Refrigerant composition comprising E-1, 3, 3, 3-tetrafluoropropene, hydro (chloro) fluorocarbon and lubricant, and refrigeration, air conditioning or heat pump system using same

Abstract

A refrigerant composition comprising E-1, 3, 3, 3-tetrafluoropropene, a hydrogen (chloro) fluorocarbon selected from the group consisting of 1, 1, 3, 3-tetrafluoro-2-propene, 1, 1, 1, 3, 3-pentafluoropropane, trans-1-chloro-3, 3, 3-trifluoropropene, and mixtures thereof, and a lubricant selected from the group consisting of polyol esters and polyalkylene glycols, where the hydrogen (chloro) fluorocarbon is based on the E-1, 3, 3, 3-tetrafluoropropene. A total amount of up to 1.0 wt%, based on the total weight of the 1, 1, 1, 3, 3-tetrafluoropropene and the hydrogen (chloro) fluorocarbon, is present in the composition.

Description

[0001] Cross - reference to related applications

[0002] This application claims priority to U.S. Provisional Application No. 63 / 428,510, filed on November 29, 2022, the entire disclosure of which is incorporated herein by reference. Technical field

[0003] The present invention relates to refrigerant compositions comprising E - 1,3,3,3 - tetrafluoropropene, hydrofluorocarbons and / or hydrochlorofluorocarbons, and a lubricant. The present invention particularly relates to refrigerant compositions comprising E - 1,3,3,3 - tetrafluoropropene (HFO - 1234ze(E)), a hydro(chloro)fluorocarbon selected from 1,1,3,3 - tetrafluoro - 2 - propene (HFO - 1234zc), 1,1,1,3,3 - pentafluoropropane (HFC - 245fa), trans - 1 - chloro - 3,3,3 - trifluoropropene (HFO - 1233zdE), and mixtures thereof, and a lubricant selected from polyol esters and polyalkylene glycols. The present invention further relates to refrigeration, air - conditioning or heat pump systems using these compositions. The present invention further relates to methods for reducing the viscosity of compositions comprising E - 1,3,3,3 - tetrafluoropropene and a lubricant, and methods for improving the miscibility of HFO - 1234ze(E) and a lubricant. Background art

[0004] The fluorocarbon industry has been working for the past few decades to find alternative refrigerants for ozone - depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) phased out by the Montreal Protocol. The solution for many applications has been the commercialization of hydrofluorocarbon (HFC) compounds used as refrigerants, solvents, fire extinguishants, blowing agents, and propellants. These currently most widely used new compounds, such as HFC refrigerants, HFC - 134a and HFC - 125, have zero ozone depletion potential and are thus not affected by the current Montreal Protocol phase - out provisions.

[0005] In addition to the ozone depletion problem, global warming is another environmental concern for many of these applications. Therefore, there is a need for compositions that meet both low ozone depletion standards and have a low global warming potential. It is believed that certain hydrofluoroolefin (HFO) compositions meet both of these goals.

[0006] HFO-1234ze (CF3CH=CHF), which has zero ozone depletion and a low global warming potential, has been identified as a potential refrigerant to meet these goals. U.S. Patent No. 7,862,742 discloses compositions containing HFO-1234ze. U.S. Patent No. 9,302,962 discloses methods for preparing HFO-1234ze. HFO-1234ze exists in two isomeric forms, the E-isomer and the Z-isomer. Generally speaking, for refrigeration applications, the E-isomer is the most useful. In the present application, the E-isomer is commonly referred to as E-1,3,3,3-tetrafluoropropene or HFO-1234ze(E), but it is also referred to as trans-HFO-1234ze or HFO-1234zeE.

[0007] For use in conventional refrigeration, air conditioning, and heat pump systems that include a compressor, alternative refrigerants should preferably be soluble in the lubricant. If the refrigerant lacks solubility in the lubricant, there is a risk of phase separation occurring between the lubricant and the refrigerant during the operation of the refrigeration or heat pump system. The phase separation will in turn reduce the overall performance of the system in terms of heat exchange efficiency and system life. Although HFO-1234ze is generally more soluble in conventional refrigeration lubricants than traditional HFCs or HCFCs, there is still a need in the art for refrigerants that provide improved solubility in refrigeration lubricants. In particular, there is a need in the art for refrigerant compositions with improved compatibility, which comprise a refrigerant containing HFO-1234ze(E) and a lubricant. Summary of the Invention

[0008] The present invention meets this need by providing a refrigerant composition that comprises (i) E-1,3,3,3-tetrafluoropropene, (ii) a hydro(chloro)fluorocarbon selected from 1,1,3,3-tetrafluoro-2-propene, 1,1,1,3,3-pentafluoropropane, trans-1-chloro-3,3,3-trifluoropropene, and mixtures thereof, and (iii) a lubricant selected from polyol esters and polyalkylene glycols. Based on the total weight of E-1,3,3,3-tetrafluoropropene (i) and the hydro(chloro)fluorocarbon (ii), the hydro(chloro)fluorocarbon (ii) is present in the composition in a total amount of up to 1.0 wt%, preferably in the range of 0.00001 wt% to 1.0 wt%, and more preferably 0.0001 wt% to 1.0 wt%.

[0009] In one embodiment, based on the total weight of E-1,3,3,3-tetrafluoropropene (i) and the hydro(chloro)fluorocarbon (ii), the hydro(chloro)fluorocarbon (ii) is present in the composition in a total amount in the range of 0.001 wt% to 0.9 wt%, preferably 0.005 wt% to 0.8 wt%, more preferably 0.01 wt% to 0.6 wt%, and most preferably 0.1 wt% to 0.5 wt%.

[0010] One embodiment relates to any one of the foregoing compositions, wherein E-1,3,3,3-tetrafluoropropene is present in the composition in an amount of 50.0% by weight or more, preferably 75.0% by weight or more, more preferably 90.0% by weight or more, even more preferably 94.0% to 99.5% by weight, and most preferably 94.5% to 99.0% by weight, based on the total weight of the composition.

[0011] One embodiment relates to any one of the foregoing compositions, wherein the lubricant is present in the composition in an amount of 45.0% by weight or less, preferably 35.0% by weight or less, more preferably 15.0% by weight or less, still more preferably in the range of 0.1% to 10.0% by weight, and most preferably 0.5% to 5.0% by weight, based on the total weight of the composition.

[0012] One embodiment relates to any one of the foregoing compositions, wherein the hydro(chloro)fluorocarbon (ii) is selected from 1,1,3,3-tetrafluoro-2-propene, 1,1,1,3,3-pentafluoropropane, and mixtures thereof. In another embodiment, the hydro(chloro)fluorocarbon (ii) is 1,1,3,3-tetrafluoro-2-propene. In yet another embodiment, the hydro(chloro)fluorocarbon (ii) is trans-1-chloro-3,3,3-trifluoropropene. In another embodiment, the hydro(chloro)fluorocarbon (ii) is a mixture of 1,1,3,3-tetrafluoro-2-propene and trans-1-chloro-3,3,3-trifluoropropene, a mixture of 1,1,3,3-tetrafluoro-2-propene and 1,1,1,3,3-pentafluoropropane, or a mixture of 1,1,3,3-tetrafluoro-2-propene, 1,1,1,3,3-pentafluoropropane, and trans-1-chloro-3,3,3-trifluoropropene.

[0013] One embodiment relates to any one of the foregoing compositions, wherein the lubricant is a polyol ester. In another embodiment, the lubricant in any one of the foregoing compositions is a polyalkylene glycol.

[0014] The present disclosure further relates to a refrigeration, air conditioning, or heat pump system, the refrigeration, air conditioning, or heat pump system including an evaporator, a condenser, a compressor, an expansion device, and a heat transfer medium, wherein the heat transfer medium comprises any one of the foregoing compositions.

[0015] The present disclosure further relates to the use of any one of the foregoing refrigerant compositions as a heat transfer medium for enhancing the cooling or heating capacity in a refrigeration, air conditioning, or heat pump system, the refrigeration, air conditioning, or heat pump system including an evaporator, a condenser, a compressor, and an expansion device.

[0016] In the above system or use, the refrigeration, air conditioning or heat pump system is preferably a refrigeration device, an air conditioning device, a cooling device, a high-temperature, medium-temperature or low-temperature refrigeration device or a high-temperature, medium-temperature or low-temperature heat pump device. Even more preferably, any one of the above devices is a stationary device. Stationary air conditioning and heat pump systems include, for example, window-type, ductless, ducted, packaged terminal, cooler, and light commercial and commercial air conditioning systems, including packaged rooftops. Stationary refrigeration systems include, for example, household or domestic refrigerators and freezers, ice makers, self-contained coolers and freezers, walk-in coolers and freezers, and supermarket systems.

[0017] The present disclosure further relates to a method of replacing a refrigerant composition containing a high-GWP refrigerant in a refrigeration, air conditioning or heat pump system, wherein the high-GWP refrigerant is selected from the group consisting of R134a, R22, R123, R11, R245fa, R114, R236fa, R124, R12, R410A, R407C, R417A, R422A, R507A, R502, and R404A, the method comprising providing to a refrigeration, air conditioning or heat pump system that uses, has used, or is designed to use a high-GWP refrigerant any one of the foregoing refrigerant compositions.

[0018] The present disclosure further relates to a method of reducing the viscosity of a refrigerant composition comprising (i) E-1,3,3,3-tetrafluoropropene and (iii) a lubricant selected from the group consisting of polyol esters and polyalkylene glycols, wherein the method comprises adding (ii) a hydro(chloro)fluorocarbon selected from the group consisting of 1,1,3,3-tetrafluoro-2-propene, 1,1,1,3,3-pentafluoropropane, trans-1-chloro-3,3,3-trifluoropropene, and mixtures thereof to a composition comprising E-1,3,3,3-tetrafluoropropene (i) and lubricant (iii), wherein the hydro(chloro)fluorocarbon (ii) is added in an amount such that (ii) is present in the composition in a total amount of up to 1.0 wt%.

[0019] The present disclosure further relates to a method for reducing the viscosity of a refrigerant blend comprising (i) E-1,3,3,3-tetrafluoropropene (e.g., R-471A, R-476A, R-515A / B) and (iii) a lubricant selected from polyol esters and polyalkylene glycols, wherein the method comprises adding (ii) a hydro(chloro)fluorocarbon selected from 1,1,3,3-tetrafluoro-2-propene, 1,1,1,3,3-pentafluoropropane, trans-1-chloro-3,3,3-trifluoropropene, and mixtures thereof to a blend of R-471A, R-476A, R-482A, R-515A / B containing E-1,3,3,3-tetrafluoropropene (i) and a lubricant (iii), wherein the hydro(chloro)fluorocarbon (ii) is added in an amount such that (ii) it is present in the blend in a total amount of up to 1.0 wt%.

[0020] The present disclosure further relates to a method for reducing the viscosity of a refrigerant blend comprising (i) E-1,3,3,3-tetrafluoropropene, such as blend numbers 464A, 470A, 470B, 444A, 444B, 445A, 446A, 447A, 447B, 448A, 448B, 450A, 456A, 459A, 459B, 460A, 460B, 460C, 475A, 476A, 482A, 515A or 515B, and (iii) a lubricant selected from polyol esters and polyalkylene glycols, wherein the method comprises adding (ii) a hydro(chloro)fluorocarbon selected from 1,1,3,3-tetrafluoro-2-propene, 1,1,1,3,3-pentafluoropropane, trans-1-chloro-3,3,3-trifluoropropene, and mixtures thereof to a blend of 464A, 470A, 470B, 444A, 444B, 445A, 446A, 447A, 447B, 448A, 448B, 450A, 456A, 459A, 459B, 460A, 460B, 460C, 475A, 476A, 482A, 515A or 515B containing E-1,3,3,3-tetrafluoropropene (i) and a lubricant (iii), wherein the hydro(chloro)fluorocarbon (ii) is added in an amount such that (ii) it is present in the blend in a total amount of up to 1.0 wt%.

[0021] The present disclosure also relates to a method for improving the miscibility of (i) E-1,3,3,3-tetrafluoropropene and (iii) a lubricant selected from polyol esters and polyalkylene glycols in a refrigerant composition, wherein the method comprises adding (ii) a hydro(chloro)fluorocarbon selected from 1,1,3,3-tetrafluoro-2-propene, 1,1,1,3,3-pentafluoropropane, trans-1-chloro-3,3,3-trifluoropropene, and mixtures thereof to a composition comprising E-1,3,3,3-tetrafluoropropene (i) and the lubricant (iii), wherein the hydro(chloro)fluorocarbon (ii) is added in an amount such that (ii) is present in the composition in a total amount of up to 1.0 wt%. Detailed Description

[0022] A refrigerant composition or mixture is described that comprises a refrigerant portion and a lubricant portion, wherein the refrigerant portion is highly miscible with the lubricant portion. More specifically, the present invention relates to a composition comprising (i) E-1,3,3,3-tetrafluoropropene, (ii) a hydrofluorocarbon and / or hydrochlorofluorocarbon, and (iii) a lubricant. The hydro(chloro)fluorocarbon (ii) is selected from 1,1,3,3-tetrafluoro-2-propene, 1,1,1,3,3-pentafluoropropane, trans-1-chloro-3,3,3-trifluoropropene, and mixtures thereof. The lubricant (iii) is selected from polyol esters and polyalkylene glycols. The hydro(chloro)fluorocarbon (ii) is present in the composition in a total amount of up to 1.0 wt% or in a range greater than 0 wt% to 1.0 wt% based on the total weight of E-1,3,3,3-tetrafluoropropene (ii) and the hydro(chloro)fluorocarbon (ii). Preferably, the hydro(chloro)fluorocarbon (ii) is present in the composition in a total amount in the range of 0.00001 wt% to 1.0 wt%, more preferably 0.0001 wt% to 1.0 wt%, and even more preferably 0.001 wt% to 1.0 wt% based on the total weight of (i) and (ii).

[0023] In a preferred embodiment, the composition comprises E-1,3,3,3-tetrafluoropropene (i), a hydro(chloro)fluorocarbon (ii), and a lubricant (iii), consists essentially of E-1,3,3,3-tetrafluoropropene (i), a hydro(chloro)fluorocarbon (ii), and a lubricant (iii), or consists of E-1,3,3,3-tetrafluoropropene (i), a hydro(chloro)fluorocarbon (ii), and a lubricant (iii). When the composition consists essentially of E-1,3,3,3-tetrafluoropropene (i), a hydro(chloro)fluorocarbon (ii), and a lubricant (iii), this means that additional HFOs, hydro(chloro)fluorocarbons, or lubricants are present only as unavoidable impurities, for example, in an amount less than 1000 ppm (by weight), preferably 100 ppm (by weight) or less, more preferably 10 ppm (by weight) or less, and most preferably 1 ppm (by weight) or less.

[0024] Refrigerant

[0025] The refrigerant portion of the composition according to the present invention comprises E-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)).

[0026] In one embodiment, based on the total weight of the composition, HFO-1234ze(E) may be present in the composition in a total amount of 50.0 wt% or more. In other embodiments, based on the total weight of the composition, HFO-1234ze(E) may be present in the composition in a total amount of 60.0 wt% or more, 65.0 wt% or more, 70.0 wt% or more, 75.0 wt% or more, 80.0 wt% or more, 85.0 wt% or more, 90.0 wt% or more, 95.0 wt% or more, 96.0 wt% or more, 97.0 wt% or more, 98.0 wt% or more, or 99.0 wt% or more. For example, based on the total weight of the composition, HFO-1234ze(E) may be present in an amount of 50.0 wt% to 99.5 wt%, or 75.0 wt% to 99.5 wt%, or 90.0 wt% to 99.5 wt%, or 94.0 wt% to 99.5 wt%, or 94.5 wt% to 99.5 wt%, or 95.0 wt% to 99.5 wt%; 50.0 wt% to 99.0 wt%, or 75.0 wt% to 99.0 wt%, or 90.0 wt% to 99.0 wt%, or 94.0 wt% to 99.0 wt%, or 94.5 wt% to 99.0 wt%, or 95.0 wt% to 99.0 wt%; 50.0 wt% to 96.5 wt%, or 75.0 wt% to 96.5 wt%, or 90.0 wt% to 96.5 wt%, or 94.0 wt% to 96.5 wt%, or 94.5 wt% to 96.5 wt%, or 95.0 wt% to 99.0 wt%; 50.0 wt% to 95.0 wt%, or 75.0 wt% to 95.0 wt%, or 90.0 wt% to 95.0 wt%; 50.0 wt% to 90.0 wt%, or 75.0 wt% to 90.0 wt%, or 80.0 wt% to 90.0 wt% in the composition. In a preferred embodiment, based on the total weight of the composition, E-1,3,3,3-tetrafluoropropene is present in an amount of 50.0 wt% or more, preferably in an amount of 75.0 wt% or more, more preferably in an amount of 90.0 wt% or more, even more preferably in an amount of 95.0 wt% to 99.5 wt%, and most preferably in an amount of 95.0 wt% to 99.0 wt%.

[0027] The refrigerant portion of the composition according to the present invention further comprises a hydrofluorocarbon and / or a hydrochlorofluorocarbon (ii), also referred to herein as a hydro(chloro)fluorocarbon. The hydro(chloro)fluorocarbon is selected from 1,1,3,3-tetrafluoro-2-propene (HFO-1234zc), 1,1,1,3,3-pentafluoropropane (HFC-245fa), trans-1-chloro-3,3,3-trifluoropropene (HFO-1233zdE), and mixtures thereof.

[0028] Based on the total weight of E-1,3,3,3-tetrafluoropropene (i) and hydro(chloro)fluorocarbon (ii), the hydro(chloro)fluorocarbon is present in the composition in a total amount of up to 1.0% by weight. In one embodiment, based on the total weight of E-1,3,3,3-tetrafluoropropene (i) and hydro(chloro)fluorocarbon (ii), the hydro(chloro)fluorocarbon is present in the composition in a total amount in the range of 0.00001% to 1.0% by weight. In other embodiments, based on the total weight of E-1,3,3,3-tetrafluoropropene (i) and hydro(chloro)fluorocarbon (ii), the hydro(chloro)fluorocarbon is present in the composition in a total amount in the range of 0.0001% to 1.0% by weight, preferably 0.001% to 1.0% by weight, 0.01% to 1.0% by weight, or 0.1% to 1.0% by weight. In still other embodiments, based on the total weight of E-1,3,3,3-tetrafluoropropene (i) and hydro(chloro)fluorocarbon (ii), the hydro(chloro)fluorocarbon is present in the composition in a total amount in the range of 0.001% to 0.9% by weight, 0.005% to 0.8% by weight, 0.01% to 0.6% by weight, or 0.1% to 0.5% by weight.

[0029] In one embodiment, the hydro(chloro)fluorocarbon is 1,1,3,3-tetrafluoro-2-propene. In another embodiment, the hydro(chloro)fluorocarbon is 1,1,1,3,3-pentafluoropropane. In yet another embodiment, the hydro(chloro)fluorocarbon is trans-1-chloro-3,3,3-trifluoropropene. In another embodiment, the hydro(chloro)fluorocarbon is a mixture of 1,1,3,3-tetrafluoro-2-propene and 1,1,1,3,3-pentafluoropropane, or a mixture of 1,1,3,3-tetrafluoro-2-propene and trans-1-chloro-3,3,3-trifluoropropene, or a mixture of 1,1,1,3,3-pentafluoropropane and trans-1-chloro-3,3,3-trifluoropropene. In another embodiment, the hydro(chloro)fluorocarbon is a mixture of 1,1,3,3-tetrafluoro-2-propene, 1,1,1,3,3-pentafluoropropane and trans-1-chloro-3,3,3-trifluoropropene. In each of these embodiments, based on the total weight of E-1,3,3,3-tetrafluoropropene (i) and hydro(chloro)fluorocarbon (ii), the hydro(chloro)fluorocarbon or the mixture of hydro(chloro)fluorocarbons can be present in the composition in any of the above total amounts.

[0030] The composition of the present invention may comprise additional fluorine-containing compounds.

[0031] In some embodiments, the compositions of the present invention further comprise one or more of HFO-1234yf, HFO-1243zf, HFO-1233zd(Z), HFO-1233xf, HFC-143a or HFC-152a. In some embodiments, based on the total weight of E-1,3,3,3-tetrafluoropropene (i), hydro(chloro)fluorocarbons (ii) and all other fluorine-containing compounds, the total amount of HFO-1234yf, HFO-1243zf, HFO-1233zd(Z), HFO-1233xf, HFC-143a or HFC-152a is 1.0 wt% or less, such as 0.0001 wt% to 1.0 wt%, or 0.001 wt% to 0.5 wt%, or 0.001 wt% to 0.1 wt%, or 0.01 wt% to 0.05 wt%.

[0032] In other embodiments, the compositions of the present invention further comprise one or more of HFO-1234ze(Z), HFO-1224yd, HFO-1224zc, HCFO-1326mxz, HFC-32, R-113, R-23, trifluoropropyne, HFC-356mff and HFC-245cb, preferably one or more of HFO-1234ze(Z), trifluoropropyne and HFC-245cb. Based on the total weight of E-1,3,3,3-tetrafluoropropene (i), hydro(chloro)fluorocarbons (ii) and all other fluorine-containing compounds, the amount of the foregoing compounds in the composition may range from 0.0001 wt% to 1.0 wt%, preferably 0.001 wt% to 0.1 wt%, and most preferably 0.01 wt% to 0.05 wt%.

[0033] In yet another embodiment, the compositions of the present invention further comprise at least one compound selected from the group consisting of: HFC-1234ye, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-365mfc, HFO-1336mzz(E), propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethyl ether, CF 3 SCF 3 、CO 2 、CF 3 I and combinations thereof. Based on the total weight of E-1,3,3,3-tetrafluoropropene (i), hydro(chloro)fluorocarbons (ii) and the foregoing compounds, the amount of the foregoing compounds may range from 0.0001 wt% to 1.0 wt%, preferably 0.001 wt% to 0.1 wt%, and most preferably 0.01 wt% to 0.05 wt%.

[0034] In some embodiments, the viscosity of a refrigerant blend comprising (i) E-1,3,3,3-tetrafluoropropene (e.g., R-471A, R-476A, R-515A / B) and (iii) a lubricant selected from polyol esters and polyalkylene glycols is reduced, wherein the method comprises adding (ii) a hydro(chloro)fluorocarbon selected from 1,1,3,3-tetrafluoro-2-propene, 1,1,1,3,3-pentafluoropropane, trans-1-chloro-3,3,3-trifluoropropene, and mixtures thereof to a blend of R-471A, R-476A, R-482A, R-515A / B and lubricant (iii) comprising E-1,3,3,3-tetrafluoropropene (i), wherein the hydro(chloro)fluorocarbon (ii) is added in an amount such that (ii) it is present in the blend in a total amount of up to 1.0 wt% (e.g., 0.1 wt%, 0.5 wt%, and all values between 0.1 wt% and 1.0 wt%).

[0035] In some embodiments, reducing the viscosity of a refrigerant blend comprises reducing the viscosity of a refrigerant blend comprising: (i) E-1,3,3,3-tetrafluoropropene, such as blend numbers 464A, 470A, 470B, 444A, 444B, 445A, 446A, 447A, 447B, 448A, 448B, 450A, 456A, 459A, 459B, 460A, 460B, 460C, 475A, 476A, 482A, 515A or 515B, and (iii) a lubricant selected from polyol esters and polyalkylene glycols, wherein the method comprises adding (ii) a hydro(chloro)fluorocarbon selected from 1,1,3,3-tetrafluoro-2-propene, 1,1,1,3,3-pentafluoropropane, trans-1-chloro-3,3,3-trifluoropropene, and mixtures thereof to a blend of blend numbers 464A, 470A, 470B, 444A, 444B, 445A, 446A, 447A, 447B, 448A, 448B, 450A, 456A, 459A, 459B, 460A, 460B, 460C, 475A, 476A, 482A, 515A or 515B comprising E-1,3,3,3-tetrafluoropropene (i) and lubricant (iii), wherein the hydro(chloro)fluorocarbon (ii) is added in an amount such that (ii) it is present in the blend in a total amount of up to 1.0 wt% (e.g., 0.1 wt%, 0.5 wt%, and all values between 0.1 wt% and 1.0 wt%).

[0036] Lubricant

[0037] The lubricants in the composition of the present invention are selected from polyol esters and polyalkylene glycols. In one embodiment, the lubricant is a polyol ester. In another embodiment, the lubricant is a polyalkylene glycol.

[0038] In one embodiment, the polyol ester is a pentaerythritol ester of one or more linear or branched carbonic acids containing up to 9 carbons. In a preferred embodiment, the polyol ester is a pentaerythritol ester of a mixture of linear and / or branched carbonic acids containing up to 9 carbons. Example ester substituents on the pentaerythritol backbone are heptanoate, 3,5,5-hexanoate, valerate, and 3-methylbutyrate. One such POE mixture is Emkarate RL32-3MAF.

[0039] In one embodiment, the polyalkylene glycol is a double-ended copolymerized alkylene oxide. As the first type of synthetic lubricating oil synthesized for HFC refrigerants, they are well-known copolymers of alkylene oxide repeating units, usually ethylene oxide and propylene oxide in a stoichiometric ratio. The end-capping alkyl groups are terminating ether alkyl groups. PAGs in the preferred range of ISO 32 to 68, having linear and / or branched end-capping alkyl groups (R and R') in the range of 1 to 4 carbons and having a ratio of propylene oxide (PO) to ethylene oxide (EO) repeating groups in the range of 1:3 to 3:1 according to the following formula:

[0040] RO-(EO) n -(PO) m -OR'

[0041] A specific PAG that can be suitably used as a lubricant in the present refrigerant composition is Denso ISO 46ND-12PAG oil.

[0042] The amount of lubricant present in the composition depends particularly on the system in which the refrigerant system will be used. Generally speaking, the amount of lubricant will be selected by considering the requirements of a given compressor and the environment to which the lubricant will be exposed. In one embodiment, based on the total weight of the composition, the lubricant is present in an amount of 45.0 wt% or less, preferably in an amount of 35.0 wt% or less, such as in an amount of 30.0 wt% or less, 25.0 wt% or less, 20.0 wt% or less, 15.0 wt% or less, 10.0 wt% or less, or 5.0 wt% or less. For example, based on the total weight of the composition, the lubricant may be present in an amount in the range of 0.1 wt% to 45.0 wt%, preferably in the range of 0.2 wt% to 20.0 wt%, more preferably in the range of 0.3 wt% to 10.0 wt%, still more preferably in the range of 0.4 wt% to 5.0 wt%, and most preferably in the range of 0.5 wt% to 3.5 wt%.

[0043] In a specific embodiment, based on the total weight of the composition, the lubricant is a polyol ester and is present in an amount of 45.0 wt% or less, preferably in an amount of 35.0 wt% or less, such as in an amount of 30.0 wt% or less, 25.0 wt% or less, 20.0 wt% or less, 15.0 wt% or less, 10.0 wt% or less, or 5.0 wt% or less. For example, based on the total weight of the composition, the polyol ester lubricant may be present in an amount in the range of 0.1 wt% to 45.0 wt%, preferably in the range of 0.2 wt% to 20.0 wt%, more preferably in the range of 0.3 wt% to 10.0 wt%, still more preferably in the range of 0.4 wt% to 5.0 wt%, and most preferably in the range of 0.5 wt% to 3.5 wt%.

[0044] In another specific embodiment, based on the total weight of the composition, the lubricant is a polyalkylene glycol and is present in an amount of 45.0 wt% or less, preferably in an amount of 35.0 wt% or less, such as in an amount of 30.0 wt% or less, 25.0 wt% or less, 20.0 wt% or less, 15.0 wt% or less, 10.0 wt% or less, or 5.0 wt% or less. For example, based on the total weight of the composition, the polyalkylene glycol lubricant may be present in an amount in the range of 0.1 wt% to 45.0 wt%, preferably in the range of 0.2 wt% to 20.0 wt%, more preferably in the range of 0.3 wt% to 10.0 wt%, still more preferably in the range of 0.4 wt% to 5.0 wt%, and most preferably in the range of 0.5 wt% to 3.5 wt%.

[0045] In some embodiments, the refrigerant composition comprises (i) E-1,3,3,3-tetrafluoropropene in an amount of 94.0 wt% to 99.0 wt% based on the total weight of the composition, (ii) R-1233zdE in an amount of 0.001 wt% to 1.0 wt% based on the total weight of (i) and (ii), and (iii) a polyol ester lubricant in an amount of 0.5 wt% to 5.0 wt% based on the total weight of the composition.

[0046] In some embodiments, the refrigerant composition comprises (i) E-1,3,3,3-tetrafluoropropene in an amount of 94.0 wt% to 99.0 wt% based on the total weight of the composition, (ii) R-1233zdE in an amount of 0.001 wt% to 1.0 wt% based on the total weight of (i) and (ii), and (iii) a polyalkylene glycol lubricant in an amount of 0.5 wt% to 5.0 wt% based on the total weight of the composition.

[0047] In some embodiments, the refrigerant composition comprises (i) E-1,3,3,3-tetrafluoropropene in an amount of 94.0 wt% to 99.0 wt% based on the total weight of the composition, (ii) R-1234zc in an amount of 0.001 wt% to 1.0 wt% based on the total weight of (i) and (ii), and (iii) a polyol ester lubricant in an amount of 0.5 wt% to 5.0 wt% based on the total weight of the composition.

[0048] In some embodiments, the refrigerant composition comprises (i) E-1,3,3,3-tetrafluoropropene in an amount of 94.0 wt% to 99.0 wt% based on the total weight of the composition, (ii) R-1234zc in an amount of 0.001 wt% to 1.0 wt% based on the total weight of (i) and (ii), and (iii) a polyalkylene glycol lubricant in an amount of 0.5 wt% to 5.0 wt% based on the total weight of the composition.

[0049] In some embodiments, the refrigerant composition comprises (i) E-1,3,3,3-tetrafluoropropene in an amount of 94.0 wt% to 99.5 wt% based on the total weight of the composition, (ii) R-1234zc in an amount of at most 1.0 wt% based on the total weight of (i) and (ii), and (iii) a polyol ester lubricant in an amount of 0.1 wt% to 5.0 wt% based on the total weight of the composition.

[0050] In some embodiments, the refrigerant composition comprises (i) E-1,3,3,3-tetrafluoropropene in an amount of 94.0 wt% to 99.5 wt% based on the total weight of the composition, (ii) R-1234zc in an amount of up to 1.0 wt% based on the total weight of (i) and (ii), and (iii) a polyalkylene glycol lubricant in an amount of 0.1 wt% to 5.0 wt% based on the total weight of the composition.

[0051] Additive

[0052] Conventionally used refrigeration system additives can be optionally added to the compositions of the present invention as needed to enhance, for example, lubricity and system stability. These additives are generally known in the field of refrigeration compressor lubrication and include anti-wear agents, extreme pressure lubricants, corrosion and oxidation inhibitors, metal surface deactivators, free radical scavengers, foaming and defoaming control agents, leak detection agents, etc. Other additives are acid scavengers, performance enhancers, and flame suppressants. Generally speaking, these additives are present only in small amounts relative to the entire composition. They are typically used at concentrations of less than 0.1% to up to 3% of each additive. These additives are selected according to the requirements of each system. Some typical examples of such additives can include, but are not limited to, lubrication enhancing additives such as alkyl or aryl esters of phosphoric and thiophosphoric acids. Additionally, organometallic compounds dialkyldithiophosphates (e.g., zinc dialkyldithiophosphate or ZDDP, Lubrizol 1375) and other components of such chemicals can be used in the compositions of the present invention. Other anti-wear additives include natural product oils and asymmetric polyhydroxy lubricating additives such as Synergol TMS (International Lubricants). Similarly, stabilizers such as antioxidants, free radical scavengers, and water scavengers can be employed. Such compounds can include, but are not limited to, butylated hydroxytoluene (BHT) and epoxides. Acid scavengers can include siloxanes, activated aromatic compounds, or a combination of both. Exemplary siloxanes that can be used include hexamethyldisiloxane, polydimethylsiloxane, polymethylphenylsiloxane, dodecamethylpentasiloxane, decamethylcyclopentasiloxane, decamethyltetrasiloxane, octamethyltrisiloxane, or any combination thereof. Activated aromatic compounds can be any aromatic molecule activated towards Friedel-Crafts addition reactions, or mixtures thereof. Performance enhancers include extreme pressure additives such as the following mixtures: (A) tolyltriazole or its substituted derivatives, (B) amines (e.g., Jeffamine M-600), and (C) a third component which is (i) an ethoxylated phosphate ester (e.g., Antara LP-700 type), or (ii) a phosphoric alcohol (e.g., ZELEC 3337 type), or (iii) zinc dialkyldithiophosphate (e.g., Lubrizol 5139, 5604, 5178, or 5186 type), or (iv) mercaptobenzothiazole, or (v) 2,5-dimercapto-1,3,4-thiadiazole derivatives (e.g., Curvan 826), or mixtures thereof.

[0053] The compositions of the present invention may further comprise a compatibilizer selected from the group consisting of polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers, and 1,1,1-trifluoroalkanes. Such compatibilizers are preferably present in an amount of up to 3.0% by weight, for example, in an amount of 0.01% to 2.0% by weight based on the weight of the composition.

[0054] The refrigerant composition of the present invention can be prepared by combining E-1,3,3,3-tetrafluoropropene, hydro(chloro)fluorocarbon, lubricant, and any optional components in the desired amounts. In one embodiment, the refrigerant composition can be prepared by a method comprising the steps of weighing the desired amounts of the components and then mixing the components in a suitable container, preferably by using stirring. In another embodiment, the refrigerant composition can be prepared by a method comprising the steps of: (i) withdrawing a volume of one or more components of the refrigerant composition from at least one container, (ii) sufficiently removing impurities to enable reuse of one or more of the withdrawn components, and (iii) optionally, combining all or a portion of the withdrawn volume of the components with at least one additional refrigerant composition or component.

[0055] The refrigerant composition can be used in various applications. In one embodiment, any of the foregoing refrigerant compositions can be used as a substitute for older-generation refrigerant compositions (such as, for example, R-404A or R-502, etc.) to provide a more environmentally friendly composition. The refrigerant composition of the present invention can be used to replace at least a portion of the older-generation refrigerant composition. Preferably, the refrigerant composition of the present invention can be used to replace all or substantially all of the older-generation refrigerant composition.

[0056] Accordingly, the present invention further relates to a method of replacing at least a portion, preferably all or substantially all, of a refrigerant composition containing a high-GWP refrigerant in a refrigeration, air conditioning, or heat pump system, preferably a refrigeration or air conditioning system, more preferably an air conditioning system, and most preferably a stationary air conditioning system, wherein the high-GWP refrigerant is selected from the group consisting of R134a, R22, R123, R11, R245fa, R114, R236fa, R124, R12, R410A, R407C, R417A, R422A, R507A, R502, and R404A, the method comprising providing the composition of the present invention to a refrigeration, air conditioning, or heat pump system that uses, has used, or is designed to use the high-GWP refrigerant.

[0057] In one embodiment, the method is a method of replacing at least a portion, preferably all or substantially all, of a refrigerant composition containing a high-GWP refrigerant in a refrigeration, air conditioning, or heat pump system, preferably a refrigeration or air conditioning system, more preferably an air conditioning system, and most preferably a stationary air conditioning system, wherein the high-GWP refrigerant is selected from the group consisting of R22, R410A, R407C, and R417A.

[0058] In a preferred embodiment, the method is a method of replacing substantially all refrigerant compositions containing high-GWP refrigerants in a stationary air-conditioning system, wherein the high-GWP refrigerant is selected from the group consisting of R22, R410A, R407C, and R417A, and is preferably R410A.

[0059] In some embodiments, the refrigerant composition of the present invention can be used as a heat transfer medium for enhancing the cooling or heating capacity in a refrigeration, air-conditioning, or heat pump system comprising an evaporator, a condenser, a compressor, and an expansion device. Preferably, the refrigeration, air-conditioning, or heat pump system is a refrigeration device, an air-conditioning device, a cooling device, a high-temperature, medium-temperature, or low-temperature refrigeration device, or a heat pump. In a preferred embodiment, the aforementioned refrigerant composition is used as a heat transfer medium in a stationary refrigeration device, a stationary air-conditioning device, a stationary cooling device, a stationary high-temperature, medium-temperature, or low-temperature refrigeration device, or a heat pump.

[0060] The present invention further relates to a refrigeration, air-conditioning, or heat pump system comprising an evaporator, a condenser, a compressor, an expansion device, and a heat transfer medium, wherein the heat transfer medium comprises the refrigerant composition of the present invention. The refrigeration, air-conditioning, or heat pump system is preferably a refrigeration device, an air-conditioning device, a cooling device, a high-temperature, medium-temperature, or low-temperature refrigeration device, or a heat pump; and most preferably a stationary refrigeration device, a stationary air-conditioning device, a stationary cooling device, a stationary high-temperature, medium-temperature, or low-temperature refrigeration device, or a heat pump.

[0061] In the refrigerant composition of the present invention comprising E-1,3,3,3-tetrafluoropropene and a hydro(chloro)fluorocarbon as described above, the refrigerant exhibits a greater solubility in POE and PAG oils in the liquid phase compared to E-1,3,3,3-tetrafluoropropene without a hydro(chloro)fluorocarbon. Accordingly, the viscosity of the refrigerant composition is reduced, and the mobility is increased.

[0062] Accordingly, the present invention further relates to a method of reducing the viscosity of a refrigerant composition comprising (i) E-1,3,3,3-tetrafluoropropene and (iii) a lubricant selected from polyol esters and polyalkylene glycols. The method comprises adding (ii) a hydro(chloro)fluorocarbon selected from 1,1,3,3-tetrafluoro-2-propene, 1,1,1,3,3-pentafluoropropane, trans-1-chloro-3,3,3-trifluoropropene, and mixtures thereof to a composition comprising E-1,3,3,3-tetrafluoropropene (i) and the lubricant (iii). The hydro(chloro)fluorocarbon (ii) is added in an amount such that (ii) is present in the composition in a total amount of up to 1.0 wt% based on the total weight of E-1,3,3,3-tetrafluoropropene (i) and the hydro(chloro)fluorocarbon (ii).

[0063] One embodiment of the method for reducing the viscosity of the refrigerant composition is a method in which, based on the total weight of E-1,3,3,3-tetrafluoropropene (i) and hydro(chloro)fluorocarbon (ii), the hydro(chloro)fluorocarbon (ii) is added in an amount such that (ii) is present in the composition in a total amount in the range of 0.00001% to 1.0% by weight, preferably 0.0001% to 1.0% by weight, more preferably 0.001% to 0.9% by weight, still more preferably 0.005% to 0.8% by weight, even more preferably 0.01% to 0.6% by weight, and most preferably 0.1% to 0.5% by weight.

[0064] Another embodiment of any of the methods for reducing the viscosity of the refrigerant composition is a method in which, based on the total weight of the composition after the addition of hydro(chloro)fluorocarbon (ii), E-1,3,3,3-tetrafluoropropene is present in the composition in an amount of 50.0% by weight or more, preferably 75.0% by weight or more, more preferably 90.0% by weight or more, even more preferably in the amount of 94.0% to 99.5% by weight, and most preferably in the amount of 94.5% to 99.0% by weight.

[0065] Another embodiment of any of the methods for reducing the viscosity of the refrigerant composition is a method in which, based on the total weight of the composition after the addition of hydro(chloro)fluorocarbon (ii), the lubricant is present in the composition in an amount of 45.0% by weight or less, preferably 35.0% by weight or less, more preferably 15.0% by weight or less, still more preferably in the amount of 0.1% to 10.0% by weight, and most preferably in the amount of 0.5% to 5.0% by weight.

[0066] Another embodiment of any of the methods for reducing the viscosity of the refrigerant composition is a method in which the hydro(chloro)fluorocarbon (ii) is selected from 1,1,3,3-tetrafluoro-2-propene, 1,1,1,3,3-pentafluoropropane, and mixtures thereof; or in which the hydro(chloro)fluorocarbon (ii) is 1,1,3,3-tetrafluoro-2-propene; or in which the hydro(chloro)fluorocarbon (ii) is trans-1-chloro-3,3,3-trifluoropropene; or in which the hydro(chloro)fluorocarbon (ii) is a mixture of 1,1,3,3-tetrafluoro-2-propene and trans-1-chloro-3,3,3-trifluoropropene, a mixture of 1,1,3,3-tetrafluoro-2-propene and 1,1,1,3,3-pentafluoropropane, or a mixture of 1,1,3,3-tetrafluoro-2-propene, 1,1,1,3,3-pentafluoropropane, and trans-1-chloro-3,3,3-trifluoropropene.

[0067] In a specific embodiment of any of the methods in the above method for reducing the viscosity of a refrigerant composition, the lubricant is a polyol ester, preferably a pentaerythritol ester of one or more linear or branched carbonic acids having up to 9 carbons, more preferably a pentaerythritol ester in which the polyol ester is a mixture of linear and / or branched carbonic acids having up to 9 carbons. In a further specific embodiment, the lubricant is a polyalkylene glycol, preferably a double-capped copolymerized polyalkylene oxide having a copolymer chain of alkylene oxide repeating units and ether alkyl end groups.

[0068] The present disclosure also relates to a method for improving the miscibility of (i) E-1,3,3,3-tetrafluoropropene and (iii) a lubricant selected from polyol esters and polyalkylene glycols in a refrigerant composition. The method comprises adding (ii) a hydro(chloro)fluorocarbon selected from 1,1,3,3-tetrafluoro-2-propene, 1,1,1,3,3-pentafluoropropane, trans-1-chloro-3,3,3-trifluoropropene, and mixtures thereof to a composition comprising E-1,3,3,3-tetrafluoropropene (i) and a lubricant (iii). The hydro(chloro)fluorocarbon (ii) is added in an amount such that (ii) is present in the composition in a total amount of up to 1.0 wt%. based on the total weight of E-1,3,3,3-tetrafluoropropene (i) and hydro(chloro)fluorocarbon (ii).

[0069] One embodiment of the method for improving the miscibility of E-1,3,3,3-tetrafluoropropene and a lubricant is a method in which the hydro(chloro)fluorocarbon (ii) is present in the composition in a total amount in the range of 0.00001 wt% to 1.0 wt%, preferably 0.0001 wt% to 1.0 wt%, more preferably 0.001 wt% to 0.9 wt%, still more preferably 0.005 wt% to 0.8 wt%, even more preferably 0.01 wt% to 0.6 wt%, and most preferably 0.1 wt% to 0.5 wt%, based on the total weight of E-1,3,3,3-tetrafluoropropene (i) and hydro(chloro)fluorocarbon (ii).

[0070] Another embodiment of any of the methods for improving the miscibility of E-1,3,3,3-tetrafluoropropene and a lubricant in the above method is a method in which E-1,3,3,3-tetrafluoropropene is present in the composition in an amount of 50.0 wt% or more, preferably 75.0 wt% or more, more preferably 90.0 wt% or more, even more preferably 94.0 wt% to 99.5 wt%, and most preferably 94.5 wt% to 99.0 wt%, based on the total weight of the composition after addition of the hydro(chloro)fluorocarbon (ii).

[0071] Another embodiment of any of the methods for improving the miscibility of E-1,3,3,3-tetrafluoropropene and a lubricant is a method in which the lubricant is present in the composition in an amount of 45.0% by weight or less, preferably 35.0% by weight or less, more preferably 15.0% by weight or less, still more preferably 0.1% to 10.0% by weight, and most preferably 0.5% to 5.0% by weight, based on the total weight of the composition after the addition of the hydro(chloro)fluorocarbon (ii).

[0072] Another embodiment of any of the methods for improving the miscibility of E-1,3,3,3-tetrafluoropropene and a lubricant is a method in which the hydro(chloro)fluorocarbon (ii) is selected from 1,1,3,3-tetrafluoro-2-propene, 1,1,1,3,3-pentafluoropropane, and mixtures thereof; or in which the hydro(chloro)fluorocarbon (ii) is 1,1,3,3-tetrafluoro-2-propene; or in which the hydro(chloro)fluorocarbon (ii) is trans-1-chloro-3,3,3-trifluoropropene; or in which the hydro(chloro)fluorocarbon (ii) is a mixture of 1,1,3,3-tetrafluoro-2-propene and trans-1-chloro-3,3,3-trifluoropropene, a mixture of 1,1,3,3-tetrafluoro-2-propene and 1,1,1,3,3-pentafluoropropane, or a mixture of 1,1,3,3-tetrafluoro-2-propene, 1,1,1,3,3-pentafluoropropane, and trans-1-chloro-3,3,3-trifluoropropene.

[0073] In a specific embodiment of any of the methods for improving the miscibility of E-1,3,3,3-tetrafluoropropene and a lubricant, the lubricant is a polyol ester, preferably a pentaerythritol ester of one or more linear or branched carbonic acids having up to 9 carbons, more preferably in which the polyol ester is a pentaerythritol ester of a mixture of linear and / or branched carbonic acids having up to 9 carbons. In a further specific embodiment, the lubricant is a polyalkylene glycol, preferably a double-capped copolymerized polyalkylene oxide having a copolymer chain of alkylene oxide repeating units and ether alkyl end groups.

[0074] The present disclosure also relates to a method for increasing the solubility of (i) E-1,3,3,3-tetrafluoropropene in (iii) a lubricant selected from polyol esters and polyalkylene glycols in a refrigerant composition comprising (i) E-1,3,3,3-tetrafluoropropene and (iii) a lubricant, wherein the method comprises adding (ii) a hydro(chloro)fluorocarbon selected from 1,1,3,3-tetrafluoro-2-propene, 1,1,1,3,3-pentafluoropropane, trans-1-chloro-3,3,3-trifluoropropene, and mixtures thereof to the composition comprising (i) E-1,3,3,3-tetrafluoropropene and (iii) a lubricant, wherein the hydro(chloro)fluorocarbon (ii) is added in an amount such that (ii) is present in the composition in a total amount of up to 1.0 wt%.

[0075] One embodiment of the method for increasing the solubility of E-1,3,3,3-tetrafluoropropene in a lubricant is a method wherein the hydro(chloro)fluorocarbon (ii) is added in an amount such that (ii) is present in the composition in a total amount in the range of 0.00001 wt% to 1.0 wt%, preferably 0.0001 wt% to 1.0 wt%, more preferably 0.001 wt% to 0.9 wt%, still more preferably 0.005 wt% to 0.8 wt%, even more preferably 0.01 wt% to 0.6 wt%, and most preferably 0.1 wt% to 0.5 wt%, based on the total weight of E-1,3,3,3-tetrafluoropropene (i) and the hydro(chloro)fluorocarbon (ii).

[0076] Another embodiment of any of the methods for increasing the solubility of E-1,3,3,3-tetrafluoropropene in a lubricant is a method wherein E-1,3,3,3-tetrafluoropropene is present in the composition in an amount of 50.0 wt% or more, preferably 75.0 wt% or more, more preferably 90.0 wt% or more, even more preferably in the range of 94.0 wt% to 99.5 wt%, and most preferably in the range of 94.5 wt% to 99.0 wt%, based on the total weight of the composition after addition of the hydro(chloro)fluorocarbon (ii).

[0077] Another embodiment of any of the methods for increasing the solubility of E-1,3,3,3-tetrafluoropropene in a lubricant is a method wherein the lubricant is present in the composition in an amount of 45.0 wt% or less, preferably 35.0 wt% or less, more preferably 15.0 wt% or less, still more preferably in the range of 0.1 wt% to 10.0 wt%, and most preferably in the range of 0.5 wt% to 5.0 wt%, based on the total weight of the composition after addition of the hydro(chloro)fluorocarbon (ii).

[0078] Another embodiment of any of the methods described above for increasing the solubility of E-1,3,3,3-tetrafluoropropene in a lubricant is a method wherein the hydro(chloro)fluorocarbon (ii) is selected from 1,1,3,3-tetrafluoro-2-propene, 1,1,1,3,3-pentafluoropropane, and mixtures thereof; or wherein the hydro(chloro)fluorocarbon (ii) is 1,1,3,3-tetrafluoro-2-propene; or wherein the hydro(chloro)fluorocarbon (ii) is trans-1-chloro-3,3,3-trifluoropropene; or wherein the hydro(chloro)fluorocarbon (ii) is a mixture of 1,1,3,3-tetrafluoro-2-propene and trans-1-chloro-3,3,3-trifluoropropene, a mixture of 1,1,3,3-tetrafluoro-2-propene and 1,1,1,3,3-pentafluoropropane, or a mixture of 1,1,3,3-tetrafluoro-2-propene, 1,1,1,3,3-pentafluoropropane, and trans-1-chloro-3,3,3-trifluoropropene.

[0079] In a specific embodiment of any of the methods described above for increasing the solubility of E-1,3,3,3-tetrafluoropropene and a lubricant, the lubricant is a polyol ester, preferably a pentaerythritol ester of one or more linear or branched carbonic acids having up to 9 carbons, more preferably wherein the polyol ester is a pentaerythritol ester of a mixture of linear and / or branched carbonic acids having up to 9 carbons. In a further specific embodiment, the lubricant is a polyalkylene glycol, preferably a double-ended copolymerized polyalkylene oxide having an alkylene oxide repeating unit and an ether alkyl capping group.

[0080] In the methods described above for reducing the viscosity of a refrigerant composition, or increasing the miscibility of E-1,3,3,3-tetrafluoropropene and a lubricant, or increasing the solubility of E-1,3,3,3-tetrafluoropropene in a lubricant, the refrigerant composition obtained after adding the hydro(chloro)fluorocarbon (ii) may further comprise HFO-1234ze(E), a lubricant, an optional co-refrigerant, and optional additives, as described above in the "Refrigerant", "Lubricant", and "Additive" sections.

[0081] Example

[0082] The invention described herein will be further described in the following examples, which do not limit the scope of the invention described in the claims.

[0083] Example 1

[0084] The solubility of E-1,3,3,3-tetrafluoropropene in POE and PAG lubricating oils was compared with the solubility of mixtures of E-1,3,3,3-tetrafluoropropene with various hydro(chloro)fluorocarbons.

[0085] To calculate solubility, the method of Charles Hansen [Hansen, Charles (2007). Hansen Solubility Parameters: A user's handbook, 2nd Edition] is used. Hansen solubility parameters (HSP) are a way to predict whether one material will dissolve in another and form a solution. They are based on the idea that like molecules dissolve like molecules chemically. That is, if a molecule interacts with itself in a way similar to another molecule, it is defined as "like" the other molecule. HSP is a decomposition of the total Hildebrand solubility parameter, which is a direct function of the cohesive energy of the material. This is directly related to the evaporation energy of the material in question. The total solubility parameter can be decomposed into contributions based on dispersive, polar, and associative intermolecular forces. Each material can be represented in this three-dimensional solubility parameter space by coordinates (δ D 、δ P 、δ H ), such that the distance between the solubility sites of any two materials represents how compatible they can be in terms of solubility.

[0086] The Hansen solubility parameters were determined using the software Hansen Solubility Parameters In Practice (HSPiP) v5.4.02 [purchased from Digital River GmbH, Cologne, Germany]. Using this program, the HSP (δ D 、δ P 、δ H ) of POE and PAG lubricating oils and HFO-1234ze(E) and various other hydrofluorocarbon and hydrochlorofluorocarbon refrigerant components were determined using the well-known Yamamoto-Molecular Break GCM / QSAR method and are listed in Table 1.

[0087] Table 1

[0088]

[0089] Then the relative distance (Ra) between each refrigerant component and each oil was calculated according to the following formula:

[0090] Ra 2 =4(δ D，油 -δ D，制冷剂 ) 2 +(δ P，油 -δ P，制冷剂 ) 2 +(δ H，油 -δ H，制冷剂 ) 2 (1)

[0091] These are listed in Table 2.

[0092] Table 2

[0093]

[0094] The relative distance Ra is a measure of the solubility of the components in the respective oils. In particular, the smaller the distance of the hydrofluorocarbon component from each oil, the better its solubility in the oil. As can be seen from Table 2, each of R-1234zc, R-245fa, and R-1233zdE has a smaller distance to POE than R-1234zeE. Similarly, each of R-1234zc, R-245fa, and R-1233zdE has a smaller distance to PAG than R-1234zeE.

[0095] Thus, the solubility of the R-1234zeE refrigerant is enhanced by adding R-1234zc, R-245fa, and / or R-1233zdE to both POE and PAG oils. For example, in both oils, adding 1 wt% of R-1234zc to pure R-1234ze reduces the distance described in equation (1) above, thereby reducing the Gibbs free energy of mixing, which increases the solubility of the refrigerant in the lubricant. Similarly, adding a small amount of each of R-1234zc, R-245fa, and R-1233zdE to R-1234zeE, such that the resulting composition is 99.4 wt% R-1234zeE, 0.2 wt% R-1234zc, 0.2 wt% R-245fa, and 0.2 wt% R-1233zdE, makes the resulting mixture more soluble in POE or PAG oil than the original R-1234zeE fluid.

[0096] The enhanced solubility improves the mobility of the lubricant through the air-conditioning and heat pump circuits, which enhances the oil return to the compressor sump. This provides better lubricity between the moving parts in the compressor, increases their lifespan, and improves the reduction of the overall heat transfer coefficient in the evaporator, thus avoiding deterioration of the cooling capacity.

[0097] Table 3 lists the percentage improvement in solubility in terms of distance shortening for R-1234zc, R-245fa, or R-1233zdE added to R-1234zeE.

[0098] For example, adding 1 wt% of R-1233zdE "pulls" the HSP locus of R-1234zeE towards the HSP locus of PAG oil. This reduces the Gibbs free energy of mixing and enables the refrigerant to be more soluble and thus less viscous. As a result, mobility is improved. Additionally, although these results were measured at 25 °C, at colder temperatures, such as during cold winter startups, the improvement in solubility is even more significant, further demonstrating the great potential of the present invention.

[0099] As shown in Tables 4 to 5 below, improvements in solubility were also found when certain hydro(chloro)fluorocarbons were added at levels of 0.5 wt% and 0.1 wt%.

[0100] Table 4

[0101] R-1234zeE with 0.5% additional molecules

[0102]

[0103] Table 5

[0104] R1234zeE with 0.1% additional molecules

[0105]

[0106] One embodiment relates to a refrigerant composition comprising (i) an E-1,3,3,3-tetrafluoropropene blend selected from one of 464A, 470A, 470B, 444A, 444B, 445A, 446A, 447A, 447B, 448A, 448B, 450A, 456A, 459A, 459B, 460A, 460B, 460C, 475A, 476A, 482A, 515A or 515B, (ii) a hydro(chloro)fluorocarbon selected from 1,1,3,3-tetrafluoro-2-propene, 1,1,1,3,3-pentafluoropropane, trans-1-chloro-3,3,3-trifluoropropene, and mixtures thereof, and (iii) a lubricant selected from polyol esters and polyalkylene glycols, wherein the hydro(chloro)fluorocarbon (ii) is present in the composition in a total amount of up to 1.0 wt% based on the total weight of the E-1,3,3,3-tetrafluoropropene (i) and the hydro(chloro)fluorocarbon (ii).

[0107] One embodiment relates to a refrigerant composition comprising (i) an E-1,3,3,3-tetrafluoropropene blend selected from one of 464A, 470A, 470B, 444A, 444B, 445A, 446A, 447A, 447B, 448A, 448B, 450A, 456A, 459A, 459B, 460A, 460B, 460C, 475A, 476A, 482A, 515A or 515B, (ii) a hydro(chloro)fluorocarbon selected from 1,1,3,3-tetrafluoro-2-propene, 1,1,1,3,3-pentafluoropropane, trans-1-chloro-3,3,3-trifluoropropene, and mixtures thereof, and (iii) a lubricant selected from polyol esters and polyalkylene glycols, wherein based on the total weight of the E-1,3,3,3-tetrafluoropropene (i) and the hydro(chloro)fluorocarbon (ii), the hydro(chloro)fluorocarbon (ii) is present in the composition in a total amount in a range selected from one of the following: 0.00001 wt% to 1.0 wt%, 0.0001 wt% to 1.0 wt%, 0.001 wt% to 0.9 wt%, 0.005 wt% to 0.8 wt%, 0.01 wt% to 0.6 wt%, 0.1 wt% to 0.5 wt%, 0.5 wt% to ≤1 wt%.

Claims

1. A refrigerant composition, the refrigerant composition comprising: (i) E-1,3,3,3-tetrafluoropropene, (ii) a hydro(chloro)fluorocarbon selected from 1,1,3,3-tetrafluoro-2-propene, 1,1,1,3,3-pentafluoropropane, trans-1-chloro-3,3,3-trifluoropropene, and mixtures thereof, and (iii) a lubricant selected from polyol esters and polyalkylene glycols, wherein the hydro(chloro)fluorocarbon (ii) is present in the composition in a total amount of up to 1.0% by weight based on the total weight of the E-1,3,3,3-tetrafluoropropene (i) and the hydro(chloro)fluorocarbon (ii).

2. The composition according to claim 1, wherein the hydro(chloro)fluorocarbon (ii) is present in the composition in a total amount in the range of 0.00001% to 1.0% by weight, preferably 0.0001% to 1.0% by weight, more preferably 0.001% to 0.9% by weight, still more preferably 0.005% to 0.8% by weight, even more preferably 0.01% to 0.6% by weight, and most preferably 0.1% to 0.5% by weight based on the total weight of the E-1,3,3,3-tetrafluoropropene (i) and the hydro(chloro)fluorocarbon (ii).

3. The composition according to claim 1 or claim 2, wherein the E-1,3,3,3-tetrafluoropropene is present in the composition in an amount of 50.0% by weight or more, preferably 75.0% by weight or more, more preferably 90.0% by weight or more, even more preferably in the range of 94.0% to 99.5% by weight, and most preferably in the range of 94.5% to 99.0% by weight based on the total weight of the composition.

4. The composition according to any one of claims 1 to 3, wherein the lubricant is present in the composition in an amount of 45.0% by weight or less, preferably 35.0% by weight or less, more preferably 15.0% by weight or less, still more preferably in the range of 0.1% to 10.0% by weight, and most preferably in the range of 0.5% to 5.0% by weight based on the total weight of the composition.

5. The composition according to any one of claims 1 to 4, wherein the hydro(chloro)fluorocarbon (ii) is selected from 1,1,3,3-tetrafluoro-2-propene, 1,1,1,3,3-pentafluoropropane, and mixtures thereof, or wherein the hydro(chloro)fluorocarbon (ii) is 1,1,3,3-tetrafluoro-2-propene, or wherein the hydro(chloro)fluorocarbon (ii) is trans-1-chloro-3,3,3-trifluoropropene.

6. The composition according to any one of claims 1 to 4, wherein the hydro(chloro)fluorocarbon (ii) is a mixture of 1,1,3,3-tetrafluoro-2-propene and trans-1-chloro-3,3,3-trifluoropropene, a mixture of 1,1,3,3-tetrafluoro-2-propene and 1,1,1,3,3-pentafluoropropane, or a mixture of 1,1,3,3-tetrafluoro-2-propene, 1,1,1,3,3-pentafluoropropane and trans-1-chloro-3,3,3-trifluoropropene.

7. The composition according to any one of claims 1 to 6, wherein the lubricant is a polyol ester.

8. The composition according to claim 7, wherein the polyol ester is a pentaerythritol ester of one or more linear or branched carbonic acids having up to 9 carbon atoms, and preferably the polyol ester is a pentaerythritol ester of a mixture of linear and / or branched carbonic acids having up to 9 carbon atoms.

9. The composition according to any one of claims 1 to 6, wherein the lubricant is a polyalkylene glycol.

10. The composition according to claim 9, wherein the polyalkylene glycol is a double-ended copolymerized polyalkylene oxide having a copolymer chain of alkylene oxide repeating units and ether alkyl end groups.

11. A refrigeration, air conditioning or heat pump system, the refrigeration, air conditioning or heat pump system comprising an evaporator, a condenser, a compressor, an expansion device and a heat transfer medium, wherein the heat transfer medium comprises the refrigerant composition according to any one of claims 1 to 10; wherein the refrigeration, air conditioning or heat pump system is preferably a refrigeration device, an air conditioning device, a cooling device, a high-temperature, medium-temperature or low-temperature refrigeration device, or a high-temperature, medium-temperature or low-temperature heat pump, more preferably a stationary refrigeration device, a stationary air conditioning device, a stationary cooling device, a stationary high-temperature, medium-temperature or low-temperature refrigeration device, or a stationary high-temperature, medium-temperature or low-temperature heat pump.

12. Use of the refrigerant composition according to any one of claims 1 to 10 as a heat transfer medium for enhancing the cooling or heating capacity in a refrigeration, air conditioning or heat pump system, the refrigeration, air conditioning or heat pump system comprising an evaporator, a condenser, a compressor and an expansion device; wherein the refrigeration, air conditioning or heat pump system is preferably a refrigeration device, an air conditioning device, a cooling device, a high-temperature, medium-temperature or low-temperature refrigeration device, or a high-temperature, medium-temperature or low-temperature heat pump, more preferably a stationary refrigeration device, a stationary air conditioning device, a stationary cooling device, a stationary high-temperature, medium-temperature or low-temperature refrigeration device, or a stationary high-temperature, medium-temperature or low-temperature heat pump.

13. A method of replacing a refrigerant composition containing a high-GWP refrigerant in a refrigeration, air-conditioning or heat pump system, wherein the high-GWP refrigerant is selected from the group consisting of R134a, R22, R123, R11, R245fa, R114, R236fa, R124, R12, R410A, R407C, R417A, R422A, R507A, R502 and R404A, the method comprising providing to the refrigeration, air-conditioning or heat pump system using, having used or designed to use the high-GWP refrigerant the composition according to any one of claims 1 to 10.

14. A method of reducing the viscosity of a refrigerant composition comprising (i) E-1,3,3,3-tetrafluoropropene and (iii) a lubricant selected from polyol esters and polyalkylene glycols, wherein the method comprises adding (ii) a hydro(chloro)fluorocarbon selected from 1,1,3,3-tetrafluoro-2-propene, 1,1,1,3,3-pentafluoropropane, trans-1-chloro-3,3,3-trifluoropropene, and mixtures thereof to the composition comprising the E-1,3,3,3-tetrafluoropropene (i) and the lubricant (iii), wherein the hydro(chloro)fluorocarbon (ii) is added in an amount such that (ii) is present in the composition in a total amount of up to 1.0 wt%.

15. A method of improving the miscibility of (i) the E-1,3,3,3-tetrafluoropropene and (iii) the lubricant in a refrigerant composition comprising E-1,3,3,3-tetrafluoropropene (i) and a lubricant (iii) selected from polyol esters and polyalkylene glycols, wherein the method comprises adding (ii) a hydro(chloro)fluorocarbon selected from 1,1,3,3-tetrafluoro-2-propene, 1,1,1,3,3-pentafluoropropane, trans-1-chloro-3,3,3-trifluoropropene, and mixtures thereof to the composition comprising the E-1,3,3,3-tetrafluoropropene (i) and the lubricant (iii), wherein the hydro(chloro)fluorocarbon (ii) is added in an amount such that (ii) is present in the composition in a total amount of up to 1.0 wt%.

16. A refrigerant composition comprising: (i) An E-1,3,3,3-tetrafluoropropene blend selected from one of 464A, 470A, 470B, 444A, 444B, 445A, 446A, 447A, 447B, 448A, 448B, 450A, 456A, 459A, 459B, 460A, 460B, 460C, 475A, 476A, 482A, 515A or 515B* (ii) Hydro(chloro)fluorocarbons selected from 1,1,3,3-tetrafluoro-2-propene, 1,1,1,3,3-pentafluoropropane, trans-1-chloro-3,3,3-trifluoropropene, and mixtures thereof, and (iii) Lubricants selected from polyol esters and polyalkylene glycols, wherein, based on the total weight of the E-1,3,3,3-tetrafluoropropene (i) and the hydro(chloro)fluorocarbons (ii), the hydro(chloro)fluorocarbons (ii) are present in the composition in a total amount of up to 1.0% by weight.

17. The composition according to claim 16, wherein, based on the total weight of the E-1,3,3,3-tetrafluoropropene (i) and the hydro(chloro)fluorocarbons (ii), the hydro(chloro)fluorocarbons (ii) are present in the composition in a total amount within a range selected from one of the following: 0.00001% to 1.0% by weight, 0.0001% to 1.0% by weight, 0.001% to 0.9% by weight, 0.005% to 0.8% by weight, 0.01% to 0.6% by weight, 0.1% to 0.5% by weight, 0.5% to ≤1% by weight.

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