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

Abstract

1. A refrigerant composition comprising: E-1,3,3,3-tetrafluoropropene; 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 a lubricant selected from a polyol ester and a polyalkylene glycol, wherein the hydro(chloro)fluorocarbon 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 and the hydro(chloro)fluorocarbon.

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims priority to U.S. Provisional Patent Application No. 63 / 428,510, filed November 29, 2022, the disclosure of which is incorporated herein by reference in its entirety.

[0002] FIELD OF THE INVENTION The present invention relates to refrigerant compositions containing E-1,3,3,3-tetrafluoropropene, a hydrofluorocarbon and / or a hydrochlorofluorocarbon, and a lubricant. The present invention particularly relates to refrigerant compositions containing a hydro(chloro)fluorocarbon selected from E-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), 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 also relates to refrigeration, air conditioning, or heat pump systems that use these compositions. The present invention further relates to a method for reducing the viscosity of a composition comprising E-1,3,3,3-tetrafluoropropene and a lubricant, and a method for increasing the miscibility of HFO-1234ze(E) with a lubricant. [Background technology]

[0003] For the past several decades, the fluorocarbon industry has been working to find replacement refrigerants for the ozone-depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) that are being phased out as a result of the Montreal Protocol. For many applications, the solution has been to commercialize hydrofluorocarbon (HFC) compounds for use as refrigerants, solvents, fire extinguishing agents, foam blowing agents, and propellants. These new compounds, including the most widely used HFC refrigerants today, HFC-134a and HFC-125, have zero ozone depletion potential and are therefore not affected by the current regulations that are being phased out as a result of the Montreal Protocol.

[0004] In addition to the problem of ozone depletion, another environmental concern in many of these applications is global warming. Therefore, there is a need for compositions that meet low ozone depletion standards and have low global warming potential. It is believed that certain hydrofluoroolefin (HFO) compositions meet both of these goals.

[0005] HFO-1234ze (CF3CH=CHF), which has zero ozone depletion potential and low global warming potential, has been identified as a potential refrigerant that meets these goals. U.S. Patent No. 7,862,742 discloses compositions containing HFO-1234ze. U.S. Patent No. 9,302,962 discloses a process for producing HFO-1234ze. HFO-1234ze exists in two isomeric forms, the E-isomer and the Z-isomer. Generally, the E-isomer is most useful in refrigeration applications. In this application, the E-isomer is generally referred to as E-1,3,3,3-tetrafluoropropene or HFO-1234ze(E), but is also known as trans-HFO-1234ze or HFO-1234zeE.

[0006] For use in conventional refrigeration, air conditioning, and heat pump systems containing compressors, alternative refrigerants should preferably be soluble in the lubricant. If the refrigerant lacks solubility in the lubricant, there is a risk of phase separation between the lubricant and the refrigerant during operation of the refrigeration or heat pump system. Phase separation then reduces the overall performance of the system in terms of heat exchange efficiency and system life. While HFO-1234ze is generally more soluble in conventional refrigeration lubricants than conventional HFCs or HCFCs, there remains a need in the art to provide refrigerants with improved solubility with refrigeration lubricants. In particular, there remains a need in the art for refrigerant compositions with improved compatibility comprising HFO-1234ze(E)-containing refrigerants and lubricants. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] U.S. Patent No. 7,862,742 [Patent Document 2] U.S. Patent No. 9,302,962 Summary of the Invention [Means for solving the problem]

[0008] The present invention meets this need by providing a 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. 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 in the range of 0.0001 wt. % to 1.0 wt. %, based on the total weight of the E-1,3,3,3-tetrafluoropropene (i) and the hydro(chloro)fluorocarbon (ii).

[0009] In one embodiment, the hydro(chloro)fluorocarbon (ii) is present in the composition in a total amount ranging from 0.001 wt. % to 0.9 wt. %, preferably from 0.005 wt. % to 0.8 wt. %, more preferably from 0.01 wt. % to 0.6 wt. %, and most preferably from 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).

[0010] One embodiment relates to any of the aforementioned compositions, 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 94.0 to 99.5 wt. %, and most preferably 94.5 to 99.0 wt. %, based on the total weight of the composition.

[0011] One embodiment relates to any of the aforementioned compositions, 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, even more preferably in an amount in the range of 0.1 to 10.0 wt. %, and most preferably 0.5 to 5.0 wt. %, based on the total weight of the composition.

[0012] One embodiment relates to any of the preceding 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 further embodiments, 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 of the aforementioned compositions wherein the lubricant is a polyol ester. In another embodiment, the lubricant in any of the aforementioned compositions is a polyalkylene glycol.

[0014] The present disclosure 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 any of the aforementioned compositions.

[0015] The present disclosure further relates to the use of any of the foregoing refrigerant compositions as a heat transfer medium to increase cooling or heating capacity in a refrigeration, air conditioning, or heat pump system comprising 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 unit, an air conditioning unit, a chiller unit, a high-, medium-, or low-temperature refrigeration unit, or a high-, medium-, or low-temperature heat pump unit. It is even more preferred that any one of the above units is a stationary unit. Stationary air conditioning and heat pump systems include, for example, window, ductless, ducted, packaged terminal, chiller, and packaged rooftop air conditioning systems for small commercial and industrial use. Stationary refrigeration systems include, for example, domestic or residential refrigerators and freezers, ice makers, built-in 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 comprising a high GWP refrigerant in a refrigeration, air conditioning, or heat pump system, where 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 any of the foregoing refrigerant compositions to a refrigeration, air conditioning, or heat pump system that uses, is being used, or is designed to use the high GWP refrigerant.

[0018] The present disclosure further relates to a method for reducing the viscosity of a refrigerant composition comprising (i) E-1,3,3,3-tetrafluoropropene and (iii) a lubricant selected from a polyol ester and a polyalkylene glycol, the method comprising the step of (ii) adding 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 lubricant (iii), wherein (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).

[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, the method comprising (ii) a lubricant 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 method includes the step of adding a hydro(chloro)fluorocarbon selected from E-1,3,3,3-tetrafluoropropene (i) and R-515A / B blends containing the lubricant (iii), wherein the hydro(chloro)fluorocarbon (ii) is added in an amount such that (ii) is present in the blend 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).

[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, e.g., Blend Nos. 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, the method comprising: (ii) 1,1,3,3-tetrafluoro-2-propene, 1,1,1,3,3-pentafluoropropane, trans-1-chloro-3,3,3-trifluoropropene, and their derivatives. a blend 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 a lubricant (iii), wherein (ii) is added in an amount such that the hydro(chloro)fluorocarbon (ii) is present in the blend 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).

[0021] The present disclosure also relates to a method for increasing 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 comprising E-1,3,3,3-tetrafluoropropene (i) and a lubricant (iii), the method comprising the step of (ii) adding 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. %, based on the total weight of the E-1,3,3,3-tetrafluoropropene (i) and the hydro(chloro)fluorocarbon (ii). DETAILED DESCRIPTION OF THE INVENTION

[0022] A refrigerant composition or mixture is described that includes 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 of greater than 0 wt. % to 1.0 wt. %, based on the total weight of the 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 ranging from 0.00001% to 1.0% by weight, more preferably from 0.0001% to 1.0% by weight, and even more preferably from 0.001 to 1.0% by weight, based on the total weight of (i) and (ii).

[0023] In a preferred embodiment, the composition comprises, consists essentially of, 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 of less than 1000 ppm (wt), preferably 100 ppm (wt) or less, more preferably 10 ppm (wt) or less, and most preferably 1 ppm (wt) or less.

[0024] refrigerant The refrigerant portion of the composition according to the present invention comprises E-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)).

[0025] In one embodiment, HFO-1234ze(E) may be present in the composition in a total amount of 50.0 wt% or greater, based on the total weight of the composition. In other embodiments, HFO-1234ze(E) may be present in the composition in a total amount of 60.0 wt% or greater, 65.0 wt% or greater, 70.0 wt% or greater, 75.0 wt% or greater, 80.0 wt% or greater, 85.0 wt% or greater, 90.0 wt% or greater, 95.0 wt% or greater, 96.0 wt% or greater, 97.0 wt% or greater, 98.0 wt% or greater, or 99.0 wt% or greater, based on the total weight of the composition. For example, 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%, based on the total weight of the composition; It may be present in the composition in a total amount of 99.0% by weight; 50.0% to 96.5% by weight, or 75.0% to 96.5% by weight, or 90.0% to 96.5% by weight, or 94.0% to 96.5% by weight, or 94.5% to 96.5% by weight, or 95.0% to 99.0% by weight; 50.0% to 95.0% by weight, or 75.0% to 95.0% by weight, or 90.0% to 95.0% by weight; 50.0% to 90.0% by weight, or 75.0% to 90.0% by weight, or 80.0% to 90.0% by weight. In a preferred embodiment, 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 95.0 to 99.5 wt. %, and most preferably 95.0 to 99.0 wt. %, based on the total weight of the composition.

[0026] The refrigerant portion of the composition according to the present invention further comprises a hydrofluorocarbon and / or hydrochlorofluorocarbon (ii), also referred to herein as 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.

[0027] The hydro(chloro)fluorocarbon 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). In one embodiment, the hydro(chloro)fluorocarbon is present in the composition in a total amount ranging from 0.00001 wt.% to 1.0 wt.%, based on the total weight of E-1,3,3,3-tetrafluoropropene (i) and hydro(chloro)fluorocarbon (ii). In other embodiments, the hydro(chloro)fluorocarbon is present in the composition in a total amount ranging from 0.0001 to 1.0 wt.%, preferably 0.001 to 1.0 wt.%, 0.01 to 1.0 wt.%, or 0.1 to 1.0 wt.%, based on the total weight of E-1,3,3,3-tetrafluoropropene (i) and hydro(chloro)fluorocarbon (ii). In still other embodiments, the hydro(chloro)fluorocarbon is present in the composition in a total amount ranging from 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, based on the total weight of E-1,3,3,3-tetrafluoropropene (i) and hydro(chloro)fluorocarbon (ii).

[0028] 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 a further 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 yet 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, the hydro(chloro)fluorocarbon or mixture of hydro(chloro)fluorocarbons can be present in the composition in any of the above total amounts, based on the total weight of E-1,3,3,3-tetrafluoropropene (i) and hydro(chloro)fluorocarbon (ii).

[0029] The compositions of the present invention may include additional fluorochemicals.

[0030] In some embodiments, the compositions of the present invention additionally comprise one or more of HFO-1234yf, HFO-1243zf, HFO-1233zd(Z), HFO-1233xf, HFC-143a, or HFC-152a. In some embodiments, the total amount of HFO-1234yf, HFO-1243zf, HFO-1233zd(Z), HFO-1233xf, HFC-143a, or HFC-152a is 1.0 wt.% or less, for example, 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.%, based on the total weight of E-1,3,3,3-tetrafluoropropene (i), hydro(chloro)fluorocarbon (ii), and any additional fluorochemicals.

[0031] In another embodiment, the composition of the present invention additionally comprises 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. The amount of the foregoing compounds in the composition can range from 0.0001 to 1.0 wt. %, preferably 0.001 to 0.1 wt. %, and most preferably 0.01 to 0.05 wt. %, based on the total weight of E-1,3,3,3-tetrafluoropropene (i), hydro(chloro)fluorocarbon (ii), and any additional fluorochemicals.

[0032] 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, CF3SCF3CO2, CF3I, and combinations thereof. The amount of the aforementioned compounds may range from 0.0001 to 1.0% by weight, preferably from 0.001 to 0.1% by weight, and most preferably from 0.01 to 0.05% by weight, based on the total weight of E-1,3,3,3-tetrafluoropropene (i), hydro(chloro)fluorocarbon (ii), and the aforementioned compounds.

[0033] In some embodiments, the viscosity of a refrigerant blend is reduced, the 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 a polyol ester and a polyalkylene glycol, the method comprising: (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 an R-471A, R-476A, R-482A, R-515A / B blend 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) 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. %, based on the total weight of the E-1,3,3,3-tetrafluoropropene (i) and the hydro(chloro)fluorocarbon (ii).

[0034] In some embodiments, the viscosity of a refrigerant blend is reduced, including the viscosity of a refrigerant blend comprising (i) E-1,3,3,3-tetrafluoropropene, e.g., Blend Nos. 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 a polyol ester and a polyalkylene glycol, the method comprising: (ii) a hydro(hydroxybenzoate) 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. 464A, 470A, 470B, 444A, 444B, 445A, 446A, 447A, 447B, 448A, 448B, 450A, 456A, 459A, 459B, 460A, 460B, 460C, 475A, 476A, 482A, 515A, or 515B, a blend of E-1,3,3,3-tetrafluoropropene (i) and a lubricant (iii). B, wherein the hydro(chloro)fluorocarbon (ii) is added in an amount such that (ii) is present in the blend in a total amount of up to 1.0 wt. %, for example, 0.1 wt. %, 0.5 wt. %, and all values ​​between 0.1 wt. % and 1.0 wt. %, based on the total weight of the E-1,3,3,3-tetrafluoropropene (i) and the hydro(chloro)fluorocarbon (ii).

[0035] lubricant The lubricant in the composition of the present invention is 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.

[0036] In one embodiment, the polyol ester is a pentaerythritol ester of one or more linear or branched chain carbonates containing up to nine carbons. In a preferred embodiment, the polyol ester is a pentaerythritol ester of a mixture of linear and / or branched chain carbonates containing up to nine carbons. Examples of ester substituents on the pentaerythritol main structure are heptanoate, 3,5,5-hexanoate, pentanoate, and 3-methylbutanonate. One such POE mixture is Emkarate RL32-3MAF.

[0037] In one embodiment, the polyalkylene glycol is a doubly capped co-alkylene oxide. As the first type of synthetic lubricating oil synthesized for HFC refrigerants, they are known as copolymer chains of alkylene oxide repeating units, typically stoichiometric ratios of ethylene oxide and propylene oxide. The capping end alkyl group is a terminal ether alkyl group. PAGs in the ISO 32-68 range are preferred, having linear and / or branched end-capped alkyl groups (R and R') ranging from 1 to 4 carbons and a ratio of propylene oxide (PO) to ethylene oxide (EO) repeating groups ranging from 1:3 to 3:1 according to the following formula: RO-(EO) n -(PO) m -OR'

[0038] A specific PAG suitable for use as a lubricant in the present refrigerant compositions is Denso ISO 46 ND-12 PAG oil.

[0039] The amount of lubricant present in the composition depends, among other things, on the system in which the refrigerant system is used. Generally, the amount of lubricant is selected by considering the requirements of a given compressor and the environment to which the lubricant will be exposed. In one embodiment, the lubricant is present in the composition in an amount of 45.0 wt.% or less, preferably 35.0 wt.% or less, such as 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, based on the total weight of the composition. For example, the lubricant may be present in the composition in an amount ranging from 0.1 to 45.0 wt.%, preferably from 0.2 to 20.0 wt.%, more preferably from 0.3 to 10.0 wt.%, even more preferably from 0.4 to 5.0 wt.%, and most preferably from 0.5 to 3.5 wt.%, based on the total weight of the composition.

[0040] In certain embodiments, the lubricant is a polyol ester and is present in the composition in an amount of 45.0 wt.% or less, preferably 35.0 wt.% or less, such as 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, based on the total weight of the composition. For example, the polyol ester lubricant may be present in the composition in an amount ranging from 0.1 to 45.0 wt.%, preferably from 0.2 to 20.0 wt.%, more preferably from 0.3 to 10.0 wt.%, even more preferably from 0.4 to 5.0 wt.%, and most preferably from 0.5 to 3.5 wt.%, based on the total weight of the composition.

[0041] In another specific embodiment, the lubricant is a polyalkylene glycol and is present in the composition in an amount of 45.0 wt.% or less, preferably 35.0 wt.% or less, such as 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, based on the total weight of the composition. For example, the polyalkylene glycol lubricant may be present in the composition in an amount ranging from 0.1 to 45.0 wt.%, preferably from 0.2 to 20.0 wt.%, more preferably from 0.3 to 10.0 wt.%, even more preferably from 0.4 to 5.0 wt.%, and most preferably from 0.5 to 3.5 wt.%, based on the total weight of the composition.

[0042] In some embodiments, the refrigerant composition comprises: (i) E-1,3,3,3-tetrafluoropropene in an amount from 94.0 to 99.0 wt.%, based on the total weight of the composition; (ii) R-1233zdE in an amount from 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 from 0.5 to 5.0 wt.%, based on the total weight of the composition.

[0043] In some embodiments, the refrigerant composition comprises: (i) E-1,3,3,3-tetrafluoropropene in an amount from 94.0 to 99.0 wt.%, based on the total weight of the composition; (ii) R-1233zdE in an amount from 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 from 0.5 to 5.0 wt.%, based on the total weight of the composition.

[0044] In some embodiments, the refrigerant composition comprises: (i) E-1,3,3,3-tetrafluoropropene in an amount from 94.0 to 99.0 wt.%, based on the total weight of the composition; (ii) R-1234zc in an amount from 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 from 0.5 to 5.0 wt.%, based on the total weight of the composition.

[0045] In some embodiments, the refrigerant composition comprises: (i) E-1,3,3,3-tetrafluoropropene in an amount from 94.0 to 99.0 wt.%, based on the total weight of the composition; (ii) R-1234zc in an amount from 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 from 0.5 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 from 94.0 to 99.5 wt.%, based on the total weight of the composition; (ii) R-1234zc in an amount up to 1.0 wt.%, based on the total weight of (i) and (ii); and (iii) a polyol ester lubricant in an amount from 0.1 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 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 to 5.0 wt.%, based on the total weight of the composition.

[0048] additives Commonly used refrigeration system additives may optionally be added to the compositions of the present invention, for example, to enhance lubricity and system stability. These additives are commonly known in the field of refrigeration compressor lubrication and include antiwear agents, extreme pressure lubricants, corrosion and oxidation inhibitors, metal surface deactivators, free radical scavengers, foam and defoam control agents, leak detection agents, and the like. Other additives include acid scavengers, performance enhancers, and flame suppressants. Generally, these additives are present in small amounts relative to the overall composition. They are typically used at concentrations of less than 0.1% to as much as 3% of each additive. These additives are selected based on the requirements of the individual system. Some typical examples of such additives include, but are not limited to, lubrication-enhancing additives such as alkyl or aryl esters of phosphoric and thiophosphates. Additionally, organometallic dialkyldithiophosphates (e.g., zinc dialkyldithiophosphate or ZDDP, Lubrizol 1375) and other members of this family of chemicals may be used in the compositions of the present invention. Other antiwear additives include natural product oils and asymmetric polyhydroxyl lubricant additives such as Synergol TMS (International Lubricants). Similarly, stabilizers such as antioxidants, free radical scavengers, and water scavengers may be used. Compounds in this category may include, but are not limited to, butylated hydroxytoluene (BHT) and epoxides. Acid scavengers may include siloxanes, activated aromatic compounds, or a combination of both. Exemplary siloxanes that may be used include hexamethyldisiloxane, polydimethylsiloxane, polymethylphenylsiloxane, dodecamethylpentasiloxane, decamethylcyclopentasiloxane, decamethyltetrasiloxane, octamethyltrisiloxane, or any combination thereof. The activated aromatic compound may be any aromatic molecule, or mixture thereof, that has been activated for Friedel-Crafts addition.Performance enhancers include extreme pressure additives such as a mixture of (A) tolyltriazole or a substituted derivative thereof, (B) an amine (e.g., Jeffamine M-600), and (C) a third component which is (i) an ethoxylated phosphate ester (e.g., Antara LP-700 type), or (ii) an alcohol phosphate (e.g., ZELEC 3337 type), or (iii) a zinc dialkyldithiophosphate (e.g., Lubrizol 5139, 5604, 5178, or 5186 type), or (iv) a mercaptobenzothiazole, or (v) a 2,5-dimercapto-1,3,4-triadiazole derivative (e.g., Curvan 826), or a mixture thereof.

[0049] 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 of the composition, e.g., 0.01 to 2.0% by weight.

[0050] The refrigerant compositions of the present invention can be prepared by combining E-1,3,3,3-tetrafluoropropene, a hydro(chloro)fluorocarbon, a lubricant, and optional components in desired amounts. In one embodiment, the refrigerant compositions can be prepared by a method comprising weighing the desired component amounts and then combining the components in a suitable vessel, preferably by using agitation. In a further embodiment, the refrigerant compositions can be prepared by a method comprising (i) reclaiming a volume of one or more components of the refrigerant composition from at least one container; (ii) removing impurities sufficiently to permit reuse of one or more reclaimed components; and (iii) optionally combining all or a portion of the volume of the reclaimed components with at least one additional refrigerant composition or component.

[0051] The refrigerant compositions may be useful in a variety of applications. In certain embodiments, any of the aforementioned refrigerant compositions may be used as a replacement for an older generation refrigerant composition (such as, for example, R-404A or R-502) to provide a more environmentally friendly composition. The refrigerant compositions of the present invention may be used to replace at least a portion of the older generation refrigerant composition. Preferably, the refrigerant compositions of the present invention may be used to replace all or substantially all of the older generation refrigerant composition.

[0052] Accordingly, the present invention further relates to a method for replacing at least a portion, preferably all or substantially all, of a refrigerant composition comprising 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 the step of providing a refrigerant composition of the present invention to a refrigeration, air conditioning, or heat pump system that uses, is being used, or is designed to use the high GWP refrigerant.

[0053] In one embodiment, the method is for replacing at least a portion, preferably all or substantially all, of a refrigerant composition comprising 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.

[0054] In a preferred embodiment, the method is for replacing substantially all of a refrigerant composition in a stationary air conditioning system that includes a high GWP refrigerant, wherein the high GWP refrigerant is selected from the group consisting of R22, R410A, R407C, and R417A, preferably R410A.

[0055] In some embodiments, the refrigerant compositions of the present invention can be used as a heat transfer medium to increase 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 unit, an air conditioning unit, a chiller unit, a high-temperature, medium-temperature, or low-temperature refrigeration unit, or a heat pump. In one preferred embodiment, the refrigerant composition is used as a heat transfer medium in a stationary refrigeration unit, a stationary air conditioning unit, a stationary chiller unit, a stationary high-temperature, medium-temperature, or low-temperature refrigeration unit, or a heat pump.

[0056] 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 refrigerator, air conditioner, chiller, high-, medium-, or low-temperature refrigerator, or heat pump, most preferably a stationary refrigerator, air conditioner, chiller, high-, medium-, or low-temperature refrigerator, or heat pump.

[0057] In the refrigerant composition of the present invention containing E-1,3,3,3-tetrafluoropropene and a hydro(chloro)fluorocarbon, the refrigerant exhibits higher solubility in the POE and PAG oils in the liquid phase than E-1,3,3,3-tetrafluoropropene without a hydro(chloro)fluorocarbon, resulting in a lower viscosity and increased fluidity of the refrigerant composition.

[0058] Accordingly, the present invention further relates to a method for reducing the viscosity of a refrigerant composition comprising (i) E-1,3,3,3-tetrafluoropropene and (iii) a lubricant selected from a polyol ester and a polyalkylene glycol, the method comprising the step of (ii) adding 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 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).

[0059] One embodiment of the method for reducing the viscosity of a refrigerant composition 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 ranging from 0.00001% to 1.0% by weight, preferably from 0.0001% to 1.0% by weight, more preferably from 0.001% to 0.9% by weight, even more preferably from 0.005% to 0.8% by weight, even more preferably from 0.01% to 0.6% by weight, and most preferably from 0.1 to 0.5% by weight, based on the total weight of E-1,3,3,3-tetrafluoropropene (i) and hydro(chloro)fluorocarbon (ii).

[0060] A further embodiment of any of the above methods for reducing the viscosity of a refrigerant composition is a method wherein E-1,3,3,3-tetrafluoropropene is present in the composition in an amount of 50.0 wt.% or greater, preferably 75.0 wt.% or greater, more preferably 90.0 wt.% or greater, even more preferably 94.0 to 99.5 wt.%, and most preferably 94.5 to 99.0 wt.%, based on the total weight of the composition after the hydro(chloro)fluorocarbon (ii) is added.

[0061] A further embodiment of any of the above methods of reducing the viscosity of a refrigerant composition 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, even more preferably in an amount in the range of 0.1 to 10.0 wt.%, and most preferably 0.5 to 5.0 wt.%, based on the total weight of the composition after the hydro(chloro)fluorocarbon (ii) is added.

[0062] Further embodiments of any of the above methods of reducing the viscosity of a refrigerant composition include 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 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.

[0063] In specific embodiments of any of the above methods for reducing the viscosity of a refrigerant composition, the lubricant is a polyol ester, preferably a pentaerythritol ester of one or more straight or branched chain carbonates containing up to 9 carbons, more preferably a pentaerythritol ester of a mixture of straight and / or branched chain carbonates containing up to 9 carbons. In further specific embodiments, the lubricant is a polyalkylene glycol, preferably a doubly capped co-alkylene oxide having a copolymer chain of alkylene oxide repeat units and an ether alkyl capping group.

[0064] The present disclosure also relates to a method for increasing 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 comprising E-1,3,3,3-tetrafluoropropene (i) and a lubricant (iii). The method comprises the steps of (ii) adding 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 the E-1,3,3,3-tetrafluoropropene (i) and the hydro(chloro)fluorocarbon (ii).

[0065] One embodiment of the method for increasing the miscibility of E-1,3,3,3-tetrafluoropropene with 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 ranging from 0.00001 wt. % to 1.0 wt. %, preferably from 0.0001 wt. % to 1.0 wt. %, more preferably from 0.001 wt. % to 0.9 wt. %, even more preferably from 0.005 wt. % to 0.8 wt. %, even more preferably from 0.01 wt. % to 0.6 wt. %, and most preferably from 0.1 to 0.5 wt. %, based on the total weight of E-1,3,3,3-tetrafluoropropene (i) and hydro(chloro)fluorocarbon (ii).

[0066] A further embodiment of any of the above methods of increasing the miscibility of E-1,3,3,3-tetrafluoropropene with 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 greater, preferably 75.0 wt % or greater, more preferably 90.0 wt % or greater, even more preferably 94.0 to 99.5 wt %, and most preferably 94.5 to 99.0 wt %, based on the total weight of the composition after the hydro(chloro)fluorocarbon (ii) has been added.

[0067] A further embodiment of any of the above methods of increasing the miscibility of E-1,3,3,3-tetrafluoropropene with 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, even more preferably in an amount in the range of 0.1 to 10.0 wt. %, and most preferably 0.5 to 5.0 wt. %, based on the total weight of the composition after the hydro(chloro)fluorocarbon (ii) has been added.

[0068] Further embodiments of any of the above methods of increasing the miscibility of E-1,3,3,3-tetrafluoropropene with a lubricant include 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 the hydro(chloro)fluorocarbon (ii) is 1,1,3,3-tetrafluoro-2-propene; or the hydro(chloro)fluorocarbon (ii) is trans-1-chloro-3,3,3- or 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.

[0069] In specific embodiments of any of the above methods for increasing the miscibility of E-1,3,3,3-tetrafluoropropene with a lubricant, the lubricant is a polyol ester, preferably a pentaerythritol ester of one or more straight or branched chain carbonates containing up to nine carbons, more preferably a pentaerythritol ester of a mixture of straight and / or branched chain carbonates containing up to nine carbons. In further specific embodiments, the lubricant is a polyalkylene glycol, preferably a doubly capped co-alkylene oxide having a copolymer chain of alkylene oxide repeat units and an ether alkyl capping group.

[0070] 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 E-1,3,3,3-tetrafluoropropene (i) and a lubricant (iii), the method comprising the step of (ii) adding 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 E-1,3,3,3-tetrafluoropropene (i) and the lubricant (iii), wherein (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).

[0071] 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 ranging from 0.00001 wt. % to 1.0 wt. %, preferably from 0.0001 wt. % to 1.0 wt. %, more preferably from 0.001 wt. % to 0.9 wt. %, even more preferably from 0.005 wt. % to 0.8 wt. %, even more preferably from 0.01 wt. % to 0.6 wt. %, and most preferably from 0.1 to 0.5 wt. %, based on the total weight of the E-1,3,3,3-tetrafluoropropene (i) and the hydro(chloro)fluorocarbon (ii).

[0072] A further embodiment of any of the above methods for increasing the solubility of E-1,3,3,3-tetrafluoropropene in a lubricant is the 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 94.0 to 99.5 wt %, and most preferably 94.5 to 99.0 wt %, based on the total weight of the composition after the hydro(chloro)fluorocarbon (ii) has been added.

[0073] A further embodiment of any of the above 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, even more preferably in an amount in the range of 0.1 to 10.0 wt %, and most preferably 0.5 to 5.0 wt %, based on the total weight of the composition after the hydro(chloro)fluorocarbon (ii) has been added.

[0074] Further embodiments of any of the above methods for increasing the solubility of E-1,3,3,3-tetrafluoropropene in a lubricant include 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- or 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.

[0075] In specific embodiments of any of the above methods for increasing the solubility of E-1,3,3,3-tetrafluoropropene in a lubricant, the lubricant is a polyol ester, preferably a pentaerythritol ester of one or more straight or branched chain carbonates containing up to nine carbons, more preferably a pentaerythritol ester of a mixture of straight and / or branched chain carbonates containing up to nine carbons. In further specific embodiments, the lubricant is a polyalkylene glycol, preferably a doubly capped co-alkylene oxide having a copolymer chain of alkylene oxide repeat units and an ether alkyl capping group.

[0076] In the above methods of reducing the viscosity of a refrigerant composition, or increasing the miscibility of E-1,3,3,3-tetrafluoropropene with a lubricant, or increasing the solubility of E-1,3,3,3-tetrafluoropropene in a lubricant, the refrigerant composition obtained after the hydro(chloro)fluorocarbon (ii) is added may also contain HFO-1234ze(E), a lubricant, an optional co-refrigerant, and optional additives as described above under "Refrigerant," "Lubricant," and "Additives." [Example]

[0077] The invention described herein is further described in the following examples, which do not limit the scope of the invention described in the claims.

[0078] Example 1 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.

[0079] To calculate the solubility, we used the method by Charles Hansen [Hansen, Charles (2007). Hansen Solubility Parameters: A user's handbook, Second Edition]. Hansen solubility parameters (HSP) are a method for predicting whether one material will dissolve in another material and form a solution. They are based on the idea that similar molecules dissolve chemically similar molecules. That is, a molecule is defined as "similar" to another molecule if it interacts in a similar way to itself. The HSP is a division 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 divided into contributions based on dispersive, polar, and associative intermolecular forces. Any material can be calculated using the coordinates (δ D , δP , δ H ), and thus the distance between the solubility loci of any two materials represents how compatible they are in terms of solubility.

[0080] Hansen Solubility Parameters were determined using the software Hansen Solubility Parameters In Practice (HSPiP) v5.4.02 (available from Digital River GmbH, Cologne, Germany). This program was used to calculate HSP (δ) values ​​for POE and PAG lubricating oils, as well as HFO-1234ze(E), and various other hydrofluorocarbon and hydrochlorofluorocarbon refrigerant components. D , δ P , δ H ) were determined by the well-known Yamamoto-Molecular Break GCM / QSAR method and are listed in Table 1.

[0081] [Table 1]

[0082] Next, the relative distance (Ra) from each refrigerant component to each oil was calculated as follows: Ra 2 =4(δ D,油 -δ D,冷媒 ) 2 +(δ P,油 -δ P,冷媒 ) 2 +(δ H,油 -δ H,冷媒 ) 2 (1)

[0083] These are listed in Table 2.

[0084] [Table 2]

[0085] The relative distance Ra is a measure for determining the solubility of a component in each oil. In particular, the smaller the distance of a hydrofluorocarbon component to each oil, the better its solubility in the oil. As can be seen from Table 2, R-1234zc, R-245fa, and R-1233zdE each have a smaller distance to POE than R-1234zeE. Similarly, R-1234zc, R-245fa, and R-1233zdE each have a smaller distance to PAG than R-1234zeE.

[0086] Thus, the solubility of R-1234zeE refrigerant is enhanced by adding R-1234zc, R-245fa, and / or R-1233zdE to both POE and PAG oils. For example, adding 1 wt. % R-1234zc to pure R-1234ze in both oils reduces the distance described in equation (1) above, thereby decreasing the Gibbs free energy of mixing and thereby increasing the solubility of the refrigerant in the lubricant. Similarly, for example, if small amounts of each of R-1234zc, R-245fa, and R-1233zdE are added 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, the resulting mixture will be more soluble in POE or PAG oil than the original R-1234zeE fluid.

[0087] The enhanced solubility improves the flow of the lubricant through the air conditioning and heat pump circuits and enhances oil return to the compressor sump, which provides better lubrication between the moving parts in the compressor, increasing their lifespan and reversing the overall reduced heat transfer coefficient in the evaporator, thus avoiding a loss of cooling capacity.

[0088] Table 3 lists the percent improvement in solubility with respect to distance reduction for R-1234zc, R-245fa, or R-1233zdE added to R-1234zeE.

[0089] As an example, the addition of 1 wt. % R-1233zdE "pull[s]" the HSP locus of R-1234zeE toward that of PAG oil. This reduces the Gibbs free energy of mixing, making the refrigerant more soluble and therefore less viscous. As a result, fluidity is increased. Furthermore, although these results were determined at 25°C, the improvement in solubility is even more pronounced at lower temperatures, such as those during start-up in cold winter weather, further demonstrating the great potential of this invention.

[0090] As shown in Tables 4-5 below, improvements in solubility were also observed when certain hydro(chloro)fluorocarbons were added at levels of 0.5% and 0.1% by weight.

[0091] [Table 3]

[0092] [Table 4]

[0093] One embodiment is 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; and (ii) 1,1,3,3-tetrafluoro-2-propene, 1,1,1,3,3-pentafluoropropene. and (iii) a lubricant selected from a polyol ester and a polyalkylene glycol, 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).

[0094] One embodiment is 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; and (ii) a hydro(chloro)carbonate 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. (b) a fluorocarbon; and (iii) a lubricant selected from a polyol ester and a polyalkylene glycol, wherein the hydro(chloro)fluorocarbon (ii) is present in the composition in a total amount within a range selected from one of 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, and 0.5% to ≦1% by weight, based on the total weight of the E-1,3,3,3-tetrafluoropropene (i) and the hydro(chloro)fluorocarbon (ii).

Claims

1. A 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; (iii) a lubricant selected from polyol esters and polyalkylene glycols; and Including, 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); Refrigerant composition.

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

3. 3. The composition of claim 1, wherein the 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 to 99.5 wt. %, and most preferably 94.5 to 99.0 wt. %, based on the total weight of the composition.

4. 4. The composition of any one of claims 1 to 3, 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, even more preferably in an amount in the range of 0.1 to 10.0 wt.%, and most preferably 0.5 to 5.0 wt.%, based on the total weight of the composition.

5. The composition of 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 the hydro(chloro)fluorocarbon (ii) is 1,1,3,3-tetrafluoro-2-propene, or 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 of any one of claims 1 to 6, wherein the lubricant is a polyol ester.

8. 8. The composition of claim 7, wherein the polyol ester is a pentaerythritol ester of one or more straight or branched chain carbonates containing up to 9 carbons, preferably the polyol ester is a pentaerythritol ester of a mixture of straight and / or branched chain carbonates containing up to 9 carbons.

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

10. 10. The composition of claim 9, wherein the polyalkylene glycol is a doubly capped co-alkylene oxide having a copolymer chain of alkylene oxide repeat units and an ether alkyl capping group.

11. 11. 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 any one of claims 1 to 10, and wherein the refrigeration, air conditioning or heat pump system is preferably a refrigerator, an air conditioner, a chiller, a high-, medium- or low-temperature refrigerator, or a high-, medium- or low-temperature heat pump, and more preferably a stationary refrigerator, a stationary air conditioner, a stationary chiller, a stationary high-, medium- or low-temperature refrigerator, or a stationary high-, medium- or low-temperature heat pump.

12. Use of the refrigerant composition of any one of claims 1 to 10 as a heat transfer medium to increase 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 a refrigeration unit, an air conditioning unit, a chiller unit, a high-, medium-, or low-temperature refrigeration unit, or a high-, medium-, or low-temperature heat pump, more preferably a stationary refrigeration unit, a stationary air conditioning unit, a stationary chiller unit, a stationary high-, medium-, or low-temperature refrigeration unit, or a stationary high-, medium-, or low-temperature heat pump.

13. 11. A method of replacing a refrigerant composition comprising 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 the composition of any one of claims 1 to 10 to the refrigeration, air conditioning, or heat pump system that uses, is being used, or is designed to use the high GWP refrigerant.

14. 1. A method for reducing the viscosity of a refrigerant composition comprising (i) E-1,3,3,3-tetrafluoropropene and (iii) a lubricant selected from a polyol ester and a polyalkylene glycol, the method comprising the step of (ii) adding 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 (ii) adds the hydro(chloro)fluorocarbon (ii) in an amount such that the hydro(chloro)fluorocarbon 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).

15. 1. A method for increasing the miscibility of a refrigerant composition comprising E-1,3,3,3-tetrafluoropropene (i) and a lubricant (iii), the miscibility of the E-1,3,3,3-tetrafluoropropene with (iii) the lubricant selected from polyol esters and polyalkylene glycols, the method comprising: (ii) increasing the miscibility of a refrigerant composition comprising 1,1,3,3-tetrafluoro-2-propene, 1,1,1,3,3-pentafluoropropane, trans-1-chloro-3,3,3-trifluoropropene, and 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 %, based on the total weight of the E-1,3,3,3-tetrafluoropropene (i) and the hydro(chloro)fluorocarbon (ii).

16. A refrigerant composition comprising: (i) 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 an E-1,3,3,3-tetrafluoropropene blend selected from one of (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; (iii) a lubricant selected from polyol esters and polyalkylene glycols; and Including, Refrigerant composition, 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).

17. 17. The composition of claim 16, wherein the hydro(chloro)fluorocarbon (ii) is present in the composition in a total amount in a range selected from one of: 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 to 0.5 wt. %, and 0.5 wt. % to ≦1 wt. %, based on the total weight of the E-1,3,3,3-tetrafluoropropene (i) and the hydro(chloro)fluorocarbon (ii).

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