weight, less than about 4% by weight, less than about 3% by weight, more preferably less than about 2.5% by weight, and most preferably greater than about 2% by weight (e.g., less than about 1.8% by weight).

[0084] Preferred additives include those described in U.S. Patent Nos. 5,152,926 and 4,755,316, which are incorporated herein by reference. In particular, preferred extreme pressure additives comprise mixtures of: (A) toluenetriazole or a substituted derivative thereof, (B) an amine (e.g., Jeffamine M-600), and (C) a third component which is (i) an ethoxylated phosphate ester (e.g., Antara LP-700), or (ii) a phosphorohydrin (e.g., ZELEC 3337), or (iii) zinc dialkyl dithiophosphate (e.g., Lubrizol 5139, 5604, 5178, or 5186), or (iv) mercaptobenzothiazole, or (v) a 2,5-dimercapto-1,3,4-thiadiazole derivative (e.g., Curvan 826) or mixtures thereof. Additional examples of additives that may be used are given in U.S. Patent No. 5,976,399 (Schnur, 5:12-6:51, which is hereby incorporated by reference).

[0085] Acid value was measured in mg KOH / g according to ASTM D664-01. Total halide ion concentration, fluoride ion concentration, and total organic acid concentration were measured by ion chromatography. The chemical stability of the refrigerant system was measured according to ASHRAE 97:2007 (RA2017), "Sealed Glass Tube Method to Test the Chemical Stability of Materials for Use within Refrigerant Systems." The viscosity of the lubricant was tested at 40°C according to ASTM D-7042.

[0086] Mouli et al. (WO 2008 / 027595 and WO 2009 / 042847) proposed the use of alkylsilanes as stabilizers in refrigerant compositions containing fluoroolefins. Phosphates, phosphites, epoxides, and phenolic additives have also been used in certain refrigerant compositions. These are described, for example, by Kaneko (U.S. Patent Application Serial No. 11 / 575,256, published as U.S. Publication 2007 / 0290164) and Singh et al. (U.S. Patent Application Serial No. 11 / 250,219, published as U.S. Publication 2006 / 0116310). All of the foregoing applications are expressly incorporated herein by reference.

[0087] Preferred flame retardants include those described and incorporated herein by reference in patent application CA 2557873 A1, entitled "Refrigerant compositions containing fluorine substituted olefins", and fluorinated products such as HFC-125, HFC-227ea, HFC-236fa, CF3I, and / or Krytox described and incorporated herein by reference in patent application WO2009018117A1, entitled "Refrigerant compositions comprising fluoroolefins and uses thereof". ® Lubricant.

[0088] In one embodiment, as used herein, “Group A fluorinated substance” includes any substance that meets the following criteria: (i) contains at least one fully fluorinated methyl (-CF3) or methylene (-CF2-) carbon atom (without any H / Cl / Br / I attached thereto); and (ii) Complies with the persistence standards in soil / sediments and water as specified in Annex XIII (Section 1.1.1) of the EU REACH Regulation. https: / / reachonline.eu / reach / en / annex-xiii-1-1.1-1.1.1.html, Accessed May 2, 2023 This standard is referenced in Annex XV Restriction Report dated March 22, 2023, and its disclosure is incorporated herein by reference. https: / / echa.europa.eu / documents / 10162 / f605d4b5-7c17-7414- 8823-b49b9fd43aea, Accessed May 2, 2023 In one implementation, Group A fluorinated substances include, but are not limited to, trifluoroacetic acid (TFA).

[0089] In another implementation, as used herein, “Group A fluorinated substances” include those with a Henry’s Law constant ≤250 Pa*m 3 / mol andAny substance containing at least one fully fluorinated methyl (-CF3) or methylene (-CF2-) carbon atom (without any H / Cl / Br / I attached thereto). In one embodiment, Group A fluorinated substances include, but are not limited to, TFA.

[0090] Therefore, according to some embodiments, the compositions of the present invention comprising or substantially comprising HFO-1252zc, HFC-32, and HFO-1234zeE are free from or substantially free from Group A fluorinated substances, such as TFA. In one embodiment, as used herein, the phrase “free from” regarding the presence of Group A fluorinated substances in the compositions of the present invention means that the amount of such substances in the composition is sufficiently low to be undetectable, including but not limited to 0%, when measured by gas chromatography with a flame ionization detector, gas chromatography with a mass detector (by analyzing a gaseous or liquid sample), and / or ion chromatography (by analyzing a water sample after bubbling a hot fluid through water). Such methods are well known to those skilled in the art. In one embodiment, as used herein, the phrase "substantially free" regarding the presence of Group A fluorinated substances in the compositions of the invention means, when measured by gas chromatography (GC), such as gas chromatography (GC) with a flame ionization or electron capture detector, or GC coupled with a mass detector (GC / MS method), by ion chromatography (IC) or ion chromatography-mass spectrometry (IC-MS), or by high performance liquid chromatography (HPLC) or high performance liquid chromatography-mass spectrometry (HPLC-MS), the amount of such substances in the composition is >0 wt% and ≤5 wt%, or >0 wt% and ≤4 wt%, or >0 wt% and ≤3 wt%, or >0 wt% and ≤2 wt%, or >0 wt% and ≤1 wt%, and all values ​​and ranges therebetween. TFA analytical standards are available for gas chromatography or ion chromatography and are obtained from, for example, Sigma Aldrich.

[0091] Additionally, in some embodiments, the degradation products of such compositions of the present invention, comprising or substantially comprising HFO-1252zc, HFC-32, and HFO-1234zeE, are free from or substantially free from Group A fluorinated substances, such as TFA. In one embodiment, as used herein, the phrase “free from” in relation to the formation of Group A fluorinated substances from the compositions of the present invention means that the theoretical molar yield of such substances in the environmental compartments of air, soil / sediment, and water generated during the tropospheric degradation of the composition is sufficiently low to be undetectable, including but not limited to 0%, when measured by GC techniques (e.g., GC or GC / MS methods with flame ionization or electron capture detectors), by IC or IC-MS techniques, or by HPLC or HPLC-MS techniques. In one embodiment, as used herein, the phrase “substantially free” regarding the formation of Group A fluorinated substances from the compositions of the present invention means, when measured by GC techniques (e.g., GC or GC / MS methods with flame ionization or electron capture detectors), by IC or IC-MS techniques, or by HPLC or HPLC-MS techniques, all values ​​and ranges between the theoretical molar yield of such substances in the environmental compartments of air, soil / sediment, and water generated during the tropospheric degradation of the composition during the tropospheric degradation of the composition, being >0% and ≤5%, or >0% and ≤4%, or >0% and ≤3%, or >0% and ≤2%, or >0% and ≤1%.

[0092] Method and system

[0093] Compositions comprising or substantially comprising HFO-1252zc, HFC-32 and HFO-1234zeE can be used in many methods and systems for providing air conditioning and heating.

[0094] In one embodiment, a cooling method is provided, comprising evaporating a composition comprising or substantially comprising HFO-1252zc, HFC-32, HFO-1234zeE near a subject to be cooled, and then condensing the composition, wherein the cooling is provided by an air conditioner or a heat pump.

[0095] In one embodiment, the air conditioning system can be a residential, commercial, or industrial air conditioning system. These air conditioning systems can include, but are not limited to, window-type, ducted, ductless, enclosed terminal, and those located outside the building but connected to it, such as rooftop systems. Due to the high critical temperature of the blend containing HFO-1252zc, HFC-32, and HFO-1234zeE, the method of the present invention can be particularly used in areas with high ambient temperatures.

[0096] In another embodiment, a heating method is provided, comprising evaporating a composition comprising HFO-1252zc, HFC-32, and HFO-1234zeE, and then condensing the composition near the subject to be heated, wherein the heating is provided by a heat pump.

[0097] The present invention claims compositions comprising or substantially comprising HFO-1252zc, HFC-32, and HFO-1234zeE, which provide heating and cooling performance with desired results. Under similar operating conditions, these compositions provide cooling and / or heating capacity within 13% of, or even within 10% of, that of R-454C. Furthermore, under similar operating conditions, compositions comprising or substantially comprising HFO-1252zc, HFC-32, and HFO-1234zeE provide improved COP compared to R-454C.

[0098] In one embodiment, the heat pump is a residential, light commercial, or industrial heat pump system. These heat pumps may include, but are not limited to, residential heat pumps providing comfortable air conditioning and heating, hot water heat pumps for heating air (via a secondary loop) or water for residential or commercial use, heat pumps for heating manufacturing process equipment, and high-temperature heat pumps. Due to the high critical temperature of blends containing HFO-1252zc, HFC-32, and HFO-1234zeE, water can be heated to temperatures higher than propane or R-454C.

[0099] In another embodiment, the method for generating cooling is particularly useful in areas where the ambient temperature may exceed 35°C.

[0100] In geographical areas with high ambient temperatures, where air conditioning becomes essential, refrigerant compositions with high critical temperatures and high thermal stability are desirable. Currently available hydrofluorocarbon (HFC) refrigerants such as R-410A, R-407C, or R-32 have relatively low critical temperatures. Therefore, these refrigerants perform poorly in extremely hot environments. During operation at high ambient temperatures, the energy efficiency of the refrigerant typically decreases as the condensing temperature approaches its critical temperature. In hot climates, R-22 remains the refrigerant of choice for many air conditioning and refrigeration applications because it is non-flammable and has a higher critical temperature, thus providing higher cooling capacity and higher energy efficiency in hot climates compared to R-410A or R-32. However, R-22 is an ozone-depleting substance under the Montreal Protocol, which aims to reduce ozone depletion. Therefore, legislation has been passed mandating the phase-out of R-22 in the air conditioning and refrigeration sectors. There is a focus on finding refrigerants with the lowest possible direct GWP and good performance in hot (or high ambient) temperature regions.

[0101] In methods for generating cooling, the subject to be cooled can be defined as any space, location, object, or subject for which cooling is desired. Examples include open or enclosed spaces requiring cooling, such as residences, such as apartments or apartment buildings, university dormitories, townhouses or other attached houses, or single-family homes; or the subject to be cooled can be any other building, such as office buildings, supermarkets, college or university classrooms or administration buildings.

[0102] In another embodiment, a method for generating air conditioning at high ambient temperatures is provided. The method includes evaporating a composition comprising or substantially comprising HFO-1252zc, HFC-32, and HFO-1234zeE, and then condensing said composition. This method is particularly useful in areas where ambient temperatures may exceed 35°C or higher.

[0103] In another embodiment, a method for replacing HCFC-22 in a high-ambient-temperature air conditioning device is provided, the method comprising providing the device with a composition comprising or substantially comprising HFO-1252zc, HFC-32, and HFO-1234zeE. This method of replacing HCFC-22 is particularly useful in areas where ambient temperatures may exceed 35°C or higher.

[0104] Similarly, in some industrial air conditioning applications, heat must be released in high ambient temperatures. HCFC-124 has been used as the working fluid in such applications. HCFC-124, as an ozone-depleting substance, is also controlled under the Montreal Protocol, and a more environmentally sustainable alternative is needed. Therefore, a method for replacing HCFC-124 in industrial air conditioning equipment is provided, comprising supplying the equipment with a composition containing, substantially composed of, or composed of, HFO-1252zc, HFC-32, and HFO-1234zeE. This method of replacing HCFC-124 is particularly useful in areas where ambient temperatures may exceed 35°C or higher.

[0105] In another embodiment, the method for generating cooling and the method for replacing HCFC-22 or HCFC-124 can be used in systems operating at ambient temperatures of 40°C or higher. In another embodiment, the method for generating cooling can be used in systems operating at ambient temperatures of 45°C or higher. In another embodiment, the method for generating cooling can be used in systems operating at ambient temperatures of 50°C or higher. In another embodiment, the method for generating cooling can be used in systems operating at ambient temperatures of 55°C or higher. In another embodiment, the method for generating cooling can be used in systems operating at ambient temperatures of 60°C or higher. In another embodiment, the method for generating cooling can be used in systems operating at ambient temperatures of 35°C to 50°C. In another embodiment, the method for generating cooling can be used in systems operating at ambient temperatures of 35°C to 60°C. In another embodiment, the method for generating cooling can be used in systems operating at ambient temperatures of 40°C to 60°C. In another embodiment, the method for generating cooling can be used in systems operating at ambient temperatures of 45°C to 60°C. In another embodiment, the method for generating cooling can be used in systems operating at ambient temperatures of 50°C to 60°C.

[0106] In another embodiment, a system for cooling or heating is provided, comprising a composition containing HFO-1252zc, HFC-32, and HFO-1234zeE, and optionally a lubricant. The system includes an evaporator, a compressor, a condenser, and an expander, each operatively connected to perform a vapor compression cycle.

[0107] Air conditioning or heat pump systems can be residential, light commercial, or industrial. Various such systems have been described previously in this article.

[0108] In another embodiment, an air conditioning or heat pump system comprising or substantially comprising HFO-1252zc, HFC-32 and HFO-1234zeE can be a secondary loop system.

[0109] The following examples are provided to illustrate certain aspects of the invention and should not limit the scope of the appended claims.

[0110] Embodiment

[0111] Embodiment 1

[0112] Under the residential heat pump conditions shown below, the composition claimed in this invention is compared with R-454C (ASHRAE designation for a refrigerant containing 78.5 wt% HFO-1234yf and 21.5 wt% HFC-32). Table 2 provides the calculation results.

[0113]

[0114] Table 2

[0115]

[0116]

[0117]

[0118] Data shows that, in both cooling and heating modes, compositions comprising HFO-1252zc, HFC-32, and HFO-1234zeE provide a higher COP (a measure of energy efficiency) than propane or R-454C. Furthermore, the cooling and heating capacity is within 13% or even 10% of that of R-454C. Therefore, the compositions of this invention provide a viable alternative to R-454C.

[0119] Embodiment 2

[0120] Under the residential air conditioning conditions shown below, the composition claimed in this invention is compared with R-454C (ASHRAE designation for a refrigerant containing 78.5 wt% HFO-1234yf and 21.5 wt% HFC-32). Table 3 provides the calculation results under the following conditions.

[0121] Average condenser temperature = 46.1℃ [115℉]

[0122] Average evaporator temperature = 10.0℃ [50℉],

[0123] Supercooled = 8.3K [15℉],

[0124] Overheat = 11.1K [20℉],

[0125] Compressor efficiency = 0.70

[0126] Table 3

[0127]

[0128] The compositions of the present invention containing HFO-1252zc, HFC-32, and HFO-1234zeE provide a capacity similar to R-454C (within 10%), which is higher than that of propane. Furthermore, the compositions provide an improved COP relative to R-454C and are also slightly superior to propane. All these properties are provided while maintaining a GWP of less than 150 and a reasonable average temperature glide.

Claims

1. A composition comprising HFO-1252zc, HFC-32 and HFO-1234zeE.

2. The composition according to claim 1, wherein the composition comprises about 0.5 wt% to 65 wt% of HFO-1252zc, about 21 wt% to 22 wt% of HFC-32 and about 13 wt% to 78 wt% of HFO-1234zeE.

3. The composition according to claim 1, wherein the composition comprises about 30% by weight of HFO-1252zc, about 21% by weight of HFC-32 and about 49% by weight of HFO-1234zeE.

4. The composition according to any one of claims 1 to 3, further comprising at least one additional compound selected from the group consisting of: HCFC-22, HFC-23, HCC-30, HCFC-31, HCC-40, HFC-41, methane, HFC-125, HFC-143, HFC-143a, HFC-152a, HFC-245cb, HCFC-253dc, HFC-254fb, HCC-260fb, HCFC-261fc, HCFC-262fc, HFC-263fb, HFC-272fb, propane, HFO-374, n- Butane, propadiene, 2-butene, cyclobutene, 2-methylpropene, HCFO-1122, HFO-1132, HFO-1132a, HFO-1141, ethylene, HCFO-1233xf, HFO-1234yf, HCFO-1242zf, HFO-1243zf, HCFO-1251, HCO-1260zf, HFO-1261zf, propylene, HFO-1345, HFO-1252ze, HFO-1252yf, HFO-1252zf, HFO-1252ye and E / Zt-BuO-CF=CH-CH3.

5. The composition according to any one of claims 1 to 4 further comprises at least one additional compound selected from the group consisting of HCFC-22, HCC-40, HFO-1234yf, HFO-1243zf, HFC-263fb, HFO-1252ze, HFO-1252yf, HFO-1252zf, and HFO-1252ye.

6. The composition according to any one of claims 1 to 5, wherein the composition further comprises 0.1 ppm to 200 ppm of water by weight; about 10 ppm to about 0.35% by volume of oxygen by volume; and / or about 100 ppm to about 1.5% by volume of air or NAG.

7. The composition according to any one of claims 1 to 3, wherein the composition comprises a stabilizer.

8. The composition according to claim 7, wherein the stabilizer is selected from the group consisting of: nitromethane, ascorbic acid, terephthalic acid, azoles, phenolic compounds, cyclic monoterpenes, terpenes, phosphites, phosphates, phosphonates, thiols, and lactones.

9. The composition according to any one of claims 7 or 8, wherein the stabilizer is selected from toluenetriazole, benzotriazole, tocopherol, hydroquinone, tert-butylhydroquinone, 2,6-di-tert-butyl-4-methylphenol, fluorinated epoxide, n-butyl glycidyl ether, hexanediol diglycidyl ether, allyl glycidyl ether, butylphenyl glycidyl ether, d-limonene, α-terpinene, β-terpinene, α-pinene, β-pinene, or butylated hydroxytoluene.

10. The composition according to any one of claims 7 to 9, wherein the stabilizer is present in an amount of about 0.001% by weight to 1.0% by weight based on the weight of the refrigerant.

11. The composition according to any one of claims 1 to 10, wherein the composition further comprises a lubricant.

12. The composition of claim 11, wherein the lubricant is at least one selected from the group consisting of: polyalkylene glycols, polyol esters, poly-α-olefins, and polyethylene ethers.

13. The composition according to claim 11 or 12, wherein the lubricant is a polyol ester or a polyethylene ether.

14. The composition according to any one of claims 11 to 13, wherein the lubricant has at least one property selected from the group consisting of: greater than 10 at 20°C. 10 Volume resistivity in Ω-m; surface tension of about 0.02 N / m to 0.04 N / m at 20 °C; kinematic viscosity of about 20 cSt to about 500 cSt at 40 °C; breakdown voltage of at least 25 kV; and hydroxyl value of up to 0.1 mg KOH / g.

15. The composition according to any one of claims 1 to 14, wherein the composition comprises at least one tracer.

16. The composition of claim 15, wherein the tracer is present in an amount from about 1.0 ppm to about 1000 ppm by weight.

17. The composition according to any one of claims 15 or 16, wherein the at least one tracer is selected from the group consisting of: hydrofluorocarbons, hydrofluoroolefins, hydrochlorocarbons, hydrochloroolefins, hydrochlorofluorocarbons, hydrochlorofluoroolefins, hydrochlorocarbons, hydrochloroolefins, chlorofluorocarbons, chlorofluoroolefins, hydrocarbons, perfluorocarbons, perfluoroolefins, and combinations thereof.

18. The composition according to any one of claims 15 to 17, wherein the at least one tracer is selected from the group consisting of: HFC-23, HCFC-31, HFC-41, HFC-161, HFC-143a, HFC-134a, HFC-125, HFC-236fa, HFC-236ea, HFC-245cb, HFC-245fa, HFC-254eb, HFC-263fb, HFC-272ca, HFC-281ea, HFC-281fa, HFC-329p, HFC-329mmz, HFC338mf, HFC-338pcc, CFC-12, CFC-11, CFC-114, CFC-114a, HCFC -22, HCFC-123, HCFC-124, HCFC-124a, HCFC-141b, HCFC-142b, HCFC-151a, HCFC-244bb, HCC-40, HFO-1141, HCFO-1130, HCFO-1130a, HCFO-1131, HCFO-1122, HFO-1123, HFO-1234yf, HFO-1234ye, HFO-1243zf, HFO-1225ye, HFO-1225zc, PFC-116, PFC-C216, PFC-218, PFC-C318, PFC-1216, PFC-31-10mc, PFC-31-10my, and combinations thereof.

19. The composition according to any one of claims 1 or 18, wherein the composition is free from or substantially free from Group A fluorinated substances, and wherein the degradation products of the composition are free from or substantially free from Group A fluorinated substances.

20. A method for cooling, the method comprising evaporating a composition according to any one of claims 1 to 19 near a body to be cooled, and then condensing the composition, wherein the cooling is provided by an air conditioner or a heat pump.

21. A method for heating, the method comprising evaporating a composition according to any one of claims 1 to 19, and then condensing the composition near a body to be heated, wherein the heating is provided by a heat pump.

22. A system for cooling or heating, said system comprising the composition according to any one of claims 1 to 19.

23. The system of claim 22, comprising an evaporator, a compressor, a condenser, and an expander, each operatively connected to perform a vapor compression cycle.

24. The system of claim 22 or 23, wherein the air conditioner or heat pump is a residential, light commercial or industrial air conditioner or heat pump.

25. A method of replacing R-454C or propane in an air conditioning or heat pump system, the method comprising providing the system with a composition according to any one of claims 1 to 19 to replace R-454C or propane.

26. Use of the composition according to any one of claims 1 to 19 as a refrigerant in an air conditioning or heat pump system.

27. The system according to any one of claims 22 to 24, wherein the system is a secondary loop system.

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