Blend composition containing difluoropropene

Abstract

This disclosure relates to a composition comprising HFO-1252zc and at least one of HFC-32 or HFO-1234ze-E. The composition is useful in heating and cooling methods, air conditioning and heat pump systems, and methods for replacing existing refrigerants.

Description

Technical Field

[0001] The present disclosure relates to compositions useful as refrigerants, particularly in air conditioning and heat pump systems. The compositions of the present disclosure are useful in methods of producing cooling and heating, methods of replacing refrigerants, and air conditioning and heat pump systems.

Background Art

[0002] Over the past decades, the fluorocarbon industry has been working to find alternative refrigerants to ozone-depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) that are being phased out as a result of the Montreal Protocol. The solution for many applications has been the commercialization of hydrofluorocarbon (HFC) compounds for use as refrigerants, solvents, fire extinguishing agents, blowing agents, and propellants. These new compounds, such as the most widely used HFC refrigerants at present, HFC-134a and HFC-125, have zero ozone depletion potential (ODP), and thus are not affected by current regulations that phase out substances pursuant to the Montreal Protocol. In addition to the problem of ozone layer depletion, another environmental concern for many of these applications is global warming. HFC refrigerants such as HFC-134a and HFC-125 have global warming potentials (GWPs) of 1,430 and 3,500 respectively, according to the Intergovernmental Panel on Climate Change Fourth Assessment Report (AR4).

[0003] This regulatory situation is constantly evolving, and characteristics other than ODP and GWP are also being considered. More specifically, there is a need for refrigerant compositions that not only meet low ODP standards and have a low global warming potential, but also provide excellent performance in various applications and meet evolving regulatory standards.

Summary of the Invention

Problem to be Solved by the Invention

[0004] This invention provides a refrigerant blend containing 1,1-difluoropropene that solves specific problems associated with conventional refrigerants and meets evolving regulatory requirements. [Means for solving the problem]

[0005] To meet the rapidly changing regulatory environment, the inventors have identified fluoroolefin compounds that offer performance characteristics that allow them to advance their use compared to existing refrigerants, taking into account the criteria of the evolving regulatory landscape.

[0006] Specific embodiments disclosed herein relate to fluoropropene compositions comprising 1,1-difluoropropene (also known as HFO-1252zc or R-1252zc). This compound is shown herein to have properties advantageous for use in refrigerant applications.

[0007] In one embodiment, disclosed herein is a composition comprising HFO-1252zc and at least one of HFO-1234ze-E (i.e., the E isomer) or HFC-32.

[0008] According to any of the embodiments described above, disclosed herein is a composition comprising about 20 to 83 weight percent of HFO-1252zc and about 17 to 80 weight percent of at least one of HFO-1234ze-E or HFC-32.

[0009] According to any of the embodiments described above, disclosed herein is a composition comprising about 20 to 81 weight percent of HFO-1252zc and about 19 to 80 weight percent of at least one of HFO-1234ze-E or HFC-32.

[0010] According to any of the embodiments described above, disclosed herein is a composition comprising about 20 to 83 weight percent of HFO-1252zc and about 17 to 80 weight percent of HFC-32.

[0011] According to any of the embodiments described above, disclosed herein is a composition comprising about 20 to 81 weight percent of HFO-1252zc and about 19 to 80 weight percent of HFO-1234ze-E.

[0012] According to any of the embodiments described herein, a composition comprising about 50 to 81 weight percent of HFO-1252zc and about 19 to 50 weight percent of HFO-1234ze-E is disclosed herein.

[0013] According to any of the embodiments described herein, disclosed herein is a composition comprising HFO-1252zc and HFC-32, wherein the concentration of HFO-1252zc in the composition is in the range of about X1 weight percent to about Y1 weight percent based on the weights of HFO-1252zc and HFC-32, and the concentration of HFC-32 in the composition is in the range of about X2 weight percent to about Y2 weight percent based on the weights of HFO-1252zc and HFC-32, where X1 is 20, 50, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, and Y1 is any number selected from 70, X2 is any number selected from 17, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, and 50, Y2 is any number selected from 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, and 80, and the sum of the weight percentages of HFO-1252zc and HFC-32 is 100.

[0014] According to any of the embodiments described herein, disclosed herein is a composition comprising HFO-1252zc and HFO-1234ze-E, wherein the concentration of HFO-1252zc in the composition is in the range of about X1 weight percent to about Y1 weight percent based on the weights of HFO-1252zc and HFO-1234ze-E, and the concentration of HFO-1234ze-E in the composition is in the range of about X3 weight percent to about Y3 weight percent based on the weights of HFO-1252zc and HFO-1234ze-E, where X1 is 1, 4, 7, 10, 13, 16, 19, 20, 22, 25, 28, 31, 34, 37, 40, 43, 46, 49, Y1 is any number selected from 4, 7, 10, 13, 16, 19, 20, 22, 25, 28, 31, 34, 37, 40, 43, 46, 49, 50, and 81, X3 is any number selected from 19, 50, 51, 54, 57, 60, 63, 66, 69, 72, 75, 78, 80, 81, 84, 87, 90, 93, and 96, Y3 is any number selected from 50, 51, 54, 57, 60, 63, 66, 69, 72, 75, 78, 80, 81, 84, 87, 90, 93, 96, and 99, and the sum of the weight percentages of HFO-1252zc and HFO-1234ze-E is 100.

[0015] According to any of the embodiments described herein, disclosed herein is a composition comprising HFO-1252zc, HFC-32, and HFO-1234ze-E, wherein the concentration of HFO-1252zc in the composition is in the range of about X1 weight percent to about Y1 weight percent based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E, and the concentration of HFC-32 in the composition is in the range of about X2 weight percent to about Y2 weight percent based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E. The values ​​are in the range of weight percent, and the concentration of HFO-1234ze-E is in the range of approximately X3 weight percent to approximately Y3 weight percent based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E, where X1 is any number selected from 0.5, 5, 10, 14, 17, 21, 22, 24, 27, 28, 30, 32, 33, 35, 37, 39, 40, 42, 44, 45, 46, 47, 48, 49, 51, 52, 54, 55, 56, 57, 58, 59, 60, 62, and 63, and Y1 is 5, 10, 14, 17, X2 is any number selected from 21, 22, 24, 27, 28, 30, 32, 33, 35, 37, 39, 40, 42, 44, 45, 46, 47, 48, 49, 51, 52, 54, 55, 56, 57, 58, 59, 60, 62, 63, and 64, X2 is any number selected from 17, 18, 19, 20, 21, 23, 24, 28, 29, 32, 33, 34, 35, 36, 38, 41, 42, 43, 78, 44, Y2 is any number selected from, X3 is 4, 5, 14, 17, 19, 21, 22, 23, 24, 26, 2 Y3 is any number selected from 7, 28, 30, 32, 34, 35, 36, 37, 38, 39, 42, 43, 44, 45, 47, 51, 54, 55, 55, 72, and 56, and Y3 is any number selected from 5, 14, 17, 19, 21, 22, 23, 24, 26, 27, 28, 30, 32, 34, 35, 36, 37, 38, 39, 42, 43, 44, 45, 47, 51, 54, 55, 55, 72, 56, and 62, and the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E is 100.

[0016] According to any of the embodiments described above, disclosed herein is a composition comprising HFO-1252zc and HFC-32, wherein HFO-1252zc is present at a concentration of about 56 to about 70 weight percent based on the weights of HFO-1252zc and HFC-32, and HFC-32 is present at a concentration of about 30 to about 44 weight percent based on the weights of HFO-1252zc and HFC-32.

[0017] According to any of the embodiments described above, disclosed herein is a composition comprising HFO-1252zc and HFC-32, wherein HFO-1252zc is present at a concentration of about 56 to about 68 weight percent based on the weights of HFO-1252zc and HFC-32, and HFC-32 is present at a concentration of about 32 to about 44 weight percent based on the weights of HFO-1252zc and HFC-32.

[0018] According to any of the embodiments described above, disclosed herein is a composition comprising HFO-1252zc and HFC-32, wherein HFO-1252zc is present at a concentration of about 56 to about 65 weight percent based on the weights of HFO-1252zc and HFC-32, and HFC-32 is present at a concentration of about 35 to about 44 weight percent based on the weights of HFO-1252zc and HFC-32.

[0019] According to any of the embodiments described herein, disclosed herein is a composition comprising HFO-1252zc, HFC-32, and HFO-1234ze-E, wherein HFO-1252zc is present at a concentration of about 33% to about 45% by weight based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E, and HFC-32 is... Based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E, they are present at concentrations of approximately 18% to 20% by weight, and based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E, they are present at concentrations of approximately 19% to 47% by weight, and the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E is 100.

[0020] According to any of the embodiments described herein, disclosed herein is a composition comprising HFO-1252zc, HFC-32, and HFO-1234ze-E, wherein HFO-1252zc is present at a concentration of about 0.05% to about 24% by weight based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E, and HFC-32 is composed of HFO-1252zc, HFC-32, Based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E, they are present at concentrations of approximately 34% to 43.78% by weight, and based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E, they are present at concentrations of approximately 37% to 62% by weight, and the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E is 100.

[0021] According to any of the embodiments described herein, disclosed herein is a composition comprising HFO-1252zc, HFC-32, and HFO-1234ze-E, wherein HFO-1252zc is present at a concentration of about 51% to about 63% by weight based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E, and HFC-32 is... Based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E, they are present at concentrations of approximately 23% to 38% by weight, and based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E, they are present at concentrations of approximately 4% to 21% by weight, and the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E is 100.

[0022] According to any of the embodiments described herein, disclosed herein is a composition comprising HFO-1252zc, HFC-32, and HFO-1234ze-E, wherein HFO-1252zc is present at a concentration of about 31% to about 64% by weight based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E, and HFC-32 is... Based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E, they are present at concentrations of approximately 17% to 43% by weight, and based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E, they are present at concentrations of approximately 1% to 31% by weight, and the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E is 100.

[0023] According to any of the foregoing embodiments, disclosed herein is a composition comprising HFO-1252zc, HFC-32, and HFO-1234ze-E, wherein HFO-1252zc is present in a concentration of from about 0.05 weight percent to about 25 weight percent, based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E, HFC-32 is present in a concentration of from about 36 weight percent to about 43.78 weight percent, based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E, HFO-1234ze-E is present in a concentration of from about 39 weight percent to about 57 weight percent, based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E, and the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E is 100.

[0024] According to any of the foregoing embodiments, disclosed herein is a composition comprising HFO-1252zc, HFC-32, and HFO-1234ze-E, wherein HFO-1252zc is present in a concentration of from about 36 weight percent to about 60 weight percent, based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E, HFC-32 is present in a concentration of from about 17 weight percent to about 22 weight percent, based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E, HFO-1234ze-E is present in a concentration of from about 18 weight percent to about 42 weight percent, based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E, and the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E is 100.

[0025] According to any of the foregoing embodiments, disclosed herein is a composition comprising HFO-1252zc and HFO-1234ze-E, wherein HFO-1252zc is present in a concentration of from about 1 weight percent to about 16 weight percent, based on the weight of HFO-1252zc and HFO-1234ze-E, HFO-1234ze-E is present in a concentration of from about 84 weight percent to about 99 weight percent, based on the weight of HFO-1252zc and HFO-1234ze-E, and the sum of the weight percentages of HFO-1252zc and HFO-1234ze-E is 100.

[0026] According to any of the foregoing embodiments, disclosed herein is a composition comprising HFO-1252zc, HFC-32 and HFO-1234ze-E, wherein HFO-125zc is present in a concentration of from about 19 weight percent to about 23 percent, based on the weight of HFO-1252zc, HFC-32 and HFO-1234zc, HFC-32 is present in a concentration of from about 18 weight percent to about 22 weight percent, based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E, and HFO-1234ze-E is present in a concentration of from about 57 weight percent to about 61 weight percent, based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E.

[0027] According to any of the embodiments described above, the following are disclosed herein: 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, allene, 2-butene, cyclobutene, 2-methylbutene The composition further comprises lobene, 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-1252zc, HFO-1252yf, HFO-1252zf, HFO-1252ye, and at least one additional compound selected from E / Zt-BuO-CF=CH-CH3.

[0028] According to any of the embodiments described above, disclosed herein is a composition further comprising at least one additional compound selected from HCFC-22, HCC-40, HFO-1234yf, HFO-1243zf, HFC-263fb, HFO-1252zc, HFO-1252yf, HFO-1252zf, and HFO-1252ye.

[0029] According to any of the embodiments described above, disclosed herein is a composition further comprising 0.1 to 200 ppm by weight of water, about 10 ppm to about 0.35 volume percent of oxygen, and / or about 100 ppm to about 1.5 volume percent of air or NAG.

[0030] According to any of the embodiments described above, what is disclosed herein is a composition comprising a stabilizer.

[0031] According to any of the embodiments described above, disclosed herein is a composition in which the stabilizer is selected from the group consisting of nitromethane, ascorbic acid, terephthalic acid, azole, phenol compounds, cyclic monoterpenes, terpenes, phosphites, phosphates, phosphonates, thiols, and lactones.

[0032] According to any of the embodiments described above, disclosed herein is a composition in which the stabilizer is selected from toltriaazole, benzotriazole, tocopherol, hydroquinone, t-butylhydroquinone, 2,6-di-tertbutyl-4-methylphenol, fluorinated epoxide, n-butylglycidyl ether, hexanediol diglycidyl ether, allylglycidyl ether, butylphenyl glycidyl ether, d-limonene, α-terpinene, β-terpinene, α-pinene, β-pinene, or butylated hydroxytoluene.

[0033] According to any of the embodiments described herein, disclosed herein is a composition in which the stabilizer is present in an amount of about 0.001 to 1.0 weight percent based on the weight of the refrigerant.

[0034] According to any of the embodiments described herein, a composition further comprising a lubricant is disclosed herein, the lubricant being at least one selected from the group consisting of polyalkylene glycol, polyol ester, poly-α-olefin, and polyvinyl ether.

[0035] According to any of the embodiments described herein, a composition is disclosed wherein the lubricant is a polyol ester or a polyvinyl ether.

[0036] According to any of the embodiments described herein, the lubricant is disclosed as having a temperature of 10°C at 20°C. 10The composition has at least one property selected from the group consisting of a volume resistivity greater than Ω-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 dielectric breakdown voltage of at least 25 kV, and a hydroxyl value of a maximum of 0.1 mg KOH / g.

[0037] According to any of the embodiments described herein, a composition comprising at least one tracer is disclosed herein.

[0038] According to any of the embodiments described herein, the present invention relates to a composition in which the tracer is present in an amount of about 1.0 ppm by weight to about 1000 ppm by weight.

[0039] According to any of the embodiments described herein, disclosed herein is a composition in which 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.

[0040] According to any of the embodiments described herein, at least one tracer is disclosed to include 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, HFC-338mf, HFC-338pcc, CFC-12, CFC-11, CFC-114, CFC-114a, HCFC-22, HCFC-123 The composition is selected from the group consisting of 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.

[0041] According to any of the embodiments described herein, the composition disclosed herein is one that does not contain or substantially contains a group A fluorinated substance, and the decomposition products of the composition do not contain or substantially contain a group A fluorinated substance.

[0042] According to any of the embodiments described herein, disclosed herein is a composition in which HFO-1252zc is present at a concentration of about 56 to about 70 weight percent based on the weights of HFO-1252zc and HFC-32, and HFC-32 is present at a concentration of about 30 to about 44 weight percent based on the weights of HFO-1252zc and HFC-32.

[0043] According to any of the embodiments described above, disclosed herein is a composition in which HFO-1252zc is present at a concentration of about 56 to about 68 weight percent based on the weights of HFO-1252zc and HFC-32, and HFC-32 is present at a concentration of about 32 to about 44 weight percent based on the weights of HFO-1252zc and HFC-32.

[0044] According to any of the embodiments described herein, disclosed herein is a composition in which HFO-1252zc is present at a concentration of about 56% to about 65% by weight, based on the weights of HFO-1252zc and HFC-32, and HFC-32 is present at a concentration of about 35% to about 44% by weight, based on the weights of HFO-1252zc and HFC-32.

[0045] According to any of the embodiments described above, disclosed herein is a composition in which HFO-1252zc is present at a concentration of about 33% to about 45% by weight based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E; HFC-32 is present at a concentration of about 18% to about 20% by weight based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 19% to about 47% by weight based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E; the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E is 100; and the GWP is <160.

[0046] According to any of the embodiments described herein, HFO-1252zc is present at a concentration of about 0.05% to about 24% by weight, based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E, and HFC-32 is present at a concentration of about 34% to about 43.78% by weight, based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E. The composition is present in the following concentrations, with HFO-1234ze-E present at a concentration of approximately 37% to 62% by weight based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E, the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E being 100, and having a flammability rating of 2L (measured according to ANSI / ASHRAE standard 34).

[0047] According to any of the embodiments described above, disclosed herein is a composition in which HFO-1252zc is present at a concentration of about 51% to about 63% by weight based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E; HFC-32 is present at a concentration of about 23% to about 38% by weight based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 4% to about 21% by weight based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E; and the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E is 100.

[0048] According to any of the embodiments described above, disclosed herein is a composition in which HFO-1252zc is present at a concentration of about 31% to about 64% by weight based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E; HFC-32 is present at a concentration of about 17% to about 43% by weight based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 1% to about 31% by weight based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E; and the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E is 100.

[0049] According to any of the embodiments described herein, HFO-1252zc is present at a concentration of about 0.05% to about 25% by weight, based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E, and HFC-32 is present at a concentration of about 36% to about 43.78% by weight, based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E. The composition contains HFO-1234ze-E at a concentration of approximately 39% to 57% by weight, based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E, with the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E being 100, and having a flammability rating of 2L (measured according to ANSI / ASHRAE standard 34).

[0050] According to any of the embodiments described above, disclosed herein is a composition in which HFO-1252zc is present at a concentration of about 36% to about 60% by weight based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E; HFC-32 is present at a concentration of about 17% to about 22% by weight based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 18% to about 42% by weight based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E; the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E is 100; and the GWP is <160.

[0051] According to any of the embodiments described above, disclosed herein is a composition in which HFO-1252zc is present at a concentration of about 1% to about 16% by weight based on the weights of HFO-1252zc and HFO-1234ze-E, HFO-1234ze-E is present at a concentration of about 84% to about 99% by weight based on the weights of HFO-1252zc and HFO-1234ze-E, the sum of the weight percentages of HFO-1252zc and HFO-1234ze-E is 100, and the composition has a flammability grade of 2 L (measured according to ANSI / ASHRAE standard 34).

[0052] According to any of the embodiments described above, disclosed herein is a composition in which HFO-125zc is present at a concentration of about 19% to about 23% by weight based on the weights of HFO-1252zc, HFC-32, and HFO-1234zc; HFC-32 is present at a concentration of about 18% to about 22% by weight based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 57% to about 61% by weight based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E; and the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E is 100.

[0053] According to any of the embodiments described above, disclosed herein is a composition in which HFO-1252zc is present at a concentration of about 56 to about 70 weight percent based on the weights of HFO-1252zc and HFC-32, HFC-32 is present at a concentration of about 30 to about 44 weight percent based on the weights of HFO-1252zc and HFC-32, the sum of the weight percentages of HFO-1252zc and HFC-32 is 100, and the heat pump is also shown to have been operated in cooling mode.

[0054] According to any of the embodiments described above, disclosed herein is a composition in which HFO-1252zc is present at a concentration of about 0.5% to about 63% by weight based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E; HFC-32 is present at a concentration of about 18% to about 43.78% by weight based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 4% to about 62% by weight based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E; and the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E is 100.

[0055] According to any of the embodiments described above, disclosed herein is a composition in which HFO-1252zc is present at a concentration of about 0.5% to about 64% by weight based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E, HFC-32 is present at a concentration of about 17% to about 43.78% by weight based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E, HFO-1234ze-E is present at a concentration of about 1% to about 57% by weight based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E, and the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E is 100.

[0056] According to any of the embodiments described above, disclosed herein is a composition in which HFO-1252zc is present at a concentration of about 18% to about 20% by weight based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E; HFC-32 is present at a concentration of about 6% to about 21% by weight relative to the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 59% to about 76% by weight relative to the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E; the sum of the weight percentages of HFO-1252ze, HFC-32, and HFO-1234ze-E is 100; and exhibits a GWP of <160 and a flammability grade of 2L.

[0057] According to any of the embodiments described above, disclosed herein is a composition in which HFO-1252zc is present at a concentration of about 20 weight percent based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E, HFC-32 is present at a concentration of about 21 weight percent based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E, HFO-1234ze-E is present at a concentration of about 59 weight percent based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E, and the sum of the weight percentages of HFO-1252ze, HFC-32, and HFO-1234ze-E is 100.

[0058] According to any of the embodiments described above, disclosed herein is a composition in which HFO-1252zc is present at a concentration of about 18% to about 22% by weight based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E, HFC-32 is present at a concentration of about 19% to about 23% by weight relative to the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E, HFO-1234ze-E is present at a concentration of about 57% to about 61% by weight relative to the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E, and the sum of the weight percentages of HFO-1252ze, HFC-32, and HFO-1234ze-E is 100.

[0059] According to any of the embodiments described herein, a method for cooling is disclosed, the method comprising evaporating a composition in the vicinity of an object to be cooled, and then condensing the composition, the cooling being provided by an air conditioner or a heat pump.

[0060] According to any of the embodiments described herein, a method for heating is disclosed, the method comprising evaporating a composition and then condensing the composition in the vicinity of an object to be heated, the heating being provided by a heat pump.

[0061] In any of the embodiments described above, what is disclosed herein is a system for cooling or heating comprising a composition of any of the embodiments described above. 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 yet another embodiment, the system may be a secondary loop system.

[0062] According to any of the embodiments described herein, a method for replacing R-454C or propane in an air conditioning or heat pump system is disclosed herein, the method comprising providing the system with a composition of any of the embodiments described above in place of R-454C or propane.

[0063] According to any of the embodiments described above, what is disclosed herein is the use of the composition described in any of the embodiments described above as a refrigerant in an air conditioning or heat pump system. [Modes for carrying out the invention]

[0064] The present invention relates to a composition comprising 1,1-difluoropropene (HFO-1252zc) and at least one of difluoromethane (HFC-32) or E-1,3,3,3-tetrafluoropropene (HFO-1234ze-E). The composition may be a candidate to replace refrigerants such as R-454C, R-410A, or propane, having a low global warming potential (GWP), improved environmental fate characteristics, and improved energy efficiency (COP).

[0065] The compositions comprise HFO-1252zc and at least one of HFC-32 or HFO-1234ze-E. These compositions not only provide refrigerant blends with a low global warming potential, an improved gradient compared to other proposed refrigerant blends, and an improved coefficient of performance compared to existing refrigerants and other proposed alternatives, but also meet evolving regulatory requirements.

[0066] A refrigerant is defined as a heat transfer fluid that undergoes a phase change from liquid to gas during the heat transfer cycle and then returns to its original state.

[0067] A heat transfer system is a system (or device) used to produce a heating or cooling effect in a specific space. A heat transfer system may be a mobile system or a fixed system.

[0068] Examples of heat transfer systems include, but are not limited to, any type of refrigeration and air conditioning systems, including, fixed heat transfer systems, air conditioners, freezers, refrigerators, heat pumps, full-liquid evaporator heat pumps, direct expansion heat pumps, chillers, full-liquid evaporator chillers, direct expansion chillers, walk-in coolers, mobile refrigerators, mobile heat transfer systems, mobile heat pumps (including heat pumps for comfortable heating and cooling of vehicle cabins), mobile air conditioning units (for cooling vehicle cabins), dehumidifiers, and combinations thereof. The focus of this application is air conditioning and heat pump systems.

[0069] Volumetric capacity is the amount of heat absorbed or released divided by the theoretical compressor displacement. The heat removed or absorbed is the enthalpy difference across the heat exchanger multiplied by the refrigerant mass flow rate. The theoretical compressor displacement is the refrigerant mass flow rate divided by the density of the gas entering the compressor (i.e., compressor suction density). More simply, volumetric capacity is the density at the compressor suction (e.g., kg / m³). 3 This is obtained by multiplying the enthalpy difference of the heat exchanger by the volumetric capacity. The higher the volumetric capacity, the smaller the compressor that can be used for the same heat load. In this specification, cooling capacity refers to the volumetric capacity in cooling mode, and heating capacity refers to the volumetric capacity in heating mode.

[0070] The coefficient of performance (COP) is calculated by dividing the amount of heat absorbed or released by the energy input required to operate the cycle (approximated by the compressor's capacity). COP is specific to the operating mode of the heat pump and therefore can be either the COP for heating or the COP for cooling. COP is directly related to the energy efficiency ratio (EER).

[0071] Supercooling refers to lowering the temperature of a liquid to below its saturation point under a given pressure. The saturation point is the temperature at which vapor completely condenses into a liquid. By cooling a liquid below its saturation temperature (or boiling point), the net cooling effect can be increased. Thus, supercooling improves the cooling capacity and energy efficiency of a system. The amount of supercooling is the amount of cooling below the saturation temperature (degrees).

[0072] Superheating refers to raising the temperature of a vapor above its saturation point at a given pressure. The vapor saturation point is the temperature at which a liquid completely evaporates into vapor. Superheating continues to heat the vapor to a higher temperature at a given pressure. By heating the vapor above its saturation temperature (or dew point temperature), the net cooling effect can be increased. Thus, when superheating occurs in an evaporator, it improves the cooling capacity and energy efficiency of the system. Superheating in a suction line does not add a net cooling effect and may reduce efficiency and capacity. The amount of superheating is the amount of heating above the saturation temperature (degrees).

[0073] A temperature gradient (sometimes simply referred to as "gradient") is the absolute difference between the start and end temperatures of the phase change process by the refrigerant in the condenser of a refrigerant system, excluding any supercooling or superheating. In the case of an evaporator, the gradient is the temperature difference between the dew point and the evaporator inlet. The gradient can be used to describe the condensation or evaporation of near-azeotropic or non-azeotropic compositions. When referring to the temperature gradient of an air conditioning system or heat pump system, it is common to provide the mean temperature gradient, which is the average value of the temperature gradient in the evaporator and the temperature gradient in the condenser. The gradient is applicable to blended refrigerants, i.e., refrigerants composed of at least two components.

[0074] Net cooling effect is the amount of heat absorbed in the evaporator by one kilogram of each refrigerant in order to produce useful cooling.

[0075] Mass flow rate is the amount (in kilograms) of refrigerant circulating through a refrigeration, heat pump, or air conditioning system over a given period of time.

[0076] As used herein, the term “lubricant” means any composition or any material added to a compressor (and in contact with any heat transfer composition in use within any heat transfer system) that provides hydrodynamic lubrication to the compressor to help prevent seizing of parts.

[0077] The Global Warming Potential (GWP) is an index used to estimate the relative contribution to global warming caused by one kilogram of atmospheric emissions of a particular greenhouse gas compared to one kilogram of carbon dioxide emissions. GWPs can be calculated for various time periods and reflect the atmospheric lifetime impact of a given gas. A GWP for a 100-year period is a commonly referenced value. For mixtures, a weighted average can be calculated based on the individual GWPs for each component. In this specification, GWP values ​​are those reported in the Intergovernmental Panel on Climate Change (IPCC) Fourth Assessment Report (AR4). The estimated GWP for 1252zc is 1.

[0078] The ozone depletion potential (ODP) is a numerical value that indicates the amount of ozone depletion caused by a substance. ODP is the ratio of the effect of a chemical substance on ozone compared to the effect of a similar mass of CFC-11 (fluorotrichloromethane). Therefore, the ODP of CFC-11 is defined as 1.0. Other CFCs and HCFCs have ODPs in the range of 0.01 to 1.0. The ODPs of hydrofluorocarbons (HFCs) and hydrofluoroolefins (HFOs) described herein are zero because they do not contain chlorine, bromine, or iodine, which are known to contribute to ozone decomposition and depletion. The ozone depletion potential of HFO-1252zc is zero.

[0079] 1,1-Difluoropropene (HFO-1252zc or R-1252zc) can be prepared by hydrogenating 3,3,3-trifluoropropene (HFO-1243zf) on a carbon-based palladium catalyst to form 1,1,1-trifluoropropane (HFC-263fb), followed by dehydrofluoridation of HFC-263fb on a chromium catalyst, or by thermal decomposition at high temperatures (see Agent Reference No. FL2084, filed together with this Specified and incorporated herein by reference).

[0080] E-1,3,3,3-tetrafluoropropene (HFO-1234ze-E or R-1234ze-E) is commercially available from Honeywell (Charlotte, North Carolina, USA). Difluoromethane (HFC-32 or R-32) is also commercially available from various suppliers worldwide.

[0081] As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having,” or any other variations thereof are intended to encompass non-exclusive inclusion. For example, a composition, process, method, article, or apparatus containing a list of elements is not necessarily limited to those elements alone, but may include other elements not expressly enumerated, or other elements inherent in such composition, process, method, article, or apparatus.

[0082] The transitional phrase "consisting of..." excludes any unspecified elements, processes, or components. In the context of patent claims, such phrases would close the claim to materials other than those listed, with the exception of impurities normally associated with the materials. If the phrase "consisting of..." appears within a clause in the body of a claim rather than immediately following the preamble, it limits the elements described within that clause only, and does not exclude other elements from the claim as a whole.

[0083] The transitional phrase "essentially consists of" is used to define a composition, method, or apparatus that includes materials, processes, features, components, or elements in addition to those literally disclosed, provided that these additionally included materials, processes, features, components, or elements do not substantially affect the fundamental and novel characteristics of the claimed invention. The term "essentially consists of" has an intermediate meaning between "includes" and "consists of." Typically, the components of a refrigerant mixture and the refrigerant mixture itself may contain small amounts (e.g., less than about 0.5 weight percent total) of impurities and / or by-products (e.g., from the manufacture of refrigerant components or the reuse of refrigerant components from other systems) that do not substantially affect the novel and fundamental characteristics of the refrigerant mixture.

[0084] Furthermore, the use of "a" or "an" is used to describe the elements and components described herein. This is done solely for convenience and to give a general sense of the scope of the invention. This description should be read as including one or at least one, and the singular form also includes the plural form unless it is obvious that a different meaning is intended.

[0085] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art to which the present invention pertains. Similar or equivalent methods and materials to those described herein may be used in the practice or testing of embodiments of the disclosed compositions, but preferred methods and materials are described below. All publications, patent applications, patents, and other references referred herein are incorporated herein by reference in their entirety unless a specific section is cited. In the event of any inconsistency, including definitions, this specification shall prevail. Furthermore, the materials, methods, and examples are illustrative and not intended to be limiting.

[0086] Refrigerant composition In one embodiment, the composition comprises, consists of, or is essentially composed of HFO-1252zc and at least one of HFC-32 or HFO-1234ze-E. These compositions provide a low global warming potential (GWP), improved environmental fate characteristics, and improved energy efficiency (COP). The claimed composition comprising, consisting of, or being essentially composed of HFO-1252zc and at least one of HFC-32 or HFO-1234ze-E also provides flammability classified as Class 2 by ASHRAE.

[0087] In another embodiment, the composition comprises, consists of, or is essentially composed of, about 20 to 83 weight percent of HFO-1252zc and about 17 to 80 weight percent of at least one of HFO-1234ze-E or HFC-32.

[0088] In another embodiment, the composition comprises, consists of, or is essentially composed of, about 20 to 81 weight percent of HFO-1252zc and about 19 to 80 weight percent of at least one of HFO-1234ze-E or HFC-32.

[0089] In another embodiment, the composition comprises, consists of, or is essentially composed of, about 20–83 weight percent of HFO-1252zc and about 17–80 weight percent of HFC-32.

[0090] In another embodiment, the composition comprises, consists of, or is essentially composed of, about 20–50 weight percent of HFO-1252zc and about 50–80 weight percent of HFC-32. These compositions provide a lower average gradient and a higher capacity. These compositions also provide an improved COP compared to R-410A and R-454C.

[0091] In another embodiment, the composition comprises, consists of, or is essentially composed of, about 50–83 weight percent of HFO-1252zc and about 17–50 weight percent of HFC-32. These compositions provide lower compressor discharge temperatures, performance more similar to R-454C, and further improved COP compared to both R-410A and R-454C.

[0092] In another embodiment, the composition comprises, consists of, or is essentially composed of, about 20–81 weight percent of HFO-1252zc and about 19–80 weight percent of HFO-1234ze-E.

[0093] In another embodiment, the composition comprises, consists of, or is essentially composed of, about 50–81 weight percent of HFO-1252zc and about 19–50 weight percent of HFO-1234ze-E. These compositions provide higher capacity. Furthermore, these compositions provide an improved COP compared to both R-410A and R-454C.

[0094] In another embodiment, the composition comprises, consists of, or is essentially composed of, about 56 to about 70 weight percent of HFO-1252zc and about 30 to about 44 weight percent of HFC-32, based on the weights of HFO-1252zc and HFC-32. When these compositions are used in a heat pump in cooling (or heating mode), the heat pump exhibits a cooling (or heating) capacity of at least 90% of the volumetric cooling capacity of R-454C.

[0095] In another embodiment, the composition comprises, consists of, or essentially consists of, about 56 to about 68 weight percent of HFO-1252zc and about 32 to about 44 weight percent of HFC-32, based on the weights of HFO-1252zc and HFC-32. When these compositions are used in a heat pump in cooling (or heating mode), the heat pump exhibits a gradient of <8K.

[0096] In another embodiment, the composition comprises, consists of, or essentially consists of, about 56 to about 65 weight percent of HFO-1252zc and about 35 to about 44 weight percent of HFC-32, based on the weights of HFO-1252zc and HFC-32. When these compositions are used in a heat pump in cooling mode, the heat pump exhibits a gradient of <8K.

[0097] In another embodiment, the composition contains, consists of, or is essentially composed of, about 33% to about 45% by weight of HFO-1252zc, HFO-1252zc, HFC-32, and HFO-1234ze-E, based on the weight of HFO-1252zc, HFO-1252zc, HFC-32, and HFO-1234ze-E, based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E, based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E, with the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E being 100. Such a composition exhibits a GWP of <160.

[0098] In another embodiment, the composition contains, consists of, or essentially consists of, about 0.05% to about 24% by weight of HFO-1252zc, HFO-32, and HFO-1234ze-E, about 34% to about 43.78% by weight of HFC-32, about 37% to about 62% by weight of HFO-1234ze-E, based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E, with the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E being 100. Such a composition exhibits a flammability rating of 2 L (measured according to ANSI / ASHRAE Standard 34).

[0099] In another embodiment, the composition contains, consists of, or essentially consists of, approximately 51% to approximately 63% by weight of HFO-1252zc, HFO-1252zc, HFC-32, and HFO-1234ze-E, approximately 23% to approximately 38% by weight of HFC-32, approximately 4% to approximately 21% by weight of HFO-1234ze-E, based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E, with the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E being 100. When such a composition is used in a heat pump in cooling mode, the heat pump exhibits a gradient of <8K.

[0100] In another embodiment, the composition contains, consists of, or essentially consists of, about 31% to about 64% by weight of HFO-1252zc, HFO-1252zc, HFC-32, and HFO-1234ze-E, based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E, based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E, based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E, based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E, with the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E being 100. When such a composition is used in a heat pump in heating mode, the heat pump exhibits a gradient of <8K.

[0101] In another embodiment, the composition contains, consists of, or essentially consists of, about 0.05% to about 25% by weight of HFO-1252zc, HFO-1252zc, HFC-32, and HFO-1234ze-E, based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E, with about 36% to about 43.78% by weight of HFC-32, HFO-1252zc, HFC-32, and HFO-1234ze-E, based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E, and the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E being 100. Such a composition exhibits a flammability rating of 2 L (measured according to ANSI / ASHRAE standard 34).

[0102] In another embodiment, the composition contains, consists of, or essentially consists of, about 36% to about 60% by weight of HFO-1252zc, HFO-1252zc, HFC-32, and HFO-1234ze-E, based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E, based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E, based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E, and the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E is 100. Such a composition exhibits a GWP of <160.

[0103] In another embodiment, the composition contains, consists of, or essentially consists of, about 1% to about 16% by weight of HFO-1252zc and HFO-1234ze-E, based on the weights of HFO-1252zc and HFO-1234ze-E, and about 84% to about 99% by weight of HFO-1234ze-E, with the sum of the weight percentages of HFO-1252zc and HFO-1234ze-E being 100. Such a composition has a flammability rating of 2 L (measured according to ANSI / ASHRAE standard 34).

[0104] In another embodiment, the composition contains, consists of, or essentially consists of, about 19% to about 23% by weight of HFO-125zc, HFO-1252zc, HFC-32, and HFO-1234ze-E, based on the weight of HFO-125zc, HFO-1252zc, HFC-32, and HFO-1234ze-E, based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E, based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E, based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E, with the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E being 100.

[0105] In another embodiment, the composition contains, consists of, or essentially consists of, about 0.5% to about 63% by weight of HFO-1252zc, HFO-1252zc, HFC-32, and HFO-1234ze-E, based on the weight of HFO-1252zc, HFO-1252zc, HFC-32, and HFO-1234ze-E, based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E, based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E, with the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E being 100. When such a composition is used in a heat pump in cooling mode, the heat pump exhibits a cooling capacity of no more than 20% of that of R-454C.

[0106] In another embodiment, the composition contains, consists of, or essentially consists of, about 0.5% to about 64% by weight of HFO-1252zc, HFO-1252zc, HFC-32, and HFO-1234ze-E, based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E, about 17% to about 43.78% by weight of HFC-32, about 1% to about 57% by weight of HFO-1234ze-E, based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E, with the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E being 100. When such a composition is used in a heat pump in heating mode, the heat pump exhibits a heating capacity of no more than 20% of that of R-454C.

[0107] In another embodiment, the composition contains, consists of, or essentially consists of, about 59 to 76 weight percent of HFO-1234ze-E, based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E, with about 18 to 20 weight percent of HFO-1252zc, HFO-1252zc, HFC-32, and HFO-1234ze-E, and about 6 to 21 weight percent of HFC-32, HFO-1252zc, HFC-32, and HFO-1234ze-E, where the sum of the weight percentages of HFO-1252ze, HFC-32, and HFO-1234ze-E is 100. Such a composition exhibits a GWP of <160 and a flammability grade of 2L.

[0108] In another embodiment, the composition contains, consists of, or essentially consists of, about 59 weight percent of HFO-1234ze-E based on about 21 weight percent of HFC-32, HFO-1252zc, HFC-32, and HFO-1234ze-E, with the total weight percentage of HFO-1252ze, HFC-32, and HFO-1234ze-E being 100.

[0109] In another embodiment, the composition contains, consists of, or essentially consists of, about 18 to about 22 weight percent of HFO-1252zc, HFO-1252zc, HFC-32, and HFO-1234ze-E based on their weights, about 19 to about 23 weight percent of HFC-32, about 57 to about 61 weight percent of HFO-1234ze-E based on their weights, with the sum of the weight percentages of HFO-1252ze, HFC-32, and HFO-1234ze-E being 100.

[0110] Flammability is a term used to describe the ability of a composition to ignite and / or propagate a flame. For refrigerants and other heat transfer compositions or working fluids, the lower flammability limit (LFL) is the lowest concentration of a heat transfer composition in air that can propagate a flame through a homogeneous mixture of the composition and air under the test conditions specified in ASTM (American Society of Testing and Material) E681. The upper flammability limit (UFL) is the highest concentration of a heat transfer composition in air that can propagate a flame through a homogeneous mixture of the composition and air under the same test conditions.

[0111] For a refrigerant to be classified as low flammability (Class 2L) by ANSI / ASHRAE, it must: 1) exhibit flame propagation when tested at 140°F (60°C) and 14.7 psia (101.3 kPa), and 2) have a flammability rating of >0.0062 lb / ft 3 (0.10 kg / m 3 ) must have an LFL of <8169 Btu / lb (19,000 kJ / kg), and 4) have a maximum burning rate of ≤3.9 inches / second (10 cm / second) when tested in dry air at 73.4°F (23.0°C) and 14.7 psia (101.3 kPa).

[0112] For a refrigerant to be classified as flammable (Class 2) by ANSI / ASHRAE, it must: 1) exhibit flame propagation when tested at 140°F (60°C) and 14.7 psia (101.3 kPa), and 2) have a flammability of >0.0062 lb / ft 3 (0.10 kg / m 3 ) It has an LFL of ) and 3) the heat of combustion must be <8169 Btu / lb (19,000 kJ / kg).

[0113] ASHRAE Standard 34 provides a methodology for calculating the heat of combustion of a refrigerant blend using a balanced stoichiometric equation based on the complete combustion of one mole of refrigerant with sufficient oxygen for a stoichiometric reaction.

[0114] HFO-1252zc, when combined with HFC-32 or HFO-1234ze-E, may provide estimated Class 2 or Class 2L flammability as defined by ANSI / ASHRAE standard 34 and ISO 817. Class 2 and Class 2L flammability may be controllable in air conditioning and heat pump applications. Specific applications may have different requirements regarding flammability.

[0115] A composition comprising, or essentially comprising, HFO-1252zc and at least one of HFC-32 or HFO-1234ze-E may further comprise at least one additional compound from the list in Table 1.

[0116] [Table 1]

[0117] In another embodiment, a composition comprising, consisting of, or essentially comprising HFO-1252zc and at least one of HFC-32 or HFO-1234ze-E may further comprise at least one additional compound selected from HCFC-22, HCC-40, HFO-1234yf, HFO-1243zf, HFO-263fb, HFO-1252zc, HFO-1252yf, HFO-1252zf, and HFO-1252ye. In another embodiment, a composition comprising, consisting of, or essentially comprising HFO-1252zc and at least one of HFC-32 or HFO-1234ze-E may further comprise at least one additional compound comprising HFO-1234yf. In another embodiment, a composition comprising, consisting of, or essentially comprising HFO-1252zc and at least one of HFC-32 or HFO-1234ze-E may further comprise at least one additional compound comprising HFO-1243zf. In another embodiment, a composition comprising, consisting of, or essentially comprising HFO-1252zc and at least one of HFC-32 or HFO-1234ze-E may further comprise at least one additional compound comprising HFO-263fb.

[0118] Some of the compounds present in the compositions of the present invention specified in Table 1 may exist as different stereoisomers or stereoisomers. The present invention is intended to include all single stereoisomers, single stereoisomers, or any combination or mixture thereof. For example, 1,2-difluoroethene (HFO-1132) means that it represents the cis-isomer (Z), the trans-isomer (E), or any combination or mixture of both isomers in any ratio. Single or multiple isomers of the same compound can be used in any proportion.

[0119] The amount of additional compounds present in any of the aforementioned refrigerant compositions may be greater than 0 ppm but less than 5,000 ppm, and in particular, may be in the range of greater than 0 to about 1,000 ppm, about 5 to about 500 ppm, and about 1 to about 100 ppm.

[0120] In one embodiment, the amount of additional compounds present in any of the aforementioned refrigerant compositions may be greater than 0 to less than 1% by weight of the refrigerant composition, preferably less than 0.5% by weight, or more preferably less than 0.1% by weight.

[0121] Compositions containing, consisting of, or essentially consisting of HFO-1252zc and at least one of HFC-32 or HFO-1234ze-E function more consistently and are more stable in the presence of small amounts of water. Therefore, the composition may further contain less than 100 ppm (by weight) of water, preferably less than 20 ppm (by weight), and more preferably less than 10 ppm (by weight).

[0122] Furthermore, compositions comprising, consisting of, or essentially consisting of HFO-1252zc and at least one of HFC-32 or HFO-1234ze-E function more consistently and are more stable in the presence of only small amounts of oxygen or air. Accordingly, the claimed composition may further contain less than about 5 volume percent of non-adsorbable gas (NAG), preferably less than 3 volume percent of NAG, and more preferably less than 1.5 volume percent of NAG. Furthermore, the claimed composition contains less than 1 volume percent of oxygen, preferably less than 0.5 volume percent of oxygen, and more preferably less than 0.3 volume percent of oxygen, due to the presence of air or NAG.

[0123] In another embodiment, a composition comprising, consisting of, or essentially consisting of HFO-1252zc and at least one of HFC-32 or HFO-1234ze-E may contain stabilizers. Such stabilizer compounds are present in small amounts and are intended to prevent decomposition due to the presence of water, air, NAG, or oxygen in the system during use or while the composition is stored. HFO-type refrigerants are thermally unstable due to the presence of double bonds and may decompose even under extreme use, handling, or storage conditions. Therefore, there may be advantages to adding stabilizers to HFO-type refrigerants. In particular, examples of stabilizers include nitromethane; ascorbic acid; terephthalic acid; azoles such as toltriazole or benzotriazole; phenol compounds such as tocopherol; hydroquinone; t-butylhydroquinone; 2,6-di-tert-butyl-4-methylphenol; epoxides such as n-butylglycidyl ether, hexanediol diglycidyl ether, allyl glycidyl ether, and butylphenyl glycidyl ether (in some cases, fluorinated or perfluorinated alkyl epoxides or alkenyl or aromatic epoxides); 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 International Publication Nos. 2019213004, 2020222864, and 2020222865, which are incorporated herein by reference.

[0124] If the composition contains a stabilizer, it may contain any of the stabilizers listed above in any amount between 0.001% and 1% by weight, preferably about 0.001% to about 0.5% by weight, and more preferably about 0.001% to about 0.3% by weight.

[0125] In some embodiments, a composition comprising, consisting of, or essentially consisting of HFO-1252zc and at least one of HFC-32 or HFO-1234ze-E may contain a tracer compound or tracer. The tracer may comprise 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 (ppm) to about 1000 ppm, based on the weight of 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.

[0126] Tracers may be present in a composition containing, consisting of, or essentially consisting of HFO-1252zc and at least one of HFC-32 or HFO-1234ze-E, in predetermined amounts that enable the detection of any dilution, contamination, or other change of the composition. The presence of a particular compound in the composition may indicate by what method or process one of the components was produced. Alternatively, a specified amount of tracer may be added to the composition to identify the source of the composition. In this way, detection of patent infringement can be achieved. Tracers may be refrigerant compounds, but they are present in the composition at levels that are unlikely to affect the performance of the refrigerant components of the composition.

[0127] The tracer compound may be hydrofluorocarbon, hydrofluoroolefin, hydrochlorocarbon, hydrochloroolefin, hydrochlorofluorocarbon, hydrochlorofluoroolefin, hydrochlorocarbon, hydrochloroolefin, chlorofluorocarbon, chlorofluoroolefin, hydrocarbon, perfluorocarbon, perfluoroolefin, or combinations thereof. Examples of tracer compounds include 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-2 36ea (1,1,1,2,3,3-hexafluoropropane), HFC-245cb (1,1,1,2,2-pentafluoropropane), HFC-245fa (1,1,1,3,3-pentafluoropropane), 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 ( HCFC-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,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 (fluoroethene), HCFO-1130 (1,2-dichloroethene), HCFO-1130a (1,1-dichloroethene), HCFO-1131 (1-chloro-2-fluoroethene), HCFO-1122 (2-chloro-1,1-difluoroethene), HFO-1123 (1,1,2-trifluoroethene), HFO-1234ye (1,2,3,3-tetrafluoropropene) Examples include, but are not limited to, 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.

[0128] In another embodiment of the present disclosure, a composition comprising, consisting of, or essentially comprising HFO-1252zc and at least one of HFC-32 or HFO-1234ze-E further comprises at least one lubricant. The lubricant may be selected from polyol esters, polyvinyl ethers, and polyalkylene glycols. The lubricant may also include what is commonly known as “mineral oil” in the field of compression refrigeration lubrication. Mineral oils include paraffins (i.e., saturated hydrocarbons of linear and branched carbon chains), naphthenes (i.e., cyclic or cyclic saturated hydrocarbons that may be paraffins), and aromatics (i.e., unsaturated cyclic hydrocarbons containing one or more rings characterized by alternating double bonds). The lubricants of the present invention further include what is commonly known as “synthetic oil” in the field of compression refrigeration lubrication. Synthetic oils include alkylaryls (i.e., linear and branched alkylalkylbenzenes), synthetic paraffins and naphthenes, silicones, and polyalphaolefins. Typical conventional lubricants of the present invention include commercially available BVM 100 N (paraffinic mineral oil sold by BVA Oils), naphthenic mineral oil sold by Crompton Co. under the trademarks Suniso® 3GS and Suniso® 5GS, naphthenic mineral oil sold by Pennzoil under the trademark Sontex® 372LT, naphthenic mineral oil sold by Calumet Lubricants under the trademark Calumet® RO-30, linear alkylbenzenes sold by Shrieve Chemicals under the trademarks Zerol® 75, Zerol® 150, and Zerol® 500, and branched alkylbenzenes sold by Nippon Oil under the trademark HAB 22.

[0129] The lubricants of the present invention are designed for use with hydrofluorocarbon refrigerants and further include those that are miscible with the refrigerants of the present invention under the operating conditions of compressed refrigeration and air conditioning systems. Examples of lubricants include, but are not limited to, polyol esters (POE), such as Castrol® 100 (Castrol, United Kingdom), polyalkylene glycols (PAG), such as RL-488A from Dow Chemical (Dow Chemical, Midland, Mich.), and polyvinyl ethers (PVE), such as PVE-FVC68D.

[0130] In one particular embodiment, a composition comprising, consisting of, or essentially consisting of HFO-1252zc and at least one of HFC-32 or HFO-1234ze-E is combined with a PAG lubricant, PVE lubricant, or POE lubricant for use in an air conditioning system or a heat pump system.

[0131] In a composition (including a lubricant) containing, consisting of, or essentially consisting of HFO-1252zc and at least one of HFC-32 or HFO-1234ze-E, the lubricant may be present in an amount of less than 80 weight percent of the total composition. The lubricant may further be present in an amount of less than 60 weight percent of the total composition. In other embodiments, the amount of lubricant may be about 0.1 to 50 weight percent of the total composition. The lubricant may also be about 0.1 to 20 weight percent of the total composition. The lubricant may also be about 0.1 to 5 weight percent of the total composition.

[0132] In another aspect of the present invention, compositions of the present invention comprising, consisting of, or essentially consisting of HFO-1252zc and at least one of HFC-32 or HFO-1234ze-E are used to introduce lubricants, and / or alternatively other additives, such as a) acid scavengers, b) performance enhancers, and c) flame suppressants, into air conditioning or heat pump systems. In one preferred embodiment, the composition comprises an acid scavenger.

[0133] Examples of acid scavengers that may be included in this composition 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 Publication No. 2020 / 222864, each of which is incorporated herein by reference in whole.

[0134] In some embodiments, the acid scavenger may include one or more epoxides, one or more amines, and / or one or more hindered amines, such as, but not limited to, epoxybutane.

[0135] Acid scavengers (e.g., activated aromatic compounds, siloxanes, or both) may be present at any concentration, resulting in a relatively low total acid number, a relatively low total halide concentration, a relatively low total organic acid concentration, or any combination thereof.

[0136] Preferably, the acid scavenger is present at a concentration of more than about 0.0050% by weight, more preferably more than about 0.05% by weight, and even more preferably more than about 0.1% by weight (e.g., more than about 0.5% by weight) based on the total weight of the refrigerant composition. The acid scavenger is present at a concentration of 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 more than about 2% by weight (e.g., less than about 1.8% by weight) based on the total weight of the refrigerant composition.

[0137] Preferred additives include those described in U.S. Patents No. 5,152,926 and No. 4,755,316, which are incorporated herein by reference. Specifically, preferred extreme pressure additives include mixtures of (A) tolyltriazole or a substituted derivative thereof, (B) an amine (e.g., Jeffamine M-600), and (C) (i) an ethoxylated phosphate ester (e.g., Antara LP-700), or (ii) a phosphoric acid alcohol (e.g., ZELEC 3337), or (iii) zinc dialkyldithiophosphate (e.g., Lubrizol 5139, 5604, 5178, or 5186), or (iv) a mercaptobenzothiazole, or (v) a 2,5-dimercapto-1,3,4-triadianazole derivative (e.g., Curvan 826), or a mixture thereof. Further examples of additives that may be used are provided in U.S. Patent No. 5,976,399 (Schnur, 5:12–6:51, incorporated herein by reference).

[0138] The acid value is measured in mg KOH / g units according to ASTM D664-01. The total halide concentration, fluoride ion concentration, and total organic acid concentration are measured by ion chromatography. The chemical stability of the refrigerant system is measured according to ASHRAE 97:2007 (RA 2017) "Sealed Glass Tube Method to Test the Chemical Stability of Materials for Use within Refrigerant Systems". The viscosity of the lubricant is tested at 40°C according to ASTM D-7042.

[0139] Mouli et al. (International Publication Nos. 2008 / 027595 and 2009 / 042847) teach 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 No. 11 / 575,256, published as U.S. Patent Application Publication No. 2007 / 0290164) and Singh et al. (U.S. Patent Application No. 11 / 250,219, published as U.S. Patent Application Publication No. 2006 / 0116310). All of these aforementioned applications are expressly incorporated herein by reference.

[0140] Preferred flame inhibitors include flame retardants described by reference in the patent application "Refrigerant compositions containing fluorine substituted olefins" (Canadian Patent No. 2557873(A1)), and fluorinated products such as HFC-125, HFC-227ea, HFC-236fa, CF3I, and / or Krytox® lubricants described by reference in the patent application "Refrigerant compositions comprising fluoroolefins and uses thereof" (International Publication No. 2009018117(A1)).

[0141] In one embodiment, as used herein, "Group A fluorinated substance" includes a substance that (i) contains at least one fully fluorinated methyl (-CF3) or methylene (-CF2-) carbon atom (the carbon atom is not bonded to any H / Cl / Br / I atoms), and (ii) meets the criteria for persistence in soil / sediments and water, which are defined in Annex XIII (Section 1.1.1) of the European Union's REACH Regulation (https: / / reachonline). This is defined in eu / reach / en / annex-xiii-1-1.1-1.1.1.html (accessed 2 May 2023) and referenced in the Regulatory Report Annex XV dated 22 March 2023, the disclosure of which is incorporated herein by reference (https: / / echa.europa.eu / documents / 10162 / f605d4b5-7c17-7414-8823-b49b9fd43aea, accessed 2 May 2023). In one embodiment, the Group A fluorinated substance is, but is not limited to, trifluoroacetic acid (TFA).

[0142] In another embodiment, as used herein, "Group A fluorinated substance" has a Henry's Law constant of ≤250 Pa * m 3 The material comprises any substance in moles that contains at least one fully fluorinated methyl (-CF3) or methylene (-CF2-) carbon atom (the carbon atom is not bonded to any H / Cl / Br / I atoms). In one embodiment, the Group A fluorinated substance is, but is not limited to, TFA.

[0143] Accordingly, according to some embodiments, compositions of the present invention comprising, consisting of, or essentially comprising HFO-1252zc and at least one of HFC-32 or HFO-1234ze-E are free of or substantially free of group A fluorinated substances such as TFA. In one embodiment, the term “free of” as used herein with respect to the presence of group A fluorinated substances in the composition means that the amount of such substances in the composition is so small that it is undetectable, including but not limited to 0%, when measured by gas chromatography with a flame ionization detector, gas chromatography with a mass detector by analysis of a gas or liquid sample, and / or ion chromatography by analysis of a water sample after bubbling a thermal fluid through water. Such methodologies are well known to those skilled in the art. In one embodiment, with respect to the presence of Group A fluorinated substances in the composition, the phrase "substantially absent" as used herein means that the amount of such substances in the composition can be determined by gas chromatography (GC) techniques, such as gas chromatography (GC) using a flame ionization detector or electron capture detector, or GC coupled with a mass detector (gas chromatography / mass spectral (GC / MS) method), by ion chromatography (IC) or ion chromatography-mass spectrometry (IC-MS) techniques, or by high-performance liquid chromatography (HPLC) or high-performance liquid chromatography-mass spectrometry (high-performance liquid chromatography-mass spectrometry). This means that, when measured by spectrometry (HPLC-MS) techniques, the values ​​are >0 wt% to ≤5 wt%, or >0 wt% to ≤4 wt%, or >0 wt% to ≤3 wt%, or >0 wt% to ≤2 wt%, or >0 wt% to ≤1 wt%, as well as all values ​​and ranges in between.TFA analytical standards can be used with either gas chromatography or ion chromatography and are available, for example, from Sigma Aldrich. In some embodiments, stabilized compositions comprising, consisting of, or essentially consisting of HFO-1252zc and at least one of HFC-32 or HFO-1234ze-E are free of Group A fluorinated substances, meaning that these substances are undetectable by the methods and techniques described herein.

[0144] Furthermore, in some embodiments, the decomposition products of such compositions of the present invention, comprising, consisting of, or essentially comprising HFO-1252zc and at least one of HFC-32 or HFO-1234ze-E, do not contain or substantially contain group A fluorinated substances such as TFA. In one embodiment, the term “does not contain” as used herein with respect to the formation of group A fluorinated substances by the composition means that the theoretical molar yield of such substances in the air, soil / sediment and water environmental compartments generated during the tropospheric decomposition 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 using flame ionization detectors or electron capture detectors, IC or IC-MS techniques, or HPLC or HPLC-MS techniques. In one embodiment, the term “substantially free” as used herein with respect to the formation of Group A fluorinated substances by the Composition means that the theoretical molar yield of such substances in the air, soil / sediment, and water environmental compartments generated during the tropospheric decomposition of the Composition is >0% to ≤5%, or >0% to ≤4%, or >0% to ≤3%, or >0% to ≤2%, or >0% to ≤1%, and all values ​​and ranges in between, when measured by GC techniques, e.g., GC or GC / MS using a flame ionization detector or electron capture detector, IC or IC-MS techniques, or HPLC or HPLC-MS techniques. In some embodiments, the decomposition products of such compositions of the present invention, which include, consist of, or are essentially derived from, stabilized compositions comprising, HFO-1252zc and at least one of HFC-32 or HFO-1234ze-E, are free from Group A fluorinated substances such as TFA, meaning that these substances are undetectable by the methods and techniques described herein.

[0145] Methods and Systems Compositions comprising, consisting of, or essentially comprising HFO-1252zc and at least one of HFC-32 or HFO-1234ze-E are useful in a number of methods and systems for providing air conditioning and heating.

[0146] In one embodiment, a cooling method is provided, comprising evaporating a composition comprising, consisting of, or essentially comprising HFO-1252zc and at least one of HFC-32 or HFO-1234ze-E in the vicinity of an object to be cooled, and then condensing the composition, wherein the cooling is provided by an air conditioner or a heat pump.

[0147] In one embodiment, the air conditioner may be a residential, commercial, or industrial air conditioning system. These may include, but are not limited to, systems located outside the building but connected to it, such as windows, ducted or unducted systems, packaged terminals, and rooftop systems. The method may be particularly useful in high ambient temperature regions due to the high critical temperature of the blend containing HFO-1252zc and at least one of HFC-32 or HFO-1234ze-E.

[0148] In another embodiment, a heating method is provided, comprising evaporating a composition comprising HFO-1252zc and at least one of HFC-32 or HFO-1234ze-E, and then condensing the composition in the vicinity of an object to be heated, the heating being provided by a heat pump.

[0149] In one embodiment, the heat pump is a residential, light commercial, or industrial heat pump system. These may include, but are not limited to, residential heat pumps that provide comfortable air conditioning and heating, hot water heat pumps for heating air (by 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 and at least one of HFC-32 or HFO-1234ze-E, it is possible to heat water to a higher temperature than propane or R-454C.

[0150] In another embodiment, the method for generating cooling is particularly useful in areas where the ambient temperature may exceed at least 35°C.

[0151] In geographical regions with high ambient temperatures, air conditioning is essential, and 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. As a result, these refrigerants do not perform well in extremely hot environments. The energy efficiency of a refrigerant generally decreases when the condensation temperature reaches the refrigerant's critical temperature during operation at high ambient temperatures. In hot climates, R-22 has continued to be the refrigerant of choice for many air conditioning and refrigeration applications because it is non-flammable and has a higher critical temperature that provides higher cooling capacity and higher energy efficiency compared to R-410A or R-32 in hot climates. However, R-22 is designated as an ozone-depleting substance under the Montreal Protocol to Reduce Ozone Depletion. Therefore, the manufacture and use of R-22 for air conditioning and refrigeration applications are mandated and mandated by law. There is interest in finding refrigerants that have the lowest possible direct GWP and that perform well even in hot climate (or high ambient) temperature regions.

[0152] In a method for producing cooling, the object to be cooled can be defined as any space, place, object, or body for which cooling is desirable. Examples include open or enclosed spaces requiring cooling, such as apartments or multi-unit dwellings, university dormitories, townhouses or other terraced houses, or single-family homes; or the object to be cooled could be any other building, such as an office building, supermarket, college or university classroom, or government building.

[0153] Another embodiment provides a method for creating air conditioning at high ambient temperatures. This method comprises evaporating a composition containing, essentially consisting of, or comprising HFO-1252zc and at least one of HFC-32 or HFO-1234ze-E, and then condensing the composition. This method is particularly useful in areas where ambient temperatures may exceed 35°C.

[0154] In another embodiment, a method is provided for replacing HCFC-22 in a high-ambient air conditioning system, the method comprising supplying the system with a composition comprising, essentially consisting of, or comprising HFO-1252zc and at least one of HFC-32 or HFO-1234ze-E. The method for replacing HCFC-22 is particularly useful in areas where ambient temperatures may exceed 35°C.

[0155] Similarly, some industrial air conditioning systems must release heat in environments with high ambient temperatures. HCFC-124 has been used as a working fluid in such applications. HCFC-124 is also regulated as an ozone-depleting substance under the Montreal Protocol, and more environmentally sustainable alternatives are desired. Therefore, a method for replacing HCFC-124 in industrial air conditioning systems is provided, comprising supplying the system with a composition containing, essentially consisting of, or comprising HFO-1252zc and at least one of HFC-32 or HFO-1234ze-E. The method for replacing HCFC-124 is particularly useful in areas where ambient temperatures may exceed 35°C.

[0156] In another embodiment, a method for generating cooling, and a method for replacing HCFC-22 or HCFC-124, is useful for systems operating at ambient temperatures of 40°C or higher. In another embodiment, a method for generating cooling is useful for systems operating at ambient temperatures of 45°C or higher. In another embodiment, a method for generating cooling is useful for systems operating at ambient temperatures of 50°C or higher. In another embodiment, a method for generating cooling is useful for systems operating at ambient temperatures of 55°C or higher. In another embodiment, a method for generating cooling is useful for systems operating at ambient temperatures of 60°C or higher. In another embodiment, a method for generating cooling is useful for systems operating at ambient temperatures of 35°C to 50°C. In another embodiment, a method for generating cooling is useful for systems operating at ambient temperatures of 35°C to 60°C. In another embodiment, a method for generating cooling is useful for systems operating at ambient temperatures of 40°C to 60°C. In another embodiment, a method for generating cooling is useful for systems operating at ambient temperatures of 45°C to 60°C. In another embodiment, a method for generating cooling is useful for systems operating at ambient temperatures of 50°C to 60°C.

[0157] In another embodiment, a system for cooling or heating is provided, comprising a composition containing, consisting of, or essentially consisting of, HFO-1252zc, at least one of HFC-32 or HFO-1234ze-E, and optionally a lubricant. The system comprises an evaporator, a compressor, a condenser, and an expansion device, each operably connected to perform a vapor compression cycle.

[0158] The air conditioner or heat pump system may be for residential, light commercial, or industrial use. Various such systems have been described herein. In another embodiment, an air conditioner or heat pump system comprising a composition containing, consisting of, or essentially consisting of HFO-1234ze-E and at least one of HFC-32 or HFO-1234ze-E may be a secondary loop system.

[0159] The following embodiments are provided to illustrate specific aspects of the present invention and are not intended to limit the scope of the appended claims. [Examples]

[0160] Example 1 The cooling and heating performance of compositions containing HFO-1252zc and HFO-1234ze-E, as well as compositions containing HFO-1252zc and HFC-32, was compared with that of R-454C (ASHRAE designated refrigerant containing 78.5% by weight of HFO-1234yf and 21.5% by weight of HFC-32) and R-410A (ASHRAE designated refrigerant containing 50% by weight of HFC-125 and 50% by weight of HFC-32) at an evaporator temperature of -10°C. The results are shown in Tables 2A and 2B.

[0161] The conditions used in the calculation are as follows:

[0162] [Table 2]

[0163] [Table 3]

[0164] [Table 4]

[0165] The data demonstrate improved COP for all compositions of the present invention compared to R-410A and R-454C. Furthermore, some of the compositions of the present invention have cooling and heating capacities similar to R-410A or R-454C, with reasonable mean temperature gradients. Moreover, the critical temperatures of compositions containing HFO-1252zc and HFO-1234ze-E are high enough for these blends to function well for cooling in high-temperature environments such as the Middle East, and can also be used to provide high-temperature water in water-heated heat pumps.

[0166] Example 2 The cooling and heating performance of compositions containing HFO-1252zc and HFO-1234ze-E, as well as compositions containing HFO-1252zc and HFC-32, was compared with that of R-454C (ASHRAE designated refrigerant containing 78.5% by weight of HFO-1234yf and 21.5% by weight of HFC-32) and R-410A (ASHRAE designated refrigerant containing 50% by weight of HFC-125 and 50% by weight of HFC-32) at an evaporator temperature of -15°C. The results are shown in Tables 3A and 3B.

[0167] The conditions used in the calculation are as follows:

[0168] [Table 5]

[0169] [Table 6]

[0170] [Table 7]

[0171] The data demonstrate improved COP for all compositions of the present invention compared to R-410A and R-454C. Furthermore, some of the compositions of the present invention have similar cooling and heating capacities to R-410A or R-454C, with reasonable mean temperature gradients. The results show that a heat pump operating in heating mode (or cooling mode) using compositions of 20–83 wt% HFO-1252z and 17–80 wt% HFC-32 exhibits at least 80% of the heating (or cooling) capacity of R-454C.

[0172] Example 3 The cooling and heating performance of compositions containing HFO-1252zc and HFO-1234ze-E, and compositions containing HFO-1252zc and HFC-32, was compared with that of R-454C (ASHRAE designated refrigerant containing 78.5% by weight of HFO-1234yf and 21.5% by weight of HFC-32) and R-410A (ASHRAE designated refrigerant containing 50% by weight of HFC-125 and 50% by weight of HFC-32) at an evaporator temperature of -20°C. The results are shown in Tables 4A and 4B.

[0173] The conditions used in the calculation are as follows:

[0174] [Table 8]

[0175] [Table 9]

[0176] [Table 10]

[0177] The data demonstrate improved COP for all compositions of the present invention compared to R-410A and R-454C. Furthermore, some of the compositions of the present invention have similar cooling and heating capabilities to R-410A or R-454C, with reasonable mean temperature gradients.

[0178] Example 4 Table 5 shows the flammability evaluation for compositions containing HFO-1252zc and HFO-1234ze-E, and compositions containing HFO-1252zc and HFC-32. HOC (heat of combustion) is the heat of combustion.

[0179] [Table 11]

[0180] All compositions claimed herein are in ASHRAE flammability class 2 and have an HOC of less than 19,000 kJ / kg.

[0181] Residential heat pump system In Tables 6 to 17B below, "T_Condenser" is the condenser temperature, "T_Evaporator" is the evaporator temperature, "COP" is the coefficient of performance (similar to energy efficiency), and "CAP" is the volumetric cooling capacity. In Examples 5 to 8, refrigerant performance was determined for exemplary compositions of the present invention in residential heat pump systems, compared with R-410A and R-454C in cooling and heating modes. Cooling mode data are based on the conditions described in Table 6. Heating mode data are based on the conditions described in Table 7.

[0182] [Table 12]

[0183] [Table 13]

[0184] Example 5: HFO-1252zc / HFC-32 (cooling mode) Refrigerant performance was determined in the cooling mode for exemplary compositions of the present invention, including HFO-1252zc and HFC-32, in residential heat pump systems, compared with R-410A and R-454C. Performance measurement criteria and composition characteristic ranges are summarized in Table 8, where the ASHRAE flammability class remains 2, the mean temperature gradient is <10K, the cooling capacity is 90% or more of the cooling capacity of R-454C, and the GWP is <300. Tables 9A and 9B list some compositions with optimal cooling efficiency and capacity.

[0185] [Table 14]

[0186] [Table 15]

[0187] [Table 16]

[0188] The results show that the HFO-1252zc and HFC-32 compositions of the present invention provide improved COP and improved capacity compared to R-410A and R-454C with respect to cooling using residential heat pump systems. The results also show that a heat pump operating in cooling mode exhibits a gradient of <8K using a composition of 56-68 wt% HFO-1252zc and 32-44 wt% HFC-32. The results also show that a heat pump operating in cooling mode exhibits at least 80% of the cooling capacity of R-454C using a composition of 56-70 wt% HFO-1252zc and 30-44 wt% HFC-32.

[0189] Example 6: HFO-1252zc / HFC-32 (heating mode) Refrigerant performance was determined in the heating mode for exemplary compositions of the present invention, including HFO-1252zc and HFC-32, compared with R-410A and R-454C in residential heat pump systems. Performance metrics and composition characteristic ranges are summarized in Table 10, where the ASHRAE flammability class remains 2, the mean temperature gradient is <10K, the heating capacity is at least 10% lower than that of R-454C, and the GWP is <300. Table 11 lists several compositions with optimal cooling efficiency and capacity.

[0190] [Table 17]

[0191] [Table 18]

[0192] [Table 19]

[0193] The results show that the HFO-1252zc and HFC-32 compositions of the present invention provide improved COP and improved capacity (in some cases more than 25%) compared to R-410A and R-454C with respect to heating using residential heat pump systems. The results also show that a heat pump operating in heating mode using a composition of 56-65 wt% HFO-1252zc and 36-44 wt% HFC-32 exhibits a gradient of <8K. The results also show that a heat pump operating in heating mode using a composition of 56-70 wt% HFO-1252zc and 30-44 wt% HFC-32 exhibits a heating capacity of at least 80% of the heating capacity of R-454C.

[0194] Example 7: HFO-1252zc / HFO-1234ze(E) / HFC-32 (cooling mode) Refrigerant performance was determined in the cooling mode for exemplary compositions of the present invention, including HFO-1252zc, HFO-1234ze(E), and HFC-32 in residential heat pump systems, compared with R-410A and R-454C. Table 12 summarizes the performance metrics and compositional characteristic ranges, where the ASHRAE flammability class remains 2L or 2, the mean temperature gradient is <10K, the cooling capacity is at least 10% lower than that of R-454C, and the GWP is <300. Table 13 summarizes the performance metrics and compositional characteristic ranges, where the ASHRAE flammability class remains 2L or 2, the mean temperature gradient is <10K, the cooling capacity is at least 10% lower than that of R-454C, and the GWP is <150. Table 14 lists several compositions for optimal cooling efficiency and capacity.

[0195] [Table 20]

[0196] [Table 21]

[0197] [Table 22]

[0198] [Table 23]

[0199] The results show that the HFO-1252zc, HFO-1234ze(E), and HFC-32 compositions of the present invention provide an improved COP or similar energy efficiency compared to R-454C with respect to cooling using residential heat pump systems. Furthermore, in many cases, the HFO-1252zc, HFO-1234ze(E), and HFC-32 compositions of the present invention provide improved cooling capacity compared to R-454C. The results also show that compositions of 0.5-24 wt% HFO-1252zc, 29-43.78 wt% HFC-32, and 37-62 wt% HFO-1234ze-E have a flammability rating of 2L. The results also show that a heat pump operating in cooling mode using a composition of 14–63 wt% HFO-1252zc, 23–44 wt% HFC-32, and 4–37 wt% HFO-1234ze-E exhibits a gradient of <8K. Finally, the results also show that a composition of 30–63 wt% HFO-1252zc, 18–23 wt% HFC-32, and 14–47 wt% HFO-1234ze-E has a GWP of <160. The results also show that a heat pump operating in cooling mode using a composition of 0.5–63 wt% HFO-1252zc, 18–43.78 wt% HFC-32, and 4–62 wt% HFO-1234ze-E exhibits a cooling capacity of at least 80% of the cooling capacity of R-454C.

[0200] Example 8: HFO-1252zc / HFO-1234ze(E) / HFC-32 (heating mode) Refrigerant performance was determined in heating mode for exemplary compositions of the present invention, including HFO-1252zc, HFO-1234ze(E), and HFC-32 in residential heat pump systems, compared with R-410A and R-454C. Table 15 summarizes the performance metrics and compositional characteristic ranges, where the ASHRAE flammability class remains 2L or 2, the mean temperature gradient is <10K, the heating capacity is at least 10% lower than that of R-454C, and the GWP is <300. Table 16 summarizes the performance metrics and compositional characteristic ranges, where the ASHRAE flammability class remains 2L or 2, the mean temperature gradient is <10K, the heating capacity is at least 10% lower than that of R-454C, and the GWP is <150. Table 17 lists several compositions with optimal cooling efficiency and capacity.

[0201] [Table 24]

[0202] [Table 25]

[0203] [Table 26]

[0204] [Table 27]

[0205] The results show that the HFO-1252zc, HFO-1234ze(E), and HFC-32 compositions of the present invention provide an improved COP or similar energy efficiency compared to R-454C with respect to heating using residential heat pump systems. Furthermore, in many cases, the HFO-1252zc, HFO-1234ze(E), and HFC-32 compositions of the present invention provide improved heating capacity compared to R-454C. The results also show that compositions of 0.5-25 wt% HFO-1252zc, 35-43.78 wt% HFC-32, and 39-57 wt% HFO-1234ze-E have a flammability rating of 2 L. The results also show that a heat pump operating in heating mode using a composition of 31–64 wt% HFO-1252zc, 17–43 wt% HFC-32, and 1–31 wt% HFO-1234ze-E exhibits a gradient of <8K. Finally, the results also show that a composition of 36–60 wt% HFO-1252zc, 17–22 wt% HFC-32, and 18–42 wt% HFO-1234ze-E has a GWP of <160. The results also show that a heat pump operating in heating mode using a composition of 0.5–64 wt% HFO-1252zc, 17–43.78 wt% HFC-32, and 1–57 wt% HFO-1234ze-E exhibits a heating capacity of at least 80% of the heating capacity of R-454C.

[0206] Example 9: HFO-1252zc / HFO-1234ze-E (cooling mode) Refrigerant performance was determined for exemplary compositions of the present invention, including HFO-1252zc and HFO-1234ze-E, in residential heat pump systems, compared with R-410A and R-454C in cooling mode. Performance metrics and composition characteristic ranges are summarized in Table 18, where the ASHRAE flammability class remains 2L or 2, the mean temperature gradient is <2K, the cooling capacity is at least 10% lower than that of R-454C, and the GWP is <300. There is no composition range where the ASHRAE flammability class remains 2L or 2, the mean temperature gradient is <10K, the cooling capacity is at least 50% of that of R-454C, and the GWP is approximately 1. Table 19 lists several compositions with optimal cooling efficiency and capacity.

[0207] [Table 28]

[0208] [Table 29]

[0209] [Table 30]

[0210] The results show that the HFO-1252zc and HFO-1234ze-E compositions of the present invention provide an improved COP compared to R-410A and R-454C with respect to cooling using residential heat pump systems. The results also show that compositions of 1-16 wt% HFO-1252zc and 84-99 wt% HFO-1234ze-E have a flammability class of 2L. The results also show that a heat pump operating in cooling mode using compositions of 1-49 wt% HFO-1252zc and 51-99 wt% HFO-1234ze-E exhibits a gradient of <1.1K.

[0211] Example 10: HFO-1252zc / HFO-1234ze(E) / HFC-32 (heating mode) In Example 10, the refrigerant performance was determined for an exemplary composition of the present invention in a residential heat pump system, compared to R-454C, in both cooling and heating modes. The data are based on the conditions described in Table 20.

[0212] [Table 31]

[0213] Tables 21A and 21B show the optimal cooling efficiency and capacity compositions.

[0214] [Table 32]

[0215] [Table 33]

[0216] The results show that compositions containing 18–20 wt percent HFO-1252zc, 6–21 wt percent HFC-32, and 59–76 wt percent HFO-1234ze(E) exhibit a GWP of <160 and a flammability rating of 2L. The results also show that heat pumps operating with such compositions exhibit a gradient of <10K. The results also show that heat pumps operating with compositions containing approximately 20 wt percent HFO-1252zc, approximately 21 wt percent R-32, and approximately 59 wt percent HFO-1234ze-E exhibit a cooling (or heating) capacity of at least 90% of that of R-454C.

Claims

1. A composition comprising HFO-1252zc and at least one of HFO-1234ze-E or HFC-32.

2. The composition according to claim 1, comprising approximately 20% to 83% by weight of HFO-1252zc and approximately 17% to 80% by weight of at least one of HFO-1234ze-E or HFC-32.

3. The composition according to claim 1 or 2, comprising approximately 20% to 81% by weight of HFO-1252zc and approximately 19% to 80% by weight of at least one of HFO-1234ze-E or HFC-32.

4. The composition according to claim 1 or 2, comprising approximately 20% to 83% by weight of HFO-1252zc and approximately 17% to 80% by weight of HFC-32.

5. The composition according to claim 1 or 2, comprising approximately 20% to 81% by weight of HFO-1252zc and approximately 19% to 80% by weight of HFO-1234ze-E.

6. 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, allene, 2-butene, cyclobutene, 2-methyl Lupropene, 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-1252zc, HFO-1252yf, HFO-1252zf, HFO-1252ye, and E / Z-t-BuO-CF=CH-CH ３ The composition according to any one of claims 1 to 5, further comprising at least one additional compound selected from the above.

7. The composition according to any one of claims 1 to 6, further comprising at least one additional compound selected from HCFC-22, HCC-40, HFO-1234yf, HFO-1243zf, HFC-263fb, HFO-1252zc, HFO-1252yf, HFO-1252zf, and HFO-1252ye.

8. The composition according to any one of claims 1 to 7, wherein the composition further comprises 0.1 ppm by weight to 200 ppm by weight of water, about 10 ppm by volume to about 0.35 volume percent of oxygen, and / or about 100 ppm by volume to about 1.5 volume percent of air or NAG.

9. The composition according to any one of claims 1 to 8, wherein the composition comprises a stabilizer.

10. The composition according to claim 9, wherein the stabilizer is selected from the group consisting of nitromethane, ascorbic acid, terephthalic acid, azole, phenol compounds, cyclic monoterpenes, terpenes, phosphites, phosphates, phosphonates, thiols, and lactones.

11. The composition according to claim 9 or 10, wherein the stabilizer is selected from toltriaazole, benzotriazole, tocopherol, hydroquinone, t-butylhydroquinone, 2,6-di-tertbutyl-4-methylphenol, fluorinated epoxide, n-butylglycidyl ether, hexanediol diglycidyl ether, allylglycidyl ether, butylphenyl glycidyl ether, d-limonene, α-terpinene, β-terpinene, α-pinene, β-pinene, or butylated hydroxytoluene.

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

13. The composition according to any one of claims 1 to 12, wherein the composition further comprises a lubricant.

14. The composition according to claim 13, wherein the lubricant is at least one selected from the group consisting of polyalkylene glycol, polyol ester, poly-α-olefin, and polyvinyl ether.

15. The composition according to claim 13 or 14, wherein the lubricant is a polyol ester or a polyvinyl ether.

16. The aforementioned lubricant is 10 at 20°C １０ The composition according to any one of claims 13 to 15, having at least one property selected from the group consisting of a volume resistivity greater than Ω-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 dielectric breakdown voltage of at least 25 kV, and a hydroxy value of a maximum of 0.1 mg KOH / g.

17. The composition according to any one of claims 1 to 16, wherein the composition comprises at least one tracer.

18. The composition according to claim 17, wherein the tracer is present in an amount of about 1.0 ppm by weight to about 1000 ppm by weight.

19. The composition according to claim 17 or 18, 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.

20. The at least one tracer is 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, C FC-12, CFC-11, CFC-114, CFC-114a, HCFC-22, HCFC-123, HCFC-124, HCFC-124a, HCF C-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 A composition according to any one of claims 17 to 19, selected from the group consisting of HFO-1225ye, HFO-1225zc, PFC-116, PFC-C216, PFC-218, PFC-C318, PFC-1216, PFC-31-10mc, PFC-31-10my, and combinations thereof.

21. The composition according to any one of claims 1 to 20, wherein the composition does not contain or substantially contains a group A fluorinated substance, and the decomposition product of the composition does not contain or substantially contains a group A fluorinated substance.

22. The composition according to any one of claims 1 or 6 to 21, wherein the HFO-1252zc is present at a concentration of about 56 weight percent to about 70 weight percent based on the weights of the HFO-1252zc and the HFC-32, and the HFC-32 is present at a concentration of about 30 weight percent to about 44 weight percent based on the weights of the HFO-1252zc and the HFC-32.

23. The composition according to any one of claims 1 or 6 to 21, wherein the HFO-1252zc is present at a concentration of about 56% to about 68% by weight based on the weights of the HFO-1252zc and the HFC-32, and the HFC-32 is present at a concentration of about 32% to about 44% by weight based on the weights of the HFO-1252zc and the HFC-32.

24. The composition according to any one of claims 1 or 6 to 21, wherein the HFO-1252zc is present at a concentration of about 56% to about 65% by weight based on the weights of the HFO-1252zc and the HFC-32, and the HFC-32 is present at a concentration of about 35% to about 44% by weight based on the weights of the HFO-1252zc and the HFC-32.

25. The HFO-1252zc is present at a concentration of approximately 33% to approximately 45% by weight, based on the weights of the HFO-1252zc, the HFC-32, and the HFO-1234ze-E, and the HFC-32 is present at a concentration of approximately 18% to approximately 20% by weight, based on the weights of the HFO-1252zc, the HFC-32, and the HFO-1234ze-E, and the HFO-1 The composition according to any one of claims 1 or 6 to 21, wherein 234ze-E is present at a concentration of about 19% to about 47% by weight based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E, the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E is 100, and the composition has a GWP of <160.

26. The HFO-1252zc is present at a concentration of approximately 0.05% to approximately 24% by weight, based on the weights of the HFO-1252zc, the HFC-32, and the HFO-1234ze-E, and the HFC-32 is present at a concentration of approximately 34% to approximately 43.78% by weight, based on the weights of the HFO-1252zc, the HFC-32, and the HFO-1234ze-E, and the HFO-1234ze-E is present at a concentration of approximately 0.05% to approximately 24% by weight, based on the weights of the HFO-1252zc, the HFC-32, and the HFO-1234ze-E The composition according to any one of claims 1 or 6 to 21, wherein the FO-1252zc, the HFC-32, and the HFO-1234ze-E are present at a concentration of about 37% to about 62% by weight based on their weights, the sum of the weight percentages of the HFO-1252zc, the HFC-32, and the HFO-1234ze-E is 100, and the composition has a flammability grade of 2 L (as measured according to ANSI / ASHRAE standard 34).

27. The HFO-1252zc is present at a concentration of approximately 51% to approximately 63% by weight, based on the weights of the HFO-1252zc, HFC-32, and HFO-1234ze-E, and the HFC-32 is present at a concentration of approximately 23% to approximately 38% by weight, based on the weights of the HFO-1252zc, HFC-32, and HFO-1234ze-E. The composition according to any one of claims 1 or 6 to 21, wherein the HFO-1234ze-E is present at a concentration of about 4% to about 21% by weight based on the weights of the HFO-1252zc, the HFC-32, and the HFO-1234ze-E, and the sum of the weight percentages of the HFO-1252zc, the HFC-32, and the HFO-1234ze-E is 100.

28. The HFO-1252zc is present at a concentration of approximately 31% to approximately 64% by weight, based on the weights of the HFO-1252zc, HFC-32, and HFO-1234ze-E, and the HFC-32 is present at a concentration of approximately 17% to approximately 43% by weight, based on the weights of the HFO-1252zc, HFC-32, and HFO-1234ze-E. The composition according to any one of claims 1 or 6 to 21, wherein the HFO-1234ze-E is present at a concentration of about 1% to about 31% by weight based on the weights of the HFO-1252zc, the HFC-32, and the HFO-1234ze-E, and the sum of the weight percentages of the HFO-1252zc, the HFC-32, and the HFO-1234ze-E is 100.

29. The HFO-1252zc is present at a concentration of approximately 0.05% to approximately 25% by weight, based on the weights of the HFO-1252zc, HFC-32, and HFO-1234ze-E; the HFC-32 is present at a concentration of approximately 36% to approximately 43.78% by weight, based on the weights of the HFO-1252zc, HFC-32, and HFO-1234ze-E; and the HFO-1234ze-E is present at a concentration of approximately 0.05% to approximately 25% by weight, based on the weights of the HFO-1252zc, HFC-32, and HFO-1234ze-E. The composition according to any one of claims 1 or 6 to 21, wherein FO-1252zc, the HFC-32, and the HFO-1234ze-E are present at a concentration of about 39% to about 57% by weight, based on their weights, the sum of the weight percentages of the HFO-1252zc, the HFC-32, and the HFO-1234ze-E is 100, and the composition has a flammability grade of 2 L (as measured according to ANSI / ASHRAE standard 34).

30. The HFO-1252zc is present at a concentration of approximately 36% to approximately 60% by weight, based on the weights of the HFO-1252zc, the HFC-32, and the HFO-1234ze-E, and the HFC-32 is present at a concentration of approximately 17% to approximately 22% by weight, based on the weights of the HFO-1252zc, the HFC-32, and the HFO-1234ze-E, and the HFO-1 The composition according to any one of claims 1 or 6 to 21, wherein 234ze-E is present at a concentration of about 18% to about 42% by weight based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E, the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E is 100, and the composition has a GWP of <160.

31. The composition according to claim 1 or any one of claims 6 to 21, wherein the HFO-1252zc is present at a concentration of about 1% to about 16% by weight based on the weights of the HFO-1252zc and the HFO-1234ze-E, the HFO-1234ze-E is present at a concentration of about 84% to about 99% by weight based on the weights of the HFO-1252zc and the HFO-1234ze-E, the sum of the weight percentages of the HFO-1252zc and the HFO-1234ze-E is 100, and the composition has a flammability grade of 2 L (measured according to ANSI / ASHRAE standard 34).

32. The HFO-125zc is present at a concentration of approximately 19% to approximately 23% based on the weights of the HFO-1252zc, HFC-32, and HFO-1234zc, and the HFC-32 is present at a concentration of approximately 18% to approximately 22% based on the weights of the HFO-1252zc, HFC-32, and HFO-1234ze-E. The composition according to any one of claims 1 or 6 to 21, wherein the HFO-1234ze-E is present at a concentration of about 57% to about 61% by weight based on the weights of the HFO-1252zc, the HFC-32, and the HFO-1234ze-E, and the sum of the weight percentages of the HFO-1252zc, the HFC-32, and the HFO-1234ze-E is 100.

33. The composition according to claim 1 or any one of claims 6 to 21, wherein the HFO-1252zc is present at a concentration of about 56 weight percent to about 70 weight percent based on the weights of the HFO-1252zc and the HFC-32, the HFC-32 is present at a concentration of about 30 weight percent to about 44 weight percent based on the weights of the HFO-1252zc and the HFC-32, and the sum of the weight percentages of the HFO-1252zc and the HFC-32 is 100.

34. The HFO-1252zc is present at a concentration of approximately 0.5% to approximately 63% by weight, based on the weights of the HFO-1252zc, HFC-32, and HFO-1234ze-E, and the HFC-32 is present at a concentration of approximately 18% to approximately 43.78% by weight, based on the weights of the HFO-1252zc, HFC-32, and HFO-1234ze-E. The composition according to any one of claims 1 or 6 to 21, wherein HFO-1234ze-E is present at a concentration of about 4% to about 62% by weight based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E, and the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E is 100.

35. The HFO-1252zc is present at a concentration of approximately 0.5% to approximately 64% by weight, based on the weights of the HFO-1252zc, HFC-32, and HFO-1234ze-E, and the HFC-32 is present at a concentration of approximately 17% to approximately 43.78% by weight, based on the weights of the HFO-1252zc, HFC-32, and HFO-1234ze-E. The composition according to any one of claims 1 or 6 to 21, wherein HFO-1234ze-E is present at a concentration of about 1% by weight to about 57% by weight based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E, and the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E is 100.

36. The HFO-1252zc is present at a concentration of approximately 18% to approximately 20% by weight, based on the weights of the HFO-1252zc, the HFC-32, and the HFO-1234ze-E, and the HFC-32 is present at a concentration of approximately 6% to approximately 21% by weight, based on the weights of the HFO-1252zc, the HFC-32, and the HFO-1234ze-E. The composition according to any one of claims 1 or 6 to 21, wherein E is present at a concentration of about 59% to about 76% by weight based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E, the sum of the weight percentages of HFO-1252ze, HFC-32, and HFO-1234ze-E is 100, and the composition exhibits a GWP of <160 and a flammability grade of 2 L.

37. The composition according to claim 1 or any one of claims 6 to 21, wherein HFO-1252zc is present at a concentration of about 20 weight percent based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E, HFC-32 is present at a concentration of about 21 weight percent based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E, HFO-1234ze-E is present at a concentration of about 59 weight percent based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E, and the sum of the weight percentages of HFO-1252ze, HFC-32, and HFO-1234ze-E is 100.

38. The HFO-1252zc is present at a concentration of approximately 18% to approximately 22% by weight, based on the weights of the HFO-1252zc, HFC-32, and HFO-1234ze-E, and the HFC-32 is present at a concentration of approximately 19% to approximately 23% by weight, based on the weights of the HFO-1252zc, HFC-32, and HFO-1234ze-E. The composition according to any one of claims 1 or 6 to 21, wherein the HFO-1234ze-E is present at a concentration of about 57% to about 61% by weight based on the weights of the HFO-1252zc, the HFC-32, and the HFO-1234ze-E, and the sum of the weight percentages of the HFO-1252ze, the HFC-32, and the HFO-1234ze-E is 100.

39. A method for cooling, comprising evaporating a composition according to any one of claims 1 to 38 in the vicinity of an object to be cooled, and then condensing the composition, wherein the cooling is provided by an air conditioner or a heat pump.

40. The method according to claim 39, wherein the HFO-1252zc is present at a concentration of about 56 weight percent to about 68 weight percent based on the weights of the HFO-1252zc and the HFC-32, the HFC-32 is present at a concentration of about 32 weight percent to about 44 weight percent based on the weights of the HFO-1252zc and the HFC-32, the cooling is provided by a heat pump, and the heat pump exhibits a gradient of <8K.

41. The HFO-1252zc is present at a concentration of approximately 51% to approximately 63% by weight, based on the weights of the HFO-1252zc, HFC-32, and HFO-1234ze-E, and the HFC-32 is present at a concentration of approximately 23% to approximately 38% by weight, based on the weights of the HFO-1252zc, HFC-32, and HFO-1234ze-E, and the HFO-1234 The method according to claim 39, wherein ze-E is present at a concentration of about 4% to about 21% by weight based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E, the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E is 100, the cooling is provided by a heat pump, the heat pump exhibits a gradient of <8K.

42. The method according to claim 39, wherein the HFO-1252zc is present at a concentration of about 56% to about 70% by weight based on the weights of the HFO-1252zc and the HFC-32, the HFC-32 is present at a concentration of about 30% to about 44% by weight based on the weights of the HFO-1252zc and the HFC-32, the sum of the weight percentages of the HFO-1252zc and the HFC-32 is 100, the cooling is provided by a heat pump, the heat pump exhibits a cooling capacity of at least 80% of the cooling capacity of R-454C.

43. The HFO-1252zc is present at a concentration of approximately 0.5% to approximately 63% by weight, based on the weights of the HFO-1252zc, the HFC-32, and the HFO-1234ze-E; the HFC-32 is present at a concentration of approximately 18% to approximately 43.78% by weight, based on the weights of the HFO-1252zc, the HFC-32, and the HFO-1234ze-E; and the HFO-1234ze-E is The method according to claim 39, wherein HFO-1252zc, the HFC-32, and the HFO-1234ze-E are present at a concentration of about 4% to about 62% by weight based on their weight, the sum of the weight percentages of HFO-1252zc, the HFC-32, and the HFO-1234ze-E is 100, the cooling is provided by a heat pump, and the heat pump exhibits a cooling capacity of at least 80% of the cooling capacity of R-454C.

44. The method according to claim 39, wherein the HFO-1252zc is present at a concentration of about 20% to about 83% by weight based on the weights of the HFO-1252zc and the HFC-32, the HFC-32 is present at a concentration of about 17% to about 80% by weight based on the weights of the HFO-1252zc and the HFC-32, the sum of the weight percentages of the HFO-1252zc and the HFC-32 is 100, the cooling is provided by a heat pump, the heat pump exhibits a cooling capacity of at least 80% of the cooling capacity of R-454C.

45. The HFO-1252zc is present at a concentration of approximately 0.5% to approximately 64% by weight, based on the weights of the HFO-1252zc, HFC-32, and HFO-1234ze-E, and the HFC-32 is present at a concentration of approximately 17% to approximately 43.78% by weight, based on the weights of the HFO-1252zc, HFC-32, and HFO-1234ze-E, and the HFO-12 The method according to claim 39, wherein 34ze-E is present at a concentration of about 1 weight percent to about 57 weight percent based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E, the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E is 100, and the heat pump exhibits a cooling capacity of at least 80% of the cooling capacity of R-454C.

46. The HFO-1252zc is present at a concentration of approximately 18% to approximately 20% by weight based on the weights of the HFO-1252zc, the HFC-32, and the HFO-1234ze-E, and the HFC-32 is present at a concentration of approximately 6% to approximately 21% by weight relative to the weights of the HFO-1252zc, the HFC-32, and the HFO-1234ze-E, and the HFO-1234ze The method according to claim 39, wherein -E is present at a concentration of about 59% to about 76% by weight relative to the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E, the sum of the weight percentages of HFO-1252ze, HFC-32, and HFO-1234ze-E is 100, the cooling is provided by a heat pump, and the heat pump exhibits a gradient of <10K.

47. The HFO-1252zc is present at a concentration of approximately 20 weight percent based on the weights of the HFO-1252zc, HFC-32, and HFO-1234ze-E, the HFC-32 is present at a concentration of approximately 21 weight percent based on the weights of the HFO-1252zc, HFC-32, and HFO-1234ze-E, and the HFO-1234ze-E is present at a concentration of approximately 20 weight percent based on the weights of the HFO-1252 The method according to claim 39, wherein zc, the HFC-32, and the HFO-1234ze-E are present at a concentration of about 59 weight percent based on their weights, the sum of the weight percentages of the HFO-1252ze, the HFC-32, and the HFO-1234ze-E is 100, the cooling is provided by a heat pump, and the heat pump exhibits a cooling capacity of at least 90% of the cooling capacity of R-454C.

48. A method for heating, comprising evaporating a composition according to any one of claims 1 to 38, and then condensing the composition in the vicinity of an object to be heated, wherein the heating is provided by a heat pump.

49. The method according to claim 48, wherein the HFO-1252zc is present at a concentration of about 56 weight percent to about 65 weight percent based on the weights of the HFO-1252zc and the HFC-32, the HFC-32 is present at a concentration of about 35 weight percent to about 44 weight percent based on the weights of the HFO-1252zc and the HFC-32, and the heat pump exhibits a gradient of <8K.

50. The HFO-1252zc is present at a concentration of approximately 31% to approximately 64% by weight, based on the weights of the HFO-1252zc, HFC-32, and HFO-1234ze-E, and the HFC-32 is present at a concentration of approximately 17% to approximately 43% by weight, based on the weights of the HFO-1252zc, HFC-32, and HFO-1234ze-E. The method according to claim 48, wherein HFO-1234ze-E is present at a concentration of about 1 weight percent to about 31 weight percent based on the weights of HFO-1252zc, HFC-32, and HFO-1234ze-E, the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E is 100, and the heat pump exhibits a gradient of <8K.

51. The method according to claim 48, wherein the HFO-1252zc is present at a concentration of about 56% to about 70% by weight based on the weights of the HFO-1252zc and the HFC-32, the HFC-32 is present at a concentration of about 30% to about 40% by weight based on the weights of the HFO-1252zc and the HFC-32, the sum of the weight percentages of the HFO-1252zc and the HFC-32 is 100, and the heat pump exhibits a heating capacity of at least 80% of the heating capacity of the R-454C.

52. The method according to claim 48, wherein the HFO-1252zc is present at a concentration of about 20% to about 83% by weight based on the weights of the HFO-1252zc and the HFC-32, the HFC-32 is present at a concentration of about 17% to about 80% by weight based on the weights of the HFO-1252zc and the HFC-32, the sum of the weight percentages of the HFO-1252zc and the HFC-32 is 100, and the heat pump exhibits a heating capacity of at least 80% of the heating capacity of the R-454C.

53. The HFO-1252zc is present at a concentration of approximately 20 weight percent based on the weights of the HFO-1252zc, HFC-32, and HFO-1234ze-E, the HFC-32 is present at a concentration of approximately 21 weight percent relative to the weights of the HFO-1252zc, HFC-32, and HFO-1234ze-E, and the HFO-1234ze-E is present at a concentration of approximately 21 weight percent relative to the weights of the HFO-1252zc, HFC-32, and HFO-1234ze-E. The method according to claim 48, wherein the HFO-1252zc, the HFC-32, and the HFO-1234ze-E are present at a concentration of about 59 weight percent based on their weights, the sum of the weight percentages of the HFO-1252ze, the HFC-32, and the HFO-1234ze-E is 100, and the heat pump exhibits a heating capacity of at least 90% of the heating capacity of R-454C.

54. A system for cooling or heating comprising the composition according to any one of claims 1 to 38.

55. The system according to claim 54, comprising an evaporator, a compressor, a condenser, and an expansion device, each operably connected to perform a vapor compression cycle.

56. The system according to claim 54 or 55, wherein the air conditioner or heat pump is an air conditioner or heat pump for residential, light commercial, or industrial use.

57. A method for replacing R-454C or propane in an air conditioning or heat pump system, comprising providing the system with a composition according to any one of claims 1 to 38 instead of R-454C or propane.

58. Use of the composition according to any one of claims 1 to 38 as a refrigerant in an air conditioning or heat pump system.

59. The system according to any one of claims 54 to 56, wherein the system is a secondary loop system.

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