Heat transfer systems, compositions, and methods

Abstract

The present invention relates to a refrigerant, a lubricant, and formula I: [Formula 1] The present invention relates to a heat transfer system and method including a zinc-containing surface in contact with a working fluid containing a protective agent containing a compound, as shown in JPEG2026529633000102.jpg38128. In the formula, R and R 1 Each of these is independently selected from the group consisting of hydrogen, alkyl, hydroxyalkyl and alkylthio, provided that R and R 1 The condition is that at least one of them is alkylthio.

Description

Technical Field

[0001] (Cross-Reference to Related Applications) This application claims priority to U.S. Non-Provisional Application No. 18 / 801,757 filed on August 13, 2024, and also claims the benefit of priority from U.S. Provisional Application No. 63 / 533,540 filed on August 18, 2023, the entire contents of which are incorporated herein by reference.

[0002] (Field of the Invention) The present invention relates to heat transfer compositions, heat transfer methods and heat transfer systems, including but not limited to air conditioning and refrigeration applications.

Background Art

[0003] Mechanical refrigeration systems, and related heat transfer devices and methods such as heat pumps and air conditioners, are well known in the art for industrial, commercial and domestic uses. Such systems typically utilize a heat transfer cycle employing a compressor that operates with a working fluid comprising a refrigerant. In a typical cooling operation of such a system, a relatively high-pressure, high-temperature refrigerant is discharged from the compressor and sent to a condenser, where the refrigerant vapor is condensed into liquid refrigerant, which then passes through an expansion device to be converted into relatively low-temperature, low-pressure liquid refrigerant. This relatively low-temperature, low-pressure refrigerant is then sent 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 undergoes a phase change from liquid to vapor by absorbing heat from (i.e., cooling) the object or fluid to be cooled. The low-pressure refrigerant vapor exiting the evaporator is sent to the suction side of the compressor so that the heat transfer cycle can be repeated.

[0004] A key requirement for the majority of such systems, apparatuses, and methods described above is that the working fluid includes a lubricant for the compressor in addition to the refrigerant. At least a portion of this lubricant circulates with the refrigerant as it passes through the heat transfer cycle. As a result, all the components mentioned above, as well as other equipment that is normally present (including numerous other pieces of equipment that may be present in a particular application, such as piping and valves), are exposed to the working fluid circulating at various temperatures and pressures. However, the applicant has come to recognize that exposure of certain structural materials to such circulating fluids can adversely affect the lifespan and / or robustness of the system and / or working fluid. In particular, the applicant has come to recognize 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 working fluid.

[0005] Therefore, one object of the present invention is to provide a heat transfer composition, a heat transfer method and a heat transfer system that (i) provides protection against corrosion of zinc-containing components or parts present in a heat transfer system that are exposed to a refrigerant and / or lubricant during operation, and / or (2) provides protection against degradation of the refrigerant and / or lubricant that are exposed to such zinc-containing components or parts during operation. [Overview of the project]

[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 improvements being: (a) One or more system components having a metal surface containing zinc, (b) Refrigerant and formula I:

[0007] [ka] The working fluid comprises at least one protective agent by a compound, In the formula, R and R 1 Each of these is independently selected from the group consisting of hydrogen, alkyl, hydroxyalkyl and alkylthio, provided that R and R 1 At least one of them is The condition is that it must be alkylthio.

[0008] The system described in this paragraph may, for convenience, be referred to as heat transfer system 1.

[0009] 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 improvements being: (a) One or more system components including a metal surface containing zinc, (b) A working fluid comprising a refrigerant and zinc and / or at least one protective agent for the refrigerant, wherein the protective agent is of formula I:

[0010] [ka] The working fluid includes a compound by, In the formula, at least one of R and R1 is a C1-C20 alkylthio group.

[0011] The system described in this paragraph may, for convenience, be referred to as heat transfer system 2A.

[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 improvements being: (a) One or more system components including a metal surface containing zinc, (b) A working fluid comprising a refrigerant and zinc and / or at least one protective agent for the refrigerant, wherein the protective agent is of formula I:

[0013] [[Chemical Structure]] comprising the working fluid, wherein the working fluid comprises the compound represented by wherein each of R and R1 is independently a C8 alkylthio group.

[0014] For convenience, the system according to this paragraph may be referred to as heat transfer system 2B herein.

[0015] The present invention also provides (a) providing a heat transfer system comprising one or more components having at least one surface formed from a metal comprising zinc; (b) providing a working fluid within the system, wherein (i) the working fluid is in contact with said at least one surface, and (ii) the working fluid comprises a refrigerant and a compound of formula I:

[0016] [[Chemical Structure]] and a protective agent comprising the compound represented by , the present invention also provides a method of providing heat transfer, comprising: wherein R and R 1 are each independently selected from the group consisting of hydrogen, alkyl, hydroxyalkyl and alkylthio, provided that R and R 1 at least one of is alkylthio.

[0017] For convenience, the method described in this paragraph may be referred to as heat transfer method 1 herein.

[0018] The present invention also provides (a) providing a heat transfer system comprising one or more components having at least one surface formed from a zinc-containing metal; (b) providing a working fluid within the system, wherein (i) the working fluid is in contact with said at least one surface, and (ii) the working fluid comprises a refrigerant and a compound of formula I:

[0019] [ka] The present invention also provides a protective agent containing a compound, and a method for providing heat transfer, which includes a protective agent containing a compound. In the formula, at least one of R and R1 is a C1-C20 alkylthio group.

[0020] For convenience, the method described in this paragraph may be referred to herein as heat transfer method 2A.

[0021] The present invention also, (a) To provide a heat transfer system comprising one or more components having at least one surface formed from a zinc-containing metal, (b) Providing a working fluid in the system, (i) the working fluid is in contact with at least one surface, and (ii) the working fluid is a refrigerant and Formula I:

[0022] [ka] The present invention also provides a protective agent containing a compound, and a method for providing heat transfer, which includes a protective agent containing a compound. In the formula, R and R1 are each a C8 alkylthio group.

[0023] For convenience, the method described in this paragraph may be referred to herein as heat transfer method 2B.

[0024] The present invention also, (a) To provide a heat transfer system comprising one or more components having at least one surface formed from a zinc-containing metal, (b) Providing a working fluid in the system, (i) the working fluid is in contact with the at least one surface, and (ii) the working fluid is a refrigerant and Formula II:

[0025] [ka] The present invention also provides a protective agent containing a compound, and a method for providing heat transfer, which includes a protective agent containing a compound.

[0026] For convenience, the method described in this paragraph may be referred to herein as heat transfer method 2C.

[0027] The present invention also, (a) At least one refrigerant selected from HFCs, HCFCs, HFOs, HCFOs, fluoroiodocarbons, and combinations of two or more of these, (b) at least one lubricant selected from POE and PVE, and (c) Formula I:

[0028] [ka] We also provide a heat transfer composition containing a protective agent containing a compound by In the formula, R and R 1 Each of these is independently selected from the group consisting of hydrogen, alkyl, hydroxyalkyl and alkylthio, provided that R and R 1 At least one of them is The condition is that it must be alkylthio.

[0029] For convenience, the method described in this paragraph may be referred to herein as heat transfer composition 1A.

[0030] The present invention also, (a) At least one refrigerant 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 any combination of two or more of these. (b) at least one lubricant selected from POE and PVE, and (c) Formula I:

[0031] [ka] We also provide a heat transfer composition containing a protective agent containing a compound by In the formula, R and R 1 Each of these is independently selected from the group consisting of hydrogen, alkyl, hydroxyalkyl and alkylthio, provided that R and R 1 At least one of them is The condition is that it must be alkylthio.

[0032] For convenience, the method described in this paragraph may be referred to herein as heat transfer composition 1B.

[0033] The present invention also, (a) At least one refrigerant selected from HFCs, HCFCs, HFOs, HCFOs, fluoroiodocarbons, and combinations of two or more of these, (b) at least one lubricant selected from POE and PVE, and (c) Formula I:

[0034] [ka] We also provide a heat transfer composition containing a protective agent containing a compound by In the formula, at least one of R and R1 is a C1-C20 alkylthio group.

[0035] For convenience, the composition described in this paragraph may be referred to herein as heat transfer composition 2A.

[0036] The present invention also, (a) At least one refrigerant selected from HFCs, HCFCs, HFOs, HCFOs, fluoroiodocarbons, and combinations of two or more of these, (b) at least one lubricant selected from POE and PVE, and (c) Formula I:

[0037] [ka] A protective agent containing a compound by In the formula, at least one of R and R1 is a C1-C20 alkylthio group, protective agent, and (d) The heat transfer composition also includes a stabilizer comprising one or more of alkylated naphthalene, an acid-consumable portion, and a phosphate, preferably a combination of two or more of these.

[0038] For convenience, the compositions described in this paragraph may be referred to herein as heat transfer composition 2B.

[0039] The present invention also, (a) At least one refrigerant selected from HFCs, HCFCs, HFOs, HCFOs, fluoroiodocarbons, and combinations of two or more of these, (b) at least one lubricant selected from POE and PVE, and (c) Formula I:

[0040] [ka] We also provide a heat transfer composition containing a protective agent containing a compound by In the formula, at least one of R and R1 is a C8 alkylthio group.

[0041] For convenience, the compositions described in this paragraph may be referred to herein as heat transfer composition 2C.

[0042] The present invention also, (a) At least one refrigerant selected from HFCs, HCFCs, HFOs, HCFOs, fluoroiodocarbons, and combinations of two or more of these, (b) at least one lubricant selected from POE and PVE, and (c) Formula I:

[0043] [ka] We also provide a heat transfer composition containing a protective agent containing a compound by In the formula, R and R1 are each a C5-C10 alkylthio group.

[0044] For convenience, the compositions described in this paragraph may be referred to herein as heat transfer composition 2D.

[0045] The present invention also, (a) At least one refrigerant selected from HFCs, HCFCs, HFOs, HCFOs, fluoroiodocarbons, and combinations of two or more of these, (b) at least one lubricant selected from POE and PVE, and (c) Formula I:

[0046] [ka] We also provide a heat transfer composition containing a protective agent containing a compound by In the formula, R and R1 are each a C8 alkylthio group.

[0047] For convenience, the compositions described in this paragraph may be referred to herein as heat transfer composition 2E.

[0048] The present invention also, (a) At least one refrigerant selected from HFCs, HCFCs, HFOs, HCFOs, fluoroiodocarbons, and combinations of two or more of these, (b) at least one lubricant selected from POE and PVE, and (c) Formula II:

[0049] [ka] We also provide a heat transfer composition containing a protective agent that includes a compound.

[0050] For convenience, the composition described in this paragraph may be referred to herein as heat transfer composition 2F. [Modes for carrying out the invention]

[0051] Definition: In this specification, the term “relative percentage” as used in relation to percentages based on a list of specific compounds means the percentage of a specific compound based on the total weight of the compounds listed.

[0052] In this specification, the term "approximately" as used with respect to weight percentages means that the amount of a particular component may vary by ±2% by weight. Unless otherwise specified or not clear from the context, amounts expressed as "percent" or "%" refer to weight percentages.

[0053] For the purposes of the present invention, the term "approximately" with respect to Celsius temperature (°C) means that the stated temperature may vary within a range of ±5°C. In preferred embodiments, the temperature designated as "approximately" is preferably ±2°C, more preferably ±1°C, and even more preferably ±0.5°C of the specified temperature.

[0054] The term "capacity" refers to the amount of cooling provided by a refrigerant in a refrigeration system, expressed in BTU / hour. This is experimentally determined by multiplying the enthalpy change (BTU / lb.) as the refrigerant passes through the evaporator by the mass flow rate of the refrigerant. Enthalpy can be determined from measurements of the refrigerant's pressure and temperature. The capacity of a refrigeration system relates to its ability to maintain a specific temperature in the area to be cooled. The capacity of a refrigerant indicates its cooling or heating capacity and is also an indicator of how much heat a compressor can transfer for a given volumetric flow rate of refrigerant. In other words, with a given compressor, a larger capacity refrigerant will provide more cooling or heating capacity.

[0055] The "Coefficient of Performance" (hereinafter "COP") is a universally accepted indicator of refrigerant performance, particularly useful for representing the relative thermodynamic efficiency of a refrigerant in a specific heating or cooling cycle involving evaporation or condensation of the refrigerant. In refrigeration engineering, this term represents the ratio of effective refrigeration or cooling capacity to the energy input by the compressor when compressing vapor, and therefore indicates the ability of a particular compressor to transfer a given volumetric flow rate of a heat transfer fluid, such as a refrigerant. In other words, with a particular compressor, a refrigerant with a high COP will exhibit greater cooling or heating capacity. One method for estimating the COP of a refrigerant under specific operating conditions is to estimate it from the thermodynamic properties of the refrigerant using standard refrigeration cycle analysis techniques (see, for example, RCDowning, FLUOROCARBON REFRIGERANTS HANDBOOK, Chapter 3, Prentice-Hall, 1988, which is incorporated herein by reference in its entirety).

[0056] The term "discharge temperature" refers to the temperature of the refrigerant at the compressor outlet. The advantage of a low discharge temperature is that it allows operation without activating the system's thermal protection features (which are preferably designed to protect compressor components) when using existing equipment, and it avoids the use of expensive control devices such as liquid injection to lower the discharge temperature.

[0057] The term "Global Warming Potential" (GWP) was developed to allow comparisons of the global warming impacts of various gases. Specifically, it is an index that shows how much energy is absorbed by 1 ton of a particular gas compared to 1 ton of carbon dioxide emissions over a given period. The larger the GWP, the more that particular gas warms the Earth compared to CO2 over that period. The period typically used for GWP is 100 years. GWP provides a common index that allows analysts to sum up emission estimates for various gases. See www.epa.gov.

[0058] The term "Life Cycle Climate Performance" (LCCP) is a method for evaluating the impact of air conditioning and refrigeration systems on global warming over their entire lifespan. LCCP includes direct impacts from refrigerant emissions and indirect impacts from energy consumption used in system operation, system manufacturing, and system transportation and safe disposal. Direct impacts from refrigerant emissions are calculated from the refrigerant's GWP value. Indirect emissions are calculated using measured refrigerant characteristics to determine system performance and energy consumption. LCCP is calculated using the following equations 1 and 2: Equation 1: Direct emissions = Refrigerant charge (kg) × (Annual loss rate × Lifespan + Disposal loss) × GWP. Equation 2: Indirect emissions = Annual power consumption × Lifespan × CO2 per kWh of electricity production. The LCCP is calculated by summing the direct emissions calculated in Equation 1 and the indirect emissions calculated in Equation 2. The analysis uses TMY2 and TMY3 data created by the National Renewable Laboratory and available in BinMaker® Pro Version 4 software. The calculations use GWP values ​​reported in the Intergovernmental Panel on Climate Change (IPCC)'s Assessment Report 4 (AR4) 2007. LCCP is expressed as the amount of carbon dioxide (kg-CO2eq) over the lifespan of the air conditioning or refrigeration system.

[0059] The term "mass flow rate" refers to the mass of refrigerant passing through a conduit per unit time.

[0060] The term "Occupational Exposure Limit (OEL)" is defined in accordance with ASHRAE standard 34-2016, "Designation and Safety Classification of Refrigerants."

[0061] As used herein, the term “substitute” means that when a particular heat transfer composition or refrigerant of the present invention is used as a “substitute” for a particular conventional refrigerant, the applicable composition of the present invention is used in a heat transfer system in which that refrigerant was conventionally commonly used. For example, when a refrigerant or heat transfer composition of the present invention is used in a heat transfer system that was previously designed for or commonly used with R410A, such as residential or commercial air conditioning (including rooftop systems, variable flow rate (VRF) systems, and chiller systems), the refrigerant of the present invention serves as a substitute for R410A in these systems.

[0062] The term "thermodynamic glide" applies to zeotropic refrigerant mixtures in which the temperature changes during a phase transition process in an evaporator or condenser under constant pressure.

[0063] The term "thermodynamic glide" applies to zeotropic refrigerant mixtures in which the temperature changes during a phase transition process in an evaporator or condenser under constant pressure.

[0064] As used herein, the term "TAN value" refers to the total acid number determined according to ASHRAE Standard 97, "Sealed Glass Tube Method for Testing the Chemical Stability of Materials for Use in Refrigerant Systems," in order to simulate the long-term stability of the heat transfer composition by accelerated degradation.

[0065] 1234ze refers to 1,1,1,3-tetrafluoropropene, without any restrictions on the isomer form.

[0066] Trans1234ze, 1234ze(E), and R-1234ze(E) each refer to trans-1,3,3,3-tetrafluoropropene.

[0067] Cis1234ze and 1234ze(Z) refer to cis-1,3,3,3-tetrafluoropropene, respectively.

[0068] 1234yf stands for 2,3,3,3-tetrafluoropropene.

[0069] 1233zd refers to 1-chloro-3,3,3-trifluoropropene, without any restrictions on the isomer form.

[0070] Trans1233zd and 1233zd(E) represent trans-1-chloro-3,3,3-trifluoropropene, respectively.

[0071] 1224yd refers to cis1-chloro-2,3,3,3-tetrafluoropropane, without any restrictions on the isomer form.

[0072] The terms "1132(E)", "R-1132(E)", and "HFO-1132(E)" all refer to trans-1,2-difluoroethene, respectively.

[0073] As used herein, the terms "R-32" and "HFC-32" mean difluoromethane, respectively.

[0074] The terms "R-125" and "HFC-125" refer to pentafluoroethane.

[0075] The terms "R-134a" and "HFC-134a" refer to 1,1,1,2-tetrafluoroethane, respectively.

[0076] The terms "R-143a" and "HFC-143a" refer to 1,1,1-trifluoroethane, respectively.

[0077] The terms "R-227ea" and "HFC-227ea" refer to 1,1,1,2,3,3,3-heptafluoropropane, respectively.

[0078] As used herein, the term "R448A" means the refrigerant designated as 448A by ASHRAE, 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.

[0079] As used herein, the term "R448B" means the refrigerant designated as 448B by ASHRAE, consisting of approximately 21% R-32, approximately 21% R-125, approximately 20% HFO-1234yf, approximately 31% R-134a, and approximately 7% HFO-1234ze(E).

[0080] As used herein, the term "R449A" means the refrigerant designated as 449A by ASHRAE, consisting of approximately 24.3% R-32, approximately 24.7% R-125, approximately 25.7% HFO-1234yf, and approximately 25.7% R-134a.

[0081] As used herein, the term "R449B" means the refrigerant designated as 449B by ASHRAE, which consists of approximately 25.2% R-32, approximately 24.3% R-125, approximately 23.2% HFO-1234yf, and approximately 27.3% R-134a.

[0082] As used herein, the term "R449C" means the refrigerant designated as 449C by ASHRAE, consisting of approximately 20% R-32, approximately 20% R-125, approximately 31% HFO-1234yf, and approximately 29% R-134a.

[0083] As used herein, the term "R450A" means the refrigerant designated as 450A by ASHRAE, consisting of 42% R-134a and 58% R-1234yf.

[0084] As used herein, the term "R452A" means the refrigerant designated as 452A by ASHRAE, which consists of approximately 11% R-32, approximately 59% R-125, and approximately 30% R-1234yf.

[0085] As used herein, the term "R452B" means the refrigerant designated as 452B by ASHRAE, which consists of approximately 67% R-32, approximately 7% R-125, and approximately 26% R-1234yf.

[0086] As used herein, the term "R454A" means the refrigerant designated as 454A by ASHRAE, which consists of 35% R-32 and 65% HFC-1234yf.

[0087] As used herein, the term "R454B" means the refrigerant designated as 454B by ASHRAE, which consists of 68.9% R-32 and 31.1% HFC-1234yf.

[0088] As used herein, the term "R454C" means the refrigerant designated as 454C by ASHRAE, which consists of 21.5% +2 / -2% R-32 and 78.5% +2 / -2% HFC-1234yf.

[0089] As used herein, the term "R455A" means the refrigerant designated as 455A by ASHRAE, which consists of 21.5% +2 / -1% R-32, 75.5% +2 / -2% HFC-1234yf, and 3% +2 / -1% CO2.

[0090] As used herein, the term "R456A" means the refrigerant designated as 456A by ASHRAE, consisting of approximately 6% R-32, approximately 45% R-134a, and approximately 49% R-1234ze(E).

[0091] As used herein, the term "R457A" means the refrigerant designated as 457A by ASHRAE, which consists of approximately 18% R-32, approximately 12% R-152a, and approximately 70% R-1234yf.

[0092] As used herein, the term "R457B" means the refrigerant designated as 457B by ASHRAE, which consists of approximately 35% R-32, approximately 10% R-152a, and approximately 55% R-1234yf.

[0093] As used herein, the term "R457C" means the refrigerant designated as 457C by ASHRAE, which consists of approximately 7.5% R-32, approximately 14.5% R-152a, and approximately 78% R-1234yf.

[0094] As used herein, the term "R466A" means the refrigerant designated as 466A by ASHRAE, which consists of approximately 49% R-32, approximately 11.5% R-125, and approximately 39.5% CF3I.

[0095] As used herein, the term "HDR139" refers to a refrigerant composed of approximately 38% R-32 and 62% CF3I.

[0096] 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.

[0097] As used herein, the term "HDR171" means a refrigerant consisting of approximately 20% R-32, approximately 40% 1234yf, and approximately 40% 1132(E).

[0098] As used herein, the term "HDR173" means a refrigerant consisting of approximately 21.5% R-32, approximately 40.5% 1234yf, and approximately 38% 1132(E).

[0099] As used herein, the term "R471A" means the refrigerant designated as 471A by ASHRAE, 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.

[0100] As used herein, the term "R474A" means the refrigerant designated as 474A by ASHRAE, consisting of approximately 23% R-1132(E) and approximately 77% R-1234yf.

[0101] As used herein, the term "R474B" means the refrigerant designated as 474B by ASHRAE, consisting of approximately 31.5% R-1132(E) and approximately 68.5% R-1234yf.

[0102] As used herein, the term "R476A" means the refrigerant designated as 476A by ASHRAE, which consists of 78.7% + / - 0.5 / -2% HFC-1234ze(E), 12% +2 / -0.5% HFC-1336mzz(E), and 10% +2 / -0.51% HFC-134a.

[0103] As used herein, the term "R479A" means the refrigerant designated as 479A by ASHRAE, consisting of approximately 28% R-1132(E), approximately 50.5% R-1234yf, and approximately 21.5% HFC-32.

[0104] As used herein, the term "R482A" means the refrigerant designated as 482A by ASHRAE, consisting of approximately 10% HFC-134a, approximately 83.5% HFC-1234ze(E), and approximately 6.5% HFO-1224yd(Z).

[0105] As used herein, the term "R-513A" means the refrigerant designated as 513A by ASHRAE, which consists of approximately 56% HFC-1234yf and approximately 44% HFC-134a.

[0106] As used herein, the term "R-513B" means the refrigerant designated as 513B by ASHRAE, consisting of approximately 58.5% HFC-1234yf and approximately 41.5% HFC-134a.

[0107] As used herein, the term "R-514A" means the refrigerant designated as 514A by ASHRAE, consisting of approximately 74.7% HFO-1336mzz(Z) and approximately 25.3% HFO-1130(E).

[0108] As used herein, the term "R-515A" means the refrigerant designated as 515A by ASHRAE, consisting of approximately 88% HFC-1234ze(E) and approximately 12% HFC-134a.

[0109] As used herein, the term "R-515B" means the refrigerant designated as 515B by ASHRAE, consisting of approximately 91.1% HFO-1234ze(E) and approximately 8.9% HFC-134a.

[0110] As used herein, the term "R-516A" means the refrigerant designated as 516A by ASHRAE, consisting of approximately 77.5% HFC-1234yf, approximately 8.5% HFC-134a, and approximately 14% HFC-152a.

[0111] As used herein, the term "protective agent 1" refers to formula I:

[0112] [ka] It means a compound caused by In the formula, at least one of R and R1 is a C1-C20 alkylthio group.

[0113] As used herein, the term "protective agent 2" refers to formula I:

[0114] [ka] It means a compound caused by In the formula, each R and R1 is independently a C1-C20 alkylthio group.

[0115] As used herein, the term "protective agent 3" refers to formula I:

[0116] [ka] It means a compound caused by In the formula, each R and R1 is independently a C5-C20 alkylthio group.

[0117] As used herein, the term "protective agent 4" refers to formula I:

[0118] [ka] It means a compound caused by In the formula, each R and R1 is independently a C5-C10 alkylthio group.

[0119] As used herein, the term “protective agent 5A” refers to Formula II:

[0120] [ka] It means a compound produced by

[0121] As used herein, the term “protective agent 5B” refers to dioctyl disulfide and formula II:

[0122] [ka] It means a compound produced by

[0123] In this specification, references to defined groups such as "heat transfer compositions 1-2" refer to each composition within that group, including cases where the definition number includes a suffix. Therefore, references to heat transfer compositions 1-2 also include references to heat transfer composition 1A, heat transfer composition 1B, heat transfer composition 2A, heat transfer composition 2B, heat transfer composition 2C, and heat transfer composition 2D, respectively.

[0124] Heat transfer composition The heat transfer compositions of the present invention (including each of heat transfer compositions 1 and 2 described herein) have been found by the applicant to offer highly advantageous properties, particularly excellent stability during use.

[0125] A unique advantage of the heat transfer composition of the present invention is that it provides excellent chemical stability during use, which is particularly evident in its use in heat transfer systems that include zinc-containing components exposed to the heat transfer composition during use. This desirable advantage can be achieved by the heat transfer composition of the present invention.

[0126] The specific heat transfer compositions of the present invention include those specified in Table 1 below, where the first column of this table contains "HTC" as an abbreviation for the defined heat transfer composition. In Table 1 below, "NR" means that the component or a specific amount is "not required" according to the definition of the specified HTC, and therefore its presence or absence in any amount is permissible. "Yes" means that the component is essential, but any type or amount is permissible. "Comp" means that the specified composition contains the items specified in the table. "CEO" means that the specified composition consists essentially of the items specified in the table, and "CO" means that the composition consists of the items specified in the table.

[0127] [Table 1-1]

[0128] [Table 1-2]

[0129] [Table 1-3]

[0130] [Table 1-4]

[0131] [Table 1-5]

[0132] [Table 1-6]

[0133] Table 1-7

[0134] Table 1-8

[0135] Table 1-9

[0136] Table 1-10

[0137] Table 1-11

[0138] Table 1-12

[0139] Table 1-13

[0140] Table 1-14

[0141] Table 1-15

[0142] Table 1-16

[0143] [Table 1-17]

[0144] [Table 1-18]

[0145] [Table 1-19]

[0146] [Table 1-20]

[0147] [Table 1-21]

[0148] [Table 1-22]

[0149] [Table 1-23]

[0150] For convenience, each heat transfer composition numbered in the first column of Table 1 above represents a definition of the heat transfer composition, and referring to a heat transfer composition by its number means referring to a composition containing that component (including the amount, if specified). Also, as stated above, references in this specification to defined groups such as "heat transfer compositions 3-46" or compositions defined by numbers refer to each composition within that group or composition, including cases where the definition number includes a suffix. For example, a reference to "heat transfer composition 3" is intended to refer to each composition containing Root 3, for example, HTC3 includes HTC3A in Table 1, HTC3B in Table 2, etc.

[0151] The heat transfer composition of the present invention comprises each of heat transfer compositions 1 to 46, and preferably contains a refrigerant in an amount exceeding 40% by weight of the heat transfer composition.

[0152] The heat transfer composition of the present invention comprises each of the heat transfer compositions 1 to 46, and preferably contains a refrigerant in an amount exceeding 50% by weight, or exceeding 70% by weight, or exceeding 80% by weight, and even exceeding 90% by weight.

[0153] The heat transfer compositions of the present invention may contain other components for the purpose of imparting or enhancing specific functions to the composition, preferably without negating the features provided by the use of the protective agent according to the present invention. Examples of such other components or additives include stabilizers, dyes, solubilizers, compatibilizers, auxiliary stabilizers, antioxidants, rust inhibitors, extreme pressure additives, and wear-resistant additives.

[0154] The heat transfer composition of the present invention comprises each of the heat transfer compositions 1 to 46, and preferably contains a stabilizer. Preferably, it contains one or more of the following stabilizers.

[0155] Stabilizer: Alkylated naphthalene The applicant has surprisingly and unexpectedly found that alkylated naphthalenes are highly effective as stabilizers in the heat transfer compositions of the present invention. As used herein, the term "alkylated naphthalene" refers to compounds having the following structure:

[0156] [ka] Here, each R1 to R8 is independently selected from a linear alkyl group, a branched alkyl group, and hydrogen. The specific length of the alkyl chain, as well as mixtures, or branched and linear chains and hydrogen, can be varied within the scope of the present invention and will be understood and recognized by those skilled in the art, but such variations will be reflected in the physical properties of the alkylated naphthalene (including the viscosity of the alkylated compound in particular), and producers of such materials often define the material by referring to one or more of these properties as an alternative to specifying a particular R group.

[0157] The applicant has found that the use of alkylated naphthalenes as stabilizers, each comprising heat transfer compositions 1 to 46 having the following properties according to the present invention, is associated with unexpected, surprising, and advantageous results, and the alkylated naphthalene compounds having the indicated properties are, for convenience, referred herein to as alkylated naphthalene 1 (or AN1) to alkylated naphthalene 5 (or AN5), as shown in rows 1 to 5 of Table AN-A below.

[0158] [Table 2]

[0159] In this specification, the term "approximately" as used in relation to viscosity at 40°C measured according to ASTM D445 means ±4 cSt.

[0160] In this specification, the term "approximately" as used in relation to viscosity at 100°C measured according to ASTM D445 means ±0.4 cSt.

[0161] In this specification, the term "approximately" as used in relation to the pour point measured according to ASTM D97 means ±5°C.

[0162] The applicant has also found that the use of alkylated naphthalene as a stabilizer, comprising each of the following heat transfer compositions 1 to 46 according to the present invention, is associated with unexpected, surprising, and advantageous results, and the alkylated naphthalene compounds having the indicated properties are, for convenience, referred herein to alkylated naphthalene 6 (or AN6) to alkylated naphthalene 10 (or AN10), as shown in rows 6 to 10 of Table AN-B below.

[0163] [Table 3]

[0164] Examples of alkylated naphthalenes in the sense of alkylated naphthalene 1 and alkylated naphthalene 6 include the following products sold by King Industries under the trademark name NA-LUBE KR-007A: KR-008, KR-009, KR-015, KR-019, KR-005FG, KR-015FG, and KR-029FG.

[0165] Examples of alkylated naphthalenes in the sense of alkylated naphthalene 2 and alkylated naphthalene 7 include those sold by King Industries under the trademark name NA-LUBE KR-007A, as well as KR-008, KR-009, and KR-005FG.

[0166] Examples of alkylated naphthalenes in the sense of alkylated naphthalene 5 and alkylated naphthalene 10 include those sold by King Industries under the trademark name NA-LUBE KR-008.

[0167] The present invention includes heat transfer compositions comprising each of the heat transfer compositions 14 and 30-32 of this specification, wherein the alkylated naphthalene is AN1, AN2, AN3, AN4, AN5, AN6, AN7, AN8, AN9, or AN10.

[0168] Acid consumable moiety (ADM) Those skilled in the art can identify various useful ADMs according to the present invention without excessive experimentation, and all such ADMs are included within the scope of this specification.

[0169] Epoxy The applicant has found that epoxides, particularly alkylated epoxides, when used in combination with alkylated naphthalene stabilizers, effectively result in the stability improvements described herein, and although the applicant is not necessarily bound by theory, this synergistic improvement is thought to be at least partly due to their effective function as ADMs in the heat transfer compositions of the present invention.

[0170] In preferred embodiments, i.e., in each of the heat transfer compositions 1 to 46, the epoxide is selected from the group consisting of epoxides that undergo a ring-opening reaction with an acid, thereby consuming the acid in the system without otherwise adversely affecting the system.

[0171] Useful epoxides include aromatic epoxides, alkyl epoxides (including alkyl ether epoxides), and alkenyl epoxides.

[0172] The preferred epoxide is the following formula I:

[0173] [ka] Contains epoxide, Here, at least one of R1 to R4 is selected from a (C2-C15) acyclic group having 2 to 15 carbon atoms, a C2-C15 aliphatic group, and a C2-C15 ether group. The group of epoxides of formula I having the R group defined in this paragraph may be referred to as ADM1A in this specification for convenience.

[0174] The preferred epoxide is the following formula I:

[0175] [ka] Contains epoxide, Here, each of R1 to R4 is independently selected from H, a C2-C15 acyclic group, a C2-C15 aliphatic group, and a C2-C15 ether group, provided that at least one of R1 to R4 is H, and at least one of R1 to R4 is selected from a C2-C15 acyclic group, a C2-C15 aliphatic group, and a C2-C15 ether group. The epoxide group of formula I having the R group as defined in this paragraph may be referred to as ADM1B in this specification for convenience.

[0176] The preferred epoxide is the following formula I:

[0177] [ka] Contains epoxide, Here, each of R1 to R4 is independently selected from H, a C2-C15 acyclic group, a C2-C15 aliphatic group, and a C2-C15 ether group, wherein at least two of R1 to R4 are H, and at least one of R1 to R4 is selected from a C2-C15 acyclic group, a C2-C15 aliphatic group, and a C2-C15 ether group. The epoxide group of formula I having the R group as defined in this paragraph may be referred to as ADM1C in this specification for convenience.

[0178] The preferred epoxide is the following formula I:

[0179] [ka] Contains epoxide, Here, each of R1 to R4 is independently selected from hydrogen (H), a C2-C15 acyclic group, a C2-C15 aliphatic group, and a C2-C15 ether group, wherein three of R1 to R4 are hydrogen (H), and one of R1 to R4 is selected from a C2-C15 acyclic group, a C2-C15 aliphatic group, or a C2-C15 ether group. The epoxide group of formula I having the R group as defined in this paragraph may be referred to as ADM1D in this specification for convenience.

[0180] In a preferred embodiment, at least one of R1 to R4 in formula I has the following structure:

[0181] [ka] It is an ether that possesses, Here, R5 and R6 are independently C1-C14 linear or branched alkyl groups, preferably unsubstituted. The group of epoxides defined in this paragraph may be referred to herein as ADM2A for convenience.

[0182] In a preferred embodiment, at least one of R1 to R4 in formula I has the following structure:

[0183] [ka] It is an ether that possesses, Here, R5 is a C1-C3 alkyl group, preferably unsubstituted, and R6 is a C3-C10 linear or branched alkyl group, preferably an unsubstituted alkyl group. The group of epoxides defined in this paragraph may be referred to herein as ADM2B for convenience.

[0184] In a preferred embodiment, one of R1 to R4 in formula I has the following structure:

[0185] [ka] It is an ether that possesses, Here, R5 and R6 are independently C1-C14 linear or branched alkyl groups, preferably unsubstituted, and the remaining three R1-R4 are hydrogen atoms. The epoxide groups defined in this paragraph may, for convenience, be referred to herein as ADM3A.

[0186] In a preferred embodiment, one of R1 to R4 in formula I has the following structure:

[0187] [ka] It is an ether that possesses, Here, R5 is bonded to the epoxide group and is a C1-C3 linear or branched, unsubstituted alkyl group, and R6 is a C3-C10 linear or branched unsubstituted alkyl group, and the remaining three R1-R4 are H. For convenience, the epoxide groups defined in this paragraph may be referred to herein as ADM3B.

[0188] In a preferred embodiment, one of R1 to R4 in formula I has the following structure:

[0189] [ka] It is an ether that possesses, Here, R5 is bonded to the epoxide group and is a C1 unsubstituted alkyl, and R6 is a C8 branched unsubstituted alkyl group, and the remaining three R1-R4 are H groups. For convenience, the epoxide groups defined in this paragraph may be referred to herein as ADM3C.

[0190] In preferred embodiments, the epoxide contains, substantially consists of, or consists solely of 2-ethylhexylglycidyl ether, and this compound has the following structural formula:

[0191]

Chem.

[0192] In a preferred embodiment, one of R1 to R4 in formula I has the following structure:

[0193]

Chem.

[0194] In a preferred embodiment, one of R1 to R4 in formula I has the following structure:

[0195]

Chem.

[0196] In a preferred embodiment, one of R1 to R4 in formula I has the following structure:

[0197]

Chem.

[0198] In a preferred embodiment, one of R1 to R4 in formula I has the following structure:

[0199] [ka] It is an ether that possesses, Here, R5 is bonded to the epoxide group and is a C1 unsubstituted alkyl, and R6 is a C8 branched oxygen-substituted alkyl group, and the remaining three R1-R4 are H. The group of epoxides of formula I having an R group as defined in this paragraph may be referred to herein as ADM5D for convenience.

[0200] In a preferred embodiment, the epoxide contains, substantially consists of, or comprises glycidyl neodecanoate, which is an ADM5C compound with an O substituent on R6, and has the following structure.

[0201] [ka]

[0202] For convenience, the epoxides used in this paragraph may be referred to as ADM6 in this specification.

[0203] The present invention comprises a heat transfer composition comprising each of heat transfer compositions 1 and 30-32, wherein the alkylated naphthalene is AN1, AN2, AN3, AN4, AN5, AN6, AN7, AN8, AN9, or AN10, and further comprises one or more of ADM1-ADM6.

[0204] In the heat transfer composition of the present invention (including each of heat transfer compositions 1 and 30 to 32), ADM is present in an amount of preferably from about 0.05% by weight to about 2.5% by weight, preferably from 0.05% by weight to about 1.5% by weight, or more preferably from 0.05% by weight to 0.5% by weight, based on the total weight of the lubricant and ADM.

[0205] In the heat transfer composition of the present invention (including each of heat transfer compositions 1 and 30 to 32), the alkylated naphthalene is present in an amount of preferably from 0.01% by weight to about 10% by weight, or from about 1.5% by weight to about 4.5% by weight, or from about 2.5% by weight to about 3.5% by weight, based on the total weight of the alkylated naphthalene and the refrigerant in the system. The amount defined in this paragraph is particularly preferred when ADM is also present.

[0206] In the heat transfer composition of the present invention (including each of heat transfer compositions 1 and 30 to 32), the alkylated naphthalene is present in an amount of preferably from 0.1% by weight to about 20% by weight, or from 1.5% by weight to about 10% by weight, or from 1.5% by weight to about 8% by weight, based on the total weight of the alkylated naphthalene and the lubricant in the system. The amount defined in this paragraph is particularly preferred when ADM is also present.

[0207] Carbodiimide ADM may comprise carbodiimide. In a preferred embodiment, the carbodiimide comprises a compound having the following structure.

[0208]

Chemical Formula

[0209] Other Stabilizers It is contemplated that the heat transfer composition of the present invention, that is, each of heat transfer compositions 1 to 46, may contain stabilizers other than alkylated naphthalene and ADM. Examples of such other stabilizers are described below.

[0210] Phenolic Compounds In preferred embodiments, the stabilizer further comprises a phenolic compound.

[0211] Phenolic compounds include 4,4'-methylenebis(2,6-di-tert-butylphenol); 4,4'-bis(2,6-di-tert-butylphenol); 2,2- or 4,4-biphenyldiol (including 4,4'-bis(2-methyl-6-tert-butylphenol)); derivatives of 2,2- or 4,4-biphenyldiol; 2,2'-methylenebis(4-ethyl-6-tert-butylphenol); 2,2'-methylenebis(4-methyl-6-tert-butylphenol) 4,4-butylidenebis(3-methyl-6-tert-butylphenol); 4,4-isopropylidenebis(2,6-di-tert-butylphenol); 2,2'-methylenebis(4-methyl-6-nonylphenol); 2,2'-isobutylidenebis(4,6-dimethylphenol); 2,2'-methylenebis(4-methyl-6-cyclohexylphenol); 2,6-di-tert-butyl-4-methyl The compounds may be one or more selected from tetraphenol (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'-dimethylaminomethyl)phenol, 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'-methylenediphenol and t-butylhydroquinone, and preferably BHT.

[0212] Phenol compounds, particularly BHT, may be provided in the heat transfer composition in amounts greater than 0, preferably in amounts of 0.0001% to about 5% by weight, preferably 0.001% to about 2.5% by weight, and more preferably 0.01% to about 1% by weight. In each case, weight percent refers to the weight of the heat transfer composition.

[0213] Phenolic compounds, particularly BHT, may be provided in the heat transfer composition in amounts greater than 0, preferably in amounts of 0.0001% to about 5% by weight, preferably 0.001% to about 2.5% by weight, and more preferably 0.01% to about 1% by weight. In each case, the weight percent refers to the weight based on the weight of the lubricant in the heat transfer composition.

[0214] The present invention also comprises a stabilizer comprising, based on the total weight of the stabilizer components in the composition, about 40% to about 95% by weight of alkylated naphthalene (including each of AN1 to AN10) and 0.1% to about 10% by weight of BHT.

[0215] The present invention also comprises a stabilizer comprising, based on the total weight of the stabilizer components in the composition, about 40% to about 95% by weight of alkylated naphthalene (including each of AN1 to AN10), 5% to about 30% by weight of ADM (including each of ADM1 to ADM6), and 0.1% to about 10% by weight of BHT.

[0216] diene compounds The diene compounds include C3-C15 dienes and compounds formed by the reaction of any two or more C3-C4 dienes. Preferably, the diene compounds are selected from the group consisting of allyl ethers, propadiene, butadiene, isoprene, and terpenes. The diene compounds are preferably terpenes, which include, but are not limited to, terebene, retinal, geraniol, terpinene, delta-3-carene, terpinolene, phellandrene, fenchen, myrcene, farnesene, pinene, nerol, citral, camphor, menthol, limonene, nerolidol, phytol, carnosic acid, and vitamin A1. Preferably, the stabilizer is farnesene. Preferred terpene stabilizers are disclosed in U.S. Provisional Patent Application No. 60 / 638,003, filed on 12 December 2004 and published as U.S. Patent Application Publication No. 2006 / 0167044(A1), which is incorporated herein by reference.

[0217] In addition, the diene compound may be provided in the heat transfer composition in an amount greater than 0, preferably 0.0001% to about 5% by weight, preferably 0.001% to about 2.5% by weight, and more preferably 0.01% to about 1% by weight. In each case, weight percent refers to the weight of the heat transfer composition.

[0218] Phosphorus compounds The phosphorus compound may be a phosphite compound or a phosphate compound. For the purposes of the present invention, the phosphite compound may be a diaryl, dialkyl, triaryl, and / or trialkyl phosphite, and / or a mixed aryl / alkyl disubstituted or trisubstituted phosphite, and in particular may be one or more compounds selected from hindered phosphite, tris-(di-tert-butylphenyl) phosphite, di-n-octyl phosphite, isooctyldiphenyl phosphite, isodecyldiphenyl phosphite, triisodecyl phosphate, triphenyl phosphite, and diphenyl phosphite, particularly diphenyl phosphite.

[0219] The phosphate compound may be a triaryl phosphate, a trialkyl phosphate, an alkyl monoacid phosphate, an aryl diacid phosphate, or an amine phosphate, and preferably a triaryl phosphate and / or a trialkyl phosphate, particularly a tri-n-butyl phosphate.

[0220] The present invention comprises a heat transfer composition comprising each of heat transfer compositions 1 to 46, wherein the composition further comprises a phosphate.

[0221] The present invention comprises a heat transfer composition comprising each of heat transfer compositions 1 to 46, wherein the composition further comprises a triaryl phosphate.

[0222] The present invention comprises a heat transfer composition comprising each of heat transfer compositions 1 to 46, wherein the composition further comprises a trialkyl phosphate.

[0223] The phosphorus compound may be provided in the heat transfer compositions of the present invention (including each of heat transfer compositions 1 to 46) in an amount greater than 0, preferably in an amount of 0.0001% to about 5% by weight, preferably 0.001% to about 2.5% by weight, and more preferably 0.01% to about 1% by weight. In each case, weight percent refers to the weight of the heat transfer composition.

[0224] The phosphorus compound may be provided in an amount greater than 0 in the heat transfer compositions of the present invention (including each of heat transfer compositions 1 to 46), preferably in an amount of 0.0002% to about 10% by weight, preferably 0.002% to about 5% by weight, and more preferably 0.02% to about 2% by weight. In each case, the weight percentages in this paragraph refer to the weights of the lubricant and the phosphate stabilizer.

[0225] Nitrogen compounds When the stabilizer is a nitrogen compound, the stabilizer may include amine compounds such as one or more secondary or tertiary amines selected from diphenylamine, p-phenylenediamine, triethylamine, tributylamine, diisopropylamine, triisopropylamine, and triisobutylamine. The amine compound may be an amine antioxidant such as a substituted piperidine compound, i.e., an alkyl-substituted piperidyl, piperidinyl, piperadinon, or alkyloxypiperidinyl derivative, in particular 2,2,6,6-tetramethyl-4-piperidone, 2,2,6,6-tetramethyl-4-piperidinol; bis-(1,2,2,6,6-pentamethylpiperidyl) sebacate; di(2,2,6,6-tetramethyl-4-piperidyl) sebacate, poly(N-hydroxyethyl-2,2 It may be 6,6-tetramethyl-4-hydroxypiperidyl succinate; an alkylated paraphenylenediamine such as N-phenyl-N'-(1,3-dimethyl-butyl)-p-phenylenediamine or N,N'-di-sec-butyl-p-phenylenediamine; a hydroxylamine such as taloamine, methylbistaloamine, and bistaloamine; or phenol-α-naphthylamine; or one or more amine-based antioxidants selected from Tinuvin® 765 (Ciba), BLS® 1944 (Mayzo Inc.), and BLS® 1770 (Mayzo Inc.). For the purposes of the present invention, the amine compound may also be an alkyldiphenylamine such as bis(nonylphenylamine), a dialkylamine such as (N-(1-methylethyl)-2-propylamine, or one or more of phenyl-α-naphthylamine (PANA), alkyl-phenyl-α-naphthylamine (APANA), and bis(nonylphenyl)amine. Preferably, the amine 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).

[0226] Alternatively, in addition to the nitrogen compounds specified above, one or more compounds selected from dinitrobenzene, nitrobenzene, nitromethane, nitrosobenzene, and TEMPO[(2,2,6,6-tetramethylpiperidine-1-yl)oxyl] may be used as stabilizers.

[0227] The nitrogen compound may be provided in the heat transfer composition in an amount greater than 0, and in an amount of 0.0001% to about 5% by weight, preferably in an amount of 0.001% to about 2.5% by weight, and more preferably in an amount of 0.01% to about 1% by weight. In each case, weight percent refers to the weight of the heat transfer composition.

[0228] Isobutylene Isobutylene may also be used as a stabilizer according to the present invention.

[0229] Lubricant The heat transfer compositions of the present invention (including each of heat transfer compositions 1 to 46) preferably include a POE lubricant and / or a 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.

[0230] POE lubricant The POE lubricant of the present invention, in preferred embodiments, includes a neopentyl POE lubricant. As used herein, the term "neopentyl POE lubricant" refers to a polyol ester (POE) derived from the reaction of a neopentyl polyol (preferably pentaerythritol, trimethylolpropane, or neopentyl glycol, and in preferred embodiments with higher viscosity, dipentaerythritol) with a linear or branched carboxylic acid.

[0231] Commercially available POEs include neopentyl glycol diperargonates, available as Emery 2917® and Hatcol 2370®, and pentaerythritol derivatives, including those sold 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 following characteristics:

[0232] [Table 4]

[0233] Other useful esters include phosphate esters, dibasic acid esters, and fluoroesters.

[0234] PVE lubricant The lubricant of the present invention may generally include a PVE lubricant. In a preferred embodiment, the PVE lubricant is the following formula II:

[0235] [ka] This is a PVE (Player Evolution) game. Here, R2 and R3 are each independently a C1-C10 hydrocarbon, preferably a C2-C8 hydrocarbon, and R1 and R4 are each independently an alkyl, alkylene glycol, or polyoxyalkylene glycol unit, and n and m are preferably selected as needed by those skilled in the art to obtain a lubricant having the desired properties, preferably n and m are selected to obtain a lubricant having a viscosity of about 30 to about 70 cSt at 40°C as measured according to ASTM D445. Examples of commercially available polyvinyl ethers include lubricants sold by Idemitsu under the trade names FVC32D and FVC68D.

[0236] Methods, uses, and systems The heat transfer compositions disclosed herein are provided for use in substantially all heat transfer applications, uses, methods and systems, finding advantages and yielding unexpected results, and all such applications, uses, methods and systems are included within the broad scope of the present invention. In preferred embodiments, the heat transfer compositions disclosed herein (including each of heat transfer compositions 1 to 46) are provided for use, finding advantages and yielding unexpected results in refrigeration applications, stationary air conditioning applications, mobile and transport air conditioning applications, and stationary and mobile heat pumps. Particularly preferred embodiments are disclosed in Table 2 below, and the following abbreviations are used, each having the following meanings: "ComRef" means commercial refrigeration, "ComAC" means commercial air conditioning, "ResAC" means household air conditioning, "Stat.Heat Pump" means stationary heat pump, "Mobile Heat Pump" means heat pump used in mobile applications such as automobiles, trucks, and buses, "Mobile AC" means air conditioning used in mobile applications such as automobiles, trucks, and buses, "IndRef" means industrial refrigeration; and "TransRef" means transport refrigeration. In the heat transfer composition column of Table 2, HTC numbers are used according to the definitions set out in Table 1 above.

[0237] [Table 5-1]

[0238] [Table 5-2]

[0239] [Table 5-3]

[0240] [Table 5-4]

[0241] Table 5-5

[0242] Table 5-6

[0243] Table 5-7

[0244] Table 5-8

[0245] Table 5-9

[0246] Table 5-10

[0247] Table 5-11

[0248] Table 5-12

[0249] Table 5-13

[0250] Table 5-14

[0251] Table 5-15

[0252] [Table 5-16]

[0253] [Table 5-17]

[0254] [Table 5-18]

[0255] With respect to the heat transfer systems, uses, and methods of the present invention (including each of those specified in Table 2 above), which include a compressor and a compressor lubricant in the system, the system may include amounts of refrigerant and lubricant such that the amount of lubricant 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 “amount of lubricant” means that the total weight of lubricant contained in the system is a percentage of the total weight of lubricant and refrigerant contained in the system. Such a system may also include amounts of lubricant that are about 5% to about 10% by weight, or about 8% by weight, of the heat transfer composition.

[0256] The heat transfer system, use, and method of the present invention (including each of those specified in Table 2 above), which includes a compressor and a compressor lubricant in the system, may include a compressor, evaporator, condenser, and expansion device, heat transfer compositions 1 to 46, and a containment material in the system, which is in fluid communication with each other, and which preferably includes: i. copper or copper alloy, ii. activated alumina, iii. zeolite molecular sieves containing copper, silver, lead, or a combination thereof, iv. anion exchange resin, v. hygroscopic material (preferably a hygroscopic molecular sieve), or vi. a combination of two or more of the above.

[0257] The present invention also includes a heat transfer method of which evaporates a refrigerant liquid to generate refrigerant vapor, compresses at least a portion of the refrigerant vapor with a compressor, and condenses the refrigerant vapor in a plurality of repeating cycles, the method comprising: (a) To provide a heat transfer composition according to the present invention (including each of heat transfer compositions 1 to 46), (b) optionally, preferably, to provide a lubricant for the compressor, and (b) Exposing at least a portion of the refrigerant and / or at least a portion of the lubricant to the containment material.

[0258] In preferred embodiments, household air conditioning systems and methods (including each of those specified 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.

[0259] In preferred embodiments, the household air conditioning systems and methods used in heating mode (including each of those specified 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 35°C to about 50°C.

[0260] In preferred embodiments, commercial air conditioning systems and methods (including each of those specified 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.

[0261] In preferred embodiments, the hot water systems and methods (including each of those specified 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.

[0262] In preferred embodiments, the medium-temperature systems and methods (including each of those specified in Table 2 above) have 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.

[0263] In preferred embodiments, the low-temperature systems and methods (including each of those specified 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.

[0264] In preferred embodiments, rooftop air conditioning systems and methods (including each of those specified 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.

[0265] In preferred embodiments, the VRF system and method (including each of those specified 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.

[0266] For the purposes of the present invention, examples of compressors commonly used for each use, system, and method (including each of those specified in Table 2) include reciprocating, rotary (including rolling pistons and rotary vanes), scroll, screw, and centrifugal compressors. Accordingly, the present invention provides each and any of the refrigerants and / or heat transfer compositions described herein for use in heat transfer systems comprising reciprocating, rotary (including rolling pistons and rotary vanes), scroll, screw, or centrifugal compressors.

[0267] For the purposes of the present invention, examples of expansion devices commonly used for each use, system, and method (including each of those specified in Table 2) include capillary tubes, fixed orifices, thermal expansion valves, and electronic expansion valves. Accordingly, the present invention provides each and any of the heat transfer compositions described herein (including heat transfer compositions 1 to 46) for use in heat transfer systems comprising capillary tubes, fixed orifices, thermal expansion valves, or electronic expansion valves.

[0268] For the purposes of the present invention, in each use, system, and method (including each of those specified 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 tube-in-tube heat exchangers. Accordingly, the present invention provides, for each use, system, and method (including each of those specified in Table 2), any and all of the heat transfer compositions described herein for use in a heat transfer system 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 tube-in-tube heat exchanger.

[0269] The systems, uses, and methods of the present invention include each use, system, and method (including each of those specified in Table 2), and therefore preferably include a containment material in contact with at least a portion of the refrigerant and / or at least a portion of the lubricant according to the present invention, wherein the temperature of the containment material and / or the temperature of the refrigerant and / or the temperature of the lubricant is preferably at least about 10°C at the time of contact, and the containment material preferably includes the following combinations: anion exchange resin, activated alumina, a zeolite molecular sieve containing silver, and a moisture removal material (preferably a molecular sieve for moisture removal).

[0270] As used herein, the term “in contact with at least a portion” is intended to broadly include each and any combination of the containment materials being in contact with the same or separate portions of the refrigerant and / or lubricant in the system, and various or specific containment materials include, but are not limited to, the following embodiments: (i) if present, being physically together with other various or specific materials; (ii) if present, being physically separated from other various or specific materials; and (iii) combinations in which two or more materials are physically together and at least one containment material is physically separated from at least one other containment material.

[0271] The heat transfer composition of the present invention can be used for heating and cooling applications.

[0272] In a particular feature of the present invention, the heat transfer composition can be used in a cooling method that includes condensing the heat transfer composition and then evaporating the composition in the vicinity of an article or object to be cooled.

[0273] Accordingly, the present invention relates to a cooling method in a heat transfer system comprising an evaporator, a condenser and a compressor, wherein the process comprises i) condensing a heat transfer composition as described herein, and ii) Evaporating the composition in the vicinity of an object or article to be cooled, Here, the evaporator temperature of the heat transfer system is in the range of approximately -40°C to approximately +10°C.

[0274] Alternatively, or in addition to the above, the heat transfer composition may be used in a heating method that involves condensing the heat transfer composition in the vicinity of an article or object to be heated, and then evaporating the composition.

[0275] Therefore, the present invention relates to a heating method in a heat transfer system comprising an evaporator, a condenser, and a compressor, and the process is as follows: i) Condensing the heat transfer composition described herein in the vicinity of an object or article to be heated, and ii) Evaporating the composition, wherein the evaporator temperature of the heat transfer system is in the range of approximately -30°C to approximately 5°C.

[0276] The heat transfer compositions of the present invention are provided for use in air conditioning applications, including both transport and stationary air conditioning applications. Therefore, any of the heat transfer compositions described herein can be used in any of the following: - Mobile air conditioning, especially for air conditioning applications including trains and buses. - Mobile heat pumps, especially heat pumps for electric vehicles; - Cooling devices, particularly positive displacement cooling devices, more specifically air-cooled or water-cooled direct expansion cooling devices, which are either modular or conventional single-package type. - Household air conditioning systems, especially ducted split or ductless split air conditioning systems. - Household heat pumps, - Household air-to-water heat pump / hot water system, - Industrial air conditioning systems, - Commercial air conditioning systems, particularly packaged rooftop units and variable refrigerant flow (VRF) systems, and - Commercial air-source, water-source, or geothermal source heat pump systems.

[0277] The heat transfer compositions of the present invention are provided for use in refrigeration systems. The term "refrigeration system" means any system or apparatus that utilizes a refrigerant to provide cooling, or any part or component of such system or apparatus. Accordingly, any of the heat transfer compositions described herein can be used in any of the following: - Low-temperature refrigeration system, - Medium temperature refrigeration system, - Commercial refrigerators, - Commercial freezers, - Ice maker, - Vending machine, - Refrigeration systems for transport, - home freezer, - Household refrigerator, - Industrial freezers, - Industrial refrigerators, and - Cooling device.

[0278] Each heat transfer composition described herein (including heat transfer compositions 1 to 46) is provided for use in household air conditioning systems (having evaporator temperatures in the range of about 0°C to about 10°C, particularly about 7°C for cooling, and / or about -20°C to about 3°C, particularly about 0.5°C for heating). Alternatively, or additionally, each heat transfer composition described herein (including heat transfer compositions 1 to 101) is provided for use in household air conditioning systems equipped with reciprocating, rotary (rolling piston or rotary vane) or scroll compressors.

[0279] Each of the heat transfer compositions described (including heat transfer compositions 1 to 46) is provided for use in air-cooled cooling systems (having evaporator temperatures in the range of about 0°C to about 10°C, particularly about 4.5°C), in particular air-cooled cooling systems equipped with positive displacement compressors, and more specifically air-cooled cooling systems equipped with reciprocating scroll compressors.

[0280] Each heat transfer composition described herein (including heat transfer compositions 1 to 46) is provided for use in household air-to-water heat pump hot water systems (with evaporator temperatures ranging from about -20°C to about 3°C, particularly about 0.5°C, or about -30°C to about 5°C, with evaporator temperatures ranging from about 0.5°C depending on the configuration).

[0281] Each heat transfer composition described herein (including heat transfer compositions 1 to 46) is provided for use in medium-temperature refrigeration systems (having evaporator temperatures in the range of about -12°C to about 0°C, particularly about -8°C).

[0282] Each heat transfer composition described herein (including heat transfer compositions 1 to 46) is provided for use in low-temperature refrigeration systems (having 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).

[0283] The heat transfer compositions of the present invention (including heat transfer compositions 1 to 46) are provided for use in a household air conditioning system, which is used, for example, to supply cool air (the air having a temperature of, for example, about 10°C to about 17°C, particularly about 12°C) to a building during the summer.

[0284] The heat transfer compositions of the present invention (including heat transfer compositions 1 to 46) are therefore provided for use in a split household air conditioning system, where the household air conditioning system is used to supply cool air (the air having a temperature of, for example, about 10°C to about 17°C, particularly about 12°C).

[0285] The heat transfer compositions of the present invention (including heat transfer compositions 1 to 46) are therefore provided for use in a ducted split household air conditioning system, where the household air conditioning system is used to supply cool air (the air having a temperature of, for example, about 10°C to about 17°C, particularly about 12°C).

[0286] The heat transfer compositions of the present invention (including heat transfer compositions 1 to 46) are therefore provided for use in a window-type household air conditioning system, where the household air conditioning system is used to supply cool air (the air having a temperature of, for example, about 10°C to about 17°C, particularly about 12°C).

[0287] The heat transfer compositions of the present invention (including heat transfer compositions 1 to 46) are therefore provided for use in portable household air conditioning systems, where the household air conditioning system is used to supply cool air (the air having a temperature of, for example, about 10°C to about 17°C, particularly about 12°C).

[0288] Including the preceding paragraph, the household air conditioning systems described herein preferably include an air-to-refrigerant evaporator (indoor coil), a compressor, an air-to-refrigerant condenser (outdoor coil), and an expansion valve. The evaporator and condenser may be round tube plate fins, finned tubes, or microchannel heat exchangers. The compressor may be reciprocating, rotary (rolling piston or rotary vane), or scroll compressor. The expansion valve may be a capillary tube, a temperature-sensitive, 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.

[0289] The heat transfer compositions of the present invention (including heat transfer compositions 1 to 46) are provided for use in a household heat pump system, which is used to supply warm air (the air having a temperature of, for example, about 18°C ​​to about 24°C, particularly about 21°C) to a building during winter. It can be the same system as a household air conditioning system, but in heat pump mode the flow of the refrigerant is reversed, with the indoor coil becoming the condenser and the outdoor coil becoming the evaporator. Typical system forms are split-type and mini-split-type heat pump systems. The evaporator and condenser are usually round-tube plate-fin, finned, or microchannel heat exchangers. The compressor is usually reciprocating, rotary (rolling piston or rotary vane), or scroll compressor. The expansion valve is usually a temperature-sensitive or electronic expansion valve. The refrigerant evaporation temperature is preferably in the range of about -20°C to about 3°C, or about -30°C to about 5°C. The condensation temperature is preferably in the range of about 35°C to about 50°C.

[0290] The heat transfer compositions of the present invention (including heat transfer compositions 1 to 46) are provided for use in commercial air conditioning systems, where the commercial air conditioning system may be a cooling system used to supply chilled water (which has a temperature of, for example, about 7°C) to large buildings such as offices and hospitals. Depending on the application, the cooling system may be operated year-round. The cooling system may be air-cooled or water-cooled. Air-cooled cooling systems typically have plate, tube-in-tube, or shell-and-tube evaporators for supplying chilled water, reciprocating or scroll compressors, round tube plate fins, finned tubes, or microchannel condensers for heat exchange with ambient air, and temperature-sensitive or electronic expansion valves. Water-cooled systems typically have shell-and-tube evaporators for supplying chilled water, reciprocating, scroll, screw, or centrifugal compressors, shell-and-tube condensers for heat exchange with water from cooling towers or lakes, seas, and other natural resources, and temperature-sensitive or electronic expansion valves. 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.

[0291] The heat transfer compositions of the present invention (including heat transfer compositions 1 to 46) are provided for use in a household air-to-water heat pump hot water system, which is used to supply hot water (the water having a temperature of, for example, about 50°C or about 55°C) to a building for underfloor heating or similar purposes in winter. The hot water system typically includes a round tube plate fin, finned tube or microchannel evaporator for heat exchange with ambient air, a reciprocating, scroll or rotary compressor, a plate, tube-in-tube or shell-in-tube condenser for heating water, and a temperature-sensitive 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.

[0292] The heat transfer compositions of the present invention (including heat transfer compositions 1 to 46) are provided for use in a medium-temperature refrigeration system, where the refrigerant preferably has an evaporation temperature in the range of about -12°C to about 0°C, and in such a system the refrigerant preferably has a condensation temperature in the range of about 40°C to about 70°C, or about 20°C to about 70°C.

[0293] Accordingly, the present invention provides a medium-temperature refrigeration system used for cooling food or beverages in a refrigerator or bottle cooler, where the refrigerant preferably has an evaporation temperature in the range of about -12°C to about 0°C, and in such a system the refrigerant preferably has a condensation temperature in the range of about 40°C to about 70°C, or about 20°C to about 70°C.

[0294] The medium-temperature systems of the present invention, including the systems described in the preceding paragraph, preferably include an air-to-refrigerant evaporator for providing cooling (e.g., cooling of food or beverage contained therein), a reciprocating, scroll, screw, or rotary compressor, an air-to-refrigerant condenser for heat exchange with ambient air, and a temperature-sensitive or electronic expansion valve. The heat transfer compositions of the present invention (including heat transfer compositions 1 to 46) are provided for use in low-temperature refrigeration systems, where the refrigerant preferably has an evaporation temperature in the range of about -40°C to about -12°C, and the refrigerant preferably has a condensation temperature in the range of about 40°C to about 70°C, or about 20°C to about 70°C.

[0295] Accordingly, the present invention provides a low-temperature refrigeration system used to provide cooling in a freezer, wherein the refrigerant preferably has an evaporation temperature in the range of about -40°C to about -12°C, and the refrigerant preferably has a condensation temperature in the range of about 40°C to about 70°C, or about 20°C to about 70°C.

[0296] Accordingly, the present invention also provides a low-temperature refrigeration system used to provide cooling in a cream machine, wherein the refrigerant preferably has an evaporation temperature in the range of about -40°C to about -12°C, and the refrigerant preferably has a condensation temperature in the range of about 40°C to about 70°C, or about 20°C to about 70°C.

[0297] The cryogenic system of the present invention, including the system described in the preceding paragraph, preferably comprises an air-to-refrigerant evaporator for cooling food or beverages, a reciprocating, scroll, or rotary compressor, an air-to-refrigerant condenser for heat exchange with ambient air, and a temperature-sensitive or electronic expansion valve.

[0298] For the purposes of the present invention, each heat transfer composition according to the present invention (including each heat transfer composition 1 to 46) is provided for use in a cooling device having 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 cooling device is provided for use in air conditioning or refrigeration, preferably in commercial air conditioning. The cooling device is preferably a positive displacement cooling device, and more specifically, an air-cooled or water-cooled direct expansion cooling device, which may be either modular or a conventional single-package type.

[0299] Accordingly, the present invention provides the use of each heat transfer composition (including each heat transfer composition 1 to 46) according to the present invention in stationary air conditioning systems, particularly household air conditioning systems, industrial air conditioning systems, or commercial air conditioning systems.

[0300] The heat transfer system may be a refrigeration system such as a low-temperature refrigeration system, a medium-temperature refrigeration system, a commercial refrigerator, a commercial freezer, an ice maker, a vending machine, a transport refrigeration system, a household freezer, a household refrigerator, an industrial freezer, an industrial refrigerator, and a cooling device. [Examples]

[0301] Comparative Examples 1A-1C - Heat transfer composition containing CF3I-containing refrigerant, POE lubricant, and stabilizer The heat transfer compositions were tested according to ASHRAE standard 97, "Sealed glass tube method for testing the chemical stability of materials for use in refrigerant systems," simulating the long-term stability of the heat transfer compositions through accelerated degradation. The tests were carried out with three different coupon combinations: Cu / Al / Fe (copper / aluminum / iron); Cu / Al / Fe / brass (copper / aluminum / brass); and Cu / Al / Fe / Zn (copper / aluminum / iron / zinc). The refrigerants tested consisted of 49 wt% R-32, 11.5 wt% R-125, and 39.5 wt% CF3I (R-466A). The POE lubricant was Danfoss 160SZ POE, which had a viscosity of approximately 30-34 cSt at 40°C and a water content of 150 ppm or less. The stabilizer package contains NA-LUBE KR-008 (AN5), tricresyl phosphate ("TCP"), and 2-ethylhexylglycidyl ether (ADM4) in the amounts shown in Table ExC1 below.

[0302] [Table 6]

[0303] After the tests, 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 the stability of the refrigerant, as this compound is believed to be a decomposition product of CF3I.

[0304] Fluid stability was tested by placing a sealed tube containing the specified coupon in an oven maintained at approximately 150°C for 14 days. The results after the 14-day period are shown in Table ExC2 below.

[0305] [Table 7]

[0306] As can be seen from the test results conducted by the applicant in the presence of copper, aluminum, and iron (ExC1A), the heat transfer composition containing the specified combination of stabilizers was able to produce acceptable results in the presence of these three metals (but not in the presence of zinc). This is indicated, 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, from its own tests, the applicant recognized that stability was significantly reduced in the presence of zinc-containing metals such as zinc (ExC1C) and brass (ExC1B). This is indicated, for example, by a dramatic increase in fluoride concentration (10 to 20 times) and a dramatic increase in iodide concentration (100 to 500 times). Similarly, the presence of zinc increased the TAN value by an order of magnitude and increased R-23 by 4 to 7 times. Furthermore, visual inspection confirmed that the fluid was not maintained stably in the presence of zinc. This performance degradation is reflected in the zinc levels measured in the tube at the end of the test. In particular, the zinc concentration increases by approximately 85 to 380 times.

[0307] Example 1 - Heat transfer composition containing CF3I-containing refrigerant, POE lubricant, stabilizer and protective agent As reported in Table Ex1A, 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% and 0.1% by weight before the test.

[0308] [Table 8]

[0309] Next, as described in Comparative Example 1, the fluid stability was tested in the presence of zinc (using two separate test tubes with a protective agent concentration of 0.05 wt%). Specifically, sealed tubes containing copper, aluminum, iron, and zinc were placed 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 also illustrated in the chart below, along with the results of the comparative example (using the average value), for ease of comparison.

[0310] [Table 9]

[0311]

number

[0312] As illustrated by the test results shown above, the addition of the protective agent of the present invention yields the unexpected result of a dramatic improvement in the performance of the fluid in terms of stability. This is demonstrated, for example, by the fact that the zinc level is only about 0.0002% of the zinc level without the protective agent of the present invention, and the R-23 level is only 0.004% of the R-23 level without the protective agent.

[0313] Heat transfer composition comprising CF3I-containing refrigerant, POE lubricant, AN stabilizer, and protective agent in Examples 2A and 2B The heat transfer composition was tested according to ASHRAE standard 97, "Sealed glass tube method for testing the chemical stability of materials for use in refrigerant systems," simulating the long-term stability of the heat transfer composition by accelerated degradation. The test was carried out using the following four coupons: Cu / Al / Fe / Zn. The refrigerant tested consisted of 49 wt% R-32, 11.5 wt% R-125, and 39.5 wt% CF3I (R-466A). The POE lubricant was the same 160SZ POE described in Comparative Example 1. Stabilizers consisting of KR-008 and ADM5 (EHGE), as well as the protective agent PA-5 of the present invention, were included in the amounts shown in Table Ex2A below.

[0314] [Table 10]

[0315] After the test, 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 a sealed tube containing the specified coupon 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 were used for a PA5 concentration of 0.1 wt, and the average of these results is reported below as Ex2BAvg. For ease of comparison, the results for comparative example C1C are also provided, and the results are illustrated graphically in the chart following the table.

[0316] [Table 11]

[0317]

number

[0318] As can be seen from the test results conducted by the applicant in the presence of copper, aluminum, iron, and zinc, the heat transfer compositions containing 0.05% by weight and 0.1% by weight of PA5, respectively, showed unexpectedly reduced levels of Zn and R-23 compared to Comparative Example 1C. Even more unexpectedly, the best performance in terms of R-23 was achieved when the protective agent concentration was greater than zero and less than 0.1% by weight.

[0319] Examples 3A and 3B - Heat transfer composition containing CF3I-containing refrigerant, POE lubricant, ADM stabilizer and protective agent The heat transfer composition was tested according to ASHRAE standard 97, "Sealed glass tube method for testing the chemical stability of materials for use in refrigerant systems," simulating the long-term stability of the heat transfer composition by accelerated degradation. The test was carried out using the following four coupons: Cu / Al / Fe / Zn. The refrigerant tested consisted of 49 wt% R-32, 11.5 wt% R-125, and 39.5 wt% CF3I (R-466A). The POE lubricant was the same 160SZ POE described in Comparative Example 1. Stabilizers consisting of AN (KR-008), TCP, and ADM5 (EHGE), as well as the protective agent PA5 of the present invention, were included in the amounts shown in Table Ex3A below.

[0320] [Table 12]

[0321] After the tests, 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 a sealed tube containing the specified coupon 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 values ​​of these results are reported below as Ex3AAvg and Ex3BAvg, respectively. For ease of comparison, the results for comparative example C1C are also provided.

[0322] [Table 13]

[0323]

number

[0324] As can be seen from the test results conducted by the applicant in the presence of copper, aluminum, iron, and zinc, heat transfer compositions containing 0.025 wt% and 0.05 wt% PA5 along with various amounts of EHGE had unexpectedly reduced levels of Zn and R-23 compared to Comparative Example C1 (0 wt% PA5), respectively. Even more unexpectedly, the best performance in terms of R-23 and copper was achieved when the protective agent concentration was greater than zero and less than 0.05 wt%.

[0325] Comparative Examples 2A to 2C-R-1234ze(E) and heat transfer composition containing POE lubricant The heat transfer composition was tested according to ASHRAE standard 97, "Sealed glass tube method for testing the chemical stability of materials for use in refrigerant systems," simulating the long-term stability of the heat transfer composition by accelerated degradation. The tested heat transfer composition consisted of 50 wt% refrigerant (r-1234ze(E)) and 50 wt% POE lubricant (RL32-3MAF sold by Emkarate, with a viscosity of approximately 31 cSt at 40°C). The test was conducted using three different coupon combinations: Cu / Al / Fe; brass; and Zn. Two (2) separate test tubes were used with the Cu / Al / Fe and brass coupons, and the results reported below are the average of those results. Four (4) separate test tubes were used with the Zn coupon, and the results reported below are the average of all results.

[0326] After the tests, 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.

[0327] Fluid stability was tested by placing a sealed tube containing the specified coupon in an oven maintained at approximately 150°C for 14 days. The results after the 14-day period are shown in Table ExC2 below.

[0328] [Table 14]

[0329] As can be seen from the test results conducted by the applicant in the presence of copper, aluminum, and iron (ExC2A), the heat transfer composition consisting of R-1234ze(E) and POE lubricant yielded acceptable results in the presence of these three metals (but not zinc), even in the absence of stabilizers. This is demonstrated, for example, by the fact that the fluoride content of ExC1A is less than 10 ppm, the iodide content is less than 1.5, the TAN value is less than 0.5, and the Zn content is less than 0.3 ppm. However, the applicant found from its own tests that stability was significantly reduced in the presence of zinc-containing metals such as zinc (ExC2C) and brass (ExC2B). This is demonstrated, for example, by the fact that the Zn concentration increased dramatically to more than 150 times that of ExC2A, and the TAN value increased to more than 3 times that of ExC2A.

[0330] Examples 4A to 4E: Heat transfer composition containing CF3I-containing refrigerant, POE lubricant, stabilizer and protective agent The test of Comparative Example 2 is repeated, except that the protective agent of the present invention, i.e., protective agent 5, is added to each fluid in amounts of 0.01% by weight, 0.025% by weight, and 0.05% by weight before testing.

[0331] Next, the stability of each fluid was tested in the presence of the same coupon identified in Comparative Example 2, and under the same conditions. The results after a 14-day period are shown in Table Ex4 below, and the results of the Zn coupon test are illustrated in the chart below, along with the results of the zinc coupon test in Comparative Example 2 (using the average value) for ease of comparison.

[0332] [Table 15]

[0333]

number

[0334] As illustrated by the above test results, the addition of the protective agent of the present invention unexpectedly improves the performance of the fluid in the presence of zinc, from a stability standpoint. This is demonstrated, for example, by the fact that using 0.01% by weight of the protective agent of the present invention results in a zinc level approximately 40% lower than that without the protective agent, and a TAN value approximately 30% lower than that without the protective agent. Even more unexpectedly, using amounts exceeding 0.01% by weight of the protective agent can reduce the zinc level by two orders of magnitude, i.e., reduce the Zn level to less than 10 ppm, and reduce the TAN value to less than 0.1 mg KOH / g. This result is highly desirable and unexpected.

[0335] Example 5a - Heat transfer composition of the present invention used in medium-temperature commercial refrigeration with and without a suction line (Sl) / liquid line (LL) heat exchanger (HX) A commercial refrigeration system having a zinc-containing surface in contact with a heat transfer composition is operated using each of the heat transfer compositions 1 to 46, based on the following average operating conditions. Condensation temperature = 45.0℃ Condensation temperature - ambient temperature = 10.0℃ • Condenser supercooling degree = 0.0°C (system with receiver) • Evaporation temperature = -8.0℃ ·Evaporator superheat degree=5.5℃ • Compressor entropy efficiency = 65.0% • Volumetric efficiency = 100% • Temperature rise in the intake line = 10.0℃ • Suction line / liquid line heat exchanger effectiveness: 0%, 35%, 55%, 75%

[0336] This system is operated over a long period of time using each of the above heat transfer compositions, and advantageously, a high level of stability and corrosion resistance is achieved.

[0337] Example 5b - Heat transfer composition of the present invention used in low-temperature commercial refrigeration with and without a suction line (Sl) / liquid line (LL) heat exchanger (HX) A commercial refrigeration system having a zinc-containing surface in contact with a heat transfer composition is operated using each of the heat transfer compositions 1 to 46, based on the following average operating conditions. Condensation temperature = 45.0℃ Condensation temperature - ambient temperature = 10.0℃ • Condenser supercooling degree = 0.0°C (system with receiver) • Evaporation temperature = -35.0℃ ·Evaporator superheat degree=5.5℃ • Compressor entropy efficiency = 65.0% • Volumetric efficiency = 100% • Temperature rise in the intake line = 10.0℃ • Suction line / liquid line heat exchanger effectiveness: 0%, 35%, 55%, 75%

[0338] This system is operated over a long period of time using each of the above heat transfer compositions, and advantageously, a high level of stability and corrosion resistance is achieved.

[0339] Example 6 - Heat transfer composition of the present invention used in commercial air conditioning A commercial air conditioning system having a zinc-containing surface in contact with a heat transfer composition is operated using each of the heat transfer compositions 1 to 46, based on the following average operating conditions. Condensation temperature = 45.0℃ Condensation temperature - ambient temperature = 10.0℃ • Condenser supercooling degree = 5.0°C (system without receiver) • Evaporation temperature = 7.0℃ ·Evaporator superheat degree=5.5℃ • Compressor entropy efficiency = 72.0% • Volumetric efficiency = 100% • Temperature rise in the intake line = 5.0℃

[0340] This system is operated over a long period of time using each of the above heat transfer compositions, and advantageously, a high level of stability and corrosion resistance is achieved.

[0341] Example 7 - Heat transfer composition of the present invention used in residential air conditioning A residential air conditioning system having a zinc-containing surface in contact with a heat transfer composition is operated using each of the heat transfer compositions 1 to 46, based on the following average operating conditions. Condensation temperature = 45.0℃ Condensation temperature - ambient temperature = 10.0℃ • Condenser supercooling degree = 5.0°C (system without receiver) • Evaporation temperature = 7.0℃ ·Evaporator superheat degree=5.5℃ • Compressor entropy efficiency = 72.0% • Volumetric efficiency = 100% • Temperature rise in the intake line = 5.0℃

[0342] This system is operated over a long period of time using each of the above heat transfer compositions, and advantageously, a high level of stability and corrosion resistance is achieved.

[0343] Example 8 - Heat transfer composition of the present invention used in a cooling device A chiller system having a zinc-containing surface in contact with a heat transfer composition is operated using each of the heat transfer compositions 1 to 46, based on the following average operating conditions. Condensation temperature = 45.0℃ Condensation temperature - ambient temperature = 10.0℃ • Condenser supercooling degree = 5.0°C (system without receiver) • Evaporation temperature = 4.0℃ ·Evaporator superheat degree=5.5℃ • Compressor entropy efficiency = 70.0% • Volumetric efficiency = 100% • Temperature rise in the intake line = 5.0℃

[0344] This system is operated over a long period of time using each of the above heat transfer compositions, and advantageously, a high level of stability and corrosion resistance is achieved.

[0345] Example 9 - Heat transfer composition of the present invention used in stationary heat pumps A stationary heat pump system having a zinc-containing surface in contact with a heat transfer composition is operated using each of the heat transfer compositions 1 to 46, based on the following average operating conditions. Condensation temperature = 45.0℃ Condensation temperature - ambient temperature = 10.0℃ • Condenser supercooling degree = 5.0°C (system without receiver) • Evaporation temperature = 0℃ ·Evaporator superheat degree=5.5℃ • Compressor entropy efficiency = 70.0% • Volumetric efficiency = 100% • Temperature rise in the intake line = 5.0℃

[0346] This system is operated over a long period of time using each of the above heat transfer compositions, and advantageously, a high level of stability and corrosion resistance is achieved.

[0347] Example 10 - Heat transfer composition of the present invention used in a mobile heat pump A mobile heat pump system, located inside an electric vehicle and having a zinc-containing surface in contact with a heat transfer composition, is operated using each of the heat transfer compositions 1 to 46, based on the following average operating conditions. Condensation temperature = 45.0℃ Condensation temperature - ambient temperature = 10.0℃ • Condenser supercooling degree = 5.0°C (system without receiver) • Evaporation temperature = 0.0℃ ·Evaporator superheat degree=5.5℃ • Compressor entropy efficiency = 65% • Volumetric efficiency = 100% • Temperature rise in the intake line = 5.0℃

[0348] This system is operated over a long period of time using each of the above heat transfer compositions, and advantageously, a high level of stability and corrosion resistance is achieved.

[0349] Example 11 - Heat transfer composition of the present invention used in mobile air conditioning A mobile air conditioning system having a zinc-containing surface in contact with a heat transfer composition is operated using each of the heat transfer compositions 1 to 46, based on the following average operating conditions. Condensation temperature = 45.0℃ Condensation temperature - ambient temperature = 10.0℃ • Condenser supercooling degree = 5.0°C (system with receiver) • Evaporation temperature = 4.0℃ ·Evaporator superheat degree=5.5℃ • Compressor entropy efficiency = 65.0% • Volumetric efficiency = 100% • Temperature rise in the intake line = 0.0℃

[0350] This system is operated over a long period of time using each of the above heat transfer compositions, and advantageously, a high level of stability and corrosion resistance is achieved.

[0351] Example 12a - Heat transfer composition of the present invention used in a medium-temperature industrial refrigeration system with and without a suction line (Sl) / liquid line (LL) heat exchanger (HX) An industrial refrigeration system having a zinc-containing surface in contact with a heat transfer composition is operated using each of the heat transfer compositions 1 to 46, based on the following average operating conditions. Condensation temperature = 45.0℃ Condensation temperature - ambient temperature = 10.0℃ • Condenser supercooling degree = 0.0°C (system with receiver) • Evaporation temperature = -8.0℃ ·Evaporator superheat degree=5.5℃ • Compressor entropy efficiency = 65% • Volumetric efficiency = 100% • Temperature rise in the suction line = 10°C • Suction line / liquid line heat exchanger effectiveness: 0%, 35%, 55%, 75%

[0352] This system is operated over a long period of time using each of the above heat transfer compositions, and advantageously, a high level of stability and corrosion resistance is achieved.

[0353] Example 12b - Heat transfer composition of the present invention used in low-temperature industrial refrigeration systems with and without a suction line (Sl) / liquid line (LL) heat exchanger (HX) An industrial refrigeration system having a zinc-containing surface in contact with a heat transfer composition is operated using each of the heat transfer compositions 1 to 46, based on the following average operating conditions. Condensation temperature = 45.0℃ Condensation temperature - ambient temperature = 10.0℃ • Condenser supercooling degree = 0.0°C (system with receiver) • Evaporation temperature = -35.0℃ ·Evaporator superheat degree=5.5℃ • Compressor entropy efficiency = 65.0% • Volumetric efficiency = 100% • Temperature rise in the suction line = 10°C • Suction line / liquid line heat exchanger effectiveness: 0%, 35%, 55%, 75%

[0354] This system is operated over a long period of time using each of the above heat transfer compositions, and advantageously, a high level of stability and corrosion resistance is achieved.

[0355] Example 13a - Heat transfer composition of the present invention used in a medium-temperature transport refrigeration system with and without a suction line (Sl) / liquid line (LL) heat exchanger (HX) A transport refrigeration system having a zinc-containing surface in contact with a heat transfer composition is operated using each of the heat transfer compositions 1 to 46, based on the following average operating conditions. Condensation temperature = 45.0℃ Condensation temperature - ambient temperature = 10.0℃ • Condenser supercooling degree = 0.0°C (system with receiver) • Evaporation temperature = -8.0℃ ·Evaporator superheat degree=5.5℃ • Compressor entropy efficiency = 65% • Volumetric efficiency = 100% • Temperature rise in the suction line = 15°C • Suction line / liquid line heat exchanger effectiveness: 0%, 35%, 55%, 75%

[0356] This system is operated over a long period of time using each of the above heat transfer compositions, and advantageously, a high level of stability and corrosion resistance is achieved.

[0357] Example 13b - Heat transfer composition of the present invention used in a cryogenic transport refrigeration system with and without a suction line (Sl) / liquid line (LL) heat exchanger (HX) A transport refrigeration system having a zinc-containing surface in contact with a heat transfer composition is operated using each of the heat transfer compositions 1 to 46, based on the following average operating conditions. Condensation temperature = 45.0℃ Condensation temperature - ambient temperature = 10.0℃ • Condenser supercooling degree = 0.0°C (system with receiver) • Evaporation temperature = -35.0℃ ·Evaporator superheat degree=5.5℃ • Compressor entropy efficiency = 65% • Volumetric efficiency = 100% • Temperature rise in the suction line = 15°C • Suction line / liquid line heat exchanger effectiveness: 0%, 35%, 55%, 75%

[0358] This system is operated over a long period of time using each of the above heat transfer compositions, and advantageously, a high level of stability and corrosion resistance is achieved.

Claims

1. An improved heat transfer system of the type having at least a circulating working fluid and one or more equipment components that are exposed to the working fluid during operation, wherein the improvement is (c) At least one of the one or more equipment components that is exposed to the circulating working fluid and has a surface containing zinc, (d) Refrigerant and formula I: 【Chemistry 1】 The working fluid comprises at least one protective agent containing a compound by, In the formula, R and R １ However, each is independently selected from the group consisting of hydrogen, alkyl, hydroxyalkyl and alkylthio, provided that R and R １ At least one of them A heat transfer system that requires alkylthio to be present.

2. The R and the R １ The improved system according to claim 1, wherein each of them is independently a 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 dioctyl disulfide.

5. A method for providing heat transfer, (c) To provide a heat transfer system comprising one or more components having at least one surface formed from a zinc-containing metal, (d) Providing a working fluid in the system, including (i) the working fluid being in contact with the at least one surface, and (ii) the working fluid comprising a refrigerant and a protective agent comprising a compound according to formula I, 【Chemistry 2】 In the formula, R and R １ However, each is independently selected from the group consisting of hydrogen, alkyl, hydroxyalkyl and alkylthio, provided that R and R １ At least one of them A method that requires the element to be alkylthio.

6. The R and the R １ The method according to claim 5, wherein each of them is independently a 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 the dioctyl disulfide.

9. A heat transfer composition, (d) At least one refrigerant selected from HFCs, HCFCs, HFOs, HCFOs, fluoroiodocarbons, and two or more combinations thereof, comprising HC as part of the blend, (e) at least one lubricant selected from POE and PVE, and (f) Formula I: 【Transformation 3】 A protective agent containing compounds by, In the formula, R and R １ However, each is independently selected from the group consisting of hydrogen, alkyl, hydroxyalkyl and alkylthio, provided that R and R １ At least one of them A heat transfer composition that is required to be alkylthio.

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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