Heat transfer systems, compositions, and methods

Abstract

The present invention relates to heat transfer systems and methods comprising contacting a zinc-containing surface with a working fluid comprising a refrigerant, a lubricant, and a protective agent comprising a compound according to Formula I: Formula I wherein R and R 1 are each independently selected from the group consisting of hydrogen, alkyl, hydroxyalkyl, and alkylthio, provided that at least one of R and R 1 is alkylthio.

Description

Cross-references to related applications

[0001] This application relates to and claims priority to U.S. Nonprovisional Application No. 18 / 801,757, filed August 13, 2024, and to U.S. Provisional Application No. 63 / 533,540, filed August 18, 2023, both of which are incorporated herein by reference in their entirety. Technical Field

[0002] This invention relates to heat transfer compositions, heat transfer methods, and heat transfer systems, including but not limited to air conditioning and refrigeration applications. Background Technology

[0003] Mechanical refrigeration systems, and related heat transfer devices and methods, such as heat pumps and air conditioners, are well known in industrial, commercial, and residential applications. Typically, such systems utilize a heat transfer cycle that employs a compressor that operates on a working fluid comprising a refrigerant. In typical cooling operation of such systems, a relatively high-pressure, high-temperature refrigerant leaves the compressor and is directed to a condenser, where refrigerant vapor is condensed into a refrigerant liquid. This liquid refrigerant is then converted into a relatively low-temperature, low-pressure refrigerant liquid by passing through an expansion device. This relatively low-temperature, low-pressure refrigerant is then directed to an evaporator, where it is exposed to the fluid or object to be cooled. In the evaporator, the relatively low-temperature, low-pressure refrigerant changes from a liquid phase to a gas phase by absorbing heat (i.e., cooling) from the object or fluid to be cooled. The low-pressure refrigerant vapor discharged from the evaporator is directed to the suction side of the compressor, thus allowing the heat transfer cycle to be repeated.

[0004] A key requirement of most such systems, apparatuses, and methods, as described above, is that, in addition to the refrigerant, the working fluid also includes a lubricant for the compressor. At least a portion of this lubricant circulates with the refrigerant as it passes through the heat transfer cycle. Therefore, all the components mentioned above, as well as other commonly present equipment (including piping, valves, etc., and many other devices that may be present for a particular application), are thus exposed to the circulating working fluid at varying temperatures and pressures. However, the applicant has recognized that exposing certain construction materials to such circulating fluid can adversely affect the lifespan and / or robustness of the system and / or the working fluid. In particular, the applicant has recognized that the presence of zinc-containing components exposed to the working fluid in such heat transfer systems can adversely affect the lifespan and / or robustness of the system and / or the working fluid.

[0005] Therefore, one object of the present invention is to provide heat transfer compositions, heat transfer methods and heat transfer systems that: (i) provide corrosion protection for zinc-containing components or parts present in the heat transfer system that are exposed to refrigerants and / or lubricants during operation; and / or (2) provide protection against deterioration for refrigerants and / or lubricants exposed to such zinc-containing components or parts during operation. Summary of the Invention

[0006] The present invention provides an improved heat transfer system of the type having at least a circulating working fluid and one or more system components exposed to the working fluid during operation, the improvement comprising:

[0007] (a) One or more system components have zinc-containing metal surfaces;

[0008] (b) The working fluid comprises a refrigerant and at least one protective agent, said at least one protective agent comprising a compound according to Formula I:

[0009] Formula I

[0010] Where R and R 1 Each is independently selected from the group consisting of hydrogen, alkyl, hydroxyalkyl, and alkylthio groups, provided that R and R are... 1 At least one of them is an alkylthio group.

[0011] For convenience, the system described in this paragraph will sometimes be referred to as heat transfer system 1.

[0012] The present invention provides an improved heat transfer system of the type having at least a circulating working fluid and one or more system components exposed to the working fluid during operation, the improvement comprising:

[0013] (a) The one or more system components include zinc-containing metal surfaces;

[0014] (b) The working fluid comprises a refrigerant and at least one protective agent for the zinc and / or the refrigerant, wherein the protective agent comprises a compound according to Formula I:

[0015] Formula I

[0016] At least one of R and R1 is a C1-C20 alkylthio group.

[0017] For convenience, the system described in this paragraph is sometimes referred to as heat transfer system 2A.

[0018] The present invention provides an improved heat transfer system of the type having at least a circulating working fluid and one or more system components exposed to the working fluid during operation, the improvement comprising:

[0019] (a) The one or more system components include zinc-containing metal surfaces;

[0020] (b) The working fluid comprises a refrigerant and at least one protective agent for the zinc and / or the refrigerant, wherein the protective agent comprises a compound according to Formula I:

[0021] Formula I

[0022] Each of R and R1 is a C8 alkylthio group.

[0023] For convenience, the system described in this paragraph is sometimes referred to as heat transfer system 2B.

[0024] The present invention also provides a method for providing heat transfer, the method comprising:

[0025] (a) Providing a heat transfer system comprising one or more components, said one or more components having at least one surface formed of a zinc-containing metal;

[0026] (b) A working fluid is provided in the system, wherein: (i) the working fluid is in contact with the at least one surface; and (ii) the working fluid comprises a refrigerant and a protective agent, the protective agent comprising a compound according to Formula I:

[0027] Formula I

[0028] Where R and R 1 Each is independently selected from the group consisting of hydrogen, alkyl, hydroxyalkyl, and alkylthio groups, provided that R and R are... 1 At least one of them is an alkylthio group.

[0029] For convenience, the method described in this section will sometimes be referred to as heat transfer method 1 in this article.

[0030] The present invention also provides a method for providing heat transfer, the method comprising:

[0031] (a) Providing a heat transfer system comprising one or more components, said one or more components having at least one surface formed of a zinc-containing metal;

[0032] (b) A working fluid is provided in the system, wherein: (i) the working fluid is in contact with the at least one surface; and (ii) the working fluid comprises a refrigerant and a protective agent, the protective agent comprising a compound according to Formula I:

[0033] Formula I

[0034] At least one of R and R1 is a C1-C20 alkylthio group.

[0035] For convenience, the method described in this paragraph is sometimes referred to as heat transfer method 2A in this paper.

[0036] The present invention also provides a method for providing heat transfer, the method comprising:

[0037] (a) Providing a heat transfer system comprising one or more components, said one or more components having at least one surface formed of a zinc-containing metal;

[0038] (b) A working fluid is provided in the system, wherein: (i) the working fluid is in contact with the at least one surface; and (ii) the working fluid comprises a refrigerant and a protective agent, the protective agent comprising a compound according to Formula I:

[0039] Formula I

[0040] Each of R and R1 is a C8 alkylthio group.

[0041] For convenience, the method described in this paragraph is sometimes referred to as heat transfer method 2B in this article.

[0042] The present invention also provides a method for providing heat transfer, the method comprising:

[0043] (a) Providing a heat transfer system comprising one or more components, said one or more components having at least one surface formed of a zinc-containing metal;

[0044] (b) A working fluid is provided in the system, wherein: (i) the working fluid is in contact with the at least one surface; and (ii) the working fluid comprises a refrigerant and a protective agent, the protective agent comprising a compound according to Formula II:

[0045]

[0046] Formula II

[0047] For convenience, the method described in this paragraph is sometimes referred to as heat transfer method 2C in this article.

[0048] The present invention also provides a heat transfer composition comprising:

[0049] (a) at least one refrigerant, said at least one refrigerant being selected from HFC, HCFC, HFO, HCFO, fluorocarbons and combinations of two or more of these;

[0050] (b) at least one lubricant, said at least one lubricant being selected from POE and PVE; and

[0051] (c) A protective agent comprising a compound according to formula I:

[0052] Formula I

[0053] Where R and R 1 Each is independently selected from the group consisting of hydrogen, alkyl, hydroxyalkyl, and alkylthio groups, provided that R and R are... 1 At least one of them is an alkylthio group.

[0054] For convenience, the method described in this paragraph is sometimes referred to herein as heat transfer composition 1A.

[0055] The present invention also provides a heat transfer composition comprising:

[0056] (a) At least one refrigerant, said at least one refrigerant being selected from the group consisting of: HFO-1234ze(E), HFO-1234ze(Z), CF3I, HFO-1234yf, HFO-1336mzz(E), HFO-1336mzz(Z), HFC-227ea, HFO-1224yd, HFO-1132(E), HCFO-1233zd(E), HFC-152a; HFC-32, and combinations of two or more of these;

[0057] (b) at least one lubricant, said at least one lubricant being selected from POE and PVE; and

[0058] (c) A protective agent comprising a compound according to formula I:

[0059] Formula I

[0060] Where R and R 1 Each is independently selected from the group consisting of hydrogen, alkyl, hydroxyalkyl, and alkylthio groups, provided that R and R are... 1 At least one of them is an alkylthio group.

[0061] For convenience, the method described in this paragraph is sometimes referred to herein as heat transfer composition 1B.

[0062] The present invention also provides a heat transfer composition comprising:

[0063] (a) at least one refrigerant, said at least one refrigerant being selected from HFC, HCFC, HFO, HCFO, fluorocarbons and combinations of two or more of these;

[0064] (b) at least one lubricant, said at least one lubricant being selected from POE and PVE; and

[0065] (c) A protective agent comprising a compound according to formula I:

[0066] Formula I

[0067] At least one of R and R1 is a C1-C20 alkylthio group.

[0068] For convenience, the composition described in this paragraph is sometimes referred to herein as heat transfer composition 2A.

[0069] The present invention also provides a heat transfer composition comprising:

[0070] (a) at least one refrigerant, said at least one refrigerant being selected from HFC, HCFC, HFO, HCFO, fluorocarbons and combinations of two or more of these;

[0071] (b) at least one lubricant, said at least one lubricant being selected from POE and PVE; and

[0072] (c) A protective agent comprising a compound according to formula I:

[0073] Formula I

[0074] Where at least one of R and R1 is a C1-C20 alkylthio group; and

[0075] (d) A stabilizer comprising one or more of the following: alkylated naphthalene, acid-consuming fraction, phosphate, and preferably a combination of two or more of these.

[0076] For convenience, the composition described in this paragraph is sometimes referred to herein as heat transfer composition 2B.

[0077] The present invention also provides a heat transfer composition comprising:

[0078] (a) at least one refrigerant, said at least one refrigerant being selected from HFC, HCFC, HFO, HCFO, fluorocarbons and combinations of two or more of these;

[0079] (b) at least one lubricant, said at least one lubricant being selected from POE and PVE; and

[0080] (c) A protective agent comprising a compound according to formula I:

[0081] Formula I

[0082] At least one of R and R1 is a C8 alkylthio group;

[0083] For convenience, the composition described in this paragraph is sometimes referred to herein as heat transfer composition 2C.

[0084] The present invention also provides a heat transfer composition comprising:

[0085] (a) at least one refrigerant, said at least one refrigerant being selected from HFC, HCFC, HFO, HCFO, fluorocarbons and combinations of two or more of these;

[0086] (b) at least one lubricant, said at least one lubricant being selected from POE and PVE; and

[0087] (c) A protective agent comprising a compound according to formula I:

[0088] Formula I

[0089] Each of R and R1 is a C5-C10 alkylthio group.

[0090] For convenience, the composition described in this paragraph is sometimes referred to herein as heat transfer composition 2D.

[0091] The present invention also provides a heat transfer composition comprising:

[0092] (a) at least one refrigerant, said at least one refrigerant being selected from HFC, HCFC, HFO, HCFO, fluorocarbons and combinations of two or more of these;

[0093] (b) at least one lubricant, said at least one lubricant being selected from POE and PVE; and

[0094] (c) A protective agent comprising a compound according to formula I:

[0095] Formula I

[0096] Each of R and R1 is a C8 alkylthio group.

[0097] For convenience, the composition described in this paragraph is sometimes referred to herein as heat transfer composition 2E.

[0098] The present invention also provides a heat transfer composition comprising:

[0099] (a) at least one refrigerant, said at least one refrigerant being selected from HFC, HCFC, HFO, HCFO, fluorocarbons and combinations of two or more of these;

[0100] (b) at least one lubricant, said at least one lubricant being selected from POE and PVE; and

[0101] (c) A protective agent comprising a compound according to formula II:

[0102]

[0103] Formula II

[0104] For convenience, the composition described in this paragraph is sometimes referred to herein as heat transfer composition 2F. Detailed Implementation

[0105] definition :

[0106] As used herein, the term "relative percentage" refers to the percentage of the identified compounds based on the total weight of the listed compounds.

[0107] As used herein, the term “about” with respect to weight percentage and the amount of a determined component means that the amount of the determined component may vary by + / - 2% by weight. Unless otherwise stated or understood in the context, amounts expressed as “percentage” or “%” refer to weight percentages.

[0108] For the purposes of this invention, the term "about" in relation to temperature in degrees Celsius (°C) means that the temperature can vary by + / - 5°C. In a preferred embodiment, the temperature designated as "about" is preferably + / - 2°C of the determined temperature, more preferably + / - 1°C, and even more preferably + / - 0.5°C.

[0109] The term "cooling capacity" refers to the amount of cooling provided by a refrigerant in a refrigeration system, measured in BTU / h. This is determined experimentally by multiplying the enthalpy change of the refrigerant as it passes through the evaporator (in BTU / lb) by the refrigerant's mass flow rate. Enthalpy can be determined from measurements of the refrigerant's pressure and temperature. The cooling capacity of a refrigeration system relates to its ability to maintain a region being cooled at a specific temperature. The cooling capacity of a refrigerant represents the amount of cooling or heating it provides and provides some measure of the compressor's ability to pump heat at a given refrigerant volumetric flow rate. In other words, for a given compressor, a refrigerant with a higher cooling capacity will provide more cooling or heating power.

[0110] The phrase “coefficient of performance” (hereinafter referred to as “COP”) is a universally accepted metric for refrigerant performance, particularly useful in representing the relative thermodynamic efficiency of a refrigerant in a specific heating or cooling cycle involving refrigerant evaporation or condensation. In refrigeration engineering, the term represents the ratio of useful cooling or refrigeration capacity to the energy consumed by the compressor in compressing vapor, and thus indicates the ability of a given compressor to pump heat for a given volumetric flow rate of a heat transfer fluid, such as a refrigerant. In other words, for a given compressor, a refrigerant with a higher COP will provide more cooling or heating power. One way to estimate the refrigerant COP under specific operating conditions is to start from the thermodynamic properties of the refrigerant and use standard refrigeration cycle analysis techniques (see, for example, RCDowning, Chapter 3 of the Fluorocarbon Refrigerant Shambook, Prentice-Hall, 1988, the full text of which is incorporated herein by reference).

[0111] The phrase "discharge temperature" refers to the temperature of the refrigerant at the compressor outlet. The advantage of a low discharge temperature is that it allows the use of existing equipment without activating the thermal protection aspects of the system, which are preferably designed to protect the compressor components, and avoids the use of expensive control measures such as liquid injection to reduce the discharge temperature.

[0112] The phrase "Global Warming Potential" (GWP) was coined to allow comparisons of the impact of different gases on global warming. Specifically, it is a measure of how much energy one ton of a gas will absorb over a given period of time, relative to one ton of carbon dioxide emissions. The higher the GWP, the greater the warming effect of a given gas compared to CO2 over that time period. A 100-year timeframe is commonly used for GWP. GWP provides a common metric that allows analysts to add together emissions estimates for different gases. See also www.epa.gov .

[0113] The phrase "Life Cycle Climate Performance" (LCCP) is a methodology for evaluating the impact of air conditioning and refrigeration systems on global warming over their lifespan. LCCP includes the direct impact of refrigerant emissions and the indirect impacts on energy consumption for the operating system, energy consumption for manufacturing the system, and energy consumption for transport and safe disposal. The direct impact of refrigerant emissions is derived from the refrigerant's Global Power Product (GWP). For indirect emissions, measured refrigerant characteristics are used to obtain system performance and energy consumption. LCCP is determined using Equations 1 and 2 below. Equation 1 is: Direct Emissions = Refrigerant Charge (kg) × (Annual Loss Rate × Lifespan + End-of-Life Loss) × GWP. Equation 2 is: Indirect Emissions = Annual Power Consumption × Lifespan × CO2 Produced per kilowatt-hour of Electricity. The direct emissions determined by Equation 1 and the indirect emissions determined by Equation 2 are added together to obtain the LCCP. Produced by the National Renewable Energy Laboratory and available at BinMaker. ® The TMY2 and TMY3 data obtained from Pro version 4 software were used for analysis. The GWP values ​​reported in the Intergovernmental Panel on Climate Change (IPCC) Fourth Assessment Report (AR4) in 2007 were used for calculation. LCCP is expressed as the mass of carbon dioxide (kg-CO2eq) over the lifespan of the air conditioning or refrigeration system.

[0114] The term "mass flow rate" refers to the mass of refrigerant that passes through a pipe per unit time.

[0115] The term “Occupational Exposure Limit (OEL)” is determined according to ASHRAE Standard 34-2016, “Designation and Safety Classification of Refrigerants”.

[0116] When used herein, the term "substitute" for a particular heat transfer composition or refrigerant of the present invention as a "substitute" for a particular existing refrigerant means the use of the specified composition of the present invention in heat transfer systems that have historically been used with that existing refrigerant. For example, when the refrigerant or heat transfer composition of the present invention is used in heat transfer systems (such as residential and commercial air conditioning systems, including rooftop systems, variable refrigerant flow (VRF) systems, and cooler systems) designed to date for use with R410A, the refrigerant of the present invention is a substitute for R410A in such systems.

[0117] The phrase "thermodynamic slip" applies to non-azeotropic refrigerant mixtures that have a changing temperature during a phase change process in an evaporator or condenser at constant pressure.

[0118] The phrase "thermodynamic slip" applies to non-azeotropic refrigerant mixtures that have a changing temperature during a phase change process in an evaporator or condenser at constant pressure.

[0119] When used in this article, “TAN value” refers to the total acid value determined according to ASHRAE Standard 97 – “Method for testing the chemical stability of materials used in refrigeration systems in sealed glass tubes”, to simulate the long-term stability of the heat transfer composition by accelerating aging.

[0120] 1234ze refers to 1,1,1,3-tetrafluoropropylene, and there are no restrictions on the isomer forms.

[0121] Trans1234ze, 1234ze(E), and R-1234ze(E) each refer to trans-1,3,3,3-tetrafluoropropylene.

[0122] Cis1234ze and 1234ze(Z) respectively refer to cis-1,3,3,3-tetrafluoropropylene.

[0123] 1234yf refers to 2,3,3,3-tetrafluoropropylene.

[0124] 1233zd refers to 1-chloro-3,3,3-trifluoropropene, and there are no restrictions on the isomer form.

[0125] Trans1233zd and 1233zd(E) respectively refer to trans-1-chloro-3,3,3-trifluoropropene.

[0126] 1224yd refers to cis-1-chloro-2,3,3,3-tetrafluoropropane, with no restrictions on isomer forms.

[0127] The terms “1132(E)”, “R-1132(E)”, and “HFO-1132(E)” each refer to trans-1,2-difluoroethylene.

[0128] As used in this article, the terms “R-32” and “HFC-32” each refer to difluoromethane.

[0129] The terms “R-125” and “HFC-125” refer to pentafluoroethane.

[0130] The terms “R-134a” and “HFC-134a” each refer to 1,1,1,2-tetrafluoroethane.

[0131] The terms “R-143a” and “HFC-143a” each refer to 1,1,1-trifluoroethane.

[0132] The terms “R-227ea” and “HFC-227ea” refer to 1,1,1,2,3,3,3-heptafluoropropane, respectively.

[0133] As used herein, the term "R448A" refers to the refrigerant designated 448A by ASHRAE and consisting of approximately 26% R-32, approximately 26% R-125, approximately 20% HFO-1234yf, approximately 21% R-134a, approximately 7% HFO-1234ze(E) and approximately 20% HFO-1234yf.

[0134] As used herein, the term "R448B" refers to the refrigerant designated 448B by ASHRAE and consisting of approximately 21% R-32, approximately 21% R-125, approximately 20% HFO-1234yf, approximately 31% R-134a and approximately 7% HFO-1234ze(E).

[0135] As used herein, the term "R449A" refers to the refrigerant designated 449A by ASHRAE and consisting of approximately 24.3% R-32, approximately 24.7% R-125, approximately 25.7% HFO-1234yf, and approximately 25.7% R-134a.

[0136] As used herein, the term "R449B" refers to the refrigerant designated 449B by ASHRAE and consisting of approximately 25.2% R-32, approximately 24.3% R-125, approximately 23.2% HFO-1234yf, and approximately 27.3% R-134a.

[0137] As used herein, the term "R449C" refers to the refrigerant designated 449C by ASHRAE and consisting of approximately 20% R-32, approximately 20% R-125, approximately 31% HFO-1234yf, and approximately 29% R-134a.

[0138] As used herein, the term "R450A" refers to the refrigerant designated 450A by ASHRAE and consisting of 42% R-134a and 58% R-1234yf.

[0139] As used herein, the term "R452A" refers to the refrigerant designated 452A by ASHRAE and consisting of approximately 11% R-32, approximately 59% R-125 and approximately 30% R-1234yf.

[0140] As used herein, the term "R452B" refers to the refrigerant designated 452B by ASHRAE and consisting of approximately 67% R-32, approximately 7% R-125, and approximately 26% R-1234yf.

[0141] As used herein, the term "R454A" refers to the refrigerant designated 454A by ASHRAE and consisting of 35% R-32 and 65% HFC-1234yf.

[0142] As used herein, the term "R454B" refers to the refrigerant designated 454B by ASHRAE and consisting of 68.9% R-32 and 31.1% HFC-1234yf.

[0143] As used herein, the term "R454C" refers to the refrigerant designated 454C by ASHRAE and consisting of 21.5% +2 / -2% R-32 and 78.5% -2 / -2% HFC-1234yf.

[0144] As used herein, the term "R455A" refers to the refrigerant designated 455A by ASHRAE and consisting of 21.5% +2 / -1% R-32, 75.5% HFC-1234yf +2 / -2% and 3% +2 / -1% CO2.

[0145] As used herein, the term "R456A" refers to the refrigerant designated 456A by ASHRAE and consisting of approximately 6% R-32, approximately 45% R-134a and approximately 49% R-1234ze(E).

[0146] As used herein, the term "R457A" refers to the refrigerant designated 457A by ASHRAE and consisting of approximately 18% R-32, approximately 12% R-152a and approximately 70% R-1234yf.

[0147] As used herein, the term "R457B" refers to the refrigerant designated 457B by ASHRAE and consisting of approximately 35% R-32, approximately 10% R-152a, and approximately 55% R-1234yf.

[0148] As used herein, the term "R457C" refers to the refrigerant designated 457C by ASHRAE and consisting of approximately 7.5% R-32, approximately 14.5% R-152a, and approximately 78% R-1234yf.

[0149] As used herein, the term "R466A" refers to the refrigerant designated 466A by ASHRAE and consisting of approximately 49% R-32, approximately 11.5% R-125 and approximately 39.5% CF3I.

[0150] As used in this article, the term "HDR139" refers to a refrigerant consisting of approximately 38% R-32 and 62% CF3I.

[0151] As used herein, the term "HDR147" refers to a refrigerant consisting of approximately 41% R-32, approximately 3.5% R-125, and approximately 55.5% CF3I.

[0152] As used herein, the term "HDR171" refers to a refrigerant consisting of approximately 20% R-32, approximately 40% 1234yf, and approximately 40% 1132(E).

[0153] As used herein, the term "HDR173" refers to a refrigerant consisting of approximately 21.5% R-32, approximately 40.5% 1234yf, and approximately 38% 1132(E).

[0154] As used herein, the term "R471A" refers to the refrigerant designated 471A by ASHRAE and consisting of 78.7% +0.4 / -1.5% HFC-1234ze(E), 17% +1.5 / -0.4% HFC-1336mzz(E), and 4.3% +1.5 / -0.4% HFC-227ea.

[0155] As used herein, the term "R474A" refers to the refrigerant designated 474A by ASHRAE and consisting of approximately 23% R-1132(E) and approximately 77% R-1234yf.

[0156] As used herein, the term "R474B" refers to the refrigerant designated 474B by ASHRAE and consisting of approximately 31.5% R-1132(E) and approximately 68.5% R-1234yf.

[0157] As used herein, the term "R476A" refers to the refrigerant designated 476A by ASHRAE and consisting of 78.7% + / - 0.5 / - 2% HFC-1234ze(E), 12% +2 / - 0.5% HFC-1336mzz(E), and 10% +2 / - 0.51% HFC-134a.

[0158] As used herein, the term "R479A" refers to the refrigerant designated 479A by ASHRAE and consisting of approximately 28% R-1132(E), approximately 50.5% R-1234yf, and approximately 21.5% HFC-32.

[0159] As used herein, the term "R482A" refers to the refrigerant designated 482A by ASHRAE and consisting of approximately 10% HFC-134a, approximately 83.5% HFC-1234ze(E) and approximately 6.5% HFO-1224yd(Z).

[0160] As used herein, the term "R-513A" refers to the refrigerant designated 513A by ASHRAE and consisting of approximately 56% HFC-1234yf and approximately 44% HFC-134a.

[0161] As used herein, the term "R-513B" refers to the refrigerant designated 513B by ASHRAE and consisting of approximately 58.5% HFC-1234yf and approximately 41.5% HFC-134a.

[0162] As used herein, the term "R-514A" refers to the refrigerant designated 514A by ASHRAE and consisting of approximately 74.7% HFO-1336mzz(Z) and approximately 25.3% HFO-1130(E).

[0163] As used herein, the term "R-515A" refers to the refrigerant designated 515A by ASHRAE and consisting of approximately 88% HFC-1234ze(E) and approximately 12% HFC-134a.

[0164] As used herein, the term "R-515B" refers to the refrigerant designated 515B by ASHRAE and consisting of approximately 91.1% HFO-1234ze(E) and approximately 8.9% HFC-134a.

[0165] As used herein, the term "R-516A" refers to the refrigerant designated 516A by ASHRAE and consisting of approximately 77.5% HFC-1234yf, approximately 8.5% HFC-134a, and approximately 14% HFC-152a.

[0166] As used herein, the term "protectant 1" refers to the compound according to formula I:

[0167] Formula I

[0168] At least one of R and R1 is a C1-C20 alkylthio group.

[0169] As used herein, the term "protectant 2" refers to the compound according to formula I:

[0170] Formula I

[0171] Each of R and R1 is independently a C1-C20 alkylthio group.

[0172] As used herein, the term "protectant 3" refers to the compound according to formula I:

[0173] Formula I

[0174] Each of R and R1 is independently a C5-C20 alkylthio group.

[0175] As used herein, the term "protectant 4" refers to the compound according to formula I:

[0176] Formula I

[0177] Each of R and R1 is independently a C5-C10 alkylthio group.

[0178] As used herein, the term "protectant 5A" refers to a compound according to formula II:

[0179]

[0180] Formula II

[0181] As used herein, the term "protectant 5B" means a composition comprising a dioctyl disulfide and a compound according to formula II:

[0182]

[0183] Formula II

[0184] As used herein, references to a defined group, such as “heat transfer compositions 1-2”, refer to each composition within that group, including cases where the definition number has a suffix. Thus, references to heat transfer compositions 1-2 include references to each of heat transfer compositions 1A, 1B, 2A, 2B, 2C, and 2D.

[0185] heat transfer composition

[0186] The applicant has discovered that the heat transfer compositions of the present invention (including each of the heat transfer compositions 1-2 described herein) can provide particularly advantageous properties, especially providing stability in use.

[0187] A particular advantage of the heat transfer compositions of the present invention is that they provide excellent chemical stability in use, especially in heat transfer systems comprising zinc-containing components exposed to the heat transfer compositions during use. This desirable advantage can be achieved by the heat transfer compositions of the present invention.

[0188] The specific heat transfer compositions of the present invention include those defined in Table 1 below, wherein the first column of the table includes "HTC" as an abbreviation for the defined heat transfer composition. In Table 1 below: "NR" means that the component or specific amount is "unnecessary" according to the specified HTC definition, and therefore its presence or absence in any amount is permitted; "Yes" means that the component is necessary, but any type or amount is permitted; "Comp" means that the specified composition contains the items defined in the table; "CEO" means that the specified composition consists primarily of the items defined in the table; and "CO" means that the composition consists of the items defined in the table.

[0189] Table 1

[0190]

[0191]

[0192]

[0193]

[0194]

[0195]

[0196]

[0197]

[0198]

[0199]

[0200]

[0201]

[0202]

[0203]

[0204]

[0205]

[0206]

[0207]

[0208]

[0209]

[0210] For convenience, each heat transfer composition identified by its number in the first column of Table 1 represents a definition of a heat transfer composition, and reference to the number indicates a composition having components (and in the amounts specified). Furthermore, as stated above, references herein to defined groups, such as “heat transfer compositions 3-46”, or compositions defined by number, refer to each composition within that group or composition, including cases where the definition number has a suffix. For example, reference to “heat transfer composition 3” is intended to include each composition with the root word 3; for instance, HTC3 includes HTC3A in Table 1, HTC3B in Table 2, etc.

[0211] Preferably, the heat transfer composition of the present invention (including each of heat transfer compositions 1-46) contains a refrigerant in an amount greater than 40% by weight of the heat transfer composition.

[0212] Preferably, the heat transfer composition of the present invention (including each of heat transfer 1-46) contains a refrigerant in an amount greater than 50% by weight, or greater than 70% by weight, or greater than 80% by weight, or greater than 90% of the heat transfer composition.

[0213] The heat transfer compositions of the present invention may contain other components intended to enhance or provide certain functions to the composition, preferably without negating the features provided by using the protective agents of the present invention. Such other components or additives may include stabilizers, dyes, solubilizers, compatibilizers, auxiliary stabilizers, antioxidants, corrosion inhibitors, extreme pressure additives, and anti-wear additives.

[0214] Preferably, the heat transfer composition of the present invention (including each of heat transfer compositions 1-46) comprises a stabilizer. Preferably, it comprises one or more stabilizers selected from the following.

[0215] stabilizer :

[0216] Alkylated naphthalene

[0217] The applicant has surprisingly and unexpectedly discovered that alkylated naphthalene is highly effective as a stabilizer in the heat transfer compositions used in this invention. As used herein, the term "alkylated naphthalene" refers to a compound having the following structure:

[0218]

[0219] Each of R1–R8 is independently selected from straight-chain alkyl groups, branched alkyl groups, and hydrogen. The specific lengths of alkyl chains and mixtures, or branched and straight chains, and hydrogen can vary within the scope of this invention, and those skilled in the art will understand and appreciate that such variations reflect the physical properties of alkylated naphthalenes, particularly the viscosity of the alkylated compounds, and that producers of such materials often define these materials by reference to one or more of these properties, as an alternative to the description of specific R groups.

[0220] The applicant has discovered that unexpected, surprising, and advantageous results relate to the use of alkylnaphthalene as a stabilizer according to the invention, comprising each of the heat transfer compositions 1-46 having the following properties, and the alkylnaphthalene compounds having the indicated properties are referred herein, for convenience, to be alkylnaphthalene 1 (or AN1)-alkylnaphthalene 5 (or AN5), respectively shown in rows 1-5 of Table AN-A below:

[0221] Table AN-A

[0222]

[0223] As used in this article in conjunction with viscosity at 40°C as measured according to ASTM D445, the term “about” means + / - 4 cSt.

[0224] As used in this article in conjunction with viscosity at 100°C as measured according to ASTM D445, the term “about” means + / - 0.4 cSt.

[0225] As used in this article in conjunction with pour point measurements according to ASTM D97, the term “about” means + / - 5°C.

[0226] The applicant also discovered that unexpected, surprising, and advantageous results relate to the use of alkylnaphthalene as a stabilizer according to the invention, comprising each of the heat transfer compositions 1-46 having the following properties, and the alkylnaphthalene compounds having the indicated properties are referred herein, for convenience, to be alkylnaphthalene 6 (or AN6)-alkylnaphthalene 10 (or AN10), respectively shown in rows 6-10 of Table AN-B below:

[0227] Table AN-B

[0228]

[0229] Within the meaning of alkylnaphthalene 1 and alkylnaphthalene 6, examples of alkylnaphthalene include those sold by King Industries under the trade names NA-LUBE KR-007A; KR-008; KR-009; KR-015; KR-019; KR-005FG; KR-015FG; and KR-029FG.

[0230] Within the meaning of alkylnaphthalene 2 and alkylnaphthalene 7, examples of alkylnaphthalene include those sold by King Industries under the trade names NA-LUBE KR-007A; KR-008; KR-009; and KR-005FG.

[0231] Within the meaning of alkylnaphthalene 5 and alkylnaphthalene 10, examples of alkylnaphthalene include products sold by King Industries under the trade name NA-LUBE KR-008.

[0232] The present invention includes heat transfer compositions, including each of heat transfer compositions 14 and 30-32 herein, wherein the alkyl naphthalene is AN1, AN2, or AN3, or AN4, or AN5, or AN6, or AN7, or AN8, or AN9 or AN10.

[0233] Acid consumption portion (ADM)

[0234] Those skilled in the art will be able to identify a variety of ADMs available according to the present invention without reversing the experiments, and all such ADMs are within the scope of the present invention.

[0235] Epoxides

[0236] The applicant has discovered that epoxides, particularly alkylated epoxides, when used in combination with alkylated naphthalene stabilizers, can effectively produce the enhanced stability discussed herein, and although the applicant is not necessarily bound by theory, it is believed that this synergistic enhancement is at least in part attributable to their effective function as an ADM in the heat transfer compositions of the present invention.

[0237] In a preferred embodiment comprising each of the heat transfer compositions 1-46, the epoxide is selected from the group consisting of epoxides that undergo a ring-opening reaction with an acid, thereby consuming the acid system without otherwise causing harmful effects on the system.

[0238] Available epoxides include aromatic epoxides, alkyl epoxides (including alkyl ether epoxides), and alkenyl epoxides.

[0239] Preferred epoxides include epoxides of formula I:

[0240] Formula I

[0241] The R1–R4 group is selected from two to fifteen carbon (C2–C15) acyclic groups, C2–C15 aliphatic groups, and C2–C15 ether groups. For convenience, the epoxide group of formula I with R group as defined in this paragraph is sometimes referred to herein as ADM1A.

[0242] Preferred epoxides also include epoxides of formula I:

[0243] Formula I

[0244] Each of R1–R4 is independently selected from H, C2–C15 acyclic groups, C2–C15 aliphatic groups, and C2–C15 ether groups, provided that at least one of R1–R4 is H, and at least one of R1–R4 is selected from C2–C15 acyclic groups, C2–C15 aliphatic groups, and C2–C15 ether groups. For convenience, the epoxide group of formula I having an R group as defined in this paragraph is sometimes referred to herein as ADM1B.

[0245] Preferred epoxides also include epoxides of formula I:

[0246] Formula I

[0247] Each of R1–R4 is independently selected from H, C2–C15 acyclic groups, C2–C15 aliphatic groups, and C2–C15 ether groups, provided that at least two of R1–R4 are H, and at least one of R1–R4 is selected from C2–C15 acyclic groups, C2–C15 aliphatic groups, and C2–C15 ether groups. For convenience, the epoxide group of formula I having an R group as defined in this paragraph is sometimes referred to herein as ADM1C.

[0248] Preferred epoxides also include epoxides of formula I:

[0249] Formula I

[0250] Each of R1–R4 is independently selected from H, a C2–C15 acyclic group, a C2–C15 aliphatic group, and a C2–C15 ether group, provided that three of R1–R4 are H, and one of R1–R4 is selected from a C2–C15 acyclic group, a C2–C15 aliphatic group, and a C2–C15 ether group. For convenience, the epoxide group of formula I having an R group as defined in this paragraph is sometimes referred to herein as ADM1D.

[0251] In a preferred embodiment, at least one of R1-R4 of Formula I is an ether having the following structure:

[0252] Formula II

[0253] Each of R5 and R6 is independently a C1-C14 straight-chain or branched group, preferably an unsubstituted alkyl group. For convenience, the epoxide group as defined in this paragraph is sometimes referred to herein as ADM2A.

[0254] In a preferred embodiment, at least one of R1-R4 of Formula I is an ether having the following structure:

[0255] Formula II

[0256] in

[0257] R5 is a C1-C3 alkyl group, preferably unsubstituted; and

[0258] R6 is a C3-C10 straight-chain or branched group, preferably an unsubstituted alkyl group. For convenience, the epoxide group defined in this paragraph is sometimes referred to herein as ADM2B.

[0259] In a preferred embodiment, one of R1-R4 of Formula I is an ether having the following structure:

[0260] Formula II

[0261] Each of R5 and R6 is independently a C1-C14 straight-chain or branched group, preferably an unsubstituted alkyl group, and the remaining three of R1–R4 are H. For convenience, the epoxide group defined in this paragraph is sometimes referred to herein as ADM3A.

[0262] In a preferred embodiment, one of R1-R4 of Formula I is an ether having the following structure:

[0263] Formula II

[0264] in

[0265] R5 is attached to the epoxy group and is an unsubstituted alkyl group with a straight or branched C1–C3 chain; and

[0266] R6 is a C3–C10 straight-chain or branched unsubstituted alkyl group, and the other three of R1–R4 are H. For convenience, the epoxide group defined in this paragraph is sometimes referred to herein as ADM3B.

[0267] In a preferred embodiment, one of R1-R4 of Formula I is an ether having the following structure:

[0268] Formula II

[0269] in

[0270] R5 is connected to the epoxy group and is an unsubstituted C1 alkyl group; and

[0271] R6 is a C8-branched, unsubstituted alkyl group, and the other three of R1–R4 are hydrogen atoms. For convenience, the epoxide groups defined in this paragraph are sometimes referred to as ADM3C herein.

[0272] In a preferred embodiment, the epoxide comprises, is substantially composed of, or is composed of, 2-ethylhexyl glycidyl ether, which is an ADM3C compound having the following structure:

[0273] For convenience, the epoxide referred to in this paragraph is sometimes called ADM4.

[0274] In a preferred embodiment, one of R1-R4 of Formula I is an ether having the following structure:

[0275] Formula II

[0276] Each of R5 and R6 is independently a C1-C14 straight-chain or branched, substituted or unsubstituted alkyl group, and the remaining three of R1–R4 are H. For convenience, the epoxide group defined in this paragraph is sometimes referred to as ADM5A herein.

[0277] In a preferred embodiment, one of R1-R4 of Formula I is an ether having the following structure:

[0278] Formula II

[0279] in

[0280] R5 is connected to the epoxy group and is a C1-C3 straight-chain or branched, unsubstituted alkyl group; and

[0281] R6 is a C3–C10 straight-chain or branched, substituted alkyl group, and the other three of R1–R4 are H. For convenience, the epoxide group defined in this paragraph is sometimes referred to as ADM5B herein.

[0282] In a preferred embodiment, one of R1-R4 of Formula I is an ether having the following structure:

[0283] Formula II

[0284] in

[0285] R5 is connected to the epoxy group and is an unsubstituted C1 alkyl group; and

[0286] R6 is a C8 branched, substituted alkyl group, and the other three of R1–R4 are H. For convenience, the epoxide group of formula I with R groups as defined in this paragraph is sometimes referred to herein as ADM5C.

[0287] In a preferred embodiment, one of R1-R4 of Formula I is an ether having the following structure:

[0288] Formula II

[0289] in

[0290] R5 is connected to the epoxy group and is an unsubstituted C1 alkyl group; and

[0291] R6 is a C8 branched, oxygen-substituted alkyl group, and the other three of R1–R4 are H. For convenience, the epoxide group of formula I with R groups as defined in this paragraph is sometimes referred to herein as ADM5D.

[0292] In a preferred embodiment, the epoxide comprises, is substantially composed of, or is composed of, glycidyl neodecanoate, which is an ADM5C compound wherein the substituent at R6 is O and has the following structure:

[0293]

[0294] For convenience, the epoxide referred to in this paragraph is sometimes referred to as ADM6.

[0295] The present invention includes heat transfer compositions, including each of heat transfer compositions 1 and 30-32, wherein the alkyl naphthalene is AN1 or AN2 or AN3 or AN4 or AN5 or AN6 or AN7 or AN8 or AN9 or AN10, and further includes any one or more of ADM1-ADM6.

[0296] In the heat transfer compositions of the present invention (including each of heat transfer compositions 1 and 30-32), ADM is preferably present in an amount of about 0.05% by weight to about 2.5% by weight, preferably 0.05% by weight to about 1.5% by weight, or preferably 0.05% by weight to 0.5% by weight, all based on the weight of the lubricant plus the ADM.

[0297] In the heat transfer compositions of the present invention (including each of heat transfer compositions 1 and 30-32), alkylnaphthalene is preferably present in an amount of 0.01% to about 10%, or about 1.5% to about 4.5%, or about 2.5% to about 3.5%, wherein the amount is a weight percentage based on the amount of alkylnaphthalene plus refrigerant in the system. The amount specified in this paragraph is particularly preferred when ADM is also present.

[0298] In the heat transfer compositions of the present invention (including each of heat transfer compositions 1 and 30-32), alkyl naphthalene is preferably present in an amount of 0.1% to about 20%, or 1.5% to about 10%, or 1.5% to about 8%, wherein the amount is a weight percentage based on the amount of alkyl naphthalene plus lubricant in the system. The amount specified in this paragraph is particularly preferred when ADM is also present.

[0299] Carbodiimide

[0300] ADM can include carbodiimide. In a preferred embodiment, the carbodiimide includes compounds having the following structure:

[0301]

[0302] Other stabilizers

[0303] Stabilizers other than alkylnaphthalene and ADM are intended to be included in the heat transfer compositions of the present invention (including each of heat transfer compositions 1-46). Examples of such other stabilizers are described below.

[0304] Phenolic compounds

[0305] In a preferred embodiment, the stabilizer further includes phenol-based compounds.

[0306] The phenol-based compound can be one or more compounds selected from the following: 4,4'-methylenebis(2,6-di-tert-butylphenol); 4,4'-bis(2,6-di-tert-butylphenol); 2,2-biphenyl glycol or 4,4-biphenyl glycol, including 4,4'-bis(2-methyl-6-tert-butylphenol); 2,2-biphenyl glycol or derivatives of 4,4-biphenyl glycol; 2,2'-methylenebis( 4-Ethyl-6-tert-butylphenol); 2,2'-Methylenebis(4-methyl-6-tert-butylphenol); 4,4-Butylbis(3-methyl-6-tert-butylphenol); 4,4-Isopropylbis(2,6-di-tert-butylphenol); 2,2'-Methylenebis(4-methyl-6-nonylphenol); 2,2'-Isobutylbis(4,6-dimethylphenol); 2,2'-Methylenebis(4 2,6-Di-tert-butyl-4-methylphenol (BHT); 2,6-Di-tert-butyl-4-ethylphenol; 2,4-dimethyl-6-tert-butylphenol; 2,6-di-tert-α-dimethylamino-p-cresol; 2,6-di-tert-butyl-4(N,N'-dimethylaminomethylphenol); 4,4'-thiobis(2-methyl-6-tert-butylphenol); 4,4'- -Thiobis(3-methyl-6-tert-butylphenol); 2,2'-Thiobis(4-methyl-6-tert-butylphenol); bis(3-methyl-4-hydroxy-5-tert-butylbenzyl) sulfide; bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, tocopherol, hydroquinone, 2,2'6,6'-tetra-tert-butyl-4,4'-methylenediol and tert-butylhydroquinone, and preferably BHT.

[0307] The amount of phenolic compound (especially BHT) provided in the heat transfer composition can be greater than 0% by weight and preferably from 0.0001% by weight to about 5% by weight, more preferably from 0.001% by weight to about 2.5% by weight, and more preferably from 0.01% by weight to about 1% by weight. In each case, the weight percentage refers to the weight of the heat transfer composition.

[0308] The amount of phenolic compound (especially BHT) provided in the heat transfer composition can be greater than 0% by weight and preferably from 0.0001% by weight to about 5% by weight, more preferably from 0.001% by weight to about 2.5% by weight, and more preferably from 0.01% by weight to about 1% by weight. In each case, the weight percentage refers to the weight based on the weight of the lubricant in the heat transfer composition.

[0309] The invention also includes a stabilizer comprising, based on the weight of all stabilizer components in the composition, about 40% to about 95% by weight of alkylated naphthalene (including each of AN1-AN10) and 0.1% to about 10% by weight of BHT.

[0310] The present invention also includes a stabilizer comprising, based on the weight of all stabilizer components in the composition, about 40% to about 95% alkylated naphthalene (including each of AN1-AN10), 5% to about 30% ADM (including each of ADM1-ADM6), and 0.1% to about 10% BHT.

[0311] Diene-based compounds

[0312] The diene-based compounds comprise C3 to C15 dienes and compounds formed by the reaction of any two or more C3 to C4 dienes. Preferably, the diene-based compounds are selected from the group consisting of allyl ethers, propadiene, butadiene, isoprene, and terpenes. The diene-based compounds are preferably terpenes, including but not limited to rutin, retinaldehyde, geraniol, terpinene, δ-3-carene, isoterpinene, phellandrene, anethole, myrcene, farnesene, pinene, nerol, citral, camphor, menthol, limonene, nerolidol, phytol, sagelinic acid, and vitamin A1. Preferably, the stabilizer is farnesene. Preferred terpene stabilizers are disclosed in U.S. Provisional Patent Application 60 / 638,003, filed December 12, 2004, entitled US 2006 / 0167044A1, which is incorporated herein by reference.

[0313] Furthermore, the amount of diene-based compound provided in the heat transfer composition may be greater than 0% by weight and preferably from 0.0001% by weight to about 5% by weight, more preferably from 0.001% by weight to about 2.5% by weight, and more preferably from 0.01% by weight to about 1% by weight. In each case, weight percentage refers to the weight of the heat transfer composition.

[0314] Phosphorus-based compounds

[0315] The phosphorus compound can be a phosphite or a phosphate compound. For the purposes of this invention, the phosphite compound can be a diaryl phosphite, a dialkyl phosphite, a triaryl phosphite, and / or a trialkyl phosphite, and / or a mixture of aryl / alkyl disubstituted or trisubstituted phosphites, particularly selected from one or more of the following compounds: hindered phosphites, tri-(di-tert-butylphenyl) phosphites, di-n-octyl phosphite, diphenylisooctyl phosphite, diphenylisodecyl phosphite, triisodecyl phosphate, triphenyl phosphite, and diphenyl phosphite, particularly diphenyl phosphite.

[0316] The phosphate ester compound can be a triaryl phosphate, a trialkyl phosphate, a monoacid alkyl phosphate, a diacid aryl phosphate, or an ammonium phosphate, preferably a triaryl phosphate and / or a trialkyl phosphate, especially tri-n-butyl phosphate.

[0317] The present invention includes heat transfer compositions, including each of heat transfer compositions 1-46, wherein the compositions further comprise phosphate esters.

[0318] The present invention includes heat transfer compositions, including each of heat transfer compositions 1-46, wherein the compositions further comprise triaryl phosphate.

[0319] The present invention includes heat transfer compositions, including each of heat transfer compositions 1-46, wherein the compositions further comprise trialkyl phosphate.

[0320] The amount of phosphorus compound provided in the heat transfer compositions of the present invention (including each of heat transfer compositions 1-46) may be greater than 0% by weight and preferably from 0.0001% by weight to about 5% by weight, more preferably from 0.001% by weight to about 2.5% by weight, and more preferably from 0.01% by weight to about 1% by weight. In each case, "by weight" refers to the weight of the heat transfer composition.

[0321] The amount of phosphorus compound provided in the heat transfer compositions of the present invention (including each of heat transfer compositions 1-46) may be greater than 0% by weight and preferably from 0.0002% by weight to about 10% by weight, more preferably from 0.002% by weight to about 5% by weight, and more preferably from 0.02% by weight to about 2% by weight. In each case, "by weight" in this paragraph refers to the weight of the lubricant and the phosphate ester stabilizer.

[0322] Nitrogen compounds

[0323] When the stabilizer is a nitrogen compound, the stabilizer may include amine-based compounds, such as one or more secondary or tertiary amines selected from the following: diphenylamine, p-phenylenediamine, triethylamine, tributylamine, diisopropylamine, triisopropylamine, and triisobutylamine. Amine-based compounds can be amine antioxidants, such as substituted piperidine compounds, i.e., alkyl-substituted piperidinyl, piperidinyl, piperazine, or alkoxypiperidinyl derivatives, particularly amine antioxidants selected from one or more of the following: 2,2,6,6-tetramethyl-4-piperidinone, 2,2,6,6-tetramethyl-4-piperidinol; bis-(1,2,2,6,6-pentamethylpiperidinyl) sebacate; bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, poly(N-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy-piperidinyl) succinate; alkylated p-phenylenediamines, such as N-phenyl-N'-(1,3-dimethyl-butyl)-p-phenylenediamine or N,N'-disec-butyl-p-phenylenediamine; and hydroxylamines, such as tallow amine, methyl ditow amine, and ditow amine, or phenol-α-naphthylamine or Tinuvin. ® 765 (Ciba), BLS ® 1944 (Mayzo Inc) and BLS ®1770 (Mayzo Inc). For the purposes of this invention, the amine-based compound may also be an alkyl diphenylamine, such as bis(nonylphenylamine), a dialkylamine, such as N-(1-methylethyl)-2-propaneamine, or one or more of phenyl-α-naphthylamine (PANA), alkyl-phenyl-α-naphthylamine (APANA), and bis(nonylphenyl)amine. Preferably, the amine-based compound is one or more of phenyl-α-naphthylamine (PANA), alkyl-phenyl-α-naphthylamine (APANA), and bis(nonylphenyl)amine, and more preferably phenyl-α-naphthylamine (PANA).

[0324] Alternatively, or in addition to the nitrogen compounds identified above, one or more compounds selected from dinitrobenzene, nitrobenzene, nitromethane, nitrosobenzene, and TEMPO [(2,2,6,6-tetramethylpiperidin-1-yl)oxy] may be used as stabilizers.

[0325] The amount of nitrogen compound provided in the heat transfer composition may be greater than 0% by weight and from 0.0001% by weight to about 5% by weight, preferably from 0.001% by weight to about 2.5% by weight, and more preferably from 0.01% by weight to about 1% by weight. In each case, weight percentage refers to the weight of the heat transfer composition.

[0326] Isobutylene

[0327] Isobutylene can also be used as a stabilizer according to the present invention.

[0328] lubricant

[0329] The heat transfer compositions of the present invention (including each of heat transfer compositions 1-46) preferably contain POE lubricant and / or PVE lubricant, wherein the lubricant is preferably present in an amount of about 0.1% to about 5% by weight, or 0.1% to about 1% by weight, or 0.1% to about 0.5% by weight, based on the weight of the heat transfer composition.

[0330] POE lubricant

[0331] In a preferred embodiment, the POE lubricant of the present invention comprises a neopentyl POE lubricant. As used herein, the term neopentyl POE lubricant refers to a polyol ester (POE) derived from the reaction between a neopentyl polyol (preferably pentaerythritol, trimethylolpropane, or neopentyl glycol, and in a preferred embodiment with higher viscosity, dipentaerythritol) and a straight-chain or branched carboxylic acid.

[0332] Commercially available POEs include neopentyl glycol dinonanoate, available under the trade names Emery 2917 (registered trademark) and Hatcol 2370 (registered trademark), and pentaerythritol derivatives, including those marketed by CPI Fluid Engineering under the trade names Emkarate RL32-3MAF and Emkarate RL68H. Emkarate RL32-3MAF and Emkarate RL68H are preferred neopentyl POE lubricants having the properties identified below:

[0333]

[0334] Other available esters include phosphate esters, diesters, and fluorinated esters.

[0335] PVE lubricant

[0336] The lubricant of the present invention may include conventional PVE lubricants. In a preferred embodiment, the PVE lubricant is a PVE according to Formula II:

[0337] Formula II

[0338] R2 and R3 are each independently C1–C10 hydrocarbons, preferably C2–C8 hydrocarbons, and R1 and R4 are each independently alkyl, alkylene glycol, or polyoxyalkylene glycol units. n and m are preferably selected according to the needs of those skilled in the art to obtain a lubricant with desired properties, and preferably n and m are selected to obtain a lubricant with a viscosity of about 30 cSt to about 70 cSt at 40°C as measured according to ASTM D445. Commercially available polyvinyl ethers include those lubricants sold from Idemitsu under the trade names FVC32D and FVC68D.

[0339] Methods, uses and systems

[0340] The heat transfer compositions disclosed herein are provided for substantially all heat transfer applications, uses, methods, and systems, and advantages and unexpected results are found in these applications, uses, methods, and systems, all of which are included within the broad scope of this invention. In a preferred embodiment, the heat transfer compositions disclosed herein (including each of heat transfer compositions 1-46) are provided for refrigeration applications, stationary air conditioning applications, mobile and transport air conditioning applications, and stationary and mobile heat pumps, and advantages and unexpected results are found in these applications. Preferred embodiments are disclosed in Table 2 below, wherein the following abbreviations are used and have the following meanings: "ComRef" refers to commercial refrigeration; "ComAC" refers to commercial air conditioning; "ResAC" refers to residential air conditioning; "Stat. Heat Pump" refers to stationary heat pump; "Mobile HeatPump" refers to heat pump used in mobile applications (such as cars, trucks, buses, etc.); "Mobile AC" refers to air conditioning used in mobile applications (such as cars, trucks, buses, etc.); "IndRef" refers to industrial refrigeration; and "TransRef" refers to transportation refrigeration. The heat transfer composition column in Table 2 uses HTC numbers as defined in Table 1 above.

[0341] Table 2

[0342]

[0343]

[0344]

[0345]

[0346]

[0347]

[0348]

[0349]

[0350]

[0351]

[0352]

[0353]

[0354]

[0355]

[0356] For the heat transfer systems, uses, and methods of the present invention that include a compressor and a lubricant for use in the compressor in the system, including each of those identified in Table 2 above, the system may be charged with refrigerant and lubricant such that the lubricant charge in the system is about 5% to 60% by weight, or about 10% to about 60% by weight, or about 20% to about 50% by weight, or about 20% to about 40% by weight, or about 20% to about 30% by weight, or about 30% to about 50% by weight, or about 30% to about 40% by weight. As used herein, the term "lubricant charge" refers to the percentage of the total weight of the lubricant contained in the system relative to the total weight of the lubricant and refrigerant contained in the system. Such systems may also contain a lubricant charge of about 5% to about 10%, or about 8%, by weight of the heat transfer composition.

[0357] The heat transfer systems, uses, and methods of the present invention, including compressors and lubricants for compressors in the system (including each of those identified in Table 2 above), may include compressors, evaporators, condensers, and expansion devices in fluid communication with each other, heat transfer compositions 1-46, and chelating materials in the system, wherein the chelating materials preferably include: i. copper or copper alloys, or ii. activated alumina, or iii. zeolite molecular sieves containing copper, silver, lead, or combinations thereof, or iv. anion exchange resins, or v. dehydrating materials, preferably dehydrating molecular sieves, or vi. combinations of two or more of the above.

[0358] The invention also includes a method for heat transfer, the type of which involves evaporating a refrigerant liquid to produce refrigerant vapor, compressing at least a portion of the refrigerant vapor in a compressor, and condensing the refrigerant vapor in multiple repeating cycles, said method comprising:

[0359] (a) Providing a heat transfer composition according to the invention, comprising each of heat transfer compositions 1-46;

[0360] (b) Optionally but preferably, a lubricant is provided to the compressor; and

[0361] (b) Exposing at least a portion of the refrigerant and / or at least a portion of the lubricant to the insulating material.

[0362] In a preferred embodiment, the residential air conditioning system and method (including those identified in Table 2 above) have a refrigerant evaporation temperature in the range of about 0°C to about 10°C, and a condensation temperature in the range of about 40°C to about 70°C.

[0363] In a preferred embodiment, the residential air conditioning system and method used in heating mode (including those identified in Table 2 above) has a refrigerant evaporation temperature in the range of about -20°C to about 3°C, and a condensation temperature in the range of about 35°C to about 50°C.

[0364] In a preferred embodiment, the commercial air conditioning system and method (including those identified in Table 2 above) has a refrigerant evaporation temperature in the range of about 0°C to about 10°C, and a condensation temperature in the range of about 40°C to about 70°C.

[0365] In a preferred embodiment, the hydraulic circulation system and method (including those identified in Table 2 above) have a refrigerant evaporation temperature in the range of about -20°C to about 3°C, and a condensation temperature in the range of about 50°C to about 90°C.

[0366] In a preferred embodiment, the intermediate temperature system and method (including those identified in Table 2 above) has a refrigerant evaporation temperature in the range of about -12°C to about 0°C, and a condensation temperature in the range of about 40°C to about 70°C.

[0367] In a preferred embodiment, the cryogenic system and method (including those identified in Table 2 above) have a refrigerant evaporation temperature in the range of about -40°C to about -12°C, and a condensation temperature in the range of about 40°C to about 70°C.

[0368] In a preferred embodiment, the rooftop air conditioning system and method (including those identified in Table 2 above) has a refrigerant evaporation temperature in the range of about 0°C to about 10°C, and a condensation temperature in the range of about 40°C to about 70°C.

[0369] In a preferred embodiment, the VRF system and method (including those identified in Table 2 above) have a refrigerant evaporation temperature in the range of about 0°C to about 10°C, and a condensation temperature in the range of about 40°C to about 70°C.

[0370] For the purposes of this invention, examples of commonly used compressors, including those for each of the uses, systems, and methods identified in Table 2, include reciprocating, rotary (including rolling piston and rotary vane), scroll, screw, and centrifugal compressors. Therefore, this invention provides for use in heat transfer systems comprising reciprocating, rotary (including rolling piston and rotary vane), scroll, screw, or centrifugal compressors.

[0371] For the purposes of this invention, examples of commonly used expansion devices, including for each of the uses, systems, and methods identified in Table 2, include capillary tubes, fixed orifices, thermal expansion valves, and electronic expansion valves. Therefore, this invention provides each or any of the heat transfer compositions described herein, including heat transfer compositions 1-46, for use in heat transfer systems comprising capillary tubes, fixed orifices, thermal expansion valves, or electronic expansion valves.

[0372] For the purposes of this invention, including for each of the uses, systems, and methods identified in Table 2, the evaporator and condenser may each be in the form of a heat exchanger, preferably selected from finned-tube heat exchangers, microchannel heat exchangers, shell-and-tube heat exchangers, plate heat exchangers, and coaxial heat exchangers. Therefore, this invention (including each of the uses, systems, and methods identified in Table 2) provides each or any of the heat transfer compositions described herein for use in heat transfer systems in which the evaporator and condenser together form a finned-tube heat exchanger, a microchannel heat exchanger, a shell-and-tube heat exchanger, a plate heat exchanger, or a coaxial heat exchanger.

[0373] The systems, uses, and methods of the present invention (including each of the uses, systems, and methods identified in Table 2) therefore preferably include an insulating material in contact with at least a portion of the refrigerant and / or at least a portion of the lubricant, wherein when in contact, the temperature of the insulating material and / or the temperature of the refrigerant and / or the temperature of the lubricant is preferably at a temperature of at least about 10°C, wherein the insulating material preferably comprises a combination of the following: anion exchange resin, activated alumina, silver-containing zeolite molecular sieve, and dehydrating material, preferably a dehydrating molecular sieve.

[0374] As used in this application, the term "in contact with at least a portion" is intended in its broad sense to include each of the insulating materials and any combination of insulating materials that are in contact with the same or separate portions of the refrigerant and / or lubricant in the system, and is intended to include, but not necessarily limited to, embodiments in which each type or particular insulating material: (i) is physically located together with each other type or particular material (if present); (ii) is physically located separately from other types or particular materials (if present); and (iii) is a combination in which two or more materials are physically together and at least one insulating material is physically separated from at least one other insulating material.

[0375] The heat transfer composition of the present invention can be used in heating and cooling applications.

[0376] In one particular feature of the invention, the heat transfer composition can be used in a cooling method comprising condensing the heat transfer composition and subsequently evaporating the composition near the article or object to be cooled.

[0377] Therefore, the present invention relates to a method for cooling in a heat transfer system comprising an evaporator, a condenser, and a compressor, the method comprising i) condensing a heat transfer composition as described herein; and

[0378] ii) Evaporating the composition near the object or article to be cooled;

[0379] The evaporator temperature of the heat transfer system is in the range of approximately -40°C to approximately +10°C.

[0380] Alternatively or additionally, the heat transfer composition may be used in a heating method comprising condensing the heat transfer composition near the article or object to be heated, and subsequently evaporating the composition.

[0381] Therefore, the present invention relates to a method for heating in a heat transfer system including an evaporator, a condenser, and a compressor, the method comprising:

[0382] i) Condensation of the heat transfer composition as described herein near the object or article to be heated, and

[0383] ii) An evaporation composition; wherein the evaporator temperature of the heat transfer system is in the range of about -30°C to about 5°C.

[0384] The heat transfer compositions of the present invention are provided for air conditioning applications, including transport and stationary air conditioning applications. Therefore, any heat transfer composition described herein can be used in any of the following:

[0385] - Air conditioning applications, including portable air conditioners, especially in train and bus air conditioning systems.

[0386] - Portable heat pumps, especially heat pumps for electric vehicles;

[0387] - Coolers, especially volumetric coolers, and more particularly air-cooled or water-cooled direct expansion coolers, which are modular or conventionally packaged separately.

[0388] - Residential air conditioning systems, especially ducted or ductless split-type air conditioning systems.

[0389] - Residential heat pumps

[0390] - Residential air-water heat pump / hydraulic circulation system

[0391] -Industrial air conditioning systems

[0392] - Commercial air conditioning systems, especially packaged roof units and variable refrigerant flow (VRF) systems, and

[0393] - Commercial air-source, water-source, or ground-source heat pump systems.

[0394] The heat transfer compositions of the present invention are provided for use in refrigeration systems. The term "refrigeration system" refers to any system or device that uses a refrigerant to provide cooling, or any part or component of such a system or device. Therefore, any heat transfer composition described herein can be used in any of the following:

[0395] - Low-temperature refrigeration system,

[0396] -Medium-temperature refrigeration system

[0397] -Commercial refrigerators

[0398] -Commercial freezers

[0399] - Ice maker

[0400] - Vending machines

[0401] -Transportation refrigeration system,

[0402] -Household freezer

[0403] -Household refrigerator

[0404] -Industrial freezers

[0405] -Industrial refrigerators and

[0406] - Cooler.

[0407] Each of the heat transfer compositions described herein (including heat transfer compositions 1-46) is particularly provided for residential air conditioning systems (evaporator temperatures in the range of about 0°C to about 10°C, particularly for cooling to about 7°C and / or in the range of about -20°C to about 3°C, particularly for heating to about 0.5°C). Alternatively or additionally, each of the heat transfer compositions described herein (including each of heat transfer compositions 1-101) is particularly provided for residential air conditioning systems having reciprocating, rotary (rolling piston or rotary vane) or scroll compressors.

[0408] Each of the heat transfer compositions (including heat transfer compositions 1-46) is particularly provided for air-cooled coolers (evaporator temperatures in the range of about 0°C to about 10°C, particularly about 4.5°C), particularly air-cooled coolers with positive displacement compressors, and even more particularly air-cooled coolers with reciprocating scroll compressors.

[0409] Each of the heat transfer compositions described herein (including heat transfer compositions 1-46) is specifically provided for residential air-water heat pump hydraulic circulation systems (evaporator temperature in the range of about -20°C to about 3°C, particularly about 0.5°C, or evaporator temperature in the range of about -30°C to about 5°C, particularly about 0.5°C).

[0410] Each of the heat transfer compositions described herein (including heat transfer compositions 1-46) is specifically provided for use in medium-temperature refrigeration systems (evaporator temperatures in the range of about -12°C to about 0°C, particularly about -8°C).

[0411] Each of the heat transfer compositions described herein (including heat transfer compositions 1-46) is specifically provided for use in cryogenic refrigeration systems (evaporator temperatures in the range of about -40°C to about -12°C, particularly about -40°C to about -23°C or preferably about -32°C).

[0412] The heat transfer compositions of the present invention (including heat transfer compositions 1-46) are provided for use in residential air conditioning systems, wherein the residential air conditioning systems are used, for example, to supply cool air to buildings in summer (the temperature of said air is, for example, from about 10°C to about 17°C, particularly about 12°C).

[0413] Therefore, the heat transfer compositions of the present invention (including heat transfer compositions 1-46) are provided for use in split-type residential air conditioning systems, wherein the residential air conditioning systems are used to supply cold air (the temperature of said air is, for example, from about 10°C to about 17°C, particularly about 12°C).

[0414] Therefore, the heat transfer compositions of the present invention (including heat transfer compositions 1-46) are provided for use in ducted split-type residential air conditioning systems, wherein the residential air conditioning system is used to supply cold air (the temperature of said air is, for example, from about 10°C to about 17°C, particularly about 12°C).

[0415] Therefore, the heat transfer compositions of the present invention (including heat transfer compositions 1-46) are provided for use in window-type residential air conditioning systems, wherein the residential air conditioning systems are used to supply cool air (the temperature of said air is, for example, from about 10°C to about 17°C, particularly about 12°C).

[0416] Therefore, the heat transfer compositions of the present invention (including heat transfer compositions 1-46) are provided for use in portable residential air conditioning systems, wherein the residential air conditioning systems are used to supply cold air (the temperature of said air is, for example, from about 10°C to about 17°C, particularly about 12°C).

[0417] The residential air conditioning system described herein (including the immediately preceding paragraphs) preferably includes an air-refrigerant evaporator (indoor coil), a compressor, an air-refrigerant condenser (outdoor coil), and an expansion valve. The evaporator and condenser can be finned tube-plate, finned tube, or microchannel heat exchangers. The compressor can be a reciprocating or rotary (rolling piston or rotary vane) or scroll compressor. The expansion valve can be a capillary, thermodynamic, or electronic expansion valve. The refrigerant evaporation temperature is preferably in the range of 0°C to 10°C. The condensation temperature is preferably in the range of 40°C to 70°C.

[0418] The heat transfer compositions of the present invention (including heat transfer compositions 1-46) are provided for use in residential heat pump systems, wherein the residential heat pump system is used to supply hot air to a building in winter (the temperature of said air is, for example, from about 18°C ​​to about 24°C, particularly about 21°C). It can be the same system as a residential air conditioning system, except that in heat pump mode, the refrigerant flow is reversed, and the indoor coil becomes the condenser, and the outdoor coil becomes the evaporator. Typical system types are split-type and small split-type heat pump systems. The evaporator and condenser are typically finned, finned, or microchannel heat exchangers. The compressor is typically a reciprocating or rotary (rolling piston or rotary vane) or scroll compressor. The expansion valve is typically a thermal expansion valve or an electronic expansion valve. The refrigerant evaporation temperature is preferably in the range of from about -20°C to about 3°C ​​or from about -30°C to about 5°C. The condensation temperature is preferably in the range of from about 35°C to about 50°C.

[0419] The heat transfer compositions of the present invention (including heat transfer compositions 1-46) are provided for use in commercial air conditioning systems, wherein the commercial air conditioning system may be a cooler for supplying cooling water (at a temperature of, for example, about 7°C) to large buildings such as offices and hospitals. Depending on the application, the cooler system may operate year-round. The cooler system may be air-cooled or water-cooled. Air-cooled coolers typically have a plate, coaxial, or shell-and-tube evaporator for supplying cooling water, a reciprocating or scroll compressor, a circular tube-plate finned, finned tube, or microchannel condenser for exchanging heat with ambient air, and a thermal expansion valve or electronic expansion valve. Water-cooled systems typically have a shell-and-tube evaporator for supplying chilled water, a reciprocating, scroll, screw, or centrifugal compressor, a shell-and-tube condenser for exchanging heat with water from cooling towers or lakes, oceans, and other natural resources, and a thermal expansion valve or electronic expansion valve. The refrigerant evaporation temperature is preferably in the range of about 0°C to about 10°C. The condensation temperature is preferably in the range of about 40°C to about 70°C.

[0420] The heat transfer compositions of the present invention (including heat transfer compositions 1-46) are provided for use in residential air-to-water heat pump hydraulic circulation systems, wherein the residential air-to-water heat pump hydraulic circulation systems are used to supply hot water (the temperature of said water is, for example, about 50°C or about 55°C) to a building in winter for floor heating or similar applications. The hydraulic circulation system typically includes a circular tube-plate finned, finned tube, or microchannel evaporator for exchanging heat with ambient air, a reciprocating, scroll, or rotary compressor, a plate, shell-and-tube, or tubular condenser for heating water, and a thermal expansion valve or electronic expansion valve. The refrigerant evaporation temperature is preferably in the range of about -20°C to about 3°C ​​or -30°C to about 5°C. The condensation temperature is preferably in the range of about 50°C to about 90°C.

[0421] The heat transfer compositions of the present invention (including heat transfer compositions 1-46) are provided for use in intermediate temperature refrigeration systems, wherein the refrigerant has an evaporation temperature preferably in the range of about -12°C to about 0°C, and in such systems, the refrigerant has a condensation temperature preferably in the range of about 40°C to about 70°C or about 20°C to about 70°C.

[0422] Therefore, the present invention provides a medium-temperature refrigeration system for cooling food or beverages, such as in a refrigerator or bottle cooler, wherein the refrigerant has an evaporation temperature preferably in the range of about -12°C to about 0°C, and in such systems, the refrigerant has a condensation temperature preferably in the range of about 40°C to about 70°C or about 20°C to about 70°C.

[0423] The intermediate-temperature system of the present invention (including the system described in the preceding paragraph) preferably includes an air-refrigerant evaporator for providing cooling to, for example, the food or beverage contained therein; a reciprocating, scroll, screw, or rotary compressor; an air-refrigerant condenser for exchanging heat with ambient air; and a thermal expansion valve or electronic expansion valve. The heat transfer compositions of the present invention (including heat transfer compositions 1-46) are provided for use in cryogenic refrigeration systems, wherein the refrigerant has an evaporation temperature preferably in the range of about -40°C to about -12°C, and the refrigerant has a condensation temperature preferably in the range of about 40°C to about 70°C or about 20°C to about 70°C.

[0424] Therefore, the present invention provides a cryogenic refrigeration system for providing cooling in a freezer, wherein the refrigerant has an evaporation temperature preferably in the range of about -40°C to about -12°C, and the refrigerant has a condensation temperature preferably in the range of about 40°C to about 70°C or about 20°C to about 70°C.

[0425] Therefore, the present invention also provides a low-temperature refrigeration system for providing cooling in a cream maker, wherein the refrigerant has an evaporation temperature preferably in the range of about -40°C to about -12°C, and the refrigerant has a condensation temperature preferably in the range of about 40°C to about 70°C or about 20°C to about 70°C.

[0426] The cryogenic system of the present invention (including the system described in the preceding paragraph) preferably includes an air-refrigerant evaporator for cooling food or beverages, a reciprocating, scroll or rotary compressor, an air-refrigerant condenser for exchanging heat with ambient air, and a thermal expansion valve or electronic expansion valve.

[0427] For the purposes of this invention, each heat transfer composition according to the invention (including each of heat transfer compositions 1-46) is provided for a cooler with an evaporation temperature in the range of about 0°C to about 10°C and a condensation temperature in the range of about 40°C to about 70°C. The cooler is provided for air conditioning or refrigeration, and preferably for commercial air conditioning. The cooler is preferably a volumetric cooler, more particularly an air-cooled or water-cooled direct expansion cooler, which is modular or conventionally packaged individually.

[0428] Therefore, the present invention provides the use of each of the heat transfer compositions according to the present invention (including each of heat transfer compositions 1-46) in stationary air conditioners, particularly residential air conditioners, industrial air conditioners or commercial air conditioners.

[0429] Heat transfer systems can be refrigeration systems, such as low-temperature refrigeration systems, medium-temperature refrigeration systems, commercial refrigerators, commercial freezers, ice makers, vending machines, transport refrigeration systems, household freezers, household refrigerators, industrial freezers, industrial refrigerators, and coolers.

[0430] Example

[0431] Comparative Examples 1A–1C: Heat transfer compositions comprising a refrigerant containing CF3I, a POE lubricant, and a stabilizer.

[0432] The heat transfer composition was tested according to ASHRAE Standard 97 – “Sealed glass tube method for testing the chemical stability of materials used in refrigeration systems” to simulate the long-term stability of the heat transfer composition through accelerated aging. Three different sample combinations were tested: Cu / Al / Fr; Cu / Al / Fe / Brass; and Cu / Al / Fe / Zn. The refrigerant tested consisted of 49% by weight R-32, 11.5% by weight R-125, and 39.5% by weight CF3I (R-466A). The POE lubricant was 160SZ POE sold by Danfos, with a viscosity of approximately 30-34 cSt at 40°C and a moisture content of 150 ppm or less. The stabilizer package contained NA-LUBE KR-008 (AN5), tricresyl phosphate (“TCP”), and 2-ethylhexyl glycidyl ether (ADM4) in the amounts shown in Table ExC1 below.

[0433] Table EXC1

[0434]

[0435] After testing, the transparency of the fluid in each test tube was observed, the total acid number (TAN) was determined, and the amounts of various substances in the fluid were identified. The TAN value is considered to reflect the stability of the lubricant in the fluid under the operating conditions of the heat transfer composition. The presence of trifluoromethane (R-23) is considered to reflect refrigerant stability, as this compound is believed to be a product of the decomposition of CF3I.

[0436] The stability of the fluid was tested by placing sealed tubes containing the specified samples in an oven maintained at approximately 150°C for 14 days. The results after the 14-day period are shown in Table ExC2 below:

[0437] Table EXC2

[0438]

[0439] The results of the applicant's tests in the presence of copper, aluminum, and iron (ExC1A) demonstrate that the heat transfer composition with the indicated stabilizer combination produces acceptable results in the presence of these three metals (but in the absence of zinc). This is illustrated, for example, by the fluoride content of ExC1A being less than 10 ppm, the iodide content less than 1.5, and the TAN value less than 0.1. However, the applicant learned from their tests that stability deteriorates significantly in the presence of zinc (ExC1C) and zinc-containing metals such as brass (ExC1B). This is illustrated, for example, by the sharp increase in fluoride concentration (10X–20X) and iodide concentration (100X–500X). Similarly, the presence of zinc causes the TAN value to increase by an order of magnitude, and R-23 to increase by 4 to 7 times. Furthermore, visual observation confirms that the fluid cannot remain stable in the presence of zinc. At the end of the tests, this performance degradation was reflected by measuring the zinc concentration in the tube. Specifically, the increase in zinc concentration was approximately 85 to 380 times.

[0440] Example 1: A heat transfer composition comprising a refrigerant containing CF3I, a POE lubricant, a stabilizer, and a protectant.

[0441] The test of Comparative Example 1 was repeated, except that the protective agent of the present invention was added to the fluid in amounts of 0.05% by weight and 0.1% by weight prior to the test, as reported in Table Ex1A.

[0442] Table Ex1A

[0443]

[0444] Then, as described in Comparative Example 1, the stability of the fluid was tested in the presence of zinc (in two separate test tubes, the concentration of the protective agent was 0.05% by weight), i.e., by placing sealed tubes containing copper, aluminum, iron, and zinc in an oven maintained at approximately 150°C for 14 days. The results after the 14-day period are shown in Table Ex1B below, and are illustrated in the following graphs together with the results of the Comparative Example (using average values) for comparison.

[0445] Table Ex1B

[0446]

[0447]

[0448] As the test results above show, from a stability point of view, the addition of the protective agent of the present invention unexpectedly leads to a significant improvement in fluid performance, for example, represented by a zinc level of only about 0.0002% of the zinc level without the protective agent of the present invention and an R-23 level of only 0.004% of the R-23 without the protective agent.

[0449] Examples 2A and 2B: Heat transfer combinations comprising a refrigerant containing CF3I, a POE lubricant, an AN stabilizer, and a protective agent. thing

[0450] The heat transfer composition was tested according to ASHRAE Standard 97 – “Sealed glass tube method for testing the chemical stability of materials used in refrigeration systems” to simulate the long-term stability of the heat transfer composition through accelerated aging. Four samples were tested: Cu / Al / Fe / Zn. The refrigerant tested consisted of 49% by weight of R-32, 11.5% by weight of R-125, and 39.5% by weight of CF3I (R-466A). The POE lubricant was the same 160SZ POE as described in Comparative Example 1, and also included a stabilizer composed of KR-008 and ADM5 (EHGE), and the protective agent PA-5 of the present invention, in amounts shown in Table Ex2A below.

[0451] Table EX2

[0452]

[0453] After testing, the transparency of the fluid in each test tube was observed, the total acid value (TAN) was determined, and the amounts of various substances in the fluid were identified. The stability of the fluid was tested by placing sealed tubes with specified samples in an oven maintained at approximately 150°C for 14 days. The results after the 14-day period are shown in Table Ex2B below. Two test tubes with a PA5 concentration of 0.1 wt5 were used, and the average of these results is reported below as Ex2BAvg. For ease of comparison, results from Comparative Example C1C are also provided, and the results are illustrated graphically in the figures following the table.

[0454] Table EX2B

[0455]

[0456]

[0457] The results of tests conducted by the applicant in the presence of copper, aluminum, iron, and zinc show that, compared to Comparative Example 1C, the heat transfer compositions containing 0.05% and 0.1% PA5 unexpectedly exhibited reduced levels of Zn and R-23, respectively. Even more surprisingly, with regard to R-23, optimal performance was achieved with a protective agent concentration greater than 0.5% but less than 0.1% by weight.

[0458] Examples 3A and 3B: Heat transfer combinations comprising a refrigerant containing CF3I, a POE lubricant, an ADM stabilizer, and a protective agent. thing

[0459] The heat transfer composition was tested according to ASHRAE Standard 97 – “Sealed glass tube method for testing the chemical stability of materials used in refrigeration systems” to simulate the long-term stability of the heat transfer composition through accelerated aging. Four samples were tested: Cu / Al / Fe / Zn. The refrigerant tested consisted of 49% by weight of R-32, 11.5% by weight of R-125, and 39.5% by weight of CF3I (R-466A). The POE lubricant was the same 160SZ POE as described in Comparative Example 1. Stabilizers consisting of AN (KR-008), TCP, and ADM5 (EHGE) were also included, as well as the protective agent PA5 of the present invention, in amounts shown in Table Ex3A below.

[0460] Table EX3A

[0461]

[0462] After testing, the transparency of the fluid in each test tube was observed, the total acid number (TAN) was determined, and the amounts of various substances in the fluid were identified. The stability of the fluid was tested by placing sealed tubes with specified samples in an oven maintained at approximately 150°C for 14 days. The results after the 14-day period are shown in Table Ex3B below. Two test tubes were used for EHGE concentrations of 0.5 wt% and 0.75 wt%, and the average results are reported below as Ex3AAvg and Ex3BAvg. Results for comparative example C1C are also provided for comparison.

[0463] Table EX3B

[0464]

[0465]

[0466] The results of tests conducted by the applicant in the presence of copper, aluminum, iron, and zinc show that, compared to Comparative Example C1 (0% PA5), the heat transfer compositions containing 0.025% and 0.0.5% PA5, as well as different amounts of EHGE, unexpectedly exhibited reduced levels of Zn and R-23. Even more surprisingly, with regard to R-23 and copper, optimal performance was achieved with a protective agent concentration greater than 0% by weight but less than 0.05% by weight.

[0467] Comparative Examples 2A–2C: Heat transfer compositions comprising R-1234ze(E) and POE lubricant

[0468] The heat transfer composition was tested according to ASHRAE Standard 97 – “Sealed glass tube method for testing the chemical stability of materials used in refrigeration systems” to simulate the long-term stability of the heat transfer composition by accelerated aging. The tested heat transfer composition consisted of 50 wt% refrigerant (composed of R-1234ze(E)) and 50 wt% POE lubricant (RL32-3MAF sold by Emkrate, with a viscosity of about 31 cSt at 40 °C). Three different sample combinations were used for testing: Cu / Al / Fe; brass; and Zn. Two (2) separate test tubes were used with Cu / Al / Fe and brass samples, and the results reported below are the average of the results. Four (4) separate test tubes were used with Zn samples, and the results reported below are the average of all the results.

[0469] After testing, the transparency of the fluid in each test tube was observed, the total acid number (TAN) was measured, and the amounts of various substances in the fluid were determined. The TAN value is considered to reflect the stability of the lubricant in the fluid under the operating conditions of the heat transfer composition.

[0470] The stability of the fluid was tested by placing sealed tubes containing the specified samples in an oven maintained at approximately 150°C for 14 days. The results after the 14-day period are shown in Table ExC2 below:

[0471] Table EXC2

[0472]

[0473] The results of the applicant's tests in the presence of copper, aluminum, and iron (ExC2A) demonstrate that the heat transfer composition consisting of R-1234ze(E) and POE lubricant produces acceptable results even in the absence of stabilizers, in the presence of these three metals (but in the absence of zinc). This is illustrated, for example, by the fluoride content of ExC1A being less than 10 ppm, the iodide content less than 1.5, the TAN value less than 0.5, and the Zn content less than 0.3 ppm. However, the applicant learned from their tests that stability significantly deteriorates in the presence of zinc (ExC2C) and zinc-containing metals such as brass (ExC2B). This is illustrated, for example, by the dramatic increase in Zn concentration (more than 150 times greater than ExC2A) and TAN value (more than 3 times greater than ExC2A).

[0474] Examples 4A–4E: Heat transfer compositions comprising a refrigerant containing CF3I, a POE lubricant, a stabilizer, and a protectant.

[0475] The test of Comparative Example 2 was repeated, except that the protective agent of the present invention (i.e., protective agent 5) was added to each fluid in amounts of 0.01 wt%, 0.025 wt%, and 0.05 wt% before the test.

[0476] The stability of each fluid was then tested in the presence and under the same conditions as the sample determined in Comparative Example 2. The results after a 14-day period are shown in Table Ex4 below, and the results of the Zn sample test are illustrated together with the results of the Zn sample test in Comparative Example 2 (using average values) in the following figures for comparison.

[0477] TableEx4

[0478]

[0479]

[0480] As the test results above show, from a stability perspective, the addition of the protective agent of the present invention unexpectedly led to improved fluid performance in the presence of zinc. This is, for example, expressed by using 0.01 wt% of the protective agent of the present invention to produce zinc levels that are about 40% lower than those without the protective agent and TAN values ​​that are about 30% lower than those without the protective agent. Even more unexpectedly, the performance of using a protective agent in amounts greater than 0.01 wt% was able to reduce Zn levels by two orders of magnitude, i.e., to Zn levels less than 10 ppm, and TAN values ​​less than 0.1 mg KOH / mg. This result is both highly desirable and unexpected.

[0481] Example 5a: Medium-temperature commercial heat exchangers (HX) with and without suction line (Sl) / liquid line (LL) The heat transfer composition of the present invention used in refrigeration

[0482] A commercial refrigeration system having a zinc-containing surface in contact with the heat transfer composition is operated using each of the heat transfer compositions 1-46 based on the following average operating conditions:

[0483] • Condensation temperature = 45.0℃

[0484] • Condensation temperature - ambient temperature = 10.0℃

[0485] • Condenser subcooling = 0.0℃ (system with receiver)

[0486] • Evaporation temperature = -8.0℃

[0487] • Evaporator superheat = 5.5℃

[0488] • Compressor isentropic efficiency = 65.0%

[0489] • Volumetric efficiency = 100%

[0490] • Temperature rise in the suction line = 10.0℃

[0491] • Suction line / liquid line heat exchanger efficiency: 0%, 35%, 55%, 75%

[0492] The system operates over extended time periods using each of the aforementioned heat transfer compositions and advantageously achieves a high level of stability and corrosion resistance.

[0493] Example 5b: Low-temperature commercial applications with and without suction line (Sl) / liquid line (LL) heat exchangers (HX) The heat transfer composition of the present invention used in refrigeration

[0494] A commercial refrigeration system having a zinc-containing surface in contact with the heat transfer composition is operated using each of the heat transfer compositions 1-46 based on the following average operating conditions:

[0495] • Condensation temperature = 45.0℃

[0496] • Condensation temperature - ambient temperature = 10.0℃

[0497] • Condenser subcooling = 0.0℃ (system with receiver)

[0498] • Evaporation temperature = -35.0℃

[0499] • Evaporator superheat = 5.5℃

[0500] • Compressor isentropic efficiency = 65.0%

[0501] • Volumetric efficiency = 100%

[0502] • Temperature rise in the suction line = 10.0℃

[0503] • Suction line / liquid line heat exchanger efficiency: 0%, 35%, 55%, 75%

[0504] The system operates over extended time periods using each of the aforementioned heat transfer compositions and advantageously achieves a high level of stability and corrosion resistance.

[0505] Example 6: The heat transfer composition of the present invention for use in commercial air conditioning

[0506] A commercial air conditioning system having a zinc-containing surface in contact with the heat transfer composition is operated using each of heat transfer compositions 1-46 under the following average operating conditions:

[0507] • Condensation temperature = 45.0℃

[0508] • Condensation temperature - ambient temperature = 10.0℃

[0509] • Condenser subcooling = 5.0℃ (for systems without receivers)

[0510] • Evaporation temperature = 7.0℃

[0511] • Evaporator superheat = 5.5℃

[0512] • Compressor isentropic efficiency = 72.0%

[0513] • Volumetric efficiency = 100%

[0514] • Temperature rise in the suction line = 5.0℃

[0515] The system operates over extended time periods using each of the aforementioned heat transfer compositions and advantageously achieves a high level of stability and corrosion resistance.

[0516] Example 7: The heat transfer composition of the present invention for use in residential air conditioning

[0517] A residential air conditioning system having a zinc-containing surface in contact with the heat transfer composition is operated with each of heat transfer compositions 1-46 under the following average operating conditions:

[0518] • Condensation temperature = 45.0℃

[0519] • Condensation temperature - ambient temperature = 10.0℃

[0520] • Condenser subcooling = 5.0℃ (for systems without receivers)

[0521] • Evaporation temperature = 7.0℃

[0522] • Evaporator superheat = 5.5℃

[0523] • Compressor isentropic efficiency = 72.0%

[0524] • Volumetric efficiency = 100%

[0525] • Temperature rise in the suction line = 5.0℃

[0526] The system operates over extended time periods using each of the aforementioned heat transfer compositions and advantageously achieves a high level of stability and corrosion resistance.

[0527] Example 8: The heat transfer composition of the present invention for use in a cooler

[0528] Based on the following average operating conditions, a cooler system having a zinc-containing surface in contact with the heat transfer composition is operated using each of heat transfer compositions 1-46:

[0529] • Condensation temperature = 45.0℃

[0530] • Condensation temperature - ambient temperature = 10.0℃

[0531] • Condenser subcooling = 5.0℃ (for systems without receivers)

[0532] • Evaporation temperature = 4.0℃

[0533] • Evaporator superheat = 5.5℃

[0534] • Compressor isentropic efficiency = 70.0%

[0535] • Volumetric efficiency = 100%

[0536] • Temperature rise in the suction line = 5.0℃

[0537] The system operates over extended time periods using each of the aforementioned heat transfer compositions and advantageously achieves a high level of stability and corrosion resistance.

[0538] Example 9: The heat transfer composition of the present invention for use in a stationary heat pump

[0539] A stationary heat pump having a zinc-containing surface in contact with the heat transfer composition is operated using each of heat transfer compositions 1-46 based on the following average operating conditions:

[0540] • Condensation temperature = 45.0℃

[0541] • Condensation temperature - ambient temperature = 10.0℃

[0542] • Condenser subcooling = 5.0℃ (for systems without receivers)

[0543] • Evaporation temperature = 0℃

[0544] • Evaporator superheat = 5.5℃

[0545] • Compressor isentropic efficiency = 70.0%

[0546] • Volumetric efficiency = 100%

[0547] • Temperature rise in the suction line = 5.0℃

[0548] The system operates over extended time periods using each of the aforementioned heat transfer compositions and advantageously achieves a high level of stability and corrosion resistance.

[0549] Example 10: The heat transfer composition of the present invention for use in a mobile heat pump

[0550] A mobile heat pump located in an electric vehicle and having a zinc-containing surface in contact with the heat transfer composition is operated using each of heat transfer compositions 1-46 based on the following average operating conditions:

[0551] • Condensation temperature = 45.0℃

[0552] • Condensation temperature - ambient temperature = 10.0℃

[0553] • Condenser subcooling = 5.0℃ (for systems without receivers)

[0554] • Evaporation temperature = 0.0℃

[0555] • Evaporator superheat = 5.5℃

[0556] • Compressor isentropic efficiency = 65%

[0557] • Volumetric efficiency = 100%

[0558] • Temperature rise in the suction line = 5.0℃

[0559] The system operates over extended time periods using each of the aforementioned heat transfer compositions and advantageously achieves a high level of stability and corrosion resistance.

[0560] Example 11: The heat transfer composition of the present invention for use in a portable air conditioner

[0561] Based on the following average operating conditions, a mobile air conditioning system having a zinc-containing surface in contact with the heat transfer composition is operated using each of heat transfer compositions 1-46:

[0562] • Condensation temperature = 45.0℃

[0563] • Condensation temperature - ambient temperature = 10.0℃

[0564] • Condenser subcooling = 5.0℃ (system with receiver)

[0565] • Evaporation temperature = 4.0℃

[0566] • Evaporator superheat = 5.5℃

[0567] • Compressor isentropic efficiency = 65.0%

[0568] • Volumetric efficiency = 100%

[0569] • Temperature rise in the suction line = 0.0℃

[0570] The system operates over extended time periods using each of the aforementioned heat transfer compositions and advantageously achieves a high level of stability and corrosion resistance.

[0571] Example 12a: Medium-temperature operation with and without suction line (Sl) / liquid line (LL) heat exchangers (HX) The heat transfer composition of the present invention used in industrial refrigeration systems

[0572] An industrial refrigeration system having a zinc-containing surface in contact with the heat transfer composition is operated using each of heat transfer compositions 1-46 based on the following average operating conditions:

[0573] • Condensation temperature = 45.0℃

[0574] • Condensation temperature - ambient temperature = 10.0℃

[0575] • Condenser subcooling = 0.0℃ (system with receiver)

[0576] • Evaporation temperature = -8.0℃

[0577] • Evaporator superheat = 5.5℃

[0578] • Compressor isentropic efficiency = 65%

[0579] • Volumetric efficiency = 100%

[0580] • Temperature rise in the suction line = 10℃

[0581] • Suction line / liquid line heat exchanger efficiency: 0%, 35%, 55%, 75%

[0582] The system operates over extended time periods using each of the aforementioned heat transfer compositions and advantageously achieves a high level of stability and corrosion resistance.

[0583] Example 12b: Cryogenic processes with and without suction line (Sl) / liquid line (LL) heat exchangers (HX) The heat transfer composition of the present invention used in industrial refrigeration systems

[0584] An industrial refrigeration system having a zinc-containing surface in contact with the heat transfer composition is operated using each of heat transfer compositions 1-46 based on the following average operating conditions:

[0585] • Condensation temperature = 45.0℃

[0586] • Condensation temperature - ambient temperature = 10.0℃

[0587] • Condenser subcooling = 0.0℃ (system with receiver)

[0588] • Evaporation temperature = -35.0℃

[0589] • Evaporator superheat = 5.5℃

[0590] • Compressor isentropic efficiency = 65.0%

[0591] • Volumetric efficiency = 100%

[0592] • Temperature rise in the suction line = 10℃

[0593] • Suction line / liquid line heat exchanger efficiency: 0%, 35%, 55%, 75%

[0594] The system operates over extended time periods using each of the aforementioned heat transfer compositions and advantageously achieves a high level of stability and corrosion resistance.

[0595] Example 13a: Medium-speed operation with and without suction line (Sl) / liquid line (LL) heat exchanger (HX) The heat transfer composition of the present invention used in refrigeration systems

[0596] Based on the following average operating conditions, a transport refrigeration system having a zinc-containing surface in contact with the heat transfer composition is operated using each of heat transfer compositions 1-46:

[0597] • Condensation temperature = 45.0℃

[0598] • Condensation temperature - ambient temperature = 10.0℃

[0599] • Condenser subcooling = 0.0℃ (system with receiver)

[0600] • Evaporation temperature = -8.0℃

[0601] • Evaporator superheat = 5.5℃

[0602] • Compressor isentropic efficiency = 65%

[0603] • Volumetric efficiency = 100%

[0604] • Temperature rise in the suction line = 15℃

[0605] • Suction line / liquid line heat exchanger efficiency: 0%, 35%, 55%, 75%

[0606] The system operates over extended time periods using each of the aforementioned heat transfer compositions and advantageously achieves a high level of stability and corrosion resistance.

[0607] Example 13b: Low transport with and without suction line (Sl) / liquid line (LL) heat exchanger (HX) The heat transfer composition of the present invention used in refrigeration systems

[0608] Based on the following average operating conditions, a transport refrigeration system having a zinc-containing surface in contact with the heat transfer composition is operated using each of heat transfer compositions 1-46:

[0609] • Condensation temperature = 45.0℃

[0610] • Condensation temperature - ambient temperature = 10.0℃

[0611] • Condenser subcooling = 0.0℃ (system with receiver)

[0612] • Evaporation temperature = -35.0℃

[0613] • Evaporator superheat = 5.5℃

[0614] • Compressor isentropic efficiency = 65%

[0615] • Volumetric efficiency = 100%

[0616] • Temperature rise in the suction line = 15℃

[0617] • Suction line / liquid line heat exchanger efficiency: 0%, 35%, 55%, 75%

[0618] The system operates over extended time periods using each of the aforementioned heat transfer compositions and advantageously achieves a high level of stability and corrosion resistance.

Claims

1. An improved heat transfer system, of the type having at least a circulating working fluid and one or more equipment components exposed to said working fluid during operation, said improvement comprising: (c) At least one of the one or more equipment components has a surface exposed to the circulating working fluid and containing zinc; (d) The working fluid comprises a refrigerant and at least one protective agent, said at least one protective agent comprising a compound according to Formula I: Equation I Where R and R 1 Each is independently selected from the group consisting of hydrogen, alkyl, hydroxyalkyl, and alkylthio groups, provided that R and R are... 1 At least one of them is an alkylthio group.

2. The improved system according to claim 1, wherein each of R and R1 is independently C8 alkylthio.

3. The improved system according to claim 1, wherein the compound of formula 1 comprises 2,5-bis(n-octyldithio)-1,3,4-thiadiazole.

4. The improved system according to claim 1, wherein the protective agent comprises the 2,5-bis(n-octyldithio)-1,3,4-thiadiazole and dioctyldisulfide.

5. A method for providing heat transfer, the method comprising: (c) Providing a heat transfer system comprising one or more components, said one or more components having at least one surface formed of a zinc-containing metal; (d) A working fluid is provided in the system, wherein: (i) the working fluid is in contact with the at least one surface; and (ii) the working fluid comprises a refrigerant and a protective agent, the protective agent comprising a compound according to Formula I: Equation I Where R and R 1 Each is independently selected from the group consisting of hydrogen, alkyl, hydroxyalkyl, and alkylthio groups, provided that R and R are... 1 At least one of them is an alkylthio group.

6. The method of claim 5, wherein each of R and R1 is independently C8 alkylthio.

7. The method according to claim 5, wherein the compound of formula 1 comprises 2,5-bis(n-octyldithio)-1,3,4-thiadiazole.

8. The method according to claim 5, wherein the protective agent comprises the 2,5-bis(n-octyldithio)-1,3,4-thiadiazole and dioctyldisulfide.

9. A heat transfer composition comprising: (d) At least one refrigerant selected from HFC, HCFC, HFO, HCFO, fluorocarbons and combinations of two or more of these, including HC as part of a blend; (e) at least one lubricant, said at least one lubricant being selected from POE and PVE; and (f) A protective agent comprising a compound according to formula I: Equation I Where R and R 1 Each is independently selected from the group consisting of hydrogen, alkyl, hydroxyalkyl, and alkylthio groups, provided that R and R are... 1 At least one of them is an alkylthio group.

10. The composition according to claim 9, wherein the compound of formula 1 comprises 2,5-bis(n-octyldithio)-1,3,4-thiadiazole.

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