Fluoro-substituted ethers, compositions comprising same, and related methods and uses thereof

Abstract

Fluoroether 3-(difluoromethoxy)-1, 1, 1, 2, 2-pentafluoropropane ("HFE-347 mcf") can be used as a refrigerant and / or heat transfer composition, such as in a single-phase cooling system and a two-phase cooling system, and a method of heating and / or cooling an electronic component or apparatus includes providing a heat transfer fluid comprising at least about 10% by weight of 3-(difluoromethoxy)-1, 1, 1, 2, 2-pentafluoropropane, and transferring heat between the electronic component and the heat transfer fluid. According to the present invention, fluoroether 3-(difluoromethoxy)-1, 1, 1, 2, 2-pentafluoropropane can be synthesized by reacting 2, 2, 3, 3, 3-pentafluoro-1-propanol with chlorodifluoromethane (R-22), and a process for producing the fluoroether 3-(difluoromethoxy)-1, 1, 1, 2, 2-pentafluoropropane.

Description

[0001] Cross - reference to related applications

[0002] This application claims the benefit of U.S. Provisional Patent Application Ser. No. 63 / 415,683, filed on Oct. 13, 2022, entitled "Fluorine substituted ethers derived from chlorodifluoromethane (R22), compositions, methods and uses including same", under 35 U.S.C. § 119(e). The entire disclosure of the provisional patent application is hereby incorporated by reference in its entirety. Technical field

[0003] The present disclosure relates to fluorine - substituted ethers, compositions (such as refrigerants and / or heat - transfer compositions) containing such ethers, and related methods and uses, including the thermal management of electronic devices (such as immersion cooling). Background art

[0004] There is still a need for inert fluorinated compounds that have a low global warming potential while providing high thermal stability, low toxicity, non - flammability, good solubility, and a wide operating temperature range to meet the requirements of various applications.

[0005] The Applicant has recognized that numerous challenging problems are associated with the development of new compounds and compositions for many important applications. In particular, the Applicant has recognized the need for compositions, methods, and systems that are simultaneously environmentally acceptable (low GWP and low ODP), nonflammable, have low toxicity or no toxicity, and have excellent properties required for a particular application (e.g., good solvency for vapor degreasing, or low dielectric constant if the application involves exposure to or potential exposure to electronic equipment or components). There also continues to be a need for improved compounds for transferring heat and / or controlling the temperature of devices and articles, including in portable and handheld electronic devices, where the desire to miniaturize while adding functionality has increased the thermal power density of the devices during operation, thus making the cooling of electronic components (including batteries) within these devices more challenging. As a general rule, the increasing computing power within desktop computers, data centers, telecommunications centers, etc. has resulted in an increased heat output when such devices are operating, again making the thermal management of such electronic devices increasingly important, difficult, and demanding. Other examples of thermal management challenges have arisen due to the increasing use of electric vehicles, especially including cars, trucks, motorcycles, etc. In electric vehicles, for several reasons, thermal management functions are particularly important and challenging, including the criticality of cooling and / or heating the battery to a relatively narrow temperature range in a reliable, efficient, and safe manner, and as the demand for battery-powered vehicles with a larger range and faster charging increases, the challenge of providing effective thermal battery management becomes increasingly greater.

[0006] The efficiency and effectiveness of batteries, especially those that provide power in electric vehicles, are a function of the operating temperature at which they operate. Therefore, thermal management systems must frequently be able to do more than simply remove heat from the battery during operation and / or charging - it must be able to achieve cooling within a relatively narrow temperature range using equipment that is as low-cost and lightweight as possible. This has led to a need for heat transfer compositions in such systems that have a combination of physical and performance properties that are difficult to achieve. In addition, in some important applications, thermal management systems must be able to add heat to the battery, not only from the perspective of thermal performance, but also from many other perspectives including environmental, safety (flammability and toxicity), dielectric properties, etc., especially when the vehicle is starting in cold weather, which further increases the difficulty of finding and developing / obtaining compounds and / or compositions that are effective in such systems.

[0007] As a specific example of the importance of dielectric constant, a system commonly used for the thermal management of electric vehicle batteries involves immersing the batteries in a composition for thermal management. Such systems add an additional constraint, namely, that when the battery or device is operating, the composition used in such systems must be electronically compatible while in intimate contact with the battery or other electronic devices or components. Generally speaking, this means that the composition must not only be nonflammable, but also have low electrical conductivity and a high level of stability when in contact with the battery or other electronic components during operation and at the relatively high temperatures that exist during operation. The applicant has recognized that such properties are also required even in the indirect cooling of operating electronic devices and batteries, as any leakage of such a composition could result in contact with operating electronic components.

[0008] Another example of a challenge faced in the supply of thermal management refrigerants is the increasing popularity of electric vehicles, particularly including vehicle types such as cars, trucks, motorcycles, etc. In electric vehicles, for several reasons, the thermal management function is particularly important and challenging, including the criticality of cooling and / or heating the battery to a relatively narrow temperature range and in a reliable, efficient, and safe manner, and as the demand for battery-powered vehicles with a larger range and faster charging increases, the challenge of providing effective battery thermal management becomes increasingly greater.

[0009] To date, perfluorinated compounds are often used in many of these demanding applications. In addition, other thermal management compositions commonly used for battery cooling, including immersion cooling, are water / glycol combinations, but other classes of materials, including certain chlorofluorocarbons, fluorohydrocarbons, chlorohydrocarbons, and hydrofluoroethers, have also been mentioned as being usable. See, for example, US2018 / 0191038.

[0010] Fluorinated ether compounds according to the following formula have been proposed as solvents, particularly for various fluorinated polyethers,

[0011] (F3C)2CH-O-CH n F 2-n -CH m F 3-m

[0012] wherein n is 1 or 2, and wherein when n is 1, m is any integer from 0 to 3, but when n is 2, then m is 0 or 2. See JP202105950. This document states that embodiments of the above formula having a 3-1 configuration (understood to mean m = 3 and n = 1) are said to have additional uses, including as drainage agents, foaming agents, heat transfer media, and fire extinguishing agents, but such uses are not specifically described nor are they exemplified.

[0013] Accordingly, the Applicant has recognized that, in addition to the other needs described herein, there is a need for thermal management methods and systems using heat transfer compositions that are environmentally acceptable (low GWP and low ODP), non-flammable, low-toxic or non-toxic, have excellent heat insulation properties, and have heat properties that provide effective cooling and / or heating (including at relatively high temperatures), and / or for use in operating electronic components, etc. with preferably low-cost, reliable, and lightweight equipment within a relatively narrow temperature range.

[0014] Other applications of fluorinated ether compounds include aerosol propellants, foaming agents, gaseous dielectrics, fire extinguishing agents, solvents, cleaning agents, aerosol propellants, working fluids for power cycles, and starting materials for preparing other organic fluorine compounds. SUMMARY OF THE INVENTION

[0015] This disclosure is based on the discovery that certain fluorinated ether compounds, especially including 3-(difluoromethoxy)-1,1,2,2-tetrafluoropropane, 3-(difluoromethoxy)-1,1,1,2,2-pentafluoropropane (sometimes referred to herein as “HFE-347mcf”), 2-(difluoromethoxy)-1,1,1,3,3,3-hexafluoropropane, and 4-(difluoromethoxy)-1,1,1,2,2,3,3-heptafluorobutane, can be used as refrigerants and / or for heat transfer compositions, as well as in other application areas disclosed herein.

[0016] In one form thereof, this disclosure provides a method for providing heat transfer to and / or from an electronic component, article, and / or device during operation of the electronic component, article, and / or device, comprising: providing a heat transfer composition comprising at least about 10 wt% of 3-(difluoromethoxy)-1,1,1,2,2-pentafluoropropane; and contacting the heat transfer composition with the electronic component, article, and / or device during operation of the electronic component, article, and / or device to cool the electronic component, article, and / or device.

[0017] In another form thereof, this disclosure provides a method for heating and / or cooling an electronic component, article, and / or device during operation of the electronic component, article, and / or device, comprising: (a) providing a heat transfer composition comprising at least about 10 wt% of 3-(difluoromethoxy)-1,1,1,2,2-pentafluoropropane; (b) immersing the electronic component, article, and / or device in the heat transfer composition during operation of the electronic component, article, and / or device; and (c) effecting heat transfer between the immersed electronic component, article, and / or device and the heat transfer composition.

[0018] In yet another form, the present disclosure provides a method for synthesizing 3-(difluoromethoxy)-1,1,1,2,2-pentafluoropropane, comprising reacting 2,2,3,3,3-pentafluoro-1-propanol with chlorodifluoromethane in the presence of a base.

[0019] The present disclosure also provides 3-(difluoromethoxy)-1,1,2,2-tetrafluoropropane (Compound 1) and a composition (Composition 1) comprising the compound.

[0020] The present disclosure also provides 3-(difluoromethoxy)-1,1,1,2,2-pentafluoropropane (sometimes referred to herein as "HFE-347mcf") (Compound 2) and a composition (Composition 2) comprising the compound.

[0021] The present disclosure also provides 2-(difluoromethoxy)-1,1,1,3,3,3-hexafluoropropane (Compound 3) and a composition (Composition 3) comprising the compound.

[0022] The present disclosure also provides 4-(difluoromethoxy)-1,1,1,2,2,3,3-heptafluorobutane (Compound 4) and a composition (Composition 4) comprising the compound.

[0023] The present disclosure also provides a heat transfer composition comprising HFE-347mcf. The heat transfer composition of this paragraph is sometimes referred to herein as heat transfer composition 1 for convenience.

[0024] The present disclosure also provides a heat transfer composition comprising at least about 10 wt% of HFE-347mcf. The heat transfer composition of this paragraph is sometimes referred to herein as heat transfer composition 2 for convenience.

[0025] The present disclosure also provides a heat transfer composition comprising at least about 50 wt% of HFE-347mcf. The heat transfer composition of this paragraph is sometimes referred to herein as heat transfer composition 3 for convenience.

[0026] The present disclosure also provides a heat transfer composition comprising at least about 75 wt% of HFE-347mcf. The heat transfer composition of this paragraph is sometimes referred to herein as heat transfer composition 4 for convenience.

[0027] The present disclosure also provides a heat transfer composition comprising at least about 90 wt% of HFE-347mcf. The heat transfer composition of this paragraph is sometimes referred to herein as heat transfer composition 5 for convenience.

[0028] The present disclosure also provides a heat transfer composition consisting essentially of HFE-347mcf. The heat transfer composition of this paragraph is sometimes referred to herein as heat transfer composition 6 for convenience.

[0029] The present disclosure also provides a heat transfer composition comprising HFE-347mcf. For convenience, the heat transfer composition according to this paragraph is sometimes referred to herein as heat transfer composition 7.

[0030] The present disclosure also provides a heat transfer composition comprising Compound 1, which is sometimes referred to herein as heat transfer composition 8 for convenience.

[0031] The present disclosure also provides a heat transfer composition comprising Compound 3, which is sometimes referred to herein as heat transfer composition 9 for convenience.

[0032] The present disclosure also provides a heat transfer composition comprising Compound 4, which is sometimes referred to herein as heat transfer composition 10 for convenience. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] The above and other features of the present disclosure and the manner of achieving them will become more apparent and the present disclosure itself will be better understood by reference to the following description of embodiments of the present disclosure in conjunction with the accompanying drawings.

[0034] Figure 1 is a schematic diagram of a thermal management system for the present disclosure.

[0035] Figure 2A is a schematic diagram of a first exemplary immersion cooling system according to the present disclosure.

[0036] Figure 2B is a schematic diagram of a second exemplary immersion cooling system according to the present disclosure.

[0037] Figure 3 is a schematic diagram of a battery thermal management system according to an embodiment of the present disclosure.

[0038] Figure 4 is a photograph showing a battery thermal management system according to an embodiment of the present disclosure.

[0039] Figure 5 is a schematic diagram of an exemplary organic Rankine cycle.

[0040] Figure 6 is a schematic diagram of an exemplary heat pump.

[0041] Figure 7 is a schematic diagram of an exemplary secondary loop system.

[0042] Figure 8 is a semi-schematic diagram of an example of a lithium-ion battery cooling system using the composition of the present disclosure.

[0043] Figure 9 is a semi-schematic diagram of an example of a lithium-ion battery having an electrolyte formulation of the present disclosure.

[0044] Figure 10 Semi-schematic view of a heat dissipation tube using the heat transfer composition of the present disclosure.

[0045] The examples presented herein illustrate embodiments of the present disclosure, and such examples should not be construed as limiting the scope of the present disclosure in any way. Detailed Description

[0046] I. Definitions

[0047] Table 1

[0048] Compound names and corresponding chemical names as used herein

[0049]

[0050] "Electronic device" and related word forms mean a device or device component that is in the process of performing its intended function by receiving and / or transmitting and / or generating electrical energy and / or electronic signals, such as a battery, an electric vehicle battery, a data center, or an integrated circuit. Thus, as used herein, the term "operating electronic device" includes, for example, a battery that is in the process of providing a source of electrical energy to another component, and also includes, for example, a battery that is being charged or recharged.

[0051] "Operating electronic device" and related word forms mean a device or device component that is in the process of performing its intended function by receiving and / or transmitting and / or generating electrical energy and / or electronic signals. Thus, as used herein, the term "operating electronic device" includes, for example, a battery that is in the process of providing a source of electrical energy to another component, and also includes a battery that is being charged or recharged, including an electric vehicle battery, as well as a data center and an integrated circuit.

[0052] The term "heat transfer composition" and related word forms mean a composition in the form of a fluid (liquid or gas) that is used to transfer heat or energy from one fluid, article, or device to another fluid, article, or device, and thus includes, for example, refrigerants for Rankine cycles, heat management compositions, and working fluids.

[0053] When the heat transfer composition is used for heat management to maintain a device or article within a specific temperature range (e.g., in electronic cooling), it is sometimes referred to herein as a heat management composition.

[0054] A component or combination of components that is present in a heat transfer composition to transfer heat (as opposed to, for example, providing lubrication or stabilization) in a heat transfer system (e.g., a vapor compression heat transfer system) is sometimes referred to herein as a refrigerant.

[0055] As used herein, the term "Rankine cycle" refers to a system that includes the following: 1) a boiler that converts a liquid into vapor at high pressure; 2) a turbine that expands the vapor to obtain mechanical energy; 3) a condenser that converts the low-pressure exhaust vapor from the turbine into a low-pressure liquid; and 4) a pump that returns the condensate to the boiler at high pressure. Such systems are commonly used for power generation.

[0056] "Thermal contact" and its related forms include direct contact with a surface, as well as indirect contact through another body or fluid that facilitates heat flow between the surface and the fluid.

[0057] "Thermal conductivity" refers to the breakdown voltage measured in kV as per ASTM D7896-19.

[0058] The Global Warming Potential ("GWP") was established to allow comparison of the global warming impacts of different gases. It is a measure of how much energy one ton of a gas emitted will absorb over a given time period relative to one ton of carbon dioxide emissions. The greater the GWP, the warmer the gas will make the Earth compared to CO2 over that time period. The time period commonly used for GWP is 100 years. GWP provides a common metric - allowing analysts to sum up emissions estimates of different gases.

[0059] The term "Ames test negative" refers to a compound or composition that gives a negative result when tested according to the Ames test method as specified in the United States Toxic Substances Control Act.

[0060] "Flash point" refers to the lowest temperature at which the vapor of a liquid will continue to burn after the ignition source has been removed, as determined according to ASTM D3828-16a.

[0061] "Non-flammable" in the context of a heat transfer composition (including a thermal management composition or fluid) means a compound or composition having a flash point of not less than 100°F (37.8°C) according to NFPA 30: Flammable and Combustible Liquid Code. The flash point of a thermal management composition or fluid is the lowest temperature at which the vapor of the composition will continue to burn after the ignition source has been removed, as determined according to ASTM D3828-16a.

[0062] In the context of refrigerant compositions, compounds or compositions that are non-flammable and of low or no toxicity will be classified as "A1" according to ASHRAE Standard 34-2016, Designation and Safety Classification of Refrigerants, and are described in Appendix B1 of ASHRAE Standard 34-2016.

[0063] "Low or no toxicity" means a fluid that is classified as class "A" according to ASHRAE Standard 34-2016, Designation and Safety Classification of Refrigerants, and is described in Appendix B1 of ASHRAE Standard 34-2016.

[0064] "Capacity" is the amount of cooling provided by the refrigerant in a refrigeration system (in BTU / h). This is determined experimentally by multiplying the change in enthalpy (in BTU / lb) of the refrigerant as it passes through the evaporator by the mass flow rate of the refrigerant. The enthalpy can be determined from measurements of the pressure and temperature of the refrigerant. The capacity of a refrigeration system relates to its ability to keep an area cooled at a specific temperature. The capacity of a refrigerant represents the amount of cooling or heating it provides and gives some measure of the compressor's ability to pump heat for a given volumetric flow rate of refrigerant. In other words, given a specific compressor, a refrigerant with a higher capacity will deliver more cooling or heating power.

[0065] Coefficient of performance (hereinafter referred to as "COP") is a generally accepted measure of refrigerant performance, and is particularly useful for representing the relative thermodynamic efficiency of a refrigerant in a specific heating or cooling cycle involving refrigerant evaporation or condensation. In refrigeration engineering, the term represents the ratio of the useful refrigeration or cooling capacity to the energy applied by the compressor in compressing the vapor, and thus represents the compressor's ability to pump heat for a given volumetric flow rate of a heat transfer fluid such as refrigerant. In other words, given a specific compressor, a refrigerant with a higher COP will deliver more cooling or heating power. 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, R.C. Downing, FLUOROCARBON REFRIGERANTS HANDBOOK, Chapter 3, Prentice-Hall, 1988, the entire text of which is incorporated herein by reference).

[0066] "Vapor degreasing" means a surface cleaning process that uses solvent vapor to wash oil and other contaminants off an article or part of an article.

[0067] "Dielectric constant" means the dielectric constant measured at room temperature and 20 gigahertz (GHz).

[0068] "Dielectric strength" means the breakdown voltage in kV as measured according to Procedure A of ASTM D87-13, with the modification to this procedure that the distance between the electrodes is 2.54 mm and the voltage ramp rate is 500 V / s.

[0069] The terms "R-1132(E)", "HFO-1132(E)" and "trans-HFO-1132(E)" each mean the trans isomer of 1,2-difluoroethylene.

[0070] The terms "R-1132a" and "HFO-1132a" each mean 1,1-difluoroethylene.

[0071] The terms "R-1234yf" and "HFO-1234yf" mean 2,3,3,3-tetrafluoropropene.

[0072] The terms "R-1234ze(E)" and "HFO-1234ze(E)" mean the trans isomer of 1,3,3,3-tetrafluoropropene.

[0073] The terms "R-1233zd(E)" and "HFCO-1233zd(E)" mean the trans isomer of 1-chloro-3,3,3-trifluoropropene.

[0074] The terms "R-1233zd(Z)" and "HFCO-1233zd(Z)" mean the cis isomer of 1-chloro-3,3,3-trifluoropropene.

[0075] The terms "R-1224yd(E)" and "HFCO-1224yd(E)" mean the trans isomer of 1-chloro-2,3,3,3-tetrafluoropropane.

[0076] The terms "R-1224yd(Z)" and "HFCO-1224yd(Z)" mean the cis isomer of 1-chloro-2,3,3,3-tetrafluoropropane.

[0077] The terms "R-1336mzz(E)" and "HFO-1336mzz(E)" mean the trans isomer of 1,1,1,4,4,4-hexafluoro-2-butene.

[0078] The term "HFE-7000" means 1-methoxyheptafluoropropane (C3F7OCH3).

[0079] The term "HFE-7100" means 1-methoxynonafluorobutane (C4F9OCH3).

[0080] The term "HFE-7200" means ethoxynonafluorobutane (C4F9OC2H5).

[0081] The term "HFE-7300" means 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-trifluoromethylpentane.

[0082] The term "HFE-7500" means 2-trifluoromethyl 3-ethoxydodecafluorohexane.

[0083] As used herein, the singular forms "a", "an", and "the" include plural references unless the context clearly dictates otherwise.

[0084] As used herein, the recitation of a numerical range by endpoints includes all numbers subsumed within that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.8, 4, and 5).

[0085] Unless otherwise indicated, all numbers expressing quantities or ingredients, properties, measurement, and so forth used in the specification and examples are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by those skilled in the art utilizing the teachings of the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0086] As used herein, the phrase "in any range that encompasses any two of these values as endpoints" literally means that any range may be selected from any two of the values listed prior to such phrase, regardless of whether those values are in the lower portion or the higher portion of the list. For example, a pair of values may be selected from two lower values, two higher values, or a lower value and a higher value.

[0087] II. Synthesis and properties of the fluoroethers of the present invention

[0088] The present disclosure relates to a method for synthesizing a fluoroether compound according to Formula 1 below:

[0089] CHF2OCH a (Cx1Fy1Hz1)(Cx2Fy2Hz2)

[0090] where a = 1 or 2;

[0091] x1 is from 1 to 4;

[0092] y1 is from 3 to 9;

[0093] z1 is from 0 to 6;

[0094] x2 is from 0 to 3;

[0095] y2 ranges from 0 to 7; and

[0096] z2 ranges from 0 to 4.

[0097] As shown in Scheme 1 below, the fluoroether of Formula I above can be synthesized from any suitable fluoroalcohol and chlorodifluoromethane (R22) in one step.

[0098] Scheme 1

[0099]

[0100] The starting materials for the reaction can include R22 and any suitable fluoroalcohol. Suitable fluoroalcohols include 2,2,3,3-tetrafluoro-1-propanol, 2,2,3,3,3-pentafluoro-1-propanol, 2,2,2,3,3,3-hexafluoro-1-propanol, and 2,2,3,3,4,4,4-heptafluoro-1-butanol.

[0101] The fluoroether product can be any one of 3-(difluoromethoxy)-1,1,2,2-tetrafluoropropane, 3-(difluoromethoxy)-1,1,1,2,2-pentafluoropropane, 2-(difluoromethoxy)-1,1,1,3,3,3-hexafluoropropane, or 4-(difluoromethoxy)-1,1,1,2,2,3,3-heptafluorobutane.

[0102] An overview of the fluoroether products contemplated by the present disclosure, their corresponding fluoroalcohol starting materials, and their physical properties are provided in Table 2 below.

[0103] Table 2

[0104] Physical properties of fluoroalcohol starting materials and fluoroethers

[0105]

[0106] The starting fluoroalcohol and R22 can be present in a stoichiometric ratio of 0.8:1.2 to 1.2:0.8.

[0107] The reaction can be carried out in an organic solvent such as dimethylformamide (DMF), acetone, acetonitrile, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), isopropanol, ethanol, and methanol.

[0108] The reaction can be catalyzed by a base such as NaOH or KOH.

[0109] The reaction can be carried out in a reactor equipped with sufficient agitation to form a homogeneous reaction mixture. Suitable agitation can be achieved by using a mechanical stirrer or a magnetic stir bar. The reactor vessel can be connected to a heating medium to maintain an appropriate reaction temperature. The reactor vessel can be connected to a cooling bath having any suitable cooling medium to maintain a suitable reaction temperature. The reactor vessel can also be connected to a condenser having a cooling medium to condense the solvent vapor.

[0110] The entire reaction can also be carried out in an autoclave at an elevated pressure (such as below 300 psig).

[0111] The reaction can be carried out at a temperature as low as 0 °C, 5 °C, 10 °C, 15 °C, 20 °C, 25 °C or as high as 30 °C, 35 °C, 40 °C, 45 °C, 50 °C, or at any temperature within a range encompassed by any two of the foregoing values as endpoints. For example, the reaction can be carried out at a temperature of 10 °C to 25 °C.

[0112] Compounds 1-4 and / or heat transfer compositions 1-10 can have a boiling point of about 35 °C to about 80 °C (such as about 46 °C).

[0113] Compounds 1-4 and / or heat transfer compositions 1-10 can have a dielectric constant of less than about 5 (such as about 3.4) at 20 GHz.

[0114] Compounds 1-4 and / or heat transfer compositions 1-10 can be non-flammable.

[0115] III. Applications

[0116] The compounds and compositions of the present disclosure, including each of compounds 1-4 and compositions 1-4, can be used in a variety of applications, including but not limited to heat transfer compositions, thermal management compositions, refrigerants, aerosol propellants, blowing agents, heat transfer media, gaseous dielectrics, fire extinguishing agents, solvents, cleaners, aerosol propellants, power cycle working fluids, and starting materials for the production of other organofluorine compounds.

[0117] In heat transfer applications, Compounds 1-4 and / or Heat Transfer Compositions 1-10 of the present disclosure can also be used with a variety of auxiliary refrigerants (or auxiliary heat transfer fluids). Preferred auxiliary refrigerants include hexafluoroisopropyl ethyl ether, hexafluoroisopropyl methyl sulfide, HFE-7000, HFE-7200, HFE-7100, HFE-7500, trans-1,2-dichloroethylene, n-pentane, cyclopentane, ethanol, perfluoro(2-methyl-3-pentanone) (Novec 1230), cis-HFO-1336mzz, trans-HFO-1336mzz, HFO-1234yf, HFO-1234ze(E), HFO-1233zd(E) or HFO-1233zd(Z).

[0118] Table 3 below defines some preferred refrigerants that are blends comprising Compound 2 (HFE-347mcf) and at least one auxiliary refrigerant. The first column of the table below identifies and defines the refrigerant blends by number (such as RB1, RB2, etc.), and the abbreviations COMP, CEO, and CO are used in this column to indicate the nature of the blend components identified in the second and third columns. Specifically, the identification COMP in the first column indicates that the refrigerant contains Compound 2 and the indicated auxiliary refrigerant. The identification CEO in the first column indicates that the refrigerant consists essentially of Compound 2 and the designated auxiliary refrigerant, and the identification CO in the first column indicates that the refrigerant consists of Compound 2 and the designated auxiliary refrigerant. The second column indicates the weight percentage content of Compound 2 that needs to be present in the blend, where "=>" means "equal to or greater than". In the third column, the auxiliary refrigerant is clearly marked, and if the specific content of the auxiliary refrigerant in the blend needs to be specified, it is also indicated, where "=<" means "equal to or less than".

[0119] Table 3

[0120]

[0121]

[0122]

[0123]

[0124]

[0125]

[0126]

[0127] The present disclosure includes refrigerant blends of the present invention, specifically each of RB1–RB20, wherein the refrigerant is non-flammable.

[0128] The present disclosure includes refrigerant blends of the present invention, specifically each of RB1–RB20, wherein the refrigerant has a dielectric constant of less than about 5 at 20 GHz.

[0129] The present disclosure includes refrigerant blends of the present invention, specifically each of RB1–RB20, wherein the refrigerant has a dielectric constant of less than about 4 at 20 GHz.

[0130] The present disclosure includes refrigerant blends of the present invention, specifically each of RB1–RB20, wherein the refrigerant has a dielectric constant of less than about 5 at 20 GHz; (ii) has a boiling point of about 35°C to about 80°C; (iii) is non-flammable; and (iv) has a negative Ames test toxicity.

[0131] The present disclosure includes refrigerant blends of the present invention, specifically each of RB1–RB20, wherein the refrigerant has a boiling point of about 35°C to about 80°C.

[0132] The refrigerant blends of the present disclosure, including each of RB1–RB20, will hereinafter be referred to as blend RB1-RB20.

[0133] As discussed above, and particularly as set forth in Table 4, Compounds 1-4 and / or Heat Transfer Compositions 1-10 and / or Blend RB1-RB20 can be advantageously used in methods, devices or systems for cooling and / or heating in electronic devices.

[0134] As discussed herein, when the heat transfer compositions of the present disclosure (including each of Compounds 1-4 and / or Heat Transfer Compositions 1-10 and / or Blend RB1-RB20) are used in methods, devices or systems for cooling and / or heating in electronic devices, the heat transfer compositions are sometimes referred to herein as thermal management compositions. Thus, the thermal management compositions correspond to the heat transfer compositions discussed in this patent application.

[0135] Compounds 1-4 and / or heat transfer compositions 1-10 and / or blends RB1-RB20 are particularly useful as heat transfer compositions due to their low vapor pressure, low dielectric properties, high boiling point, and non-flammability. For example, when excess heat cannot be controlled by air cooling alone (such as during a "data tsunami"), Compounds 1-4 and / or heat transfer compositions 1-10 and / or blends RB1-RB20 can be employed in data centers. Compounds 1-4 and / or heat transfer compositions 1-10 and / or blends RB1-RB20 can be used in immersion cooling systems, which can efficiently dissipate heat while maintaining the integrity of data transmission crucial for microprocessing equipment.

[0136] These applications are discussed below:

[0137] Heat transfer compositions

[0138] As mentioned above, the present disclosure provides various methods, processes, and uses of the compounds disclosed herein as heat transfer compositions. Compounds 1-4 and / or heat transfer compositions 1-10 and / or blends RB1-RB20 can be used to transfer heat from one location to another (or from one body, article, or fluid to another body, article, or fluid). For example, the heat transfer composition can be used to keep the temperature of a device below a defined upper limit and / or above a defined lower limit temperature. In another example, the heat transfer composition can be used for energy conversion, such as capturing waste heat from an industrial or other process and converting it into electrical or mechanical energy.

[0139] Accordingly, the present disclosure encompasses various methods, processes, and uses of the compounds of the present disclosure (including each of Compounds 1-4 and / or heat transfer compositions 1-10 and / or blends RB1-RB20) as thermal management compositions (hereinafter sometimes referred to as TMCs), which are used to help maintain an article or device (preferably an electronic device or a battery) or a fluid within a certain temperature range, particularly when the article, device, or fluid is operating according to its intended purpose. For example, the TMCs of the present disclosure can be used to keep the temperature of a device below a defined upper limit temperature and / or above a defined lower limit temperature.

[0140] Preferred embodiments of the thermal management method of the present invention can be referred to Figure 1, which schematically shows an operating electronic device 10 having a source of electrical energy and / or signals 20 flowing in and / or out, and generating heat due to operation based on electrical energy and / or signals 20. The thermal management composition of the present disclosure is arranged to be in thermal contact with the operating device 10 such that it removes heat as represented by the outflow arrow 30. Heat is removed from the operating electronic device by adding sensible heat to the liquid thermal management composition of the present disclosure (i.e., increasing the temperature of the liquid), or by causing a phase change of the thermal management liquid (i.e., evaporating the liquid), or a combination of these. In a preferred embodiment, the method provides a supply of the TMC of the present disclosure (including each of compounds 1-4 and / or heat transfer compositions 1-10 and / or blends RB1-RB20) to the device 10 such that the heat flow from the device 10 through the heat transfer composition 30 of the present invention maintains the operating electronic device at or within a preferred operating temperature range. In a preferred embodiment, the preferred operating temperature range of the electronic device is from about 70°C to about 150°C, and even more preferably from about 70°C to about 120°C, and the heat flow 30 from the device 10 through the heat transfer fluid energy of the present invention maintains the operating electronic device at or within such a preferred temperature range. Preferably, the TMC 30 of the present disclosure that has absorbed heat from the device is in thermal contact with a heat sink (schematically represented as 40) at a temperature lower than the temperature of the heat transfer composition 30, thereby transferring the heat generated by the device 10 to the heat sink 40. Thus, the heat-depleted heat transfer fluid 50 of the present disclosure can return to the electronic device 10 to repeat the cooling cycle.

[0141] In a preferred embodiment of the method of the present invention, the step of removing heat by the heat transfer composition of the present disclosure (including each of compounds 1-4 and / or heat transfer compositions 1-10 and / or blends RB1-RB20) includes evaporating the heat transfer composition of the present disclosure using the heat generated by the operation of the electronic device, and the step of transferring the heat from the heat transfer composition to the heat sink includes condensing the heat transfer composition by discharging the heat to the heat sink. In such a method, during the evaporation step, the temperature of the heat transfer composition of the present disclosure (including each of compounds 1-4 and / or heat transfer compositions 1-10 and / or blends RB1-RB20) is preferably higher than 50°C, or preferably higher than about 55°C, or preferably in the range of about 55°C to about 85°C, or preferably in the range of about 65°C to about 75°C. The applicant has found that the thermal management composition of the present invention provides excellent performance in such methods and at the same time allows the use of relatively low-cost, lightweight and reliable equipment to provide the necessary cooling, as will be further illustrated in connection with the specific embodiments described below Figure 2A as will be further illustrated in connection with the specific embodiments described below.

[0142] In another preferred embodiment of the method of the present invention, the step of removing heat by the heat transfer composition of the present invention (including each of Compounds 1-4 and / or Heat Transfer Compositions 1-10 and / or Blends RB1-RB20) includes adding sensible heat to the liquid heat transfer composition of the present disclosure using the heat generated by the operating electronic device (e.g., raising the liquid temperature to a maximum of about 70 °C or a lower temperature at about atmospheric pressure, i.e., where there is no need for the fluid to be in a high-pressure vessel or container), and the step of transferring heat from the heat transfer composition to a heat sink to reduce the liquid temperature by discharging the heat to the heat sink. The cooled liquid then returns to make thermal contact with the electronic device, where the cycle begins again. In a preferred embodiment, the temperature of the heat transfer liquid used to transfer heat to the heat sink is higher than about 40 °C, or preferably higher than about 55 °C, or preferably in the range of about 45 °C to about 70 °C, or preferably in the range of about 45 °C to about 65 °C, and preferably at a pressure of about atmospheric pressure. The Applicant has found that the heat transfer liquids of the present invention (including each of Compounds 1-4 and / or Heat Transfer Compositions 1-10 and / or Blends RB1-RB20) provide excellent performance in such methods and at the same time allow the use of relatively low-cost, lightweight, and reliable equipment to provide the necessary cooling, as will be further illustrated in connection with the specific embodiments described below in connection with Figure 2B the specific embodiments described.

[0143] Those skilled in the art will appreciate that the present disclosure includes systems and methods that use both sensible heat transfer and phase change heat transfer as described above.

[0144] Now, in connection with Figure 2A and Figure 2B a specific method according to the present disclosure will be described, in which the electronic device 10 is housed in a suitable container 12, preferably in a sealed container, and is in direct contact with the liquid heat transfer composition 11A of the present disclosure (including each of Compounds 1-4 and / or Heat Transfer Compositions 1-10 and / or Blends RB1-RB20), preferably completely immersed therein (schematically shown by the gray shading). For convenience, such cooling methods, devices, and systems are sometimes referred to herein as "immersion cooling" methods, devices, and systems.

[0145] In immersion cooling methods, devices, and systems for cooling electronic devices or components, an operating electronic device 10 has a source of electrical energy and / or signals 20 flowing into and / or out of a container 12 and into and / or out of the device 10, and the operating electronic device generates heat due to its operation based on the electrical energy and / or signals 20. Those skilled in the art will appreciate that developing a heat transfer composition that can operate efficiently in such applications presents significant challenges, as the composition must not only possess all of the other properties mentioned above but must also be able to ensure that these properties are maintained when in close contact with an operating electronic device (i.e., a device involving current / signal flow). It should be understood that many compounds that may be viable in other ways in such applications will be unavailable because they will short-circuit the device, degrade when exposed to the conditions generated by the operation of the electronic device (i.e., reduce the cooling effect and / or the operating stability of the device over time), or have some other property that is harmful to the operation when in contact with the operating electronic device.

[0146] In contrast, the method of the present invention produces excellent and unexpected results by providing the heat management compositions of the present disclosure (including each of Compounds 1-4 and / or Heat Transfer Compositions 1-10 and / or Blends RB1-RB20), which are in direct thermal contact and physical contact with the device 10 during its operation. The operating heat is safely and effectively transferred to the heat management composition 11A (including each of Compounds 1-4 and / or Heat Transfer Compositions 1-10 and / or Blends RB1-RB20) by: (a) evaporating the liquid phase of the fluid to form a vapor 11B; or (b) raising the temperature of the liquid heat management composition 11A; or (c) a combination of (a) and (b).

[0147] When the heat management composition is a single-phase liquid, it will remain liquid when heated by the heat-generating component. Thus, the heat management composition can be brought into contact with the heat-generating component, resulting in the removal of heat from the heat-generating component and producing a heat management composition with a higher temperature. The heat management composition is then transported to a secondary cooling circuit, such as a radiator or another refrigeration system. An example of such a system is shown in Figure 2, where the heat management composition enters and exits a battery pack housing containing a plurality of battery cells, thereby absorbing heat from the battery pack.

[0148] When the heat management compositions of the present disclosure (including each of Compounds 1-4 and / or Heat Transfer Compositions 1-10 and / or Blends RB1-RB20) are present in two phases, the heat-generating component is in thermal contact with the heat management composition and transfers heat to the heat management composition, causing the heat management composition to boil. The heat management composition then condenses. An example of such a system is one in which the heat-generating component is immersed in the heat management composition and an external cooling circuit condenses the boiling fluid into a liquid state.

[0149] For the phase change heat transfer system of the present disclosure, reference is made herein to Figure 2A . In such an operation, as the liquid evaporates and the vapor rises through the remaining heat management liquid in the container 12 (including each of the compounds 1-4 and / or the heat transfer compositions 1-10 and / or the blends RB1-RB20), heat is removed from the device 10. The heat management composition vapor 11B then dissipates the heat it has absorbed to the radiator 40, which can be the enclosed radiator 40A and / or the external radiator 40B. Examples of radiators inside the container 12 are the condenser coils 30A and 30B, which have a circulating liquid, such as water, with a temperature lower than the condensation temperature of the heat management composition vapor. An example of a radiator outside the container 12 will pass relatively cold ambient air over the container 12 (preferably including fins, etc. in this case), which will be used to condense the heat transfer vapor 11B on the inner surface of the container. As a result of this condensation, the liquid heat management composition returns to the pool of the liquid fluid 11A, and the device 10 remains immersed in this pool during operation.

[0150] For the sensible heat transfer system of the present disclosure, reference is made herein to Figure 2B . In such an operation, as the temperature of the liquid 11A (including each of the compounds 1-4 and / or the heat transfer compositions 1-10 and / or the blends RB1-RB20) rises while receiving the heat generated by the device, heat is removed from the device, which is immersed and preferably substantially completely immersed in the heat management composition 11A of the present disclosure. The higher temperature heat management composition liquid 11A then discharges the heat it has absorbed to the radiator 40, which can be the enclosed radiator 40A and / or the external radiator 40B. Examples of radiators inside the container 12 are the cooling coils 30A and 30B, which have a circulating liquid, such as water, with a temperature lower than the temperature of the heated liquid. An example of a radiator outside the container 12 will remove the heated liquid 11A from the container through the conduit 45, in which the heated liquid is in thermal contact with a cooling fluid, such as can be provided by relatively cold ambient air, or cooling water or refrigerant, which will be used to reduce the temperature of the liquid. The cooled liquid then returns via the conduit 46.

[0151] Optionally but preferably, in certain embodiments relating to the heat management of a battery for an electric vehicle, the heat management system includes a heating element capable of heating the heat management composition (including each of the compounds 1-4 and / or the heat transfer compositions 1-10 and / or the blends RB1-RB20), such as the electric heating element 60 also immersed in the heat management composition. Those skilled in the art will understand that the battery in an electric vehicle (which will correspond to Figure 2A and Figure 2BThe working electronic device 10) can reach a relatively low temperature when parked in many geographical locations outside the winter months, and in many cases such low temperature conditions are not desirable for battery operation. Therefore, the thermal management system of the present disclosure may include sensors and a control module (not shown) that turn on the heating element when the battery temperature is below a predetermined level. In this case, the heater 60 will be activated, the thermal management liquid 11A will be heated, and in turn, this heat will be transferred to the electronic device 10 until the minimum temperature is reached. Thereafter, during operation, the thermal management composition of the present disclosure (including each of Compounds 1-4 and / or Heat Transfer Compositions 1-10 and / or Blends RB1-RB20) will perform the cooling function as described above.

[0152] For the purposes of the present disclosure, the thermal management composition (including each of Compounds 1-4 and / or Heat Transfer Compositions 1-10 and / or Blends RB1-RB20) can be in direct contact with the heat-generating component or in indirect contact with the heat-generating component.

[0153] When the thermal management composition (including each of Compounds 1-4 and / or Heat Transfer Compositions 1-10 and / or Blends RB1-RB20) is in indirect contact with the heat-generating component, the thermal management composition can be used in a closed system in an electronic device, and the closed system can include at least two heat exchangers. When the thermal management composition is used to cool the heat-generating component, heat can be transferred from the component to the thermal management composition, typically through a heat exchanger in contact with at least a portion of the component, or the heat can be transferred to circulating air, which can conduct the heat to a heat exchanger in thermal contact with the thermal management composition.

[0154] In a particularly preferred feature of the present disclosure, the thermal management composition (including each of Compounds 1-4 and / or Heat Transfer Compositions 1-10 and / or Blends RB1-RB20) is in direct contact with the heat-generating component. Specifically, the heat-generating component is completely or partially immersed in the thermal management composition. Preferably, the heat-generating component is completely immersed in the thermal management composition, including each of Compounds 1-4 and / or Heat Transfer Compositions 1-10 and / or Blends RB1-RB20. The thermal management composition, as a warm fluid or as a vapor, can then be circulated to a heat exchanger that extracts heat from the fluid or vapor through a radiator (such as ambient air or water cooled by ambient air or otherwise) and transfers this heat to the external environment. After this heat transfer, the cooled thermal management composition (cooled or condensed) is recycled back into the system to cool the heat-generating component.

[0155] If the fluid comes into direct contact with the electronic components of an electronic device (such as by direct immersion cooling), or if the thermal management composition leaks from the cooling circuit or spills during maintenance and contacts the circuitry, then the conductivity and / or dielectric strength of the thermal management composition becomes important. Accordingly, the thermal management compositions of the present disclosure, as well as each of Compounds 1-4 and / or Heat Transfer Compositions 1-10 and / or Blends RB1-RB20, are preferably electrically insulating thermal management compositions.

[0156] The thermal management compositions of the present disclosure (including each of Compounds 1-4 and / or Heat Transfer Compositions 1-10 and / or Blends RB1-RB20) can be passively or actively recirculated in the device (such as by using mechanical equipment, such as a pump). In a preferred feature of the present disclosure, the thermal management compositions of the present disclosure (including each of Compounds 1-4 and / or Heat Transfer Compositions 1-10 and / or Blends RB1-RB20) are passively recirculated in the device.

[0157] A passive recirculation system works by transferring heat from a heat-generating component to the thermal management composition until it is typically vaporized, thereby allowing the heated vapor to travel to a heat exchange surface where the heated vapor transfers its heat to the heat exchanger surface and condenses back to a liquid. It should be understood that the heat exchange surface can be part of a separate heat exchange unit and / or can be integral with the container, as described above, for example, in connection with FIG. 2. The condensed liquid then preferably returns completely passively, by gravity and / or a wicking structure, to the thermal management composition in contact with the heat-generating component. Accordingly, in a preferred feature of the present disclosure, the step of transferring heat from a heat-generating component to the thermal management compositions of the present disclosure (including each of Compounds 1-4 and / or Heat Transfer Compositions 1-10 and / or Blends RB1-RB20) causes the thermal management composition to evaporate.

[0158] Examples of passive recirculation systems include heat pipes or thermosyphons. Such systems passively recirculate the thermal management compositions of the present disclosure, including each of Compounds 1-4 and / or Heat Transfer Compositions 1-10 and / or Blends RB1-RB20, using gravity. In such systems, the thermal management composition is heated by the heat-generating component, thereby creating a heated thermal management composition that is less dense and more buoyant. The thermal management composition travels to a storage container, such as a tank where the thermal management composition is cooled and condensed. The cooled thermal management composition then flows back to the heat source.

[0159] Cooling of electrical equipment

[0160] The present disclosure includes the use of the compounds of the invention (including each of Compounds 1-4 and / or Heat Transfer Compositions 1-10 and / or Blends RB1-RB20) for cooling and optionally heating an electronic device that generates or includes a component that is a heat-generating part. The heat-generating part can be any component that includes an electronic element that generates heat as part of its operation. For the purposes of the present disclosure, heat-generating parts include, but are not limited to: semiconductor integrated circuits (ICs), electrochemical cells, power transistors, resistors, and electroluminescent elements, such as microprocessors, wafers for manufacturing semiconductor devices, power control semiconductors, power distribution switching devices, power transformers, circuit boards, multi-chip modules, packaged or unpackaged semiconductor devices, semiconductor integrated circuits, fuel cells, lasers (conventional diodes or laser diodes), light-emitting diodes (LEDs), and electrochemical cells, such as electrochemical cells for high-power applications (such as, for example, hybrid vehicles or electric vehicles).

[0161] For the purposes of the present disclosure, electronic devices include, but are not limited to, personal computers, microprocessors, servers, mobile phones, tablets, digital household appliances (such as televisions, media players, gaming consoles, etc.), personal digital assistants, data centers, stationary batteries and batteries in vehicles (including Li-ion batteries and other batteries used in hybrid vehicles or electric vehicles), wind turbines, train engines, or generators. Preferably, the electronic device is a hybrid vehicle or an electric vehicle.

[0162] The present disclosure also relates to an electronic device comprising a heat management composition of the present disclosure (including each of Compounds 1-4 and / or Heat Transfer Compositions 1-10 and / or Blends RB1-RB20). For the purposes of the present disclosure, the heat management composition is provided for cooling and / or heating the electronic device.

[0163] The present disclosure also relates to an electronic device comprising a heat-generating part and a heat management composition of the present disclosure (including each of Compounds 1-4 and / or Heat Transfer Compositions 1-10 and / or Blends RB1-RB20), the heat management composition being for cooling and optionally heating the electronic device.

[0164] The present disclosure also relates to an electronic device comprising a heating component, a heat exchanger, a pump, and the thermal management composition of the present disclosure (comprising each of Compounds 1-4 and / or Heat Transfer Compositions 1-10 and / or Blends RB1-RB20). For the purposes of the present disclosure, an electronic device can be any such device, including but not limited to a personal computer, a microprocessor, a server, a mobile phone, a tablet computer, a digital household appliance (such as a television, a media player, a gaming console, etc.), a personal digital assistant, a data center, a hybrid vehicle or an electric vehicle, a stationary battery and a battery in a vehicle, an electric drive motor, a fuel cell (such as, a hydrogen fuel cell), and a generator, preferably wherein the electronic device is in a hybrid vehicle, or an electric vehicle, or a wind turbine, or a train.

[0165] For the purposes of the present disclosure, a heating component can be any electronic component that generates heat during operation, but preferably is an electronic component that generates heat at a high level of heat flux. Examples of heating components that can be cooled according to the present disclosure include semiconductor integrated circuits (ICs), electrochemical cells, power transistors, resistors, and electroluminescent elements, such as microprocessors, wafers for manufacturing semiconductor devices, power control semiconductors, power distribution switchgear, power transformers, printed circuit boards (PCBs), multi-chip modules, packaged or unpackaged semiconductor devices, semiconductor integrated circuits, fuel cells, lasers (conventional or laser diodes), light emitting diodes (LEDs), and electrochemical cells for high power applications such as, for example, hybrid vehicles or electric vehicles.

[0166] Lithium-ion battery cooling system

[0167] Now will be described in conjunction with Figure 8Examples of the thermal management method of the present invention that can be used for the cooling of lithium-ion batteries are described, including heat transfer methods 1 and 2 and thermal management method 1-2. A vehicle battery pack having a self-contained liquid cooling system 10 includes a module 12 formed by a container 14 having an internal space 16 for supporting battery components 18. The container 14 is a closed and sealed container 14 for forming the self-contained liquid cooling system 10. The battery components 18 include a plurality of battery cells 20, such as a plurality of lithium-ion (Li-ion) batteries for use in a hybrid vehicle. In another embodiment, the plurality of battery cells 20 are Li-ion batteries used in a battery electric vehicle (BEV). Additional batteries for use with other prime mover vehicles may be provided with the liquid cooling system 10 of the present disclosure, wherein each battery cell includes active materials for generating electricity from an electrochemical reaction within the internal space 16 of the container 14. The battery cells 20 are preferably stacked to form a battery cell stack 22. In the illustrated embodiment, the gap 24 between each battery cell 20 is between 0.25 mm and 0.50 mm, thereby forming a fluid channel 26 between each battery cell 20. In another embodiment, the gap 24 may be less than 0.25 mm. It should be understood that other gap sizes may be used as needed.

[0168] The compositions of the present disclosure (including each of compounds 1-4 and / or heat transfer compositions 1-10 and / or blends RB1-RB20) are disposed within the internal space 16 of the container 14, and the indicated liquid level is such that the battery components 18 are completely immersed within the compositions of the present disclosure. The compositions of the present disclosure (including each of compounds 1-4 and / or heat transfer compositions 1-10 and / or blends RB1-RB20) contact the battery cells 20 through the fluid channels 26 formed by the gaps 24.

[0169] A heating element 34 is located at the base region 36 of the container 14. The illustrated heating element 34 is an electronic heating element. It should be understood that other types of heating elements may be used. The heating element 34 is shown as a single element; however, a plurality of heating elements 34, such as a heating plate, may be provided.

[0170] A cooling element 38 is located at the upper region 40 of the container 14. The cooling element 38 may be a cold water condenser having an inlet 42 and an outlet 44 that extend beyond the wall of the sealed container 14 for inputting and outputting water to the cooling element 38. In another embodiment, the cooling element 38 may be a cold water plate. In yet another embodiment, the cooling element 38 may be a thin aluminum radiator having external cold water traveling through the cooling element 38. The cooling element 38 may be a graphite foil impregnated with a non-conductive polymer. The cooling element may also be formed of copper.

[0171] In the illustrated embodiment, arrows “A” and “B” indicate the flow 28 of the disclosed compositions (including each of Compounds 1-4 and / or Heat Transfer Compositions 1-10 and / or Blends RB1-RB20, and each of the heat transfer compositions), and coolant 28 of the present disclosure. When each battery cell 20 is heated by heating element 34, the coolant 28 of the present disclosure (including each of Compounds 1-4 and / or Heat Transfer Compositions 1-10 and / or Blends RB1-RB20) is exposed to the front surface area 30 and the rear surface area 32 of the battery cell 20 and will boil. The heated coolant 28 will rise and flow to the top of the battery cell stack 22 to be cooled by cooling element 38. The cooled coolant 28 will generally follow coolant path “A” or “B” back to the base area 36. In the case where the general location of the coolant 28 at the moment of boiling is within the fluid channel 26 of the battery cell 20 in the central area of the container 14 and toward the side 50 of the container, the coolant 28 will tend to follow flow path “A”. Similarly, if the general location of the dielectric coolant 28 at the moment of boiling is within the fluid channel 26 of the battery cell 20 in the central area of the container 14 and toward the opposite side 52 of the container, the coolant 28 will tend to follow flow path “B”.

[0172] A coolant temperature sensor 46 is located on or near the cooling element 38. In the illustrated embodiment, the temperature sensor 46 is located in the area of the outlet 44 of the cooling element 38 and measures the temperature of the dielectric coolant 28 of the present disclosure at the point of exposure to the cooling element. The temperature sensor 46 can be located anywhere within the battery cell stack 22 as needed.

[0173] A coolant level sensor 48 is also provided and is located near the upper area 40 of the container 14 to measure the level of the dielectric coolant 28 within the container 14, thus ensuring that the battery assembly 18 is fully submerged within the dielectric coolant 28.

[0174] Cooling and heating of heat dissipation tubes

[0175] Now with respect to Figure 10An example of the heat transfer method of the present invention using a heat pipe is described. This figure is a specific example of the heat pipe in the energy storage assembly 1 according to an exemplary embodiment of the present disclosure. The energy storage assembly 1 can be part of a motor vehicle 12 (especially a hybrid vehicle or an electric vehicle) and is provided for supplying electric power to an electric consumption device on the motor vehicle side, such as an electric drive unit (not shown). The energy storage assembly 1 includes a plurality of electrical energy storage devices. 2. The electrical energy storage devices 2 are electrically connected via electrical connection elements (not shown), especially in the form of conductive rails or conductor rails ("busbars"), i.e., connected in series or in parallel. The electrical connection elements contact corresponding electrical connectors (not shown) here, which are arranged on the respective exposed outer wall sections of the corresponding energy storage housings (not shown) of the parallel-aligned energy storage devices 2 arranged adjacent to each other, thereby forming an energy storage stack ("stack"). Plate-shaped spacer elements 3 are respectively arranged between the energy storage devices 2 to separate the energy storage devices and at the same time the spacer elements have heat-conducting properties. Thus, on the one hand, the spacer elements 3 provide a space between the directly adjacent energy storage devices 2, so that the directly adjacent energy storage devices 2 are in electrical contact or mechanical contact with each other. On the other hand, due to their heat-conducting properties, the spacer elements 3 act as heat conductors to cool the energy storage devices 2 or the energy storage assembly 1 by dissipating heat especially from the contacting energy storage devices 2, or to heat the energy storage devices 2 or the energy storage assembly 1 by supplying heat especially to the contacting energy storage devices 2. A heat pipe 4 of the first heat pipe assembly 5 and a heat pipe 6 of the second heat pipe assembly 7 are provided. The heat pipes 4, 6 thus extend along this side surface of the energy storage stack and are respectively thermally coupled to the spacer elements 3. Thus, the spacer elements 3 form a thermal bridge on the one hand between the heat pipe 4 of the first heat pipe assembly 5 and the heat pipe 6 of the second heat pipe assembly 7, and on the other hand between the energy storage devices 2. The respective heat pipes 4 of the first heat pipe assembly 5 are arranged and aligned to be thermally coupled to the respective evaporation zones, in which the heat management composition of the present disclosure (especially each of compounds 1-4 and / or heat transfer compositions 1-10 and / or blends RB1-RB20) contained therein can be evaporated to the spacer elements 3. Thus, the heat (evaporation heat) required to evaporate the TMC of the present invention is removed from the spacer elements 3 or via the spacer elements 3 from the energy storage devices 2. The energy storage devices 2 including the energy storage assembly 1 can thus be cooled via the heat pipes 4 of the first heat pipe assembly 5. In addition, the respective condensation zones of the heat pipes 4 of the first heat pipe assembly 5 are thermally coupled to a radiator 8 in the form of a motor vehicle side heat exchanger, in which the gaseous heat management composition of the present disclosure (especially each of compounds 1-4 and / or heat transfer compositions 1-10 and / or blends RB1-RB20) contained therein can be condensed. Thus, the heat (condensation heat) generated during the condensation of the TMC of the present invention can be transferred to the radiator 8.The heat exchanger can be part of the energy storage assembly 1, i.e., belong to or be associated with the energy storage assembly 1. The respective heat pipes 6 of the second heat pipe assembly 7 are arranged and aligned so as to be thermally coupled to their respective condensation zones in which the gaseous TMC contained in the present disclosure can be condensed onto the spacer element 3. Thus, heat (condensation heat) can be transferred to the spacer element 3 during the condensation of the TMC of the present invention or via the spacer element 3 to the energy storage device 2. Accordingly, the energy storage device 2 and the energy storage assembly 1 can be heated via the heat pipes 6 of the second heat pipe assembly 7. In addition, the respective evaporation zones of the heat pipes 6 of the second heat pipe assembly 7 (in which the TMC contained in the present disclosure can be evaporated) are thermally coupled to a heat source 9 in the form of a functional component, i.e., for example, a charger or a control device or control electronics associated with the energy storage assembly 1. The heat (evaporation heat) required for the evaporation of the TMC can thus be removed from the heat source 9. Accordingly, the functional component can be cooled via the heat pipes 6 of the second heat pipe assembly 7. The two heat pipe assemblies 5, 7 and their associated heat pipes 4, 6 enable a temperature control device to control the temperature of the energy storage device 2 of the energy storage assembly 1 (i.e., for heating or cooling). Heat pipes useful according to the present disclosure include gravity reflux heat pipes, capillary reflux heat pipes, and gravity / capillary reflux heat pipes.

[0176] The following table defines some preferred uses of the compounds of the present invention and methods of using the compounds of the present invention, including application scenarios related to the examples herein. Column 1 of the following table identifies and defines various uses as "Use 1", "Use 2", etc., and Column 2 lists one or more of the above refrigerants (Ref.), including Compounds 1-4 and / or Heat Transfer Compositions 1-7 and / or Blends RB1-RB20, represented by the abbreviations TMC1, TMC2, etc. The specific definitions of the devices or articles are as follows: where "EV battery" means an electric vehicle battery and "IC" means an integrated circuit. The designation "NR" should be understood to mean that for the specific uses defined in the respective rows of the table, the corresponding components or properties are not necessary (but may be present).

[0177] Table 4

[0178] Exemplary uses

[0179]

[0180]

[0181]

[0182]

[0183]

[0184]

[0185]

[0186]

[0187]

[0188]

[0189]

[0190]

[0191]

[0192]

[0193] Organic Rankine cycle

[0194] The heat transfer fluids of the present disclosure (including Compounds 1-4 and / or Heat Transfer Compositions 1-10 and / or Blends RB1-RB20) can be referred to as working fluids when used in an organic Rankine cycle.

[0195] Thus, the working fluid corresponds to the heat transfer fluid discussed in this patent application. All of the preferred features of the heat transfer fluid apply to the working fluid as described herein.

[0196] It is known that a Rankine cycle system is a simple and reliable device for converting thermal energy into mechanical energy in the form of shaft power. In industrial settings, combustible working fluids (such as toluene and pentane) may be used, especially when the industrial setting already has a large amount of combustibles on-site in the process or storage. However, in situations where the risks associated with using flammable and / or toxic working fluids are unacceptable, such as when generating electricity in populated areas or near buildings, it is necessary or at least highly desirable to use non-flammable and / or non-toxic refrigerants as the working fluid. There is also a drive in the industry to make these materials environmentally acceptable in terms of GWP.

[0197] The process for recovering waste heat in an organic Rankine cycle according to the present disclosure preferably involves pumping the liquid-phase working fluid of the present disclosure (including each of Compounds 1-4 and / or Heat Transfer Compositions 1-10 and / or Blends RB1-RB20) through a boiler, where an external (waste) heat source (such as a process stream) heats the working fluid to evaporate it into saturated or superheated vapor. The vapor expands through a turbine, where the waste heat energy is converted into mechanical energy. Subsequently, the gaseous working fluid is condensed into a liquid and pumped back to the boiler to repeat the regenerative cycle.

[0198] See Figure 4 Figure 4 , in an exemplary organic Rankine cycle system 70, the working fluids of the present disclosure (including each of Compounds 1-4 and / or Heat Transfer Compositions 1-10 and / or Blends RB1-RB20) are circulated between an evaporator 71 and a condenser 75, with a pump 72 and an expansion device 74 functionally disposed therebetween. In the illustrated embodiment, an external fluid stream is directed to the evaporator 71 via an external warm conduit 76. The external warm conduit 76 may carry a fluid from a warm heat source, such as a waste heat source from an industrial process (e.g., power generation), flue gas, exhaust gas, a geothermal heat source, and the like.

[0199] The evaporator 71 is preferably configured as a heat exchanger, which may include, for example, a series of thermally connected but fluidically isolated tubes that respectively carry a fluid from the external warm conduit 76 and a fluid from a working fluid conduit 77B. Thus, the evaporator 71 facilitates the transfer of heat QIN from the warm fluid arriving via the external warm conduit 76 to the relatively cooler (e.g., "cold") working fluid arriving from the expansion device 74 via the working fluid conduit 77B.

[0200] Thus, the working fluids of the present disclosure (including each of Compounds 1-4 and / or Heat Transfer Compositions 1-10 and / or Blends RB1-RB20) are heated after absorbing the heat QIN, and then discharged from the evaporator 71, and subsequently conveyed to the pump 72 through a working fluid conduit 78A. The pump 72 pressurizes the working fluid, thereby further heating the fluid by an external energy input (e.g., electricity). The resulting "hot" fluid is optionally conveyed to the input of the condenser 75 via a conduit 78B through a regenerator 73 as described below.

[0201] The condenser 75 is configured as a heat exchanger similar to the evaporator 71, and may include, for example, a series of thermally connected but fluidically isolated tubes that respectively carry a fluid from a cooling conduit 79 and a fluid from a working fluid conduit 78B. The condenser 75 effects the transfer of heat QOUT to a cooling fluid from an external cooling conduit 79, which exchanges heat with the relatively higher temperature (e.g., "hot") working fluid of the present disclosure conveyed from the pump 72 via the working fluid conduit 78B, and the working fluid includes each of Compounds 1-4.

[0202] The working fluid of the present disclosure (Compound 1-4 and / or Heat Transfer Composition 1-10 and / or Blend RB1-RB20) discharged from the condenser 75 has thus been cooled by the heat loss QOUT and then transported through the working fluid conduit 77A to the expansion device 74. The expansion device 74 allows the working fluid to expand, thereby further cooling the fluid. At this stage, the fluid of the present disclosure (including each of Compound 1-4 and / or Heat Transfer Composition 1-10 and / or Blend RB1-RB20) can do work (e.g., by driving a turbine). The resulting "cold" fluid is optionally transferred via the conduit 77B to the input of the evaporator 71 through the regenerator 73 as described below, and the cycle starts again.

[0203] Therefore, the working fluid conduits 77A, 77B, 78A, and 78B define a closed loop such that the working fluid contained therein can be reused infinitely or until routine maintenance is required.

[0204] In the illustrated embodiment, the regenerator 73 can be functionally disposed between the evaporator 71 and the condenser 75. The regenerator 73 allows some heat exchange between the "hot" working fluid of the present disclosure (including each of Compound 1-4 and / or Heat Transfer Composition 1-10 and / or Blend RB1-RB20) discharged from the pump 72 and the "cold" working fluid flowing out of the expansion device 74, and there may be a time lag between the heat released by the hot working fluid and the heat received by the cold working fluid. In some applications, this can increase the overall thermal efficiency of the Rankine cycle system 70.

[0205] Therefore, the present disclosure relates to an organic Rankine cycle comprising the working fluid of the present disclosure (including each of Compound 1-4 and / or Heat Transfer Composition 1-10 and / or Blend RB1-RB20).

[0206] The present disclosure also provides a method for converting thermal energy into mechanical energy in a Rankine cycle, the method comprising the steps of: i) evaporating the working fluid of the present disclosure (including each of Compound 1-4 and / or Heat Transfer Composition 1-10 and / or Blend RB1-RB20) with a heat source and expanding the resulting vapor; and then ii) cooling the working fluid with a radiator to condense the vapor, wherein the working fluid is the refrigerant or heat transfer composition of the present disclosure (including each of Compound 1-4 and / or Heat Transfer Composition 1-10 and / or Blend RB1-RB20).

[0207] The mechanical work can be transmitted to an electrical device such as a generator to generate electricity.

[0208] The heat source can be provided by, for example, a heat energy source selected from industrial waste heat, solar energy, geothermal hot water, low-pressure steam, distributed power generation equipment using fuel cells, heat from a prime mover or an internal combustion engine. The low-pressure steam is preferably low-pressure geothermal steam or is provided by a power plant using fossil fuels for power generation.

[0209] The heat source is preferably provided by a heat energy source selected from industrial waste heat or an internal combustion engine.

[0210] It should be understood that the heat source temperature can vary widely, for example, from about 90 °C to >800 °C, and can depend on many factors of certain combustion gases and some fuel cells, including geographical location, time of year, etc.

[0211] The source temperature of a system based on sources such as wastewater or low-pressure steam (from, for example, plastic manufacturing plants and / or from chemical or other industrial plants, refineries) and related forms, as well as geothermal sources, can be equal to or lower than about 175 °C or equal to or lower than about 100 °C, and in some cases as low as about 90 °C or even as low as about 80 °C. The source temperature of a gaseous heat source (such as exhaust gas from a combustion process or from any heat source where subsequent treatment for removing particulate and / or corrosive substances results in a low temperature) can also be equal to or lower than 200 °C, equal to or lower than about 175 °C, equal to or lower than about 130 °C, equal to or lower than about 120 °C, equal to or lower than about 100 °C, equal to or lower than about 100 °C, and in some cases as low as about 90 °C or even as low as about 80 °C.

[0212] However, in some applications, it is preferred that the heat source has a temperature of at least about 200 °C, for example, from about 200 °C to about 400 °C.

[0213] In an alternative preferred embodiment, the heat source has a temperature of 400 °C to 800 °C, more preferably 400 °C to 600 °C.

[0214] Heat pump

[0215] As discussed above, the heat transfer fluid of the present disclosure (including each of Compounds 1-4 and / or Heat Transfer Compositions 1-10 and / or Blends RB1-RB20) is referred to as a refrigerant when used in a heat pump. Thus, the refrigerant corresponds to the heat transfer fluid discussed in this patent application. All the preferred features of the described heat transfer fluid apply to the refrigerant as described herein.

[0216] The refrigerant or heat transfer composition of the present disclosure (including each of Compounds 1-4 and / or Heat Transfer Compositions 1-10 and / or Blends RB1-RB20) can be used in a high-temperature heat pump system.

[0217] See Figure 5, in an exemplary heat pump system, a compressor 80 (such as a rotary compressor, a piston compressor, a screw compressor, or a scroll compressor) compresses the refrigerant of the present disclosure (including each of compounds 1-4 and / or heat transfer compositions 1-10 and / or blends RB1-RB20). The refrigerant of the present disclosure is transferred to a condenser 82 to release heat QOUT to a first location, after which the refrigerant passes through an expansion device 84 to reduce the refrigerant pressure, and then the refrigerant passes through an evaporator 86 to absorb heat QIN from a second location. The refrigerant is then transferred back to the compressor 80 for compression.

[0218] The present disclosure provides a method of using a high-temperature heat pump to heat a fluid or a body, the method comprising the steps of: (a) condensing the refrigerant composition of the present disclosure (compounds 1-4 and / or heat transfer compositions 1-10 and / or blends RB1-RB20) near the fluid or body to be heated, and (b) evaporating the refrigerant.

[0219] Examples of high-temperature heat pumps include heat pump tumble dryers or industrial heat pumps. It should be understood that a heat pump may include a suction line / liquid line heat exchanger (SL-LL HX). A so-called "high-temperature heat pump" refers to a heat pump capable of generating a temperature of at least about 80°C, preferably at least about 90°C, preferably at least about 100°C, more preferably at least about 110°C.

[0220] Secondary loop system

[0221] The heat transfer fluid of the present disclosure (including each of compounds 1-4 and / or heat transfer compositions 1-10 and / or blends RB1-RB20) is referred to as a refrigerant when used in a secondary loop system.

[0222] The refrigerant of the present disclosure (including each of compounds 1-4 and / or heat transfer compositions 1-10 and / or blends RB1-RB20) can be used as a secondary refrigerant fluid in a secondary loop system.

[0223] A secondary loop system includes a primary vapor compression system loop that uses a primary refrigerant and whose evaporator cools the secondary loop fluid. The secondary refrigerant fluid (including each of compounds 1-4 and / or heat transfer compositions 1-10 and / or blends RB1-RB20) then provides the necessary cooling for the application. The secondary refrigerant fluid should preferably be non-flammable and have low toxicity because the fluid in such loops is potentially exposed to humans near the cooled space. In other words, the refrigerant or heat transfer composition of the present disclosure (including each of compounds 1-4 and / or heat transfer compositions 1-10 and / or blends RB1-RB20) can be used as a "secondary refrigerant fluid" in a secondary loop system.

[0224] See Figure 6 , an exemplary secondary loop system includes a primary loop 90 and a secondary loop 92. In the primary loop 90, a compressor 94 (such as a rotary compressor, a piston compressor, a screw compressor, or a scroll compressor) compresses a primary refrigerant, which is transferred to a condenser 96 to release heat QOUT to a first location, and then the primary refrigerant passes through an expansion device 98 to reduce the refrigerant pressure, and then the primary refrigerant passes through a refrigerant / secondary fluid heat exchanger 100 to exchange heat QIN with a secondary fluid (including each of compounds 1-4 and / or heat transfer compositions 1-10 and / or blends RB1-RB20), wherein the secondary fluid is pumped through the secondary loop 92 via a pump 102 to a secondary loop heat exchanger 104 to exchange heat with another location, such as absorbing heat QIN-S to provide cooling to the another location.

[0225] The primary fluid for the primary loop (vapor compression cycle, the external / outdoor portion of the loop) can be selected from but not limited to HFO-1234ze(E), HFO-1234yf, propane, R455A, R32, R466A, R44B, R290, R717, R452B, R448A, and R449A, preferably HFO-1234ze(E), HFO-1234yf, or propane.

[0226] The secondary loop system can be used in refrigeration or air conditioning applications, that is, the secondary loop system can be a secondary loop refrigeration system or a secondary loop air conditioning system.

[0227] Examples of refrigeration systems that can include a secondary loop refrigeration system include: cryogenic refrigeration systems, medium temperature refrigeration systems, commercial refrigerators, commercial freezers, industrial freezers, industrial refrigerators, and chillers, and these examples include the secondary refrigerants of the present disclosure, including each of compounds 1-4 and / or heat transfer compositions 1-10 and / or blends RB1-RB20.

[0228] Examples of air conditioning systems that can include a secondary loop air conditioning system include mobile air conditioning systems or stationary air conditioning systems, and these examples utilize the refrigerants of the present disclosure, including each of compounds 1-4 and / or heat transfer compositions 1-10 and / or blends RB1-RB20. Mobile air conditioning systems include air conditioners for road vehicles such as cars, trucks, and buses, as well as air conditioners for boats and trains. For example, where the vehicle includes a battery or a power supply.

[0229] Examples of stationary air conditioning systems that may include a secondary loop air conditioning system include: chillers, particularly positive displacement chillers, more specifically modular or traditional single-packaged air-cooled or water-cooled direct expansion chillers; residential air conditioning systems, particularly ducted or ductless split air conditioning systems; residential heat pumps; residential air-to-water heat pumps / water loop systems; 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 ground source heat pump systems, which examples utilize the refrigerants of the present disclosure, including each of compounds 1-4 and / or heat transfer compositions 1-10 and / or blends RB1-RB20.

[0230] According to the present disclosure, a particularly preferred heat transfer system is a motor vehicle air conditioning system that includes a vapor compression system (primary loop) and a secondary loop air conditioning system, wherein the primary loop includes HFO-1234yf as a refrigerant and the secondary loop includes a refrigerant or heat transfer composition of the present disclosure (including each of compounds 1-4 and / or heat transfer compositions 1-10 and / or blends RB1-RB20). Specifically, the secondary loop can be used to cool components in an automotive engine, such as a battery.

[0231] It should be understood that a secondary loop air conditioning or refrigeration system may include a suction line / liquid line heat exchanger (SL-LLHX).

[0232] The heat transfer fluid or heat transfer composition of the present invention that may include a secondary loop air conditioning system can be used as a replacement for existing fluids, wherein these heat transfer fluids or heat transfer compositions of the present invention utilize the refrigerants of the present disclosure, including each of compounds 1-4 and / or heat transfer compositions 1-10 and / or blends RB1-RB20.

[0233] The present disclosure includes a method of replacing an existing heat transfer fluid in a heat transfer system, the method comprising the steps of: (a) removing at least a portion of the existing heat transfer fluid from the system, and subsequently (b) introducing a heat transfer fluid of the present disclosure into the system. Step (a) may involve removing at least about 5 wt%, at least about 10 wt%, at least about 15 wt%, at least about 50 wt%, at least about 70 wt%, at least about 90 wt%, at least about 95 wt%, at least about 99 wt%, or at least about 99.5 wt% or substantially all of the existing heat transfer fluid from the system prior to step (b).

[0234] The method may optionally include the step of flushing the system with a solvent after performing step (a) and prior to performing step (b).

[0235] For the purposes of the present disclosure, the heat transfer fluids of the present disclosure (including each of Compounds 1-4 and / or Heat Transfer Compositions 1-10 and / or Blends RB1-RB20) can be used to replace existing fluids in electronic devices, organic Rankine cycles, high-temperature heat pumps, or secondary loops.

[0236] For example, the heat management compositions of the present disclosure (including each of Compounds 1-4 and / or Heat Transfer Compositions 1-10 and / or Blends RB1-RB20) can be used as replacements for existing fluids such as HFC-4310mee, HFE-7100, and HFE-7200. Alternatively, the heat management composition (including each of Compounds 1-4 and / or Heat Transfer Compositions 1-10 and / or Blends RB1-RB20) can be used to replace water and glycols. The replacement can be carried out in existing systems or in new systems designed to operate with existing fluids. Alternatively, the heat management composition (including each of Compounds 1-4 and / or Heat Transfer Compositions 1-10 and / or Blends RB1-RB20) can be used in applications that previously used existing refrigerants. Alternatively, the refrigerants of the present disclosure (including each of Compounds 1-4 and / or Heat Transfer Compositions 1-10 and / or Blends RB1-RB20) can be used to retrofit existing refrigerants in existing systems. Alternatively, the refrigerants of the present disclosure (including each of Compounds 1-4 and / or Heat Transfer Compositions 1-10 and / or Blends RB1-RB20) can be used in new systems designed to operate with existing refrigerants.

[0237] The present disclosure provides a method for replacing an existing refrigerant in a heat transfer system, the method comprising the steps of: (a) removing at least a portion of the existing refrigerant from the system, and subsequently (b) introducing a refrigerant of the present disclosure (including each of Compounds 1-4 and / or Heat Transfer Compositions 1-10 and / or Blends RB1-RB20) into the system. The existing refrigerant can be selected from, for example, HFC-4310mee, HFE-7100, and HFE-7200.

[0238] Step (a) can involve removing at least about 5 wt%, at least about 10 wt%, at least about 15 wt%, at least about 50 wt%, at least about 70 wt%, at least about 90 wt%, at least about 95 wt%, at least about 99 wt%, or at least about 99.5 wt% of the existing refrigerant from the system prior to step (b).

[0239] The method can optionally include the step of flushing the system with a solvent after performing step (a) and prior to performing step (b).

[0240] Solvent and cleaning uses, methods and systems

[0241] The present disclosure provides solventization methods. Such methods generally include cleaning methods, etching methods, carrier solvent applications (for coating applications, lubricant depositions, silicone depositions, and other coatings, including coatings related to coatings of medical devices, such as heparin and PTFE).

[0242] Regarding cleaning methods, all such methods are included within the scope of the present disclosure. Preferred cleaning methods include vapor degreasing by contacting an article, device, or a component thereof with a composition of the present disclosure (including Compounds 1-4 and each of Compositions 1-4). A variety of contaminants can be removed from a variety of articles, devices, and components. Examples of contaminants that can be removed using the compositions of the present disclosure (including Compounds 1-4 and each of Compositions 1-4) include, for example, light oils, neutral oils, Fluorolube, greases, silicones, and waxes. Examples of articles, devices, and components that can be cleaned using the compositions of the present disclosure (including Compounds 1-4 and each of Compositions 1-4) include, for example, electronic components (including silicon wafers, PCBs, semiconductor surfaces), precision parts (including aircraft parts and components), light oils, neutral oils, Fluorolube, greases, silicones, and waxes.

[0243] Preferred solvent vapor degreasing and desoldering methods of the present disclosure include immersing a contaminated substrate or part (e.g., a printed circuit board, or a machined metal, glass, ceramic, plastic, or elastomeric part or composite material) or a portion of the substrate or part into a boiling, non-flammable liquid according to the present disclosure (including Compounds 1-4 and each of Compositions 1-4), and subsequently, in a second tank or cleaning zone, rinsing the part by immersion or distillation spray using a cleaning solvent, which can also be any one of the compositions of the present disclosure. The part is then dried by holding the cooled part in the condensing vapor until the temperature reaches equilibrium.

[0244] Solvent cleaning of various types of parts is generally carried out in batch, lift-assisted batch, conveyor batch, or in-line conveyor-type degreasing and desoldering equipment. Parts can also be

[0245] cleaned in open desoldering or degreasing equipment. In both types of equipment, the inlet end and / or the outlet end of the equipment can be in open communication with the surrounding environment and the solvent within the equipment. Conventional practices in the art are used to minimize the loss of solvent from the equipment by convection or diffusion.

[0246] The solvent compositions included in the present disclosure are composed of any one of Compounds 1-4 combined with a cosolvent. The cosolvent can be selected from the group consisting of: hexafluoroisopropyl ethyl ether, hexafluoroisopropyl methyl sulfide, HFE-7000, HFE-7200, HFE-7100, HFE-7300, HFE-7500, HFE-7600, trans-1,2-dichloroethylene, n-pentane, cyclopentane, ethanol, perfluoro(2-methyl-3-pentanone) (Novec1230), cis-HFO-1336mzz, trans-HFO-1336mzz, HF-1234yf, HFO-1234ze(E), HFO-1233zd(E), and HFO-1233zd(Z).

[0247] Electrolyte formulations and batteries

[0248] The present disclosure also provides electrolyte formulations and batteries comprising the electrolyte formulations, which electrolyte formulations comprise the compounds of the present disclosure, including each of Compounds 1-4 and Compositions 1-4. Generally speaking, the electrolyte formulation comprises: (a) an electrolyte; (b) an organic solvent for the electrolyte; and (c) additives, which are included in the formulation to provide or improve desired properties of the electrolyte formulation and / or the battery containing the electrolyte. The compounds of the present disclosure (including each of Compounds 1-4 and Compositions 1-4) can be included in the formulation as a solvent (or cosolvent) for the electrolyte and / or as an additive.

[0249] Therefore, the present disclosure provides the following electrolyte formulations, which comprise: a salt, preferably a lithium ion salt; a solvent for the salt, the solvent comprising the compounds of the present disclosure, including each of Compounds 1-4 and Compositions 1-4, with or without a cosolvent; and one or more additives different from the compounds of the present disclosure. The present invention also provides the following electrolyte formulations, which comprise: (a) an electrolyte, preferably a lithium ion electrolyte; (b) a solvent for the lithium ion electrolyte; and (c) an additive comprising the compounds of the present disclosure (including each of Compounds 1-4 and Compositions 1-4), with or without additional additives.

[0250] The present disclosure generally also provides batteries, particularly rechargeable lithium ion batteries, which comprise an electrolyte formulation containing the compounds of the present disclosure (including each of Compounds 1-4 and Compositions 1-4). Exemplary rechargeable lithium ion batteries are shown in their Figure 9 which shows a cathode and an anode and the electrolyte formulation of the present disclosure that facilitates the flow of lithium ions between the cathode and the anode.

[0251] Although it is expected that the electrolyte formulation of the present invention can generally be used in batteries, in a preferred embodiment, the electrolyte formulation comprises a lithium-ion electrolyte that can be used in rechargeable batteries. Non-limiting examples of lithium salts that can constitute the electrolyte portion of the formulation include: LiPF6, LiAsF6, LiCIO4*LiBF4, LiBC4Og (LiBOB), LiBCO4F (LiODFB), LiPF3(C2F5)3 (LiFAP), LiBF3(C2F5)LiPF3(C,F5)3 (LiFAB), LiN(CF3SO,), LiN(C,F5SO,), LiCF3SO3, LiC(CF3SO)3, LiPF4(CF3)2, LiPF3(CF3)3, LiPF3(iSO-C3C7)3, LiPF5 (iso-C3F7). The total salt concentration can vary according to the specific needs of the application. In some embodiments, the electrolyte can be present in the formulation in an amount between about 0.3 M and about 2.5 M, or about 0.7 M to about 1.5 M.

[0252] Examples

[0253] Example 1 – Synthesis of 3-(difluoromethoxy)-1,1,2,2-tetrafluoropropane

[0254] In a 2-liter three-necked flask equipped with a mechanical stirrer and a water-cooled condenser (the condenser is connected to a dry ice trap before admitting air), 400 ml of diglyme, 153.0 g of 2,2,3,3,3-pentafluoro-1-propanol, and 800 g of 25 wt% NaOH solution were added. The mixture was heated to 30 °C with stirring, and 103.8 g of R22 was bubbled into the mixture through a gas distributor at a rate of 150 ml / min (for about 3.5 hours), and heating was stopped since the addition of R22 started. The internal temperature was maintained at about 30 °C by controlling the rate of R22 introduction, and intermittent ice water cooling was employed if the internal temperature rose to 40 °C. After completion, the mixture was cooled to room temperature and quenched into 3 L of ice water. The bottom organic layer was collected, and 185.6 g of a crude mixture was isolated, with a GC yield of 32% of 3-(difluoromethoxy)-1,1,2,2-tetrafluoropropane.

[0255] Example 2 – Synthesis of 3-(difluoromethoxy)-1,1,2,2-tetrafluoropropane

[0256] 147.6 g of 2,2,3,3 - tetrafluoro - 1 - propanol, 50 ml of diglyme, 2.3 g of Aliquat 336 and 116.8 g of chlorodifluoromethane were placed in a 600 ml stainless steel autoclave and reacted with 361.2 g of 50 wt% sodium hydroxide solution at 15 °C to 30 °C for 4 hours, and then left standing overnight at 23 °C. After completion, the pressure in the autoclave was released through 10% potassium hydroxide caustic solution, the reaction product was quenched into 1.5 L of deionized water, and the bottom organic layer was collected to obtain 195.0 g of a clear liquid. GC analysis showed that the content of the product 3 - (difluoromethoxy) - 1,1,2,2 - tetrafluoropropane in the mixture was 65.9%, and the GC yield was 63.2%.

[0257] Example 3 – Synthesis of 3-(difluoromethoxy)-1,1,2,2-tetrafluoropropane

[0258] 143.2 g of 2,2,3,3 - tetrafluoro - 1 - propanol, 50 ml of diglyme, 2.1 g of Aliquat 336 and 114.8 g of chlorodifluoromethane were placed in a 600 ml stainless steel autoclave and reacted with 353 g of 50 wt% sodium hydroxide solution at 15 °C to 45 °C for 4 hours, and then left standing overnight at 23 °C. After completion, the pressure in the autoclave was released through 10% potassium hydroxide caustic solution, the reaction product was quenched into 1.5 L of deionized water, and the bottom organic layer was collected to obtain 184.0 g of a clear liquid. GC analysis showed that the content of the product 3 - (difluoromethoxy) - 1,1,2,2 - tetrafluoropropane in the mixture was 55.3%, and the GC yield was 51.5%.

[0259] The crude product of 3 - (difluoromethoxy) - 1,1,2,2 - tetrafluoropropane collected from Examples 5 and 6 usually contained by - products 1,1,2,2 - tetrafluoro - 3 - fluoro(2,2,3,3 - tetrafluoropropoxy)methoxy)propane ((CF2HCF2CH2O)2CHF) 3.8%, tris(2,2,3,3 - tetrafluoropropoxy)methane ((CF2HCF2CH2O)3CH) 2.8%, plus some solvents. The dimer (CF2HCF2CH2O)2CHF is liable to lose HF during storage and distillation and is thus corrosive to glassware. Therefore, the crude product mixtures were combined and rotary evaporated under 100 torr vacuum. The liquid product collected in the dry ice trap was free of dimer and trimer. 531.5 g of the crude product mixture (GC yield 53.2%) was rotary evaporated to obtain 304 g of a clear liquid with a GC purity of 88.2%, containing some starting materials and solvents, and no dimer or trimer was detected in the mixture.

[0260] Example 4 – Synthesis of 3-(difluoromethoxy)-1,1,1,2,2-pentafluoropropane

[0261] 153.0 g of 2,2,3,3,3-pentafluoro-1-propanol, 50 ml of diglyme, 2.2 g of Aliquat 336 and 124.2 g of chlorodifluoromethane (R22) were placed in a 600 ml stainless steel autoclave and reacted with 411.8 g of 50 wt% sodium hydroxide solution at 15 °C to 23 °C for 16 hours. After completion, the pressure in the autoclave was released through 10% potassium hydroxide caustic solution, and the reaction product was quenched into 1.5 L of deionized water. The bottom organic layer was collected to obtain 186.9 g of a clear liquid. GC analysis showed that the content of the product 3-(difluoromethoxy)-1,1,1,2,2-pentafluoropropane in the mixture was 46.94%, and the GC yield was 42.9%.

[0262] Example 5 – Synthesis of 3-(difluoromethoxy)-1,1,1,2,2-pentafluoropropane

[0263] In a 2 L three-necked flask equipped with a mechanical stirrer, 100 ml of dioxane, 148.8 g of 2,2,3,3,3-pentafluoro-1-propanol and 408 g of 50 wt% NaOH solution were charged. The mixture was heated to 50 °C and then the heating was stopped while R22 was bubbled into the solution at a rate of 100 ml / min for 4.5 hours. GCMS showed that 13% of the starting material remained. R22 was fed continuously for another 1.5 hours until there was no starting material left in the mixture. After the mixture was cooled to 20 °C, it was quenched into 1.5 L of ice water. 81.9 g of a clear liquid was collected from the bottom layer. GC showed that it contained 59.4% of the target product plus other by-products, and the GC yield was 24.3%.

[0264] Example 6 – Synthesis of 3-(difluoromethoxy)-1,1,1,2,2-pentafluoropropane

[0265] 150.5 g of 2,2,3,3,3-pentafluoro-1-propanol and 70 ml of diglyme in a 600 ml stainless steel autoclave

[0266] were cooled to -60 °C with a dry ice-acetone mixture and evacuated. 110 g of chlorodifluoromethane (R22) was condensed and introduced into the reaction vessel and sealed. 409 g of 50 wt% sodium hydroxide solution was added at a rate of 1.5 ml / min via an Eldex liquid pump and stirred at 23 °C to 39 °C for 4 hours. After the addition was completed, stirring was continued at 23 °C overnight. After completion, the pressure in the autoclave was released through 10% potassium hydroxide caustic solution, and the reaction product was quenched into 1.5 L of deionized water. The bottom organic layer was collected to obtain 143.5 g of a clear liquid. GC analysis showed that the content of the product 3-(difluoromethoxy)-1,1,1,2,2-pentafluoropropane in the mixture was 53.6%, and the GC yield was 38.4%.

[0267] The crude product of 3-(difluoromethoxy)-1,1,1,2,2-pentafluoropropane collected from Examples 5 and 6 usually contains 10.6% of the by-product 1,1,1,2,2-pentafluoro-3-fluoro(2,2,3,3,3-pentafluoropropoxy)methoxy)propane ((CF3CF2CH2O)2CHF), 2.5% of tris(2,2,3,3,3-tetrafluoropropoxy)methane ((CF3CF2CH2O)3CH), plus some solvents. After distillation of 298.7 g of the combined crude product (GC yield 31%) in a 1-foot packed column, 101.8 g of 3-(difluoromethoxy)-1,1,1,2,2-pentafluoropropane with a purity of 98.5% was obtained, plus some impurity-containing fractions.

[0268] Example 7 – Synthesis of 4-(difluoromethoxy)-1,1,1,2,2,3,3-heptafluorobutane

[0269] 100 g of 2,2,3,3,4,4,4-heptafluoro-1-butanol, 400 ml of 21% aqueous NaOH solution and 350 ml of diglyme were added to a 1 L leak-tested autoclave, which was then sealed. The temperature and pressure inside the autoclave were recorded. The autoclave was heated to 50 °C and once the temperature reached the specified value, the heating jacket was removed. 60 g of R22 (CHF2Cl) was bubbled into the autoclave at a rate of 0.25 g / min to 0.4 g / min with stirring.

[0270] After the addition of R22 was complete, stirring was continued for 2 to 3 hours. Subsequently, the reaction mixture was transferred to a 5 L flask and distilled under vacuum for 1.5 hours, and the product was collected successively through a dry ice trap and a liquid nitrogen trap. After warming the product in the cold trap to room temperature, it was transferred to a separatory funnel and washed twice with 50 ml of water. 76 g of the bottom organic layer was collected, and GC analysis showed that the mixture contained 85% of 4-(difluoromethoxy)-1,1,1,2,2,3,3-heptafluorobutane, with a GC yield of 52%.

[0271] Example 8 – Measurement of dielectric constant

[0272] The electrostatic dielectric constant of the new molecule was calculated using the Kirkwood theory as described in the literature of Wang and Anderko [P. Wang and A. Anderko, Computation of dielectric constants of solvent mixtures and electrolyte solutions, Fluid Phase Equilibria, Vol. 186 (2001), pp. 103 - 122] and Harvey and Lemmon [A. H. Harvey and E. W. Lemmon, Method for estimating dielectric constant of natural gas mixtures, International Journal of Thermophysics, Vol. 26 (2005), pp. 31 - 46].

[0273] Dielectric property experiments of all liquid samples were carried out using an Agilent 85070 dielectric probe. All measurements were performed at ambient pressure and room temperature (about 23 °C). Before the measurements, the system was calibrated in the frequency range of 1 GHz to 20 GHz using open circuit, short circuit, and deionized water (22.4 °C) as standards. The calibration results of deionized water are shown in Table 5 below, which are consistent with deionized water at 22.4 °C. The measurement accuracy of this probe is as follows: dielectric constant, er’ = er’ + / - 0.05|er*|, er” = er” + / - 0.05|er*|, (loss = er” / er’).

[0274] Table 5

[0275]

[0276] Example 9 – Organic Rankine cycle

[0277] This example illustrates that based on the comparison of the estimated thermal efficiencies of various working fluids in an organic Rankine cycle, each of the compositions of the present disclosure (including each of Compounds 1 - 4 and / or Heat Transfer Compositions 1 - 10 and / or Blends RB1 - RB20) can be used as a working fluid in an organic Rankine cycle. In this example, it is assumed that the ORC system includes a condenser, a pump, a boiler, and a turbine, and the following qualitative results as shown in Table 6 below will occur.

[0278] Table 6

[0279]

[0280] Example 10

[0281] The battery of an electric vehicle generates heat during operation while charging and discharging. The typical designs of vehicle batteries differ among three types: cylindrical batteries, pouch batteries, and prismatic batteries. All three types have different considerations regarding heat transfer due to their shapes. Prismatic battery cells and pouch battery cells are often used with cooling plates due to their straight outer surfaces. Cylindrical battery cells employ cooling bands that are in thermal contact with the outer casing of the battery cells. The generation of a large amount of heat during the charging and discharging of the battery can lead to a temperature rise, which can result in reduced performance and shortened battery life.

[0282] A battery cooling plate device can be used to provide active cooling to the battery and remove heat (e.g., remove heat from the battery of an electric vehicle). In this embodiment, the cooling performance of the fluid of the present disclosure (including each of Compounds 1-4 and / or Heat Transfer Compositions 1-10 and / or Blends RB1-RB20) and 3M Novec 7200 in single-phase heat transfer is analyzed.

[0283] It should be understood that convective heat transfer can occur through direct contact (i.e., when the battery is immersed in a fluid that can be pumped through the battery casing) or indirectly (i.e., by using a cooling plate having a combination of convective heat transfer and conductive heat transfer).

[0284] This embodiment uses a round tube with an inner diameter of 0.55 inches to provide a cooling load of 10246 BTU / h (3 kW). The length of the tube is 30 feet (9.14 m), and the pressure drop is assumed to be 2.9 PSI (20 kPa). The fluid temperature is 7.2 °C (45 °F). The internal heat transfer coefficient for turbulent flow is determined. The mass flow rates required for the two fluids to remove the cooling load are determined. The comparison results are shown in Table 7 below. It can be seen from the results that the mass flow rate required to remove the generated heat is approximately equal to or less than that of 3M Novec 7200, and the useful output (i.e., the heat transfer coefficient) is approximately equal to or higher than that of 3M Novec 7200.

[0285] Table 7

[0286]

[0287] Example 11 – Secondary air conditioner (AC) system

[0288] The efficiency of the secondary loop air-conditioning system is evaluated by the estimated coefficient of performance (COP). The system uses each of Compound 1-4 and / or heat transfer composition 1-10 and / or blends RB1-RB20 as the secondary refrigerant, and is used in conjunction with primary refrigerant options such as R1234ze(E), R1234yf, and propane. The system consists of a vapor compression primary loop and a pumped two-phase secondary loop thermally connected through an internal heat exchanger. The internal heat exchanger serves as the evaporator for the primary loop and the condenser for the secondary loop. Under the specified conditions of each unit operation, the COP (see Table 9) is evaluated with respect to the performance of R410A in the air-conditioning system using the thermodynamic properties of the primary refrigerant and the secondary refrigerant as defined in Table 8.

[0289] Table 8

[0290]

[0291] Table 9

[0292]

[0293] Table 9 shows the thermodynamic performance of secondary air-conditioning systems with different primary refrigerants and using each of Compound 1-4 as the secondary refrigerant, where the capacity of the secondary air-conditioning system is matched to the R410A system in all cases.

[0294] Example 12 – High-temperature heat pump application

[0295] High-temperature heat pumps can utilize waste heat and provide high radiator temperatures. Compounds 1-4 and / or heat transfer composition 1-10 and / or blends RB1-RB20 in Table 4 of the present disclosure each provide efficiency approximately equal to or better than R245fa over a wide range of condensation temperatures. Using the following operating conditions

[0296] · Condensation temperature varies between 90 °C, 100 °C, and 110 °C

[0297] · Subcooling: 10 °C

[0298] · Evaporation temperature: 25 °C

[0299] · Evaporator superheat: 15 °C

[0300] · Isentropic efficiency: 65%

[0301] Table 10

[0302]

[0303] Example 13 – Thermodynamic performance of a secondary loop medium-temperature refrigeration system

[0304] The efficiency of the medium-temperature refrigeration system in the secondary loop is evaluated by the estimated coefficient of performance (COP). The system employs each of Compounds 1-4 and / or heat transfer compositions 1-10 and / or blends RB1-RB20 and is used in conjunction with primary refrigerant options such as R1234ze(E), R1234yf, and propane. The system consists of a vapor compression primary loop and a pumped two-phase secondary loop thermally connected by an internal heat exchanger. This internal heat exchanger serves as the evaporator for the primary loop and the condenser for the secondary loop. It has been evaluated that the COP of each of Compounds 1-4 and / or heat transfer compositions 1-10 and / or blends RB1-RB20 is approximately equivalent to or better than that of R134a with respect to the performance in an air-conditioning system.

[0305] Example 14A – Single-phase sensible immersion cooling in battery applications

[0306] The battery of an electric vehicle generates heat during operation when charging and discharging. The typical designs of vehicle batteries differ among three types: cylindrical batteries, pouch batteries, and prismatic batteries. All three types have different considerations regarding heat transfer due to their shapes. The generation of a large amount of heat during the charging and discharging of the battery can lead to a temperature increase, which can result in reduced performance and shortened battery life.

[0307] Compounds 1-4 and / or heat transfer compositions 1-10 and / or blends RB1-RB20 preferably have a low dielectric constant, a high dielectric strength, and are non-flammable fluids, which allows for the direct cooling of battery cells immersed in each of Compounds 1-4 and / or heat transfer compositions 1-10 and / or blends RB1-RB20.

[0308] This example considers a battery module composed of 1792 18650-type cylindrical battery cells. In one case, the battery module is cooled by a 50 / 50 mixture of water / glycol in a flat tube heat exchanger in contact with the battery cells. In another case, these battery cells are immersed in each of Compounds 1-4 and / or heat transfer compositions 1-10 and / or blends RB1-RB20, i.e., in direct contact with the fluid. The waste heat of the battery module is 8750 W, which is evenly distributed over the total number of battery cells. The assumed conditions and operating conditions are listed in Tables 11 and 12.

[0309] Table 11

[0310]

[0311] Table 12

[0312]

[0313] Example 14B – Single-phase sensible data center cooling

[0314] A data center (also described herein as a server group or server hub) is designed to maximize computing and storage capacity while minimizing space requirements. This results in a dense arrangement of servers and network equipment, which can cause heat to build up. In addition, data centers operate 24 / 7, further exacerbating heat accumulation. By using effective cooling, the efficiency of server hardware can be increased and its lifespan extended.

[0315] Compounds 1-4 and / or heat transfer compositions 1-10 and / or blends RB1-RB20 preferably have a low dielectric constant, a high dielectric strength, and are non-flammable fluids, which allows for direct cooling of data centers immersed in each of compounds 1-4 and / or heat transfer compositions 1-10 and / or blends RB1-RB20.

[0316] Cooling a data center with compounds 1-4 and / or heat transfer compositions 1-10 and / or blends RB1-RB20 results in a system that operates effectively, efficiently, safely, and reliably. When the data center performs its functions, the electronic components are maintained within the most desirable operating temperature range.

[0317] Example 15A – Two-phase immersion cooling in data center applications

[0318] Reference Figure 7 Examples of data center cooling are provided. A data center (generally designated 200) includes a plurality of electronic subsystems 220 housed in one or more electronic racks 210. At least one and preferably a plurality and preferably all of the electronic subsystems 220 are associated with a cooling station 240 that, in one embodiment, includes a vertically extending liquid-to-gas heat exchanger 243 and supply duct 241 and return duct 242 for directing a cooling air flow 244 across the liquid-to-gas heat exchanger 243. A cooling subsystem 219 is associated with at least one and preferably a plurality and preferably all of the electronic subsystems 220. In a preferred embodiment, as Figure 7As shown, all of the subsystems in subsystem 220 are associated with cooling station 240 and cooling subsystem 219. Each cooling subsystem 219 (in this embodiment) includes a housing 221 (which is preferably a low-pressure housing) that encapsulates a corresponding electronic subsystem 220 that includes a plurality of electronic components 223. The electronic components operate as part of a data center and generate heat as a result of performing their functions in the data center. By way of example, the components include printed circuit boards, microprocessor modules, and memory devices. When each electronic subsystem is operating, its heat-generating components are immersed in the thermal management composition 224 of the present disclosure (including each of compounds 1-4 and / or heat transfer compositions 1-10 and / or blends RB1-RB20). According to the present disclosure, the fluid 224 boils under typical operating conditions, thereby generating dielectric vapor 225. In the illustrated embodiment, the electronic subsystem 220 is angled by providing upwardly inclined support rails 222 within the electronic support 210 to angularly accommodate the electronic subsystem 220. The angling of the electronic subsystem as shown facilitates the buoyancy-driven circulation of the vapor 225 between the cooling subsystem 219 and the liquid-vapor heat exchanger 243 of the associated local cooling station 240. However, according to the present disclosure and this example, excellent results are achieved equally well even without such an angled design. A plurality of coolant loops 226 fluidly and thermally couple the liquid-cooled electronic subsystems and corresponding portions of the liquid-vapor heat exchanger 243. Specifically, a plurality of tube segments 300 pass through the liquid-vapor heat exchanger 243, which in this embodiment includes a plurality of air-cooled fins 310. The vapor 225 is buoyancy-driven from the housing 221 to the corresponding tube segments 300 of the liquid-vapor heat exchanger 243, where the vapor condenses and then returns as a liquid to the associated liquid-cooled electronic subsystem. The cooling air flow 244 is provided parallel to the supply ducts 241 of the plurality of local cooling stations 240 of the data center 200, and the heated air flow is exhausted via the return ducts 242. Equipment as described herein but without the fluid of the present disclosure is disclosed in US2013 / 0019614, which is incorporated herein by reference.

[0319] The system as described above uses a thermal management composition consisting of the present disclosure (including each of compounds 1-4 and / or heat transfer compositions 1-10 and / or blends RB1-RB20) and ambient air and operates as a radiator for a condenser to effectively, efficiently, safely, and reliably maintain electronic components within the most desirable operating temperature range when performing its functions within an operating data center.

[0320] Example 15B – Two-phase immersion cooling of batteries

[0321] As described in Example 15A above, Compounds 1-4 and / or Heat Transfer Compositions 1-10 and / or Blends RB1-RB20 are suitable as heat management compositions for two-phase immersion cooling systems.

[0322] In this example, the two-phase immersion cooling system of Example 15A is used to cool a battery array. The immersion cooling system effectively, efficiently, safely, and reliably maintains the battery within the most desired operating temperature range.

[0323] Example 16 – Compounds 1-4 used as solvents or additives in lithium-ion batteries

[0324] Electrolyte solvents and additives play important roles in the performance of lithium-ion batteries (LIBs). Compounds 1-4 of the present disclosure are used as solvents or additives in various electrolyte compositions for lithium-ion batteries. Generally, the electrolyte composition contains a dissolved lithium salt, such as lithium hexafluorophosphate (LiPF6), lithium bis(fluorosulfonyl)imide (LiFSI), lithium trifluoromethanesulfonate (LiTf); a solvent or solvent combination containing components such as ethylene carbonate (EC), propylene carbonate (PC), diethyl carbonate (DEC), dimethyl carbonate (DMC), and many other organic carbonates and esters; and additives such as vinylene carbonate, crown ethers, borates, borate esters, and many other compounds. The role of the solvent in an LIB is to act as a medium for transferring charge between a pair of electrodes, which is in the form of ions. It is also known to perform various modifications to the electrolyte using solvents or additives with different components [for a detailed description, see Kang Xu, "Non-Aqueous Electrolytes for Lithium Based Rechargeable Batteries", Chem Rev. 2012, Vol. 104, pp. 4303-4417]. The compounds of the present disclosure (including Compounds 1-4) can be added as solvents and / or additives to improve the performance of lithium-ion batteries because such materials of the present invention have desired properties such as chemical stability and thermal stability, desired dielectric constants, and electrochemical windows. The compounds and compositions of the present invention can be used as solvents in various electrolyte compositions in an amount, for example, in the range of 5 wt% to 50 wt%, and as additives in an amount in the range of 0.1 wt% to 5 wt%.

[0325] Example 17 - Integrated circuit cooling

[0326] The working fluids of the present disclosure (including Compounds 1-4 and / or Heat Transfer Compositions 1-10 and / or Blends RB1-RB20) are used to cool integrated circuits, such as computer chips, circuit boards, and / or any heat sinks or radiators associated with or connected to a computer chip or circuit board, by circulating Compounds 1-4 and / or Heat Transfer Compositions 1-10 and / or Blends RB1-RB20 around the integrated circuit components or immersing the integrated circuit components in Compounds 1-4 and / or Heat Transfer Compositions 1-10 and / or Blends RB1-RB20. The cooling system effectively, efficiently, safely, and reliably maintains the integrated circuit components within the most desirable operating temperature range.

[0327] Example 18 – Solvent degreasing

[0328] The working fluids of the present disclosure (including Compound 1-4) are used as solvents in degreasing equipment, successfully removing various contaminants (including all contaminants mentioned above) from a variety of substrates (including all substrates mentioned above).

[0329] Aspects

[0330] Aspect 1 is a method of providing heat transfer to and / or from an electronic component, article, and / or device during operation of the electronic component, article, and / or device, comprising: providing a heat transfer composition comprising at least about 10 wt% of 3-(difluoromethoxy)-1,1,1,2,2-pentafluoropropane; and contacting the heat transfer composition with the electronic component, article, and / or device during operation of the electronic component, article, and / or device to cool the electronic component, article, and / or device.

[0331] Aspect 2 is the method according to Aspect 1, wherein the heat transfer composition has a dielectric constant of less than about 5 at 20 GHz.

[0332] Aspect 3 is the method according to Aspect 2, wherein the heat transfer composition has a dielectric constant of about 3.4 at 20 GHz.

[0333] Aspect 4 is the method according to any one of Aspects 1 to 3, wherein the heat transfer composition has a boiling point of about 35°C to about 80°C.

[0334] Aspect 5 is the method according to Aspect 4, wherein the heat transfer composition has a boiling point of about 46°C.

[0335] Aspect 6 is the method according to any one of Aspects 1 to 5, wherein the heat transfer composition has a global warming potential (GWP) of about 500 or less.

[0336] Aspect 7 is the method according to any one of Aspects 1 to 6, wherein the heat transfer composition is non-flammable.

[0337] Aspect 8 is the method according to any one of Aspects 1 to 7, wherein the heat transfer composition comprises at least about 50% by weight of 3-(difluoromethoxy)-1,1,1,2,2-pentafluoropropane.

[0338] Aspect 9 is the method according to any one of Aspects 1 to 8, wherein the electronic device is selected from a data center and a battery.

[0339] Aspect 10 is a method of heating and / or cooling an electronic component, article, and / or device, comprising: (a) providing a refrigerant comprising at least about 10% by weight of 3-(difluoromethoxy)-1,1,1,2,2-pentafluoropropane; (b) immersing the electronic component, article, and / or device in the refrigerant while the electronic component, article, and / or device is operating; and (c) effecting heat transfer between the immersed electronic component, article, and / or device and the refrigerant.

[0340] Aspect 11 is the method according to Aspect 10, wherein the refrigerant has a dielectric constant of less than about 5 at 20 GHz.

[0341] Aspect 12 is the method according to Aspect 11, wherein the refrigerant has a dielectric constant of about 3.4 at 20 GHz.

[0342] Aspect 13 is the method according to any one of Aspects 10 to 12, wherein the refrigerant has a boiling point of about 35°C to about 80°C.

[0343] Aspect 14 is the method according to Aspect 13, wherein the refrigerant has a boiling point of about 46°C.

[0344] Aspect 15 is the method according to any one of Aspects 10 to 14, wherein the refrigerant has a global warming potential (GWP) of about 500 or less.

[0345] Aspect 16 is the method according to any one of Aspects 10 to 15, wherein the refrigerant is non-flammable.

[0346] Aspect 17 is the method according to any one of Aspects 10 to 16, wherein the refrigerant comprises at least about 50% by weight of 3-(difluoromethoxy)-1,1,1,2,2-pentafluoropropane.

[0347] Aspect 18 is the method according to any one of Aspects 10 to 17, wherein the electronic device is selected from a data center and a battery.

[0348] Aspect 19 is a method for synthesizing 3-(difluoromethoxy)-1,1,1,2,2-pentafluoropropane, which includes reacting 2,2,3,3,3-pentafluoro-1-propanol with chlorodifluoromethane in the presence of a base.

[0349] Aspect 20 is the method according to aspect 19, further including at least one of the following: the reaction step is carried out in the presence of an organic solvent selected from diglyme, dioxane, and combinations thereof; the base is NaOH; and the reaction step is carried out at a temperature of about 10 °C to about 45 °C.

[0350] Aspect 21 is a composition comprising a fluoroether according to formula 1:

[0351] CHF2OCH a (Cx1Fy1Hz1)(Cx2Fy2Hz2)

[0352] where a = 1 or 2;

[0353] x1 is from 1 to 4;

[0354] y1 is from 3 to 9;

[0355] z1 is from 0 to 6;

[0356] x2 is from 0 to 3;

[0357] y2 is from 0 to 7; and

[0358] z2 is from 0 to 4.

[0359] Aspect 22 is the composition according to aspect 21, wherein the fluoroether includes at least one of the following:

[0360] 3-(difluoromethoxy)-1,1,2,2-tetrafluoropropane (CHF2CF2CH2OCHF2),

[0361] 3-(difluoromethoxy)-1,1,1,2,2-pentafluoropropane (CF3CF2CH2OCHF2),

[0362] 2-(difluoromethoxy)-1,1,1,3,3,3-hexafluoropropane ((CF3)2CHOCHF2),

[0363] 4-(difluoromethoxy)-1,1,1,2,2,3,3-heptafluorobutane (CF3CF2CF2CH2OCHF2), and combinations of the foregoing substances.

[0364] Aspect 23 is a heat transfer composition comprising the fluoroether composition according to aspect 21 or aspect 22.

[0365] Aspect 24 is a thermal management composition comprising the fluoroether composition described in Aspect 21 or Aspect 22.

[0366] Aspect 25 is an electrolyte composition comprising the fluoroether composition described in Aspect 21 or Aspect 22.

[0367] Aspect 26 is a solvent composition comprising the fluoroether composition described in Aspect 21 or Aspect 22.

[0368] Aspect 27 is a method for synthesizing a fluoroether according to Formula 1:

[0369] CHF2OCH a (Cx1Fy1Hz1)(Cx2Fy2Hz2)

[0370] where a = 1 or 2;

[0371] x1 is from 1 to 4;

[0372] y1 is from 3 to 9;

[0373] z1 is from 0 to 6;

[0374] x2 is from 0 to 3;

[0375] y2 is from 0 to 7; and

[0376] z2 is from 0 to 4.

[0377] The method comprises reacting a fluoroalcohol with chlorodifluoromethane in the presence of a catalyst to provide the fluoroether of Formula 1.

[0378] Aspect 28 is the method according to Aspect 27, wherein the fluoroalcohol is 2,2,3,3-tetrafluoro-1-propanol and the fluoroether is 3-(difluoromethoxy)-1,1,2,2-tetrafluoropropane.

[0379] Aspect 29 is the method according to Aspect 27, wherein the fluoroalcohol is 2,2,3,3,3-pentafluoro-1-propanol and the fluoroether is 3-(difluoromethoxy)-1,1,1,2,2-pentafluoropropane.

[0380] Aspect 30 is the method according to Aspect 27, wherein the fluoroalcohol is 2,2,2,3,3,3-hexafluoro-1-propanol and the fluoroether is 2-(difluoromethoxy)-1,1,1,3,3,3-hexafluoropropane.

[0381] Aspect 31 is the method according to Aspect 27, wherein the fluoroalcohol is 2,2,3,3,4,4,4-heptafluoro-1-butanol and the fluoroether is 4-(difluoromethoxy)-1,1,1,2,2,3,3-heptafluorobutane.

[0382] Aspect 32 is the method according to any one of aspects 27 to 31, wherein the reaction step further comprises reacting in the presence of an organic solvent.

[0383] Aspect 33 is the method according to aspect 32, wherein the organic solvent is selected from diglyme, dioxane, and combinations thereof.

[0384] Aspect 34 is the method according to any one of aspects 27 to 31, wherein the catalyst is NaOH.

[0385] Aspect 35 is the method according to any one of aspects 27 to 31, wherein the reaction step further comprises conducting the reaction at a temperature of 10 °C to 45 °C.

[0386] Aspect 36 is a method for operating an electronic device in a cooling mode, comprising: providing a refrigerant comprising a fluoroether according to Formula 1:

[0387] CHF2OCH a (Cx1Fy1Hz1)(Cx2Fy2Hz2)

[0388] wherein a = 1 or 2;

[0389] x1 is from 1 to 4;

[0390] y1 is from 3 to 9;

[0391] z1 is from 0 to 6;

[0392] x2 is from 0 to 3;

[0393] y2 is from 0 to 7;

[0394] z2 is from 0 to 4; and

[0395] immersing the electronic device or component in the refrigerant.

[0396] Aspect 37 is the method according to aspect 36, wherein the refrigerant has a global warming potential (GWP) of about 200 or less.

[0397] Aspect 38 is the method according to aspect 36 or aspect 37, wherein the refrigerant is non-flammable.

[0398] Aspect 39 is the method according to any one of aspects 36 to 38, wherein the refrigerant has a dielectric constant of less than 5 at 20 GHz.

[0399] Aspect 40 is the method according to any one of aspects 36 to 39, wherein the refrigerant has a boiling point of about 35 °C to about 80 °C.

[0400] Aspect 41 is the method according to any one of aspects 36 to 40, wherein the refrigerant: (i) has a dielectric constant of less than 5 at 20 GHz; (ii) has a boiling point of about 35 °C to about 80 °C; (iii) is non-flammable; and (iv) has a negative Ames test toxicity.

[0401] Aspect 42 is the method according to any one of aspects 36 to 41, wherein the refrigerant comprises at least about 50 wt% of a fluoroether according to Formula 1:

[0402] CHF2OCH a (Cx1Fy1Hz1)(Cx2Fy2Hz2)

[0403] where a = 1 or 2;

[0404] x1 is from 1 to 4;

[0405] y1 is from 3 to 9;

[0406] z1 is from 0 to 6;

[0407] x2 is from 0 to 3;

[0408] y2 is from 0 to 7; and

[0409] z2 is from 0 to 4.

[0410] Aspect 43 is the method according to any one of aspects 36 to 42, wherein the electronic device or component includes one or more of the following: a battery, a semiconductor integrated circuit (IC), an electrochemical cell, a power transistor, a resistor, an electroluminescent element, a microprocessor, a power control semiconductor, a power distribution switching device, a power transformer, a printed circuit board, a multi-chip module, a packaged or unpackaged semiconductor device, a semiconductor integrated circuit, a fuel cell, a laser light-emitting diode (LED), an electrochemical cell, an electric drive motor, and combinations thereof.

[0411] Aspect 44 is the method according to any one of aspects 36 to 43, which is applied to an electric vehicle and / or an oil / electric hybrid vehicle and / or a data center and / or a server and / or a cryptocurrency mining center.

[0412] It should be understood that the above description is merely illustrative of the present disclosure. Without departing from the present disclosure, those skilled in the art can design various alternative solutions and modifications. Therefore, the present disclosure is intended to cover all such alternative solutions, modifications, and variations that fall within the scope of the appended claims.

Claims

1. A method for providing heat transfer to and / or from an electronic component, article, and / or device during operation of the electronic component, article, and / or device, comprising: providing a heat transfer composition comprising at least about 10 wt% of 3-(difluoromethoxy)-1,1,1,2,2-pentafluoropropane; and during operation of the electronic component, article, and / or device, contacting the heat transfer composition with the electronic component, article, and / or device to cool the electronic component, article, and / or device.

2. The method according to claim 1, wherein the heat transfer composition has a dielectric constant of less than about 5 at 20 GHz.

3. The method according to claim 2, wherein the heat transfer composition has a dielectric constant of about 3.4 at 20 GHz.

4. The method according to any one of claims 1 to 3, wherein the heat transfer composition has a boiling point of about 35 °C to about 80 °C.

5. The method according to claim 1, wherein the heat transfer composition further has the following properties: a boiling point of about 46 °C; a global warming potential (GWP) of about 500 or less; and non-flammable.

6. The method according to any one of claims 1 to 5, wherein the heat transfer composition comprises at least about 50 wt% of 3-(difluoromethoxy)-1,1,1,2,2-pentafluoropropane.

7. The method according to any one of claims 1 to 6, wherein the electronic device is selected from a data center and a battery.

8. A method for heating and / or cooling an electronic component, article, and / or device, comprising: (a) providing a refrigerant comprising at least about 10 wt% of 3-(difluoromethoxy)-1,1,1,2,2-pentafluoropropane; (b) immersing the electronic component, article, and / or device in the refrigerant during operation of the electronic component, article, and / or device; and (c) effecting heat transfer between the immersed electronic component, article, and / or device and the refrigerant.

9. The method according to claim 8, wherein the refrigerant has a dielectric constant of less than about 5 at 20 GHz.

10. The method according to claim 9, wherein the refrigerant has a dielectric constant of about 3.4 at 20 GHz.

11. The method according to any one of claims 8 to 10, wherein the refrigerant has a boiling point of about 35 °C to about 80 °C.

12. The method according to claim 8, wherein the refrigerant further has the following properties: a boiling point of about 46 °C; a global warming potential (GWP) of about 500 or less; and non-flammable.

13. The method according to any one of claims 8 to 12, wherein the refrigerant comprises at least about 50 wt% of 3-(difluoromethoxy)-1,1,1,2,2-pentafluoropropane.

14. The method according to any one of claims 8 to 13, wherein the electronic device is selected from a data center and a battery.

15. A method for synthesizing 3-(difluoromethoxy)-1,1,1,2,2-pentafluoropropane, comprising reacting 2,2,3,3,3-pentafluoro-1-propanol with chlorodifluoromethane in the presence of a base.

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