Hydrofluoroether and method for using the same

Abstract

A compound having the structural formula (II): 2 is H, CH3, CF3, CH2CF2CF2H, or CH2CF2CF2CF2CF2H, and R 2 f is a perfluoroalkyl group having 1 to 4 carbon atoms, optionally containing either or both of a nitrogen heteroatom and an oxygen heteroatom in a chain; R 2 f' is CF3 or CF2CF3, and R 2 f" is CF3 or CF2CF3, where R 2 When f' is CF3, R 2 f" is CF3 and R 2 is H or CH3, R 2 f is CF 3 isn't it]. JPEG2023510374000042.jpg26115

Description

Technical Field

[0001] The present invention relates to hydrofluoroethers, working fluids containing the same, systems and devices containing the same, and methods of using the same.

Background Art

[0002] Various hydrofluoroethers and their uses are described, for example, in U.S. Patent No. 5,718,293, U.S. Patent No. 5,925,611, and U.S. Patent No. 6,046,368.

Mode for Carrying Out the Invention

[0003] In view of the increasing demand for environmentally friendly compounds, while further reducing the environmental impact, the performance requirements (e.g., non-flammability, dissolving power, stability, and operating temperature range) for various applications (e.g., heat transfer, immersion cooling, foaming agents, solvent cleaning, and adhesion coating solvents) are further met or exceeded, and it is recognized that there is still a need for a new working fluid that can be manufactured cost-effectively.

[0004] Generally, the present disclosure relates to hydrofluoroether compounds containing a tertiary perfluoroalkyl group bonded to oxygen. These hydrofluoroether compounds exhibit surprisingly high hydrolyzability and base stability compared to related hydrofluoroether compounds that do not contain a tertiary perfluoroalkyl group bonded to oxygen. Further, the hydrofluoroether compounds of the present disclosure exhibit a shorter atmospheric lifetime and a lower global warming potential than equivalent fluorinated compounds useful as working fluids (e.g., perfluorinated hydrocarbons, or hydrofluorocarbons, or hydrofluoroether compounds that do not contain a tertiary perfluoroalkyl group bonded to oxygen).

[0005] As used herein, "heteroatoms linked in a chain" means atoms other than carbon (e.g., oxygen, nitrogen, or sulfur) that are bonded to at least two carbon atoms of a carbon chain (linear, branched, or within a ring) to form a carbon - heteroatom - carbon linkage.

[0006] As used herein, "fluoro" (e.g., with respect to a group or moiety such as in the case of "fluoroalkene" or "fluoroalkenyl" or "fluoroalkane" or "fluoroalkyl" or "fluorocarbon") or "fluorinated" means (i) being partially fluorinated and having at least one hydrogen atom bonded to carbon, or (ii) being perfluorinated.

[0007] As used herein, "perfluoro" (e.g., with respect to a group or moiety such as in the case of "fluoroalkene" or "fluoroalkenyl" or "fluoroalkane" or "fluoroalkyl" or "fluorocarbon") or "perfluorinated" means being completely fluorinated and having no hydrogen atoms bonded to carbon that can be replaced by fluorine, unless otherwise indicated.

[0008] As used herein, "alkyl" means a molecular fragment composed of a valence - saturated carbon - based backbone (i.e., derived from an alkane) that can be linear, branched, or cyclic.

[0009] As used herein, "alkenyl" means a molecular fragment composed of a carbon - based backbone that contains at least one carbon - carbon double bond (i.e., derived from an alkene, diene, etc.), and the alkenyl fragment can be linear, branched, or cyclic.

[0010] As used herein, the singular forms "a", "an", and "the" include plural referents unless the context clearly dictates otherwise. As used in this specification and the appended embodiments, the term "or" is generally used in the sense of "and / or" unless the context clearly dictates otherwise.

[0011] As used herein, a description 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).

[0012] Unless otherwise indicated, all numbers expressing quantities or ingredients, properties, and so forth used in this specification and the embodiments 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 list of embodiments 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 at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0013] In some embodiments, the present disclosure relates to Structural Formula (I)

Chemical Formula

[0014] In some embodiments, R H is CH 3 , or CH 2 CH 3 and can be. In some embodiments, R H can be a partially fluorinated alkyl group having 1 to 5 carbon atoms.

[0015] In some embodiments, at least one of R f ' and R f " is a perfluoroalkyl group having 2 carbon atoms (i.e., a perfluoroethyl group).

[0016] In some embodiments, both R f ' and R f " are perfluoroalkyl groups having 2 carbon atoms (i.e., perfluoroethyl groups).

[0017] In any of the above embodiments, Rf can include either or both of a chain-linked nitrogen heteroatom and a chain-linked oxygen heteroatom. In any of the above embodiments, Rf can include a chain-linked nitrogen heteroatom. In any of the above embodiments, Rf can include a chain-linked oxygen heteroatom. In any of the above embodiments, Rf can include a chain-linked nitrogen heteroatom and a chain-linked oxygen heteroatom.

[0018] As discussed in great detail below, a subset of the compounds within structural formula (I) can be produced particularly cost-effectively. Such compounds have the structural formula (II):

Chemical formula

[0019] In some embodiments, R 2 is H or CH 3 is.

[0020] In various embodiments, representative examples of the compounds of structural formulas (I) and (II) include the following:

Chemical formula

[0021] ​In some embodiments, the fluorine content in the compounds of the present disclosure (i.e., compounds having structural formula (I) or (II)) may be sufficient to render the compounds nonflammable by the ASTM D - 3278 - 96 e - 1 test method ("Flash Point of Liquids by Small Scale Closed Cup Apparatus").

[0022] In some embodiments, the compounds of the present disclosure (i.e., tert - fluoroalkyl - containing hydrofluoroethers of structural formulas (I) and (II)) may be useful over a wide operating temperature range. In this regard, in some embodiments, the compounds of the present disclosure may have a boiling point of 30, 40, 50, 60, 70, 80, or 90 degrees Celsius or higher and 290, 270, 250, 230, 210, 190, 170, 150, 130, 120, 110, 100, 90, or 80 degrees Celsius or lower.

[0023] In some embodiments, the compounds of the present disclosure may be hydrophobic, relatively unreactive chemically, and thermally stable. Fluorinated compounds may have less impact on the environment. In this regard, the fluorinated compounds of the present disclosure may have a global warming potential (GWP, 100 - year ITH) of 500, 300, 200, 100, 50, less than 10, or less than 1. As used herein, GWP is a relative measure of the global warming potential of a compound based on the compound's structure. The GWP of a compound was defined by the Intergovernmental Panel on Climate Change (IPCC) in 1990 and revised in 2007 and is calculated as the warming due to the release of 1 kilogram of the compound relative to the warming due to the release of 1 kilogram of CO 2 emissions over a specific integration time horizon (ITH).

Number

[0024] In this formula, a iis the radiative forcing per unit mass increase of the compound in the atmosphere (the change in the radiative flux through the atmosphere due to the IR absorbance of that compound), C is the atmospheric concentration of the compound, τ is the atmospheric lifetime of the compound, t is time, and i is the compound of interest. The commonly accepted ITH is 100 years, which represents a compromise between short-term effects (20 years) and long-term effects (500 years or more). The concentration of organic compound i in the atmosphere is assumed to follow pseudo-first-order kinetics (i.e., exponential decay). The concentration of CO 2 over the same time interval incorporates a more complex model for the exchange and removal of CO 2 from the atmosphere (the Bern carbon cycle model).

[0025] In some embodiments, the compounds of the present disclosure can be prepared from their respective perfluorinated acid fluorides or ketones in the presence of a metal fluoride catalyst / reagent ([M]F), such as KF or CsF, in an aprotic organic solvent (e.g., diglyme, tetraglyme, N,N-dimethylformamide, or N-methylpyrrolidine), in combination with tetrafluoroethylene (TFE) or perfluoroalkyltrimethylsilane. The metal perfluoroalkoxide intermediate is then quenched by the addition of an electrophilic R H -X (e.g., iodomethane, bromomethane, dimethyl sulfate, iodoethane, bromoethane, diethyl sulfate, 2,2,2-trifluoroethyl trifluoromethanesulfonate, 2,2,3,3,3-pentafluoropropyl trifluoromethanesulfonate, 2,2,3,3,4,4,4-heptafluorobutyl trifluoromethanesulfonate, and 2,2,2-trifluoroethyl 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate) to obtain the desired composition. Readily available and low-cost fluorochemical building blocks such as perfluorinated acid fluorides, perfluoroketones, and tetrafluoroethylene (TFE) make the compositions of the present disclosure cost-effective working fluids. Furthermore, the use of inexpensive fluoride salts such as KF and alkylating reagents (e.g., dimethyl sulfate and diethyl sulfate) further aids in the low-cost synthesis of the compounds of the present disclosure.

[0026] In some embodiments, the present disclosure further targets a working fluid comprising, as a main component, one or more of the above-described compounds. For example, the working fluid may comprise the above-described compound in an amount of at least 25 wt%, at least 50 wt%, at least 70 wt%, at least 80 wt%, at least 90 wt%, at least 95 wt%, or at least 99 wt% based on the total weight of the working fluid. In addition to the compounds of the present disclosure, the working fluid may further comprise one or more of the following components: alcohol, ether, alkane, alkene, haloalkene, perfluorocarbon, perfluorinated tertiary amines, perfluoroether, cycloalkane, ester, ketone, oxirane, aromatic, siloxane, hydrochlorocarbon, hydrochlorofluorocarbon, hydrofluorocarbon, hydrochlorochloroolefin, hydrochlorofluorochloroolefin, sulfone, or a mixture thereof, in a total amount of up to 75 wt%, up to 50 wt%, up to 30 wt%, up to 20 wt%, up to 10 wt%, or up to 5 wt% based on the total weight of the working fluid. Such additional components can be selected to modify or enhance the properties of the composition for a particular application.

[0027] In some embodiments, the compounds of the present disclosure (or the working fluid containing the same) can be used as a heat transfer agent in various applications (e.g., for cooling or heating integrated circuit tools in the semiconductor industry, including dry etchers, integrated circuit testers, photolithography exposure tools (steppers), asher, chemical vapor deposition equipment, automatic test equipment (probers), physical vapor deposition equipment (e.g., sputtering apparatuses), as well as vapor phase soldering fluids and thermal shock fluids).

[0028] In some embodiments, the present disclosure further targets an apparatus for heat transfer, comprising a device and a mechanism for transferring heat to or from the device. The mechanism for transferring heat may include a heat transfer fluid or a working fluid containing one or more of the compounds of the present disclosure.

[0029] The apparatus provided for heat transfer may include a device. The device may be a component, an object to be processed, an assembly, etc. that is cooled, heated, or maintained at a predetermined temperature or temperature range. Such devices include electrical components, mechanical components, and optical components. Examples of the devices of the present disclosure include, but are not limited to, microprocessors, wafers used to manufacture semiconductor devices, power control semiconductors, power distribution switchgear, power transformers, circuit boards, multi-chip modules, packaged and unpackaged semiconductor devices, lasers, chemical reactors, fuel cells, heat exchangers, and electrochemical cells. In some embodiments, the device may include a cooler, a heater, or a combination thereof.

[0030] In still other embodiments, the device may include an electronic device, such as a processor including a microprocessor. As these electronic devices become more powerful, the amount of heat generated per unit time increases. Therefore, the heat transfer mechanism plays an important role in the performance of the processor. The heat transfer fluid typically has good heat transfer performance, good electrical compatibility (even when used in "indirect contact" applications such as those employing a cooling plate), and low toxicity, low flammability (or non-flammability), and a small environmental impact. Good electrical compatibility requires that the heat transfer fluid candidate exhibit high dielectric strength, high volume resistivity, and poor solubility in polar substances. In addition, the heat transfer fluid should exhibit good mechanical compatibility, i.e., it should not adversely affect typical constituent materials and should have a low pour point and low viscosity to maintain fluidity during low-temperature operation.

[0031] The provided apparatus may include a mechanism for transferring heat. The mechanism may include a heat transfer fluid. The heat transfer fluid may include one or more of the disclosed fluorinated aromatics. Heat may be transferred by disposing the heat transfer mechanism in thermal contact with the device. When disposed in thermal contact with the device, the heat transfer mechanism removes heat from the device, supplies heat to the device, or maintains the device at a selected temperature or temperature range. The direction of heat flow (from or to the device) is determined by the relative temperature difference between the device and the heat transfer mechanism.

[0032] Examples of heat transfer mechanisms include, but are not limited to, equipment for managing heat transfer fluids, such as pumps, valves, fluid storage systems, pressure control systems, condensers, heat exchangers, heat sources, heat sinks, refrigeration systems, active temperature control systems, and passive temperature control systems. Examples of suitable heat transfer mechanisms include, but are not limited to, a temperature-controlled wafer chuck of a plasma enhanced chemical vapor deposition (PECVD) tool, a temperature-controlled test head for die performance testing, a temperature-controlled operating region within a semiconductor processing apparatus, a liquid containment vessel of a thermal shock test chamber, and a constant temperature bath. In some systems, such as etchers, asher, PECVD chambers, vapor phase soldering devices, and thermal shock testers, the upper limit of the desired operating temperature can be as high as 170 °C, 200 °C, or even 230 °C.

[0033] Heat may be transferred by disposing the heat transfer mechanism in thermal communication with the device. When disposed in thermal communication with the device, the heat transfer mechanism removes heat from the device, supplies heat to the device, or maintains the device at a selected temperature or temperature range. The direction of heat flow (from or to the device) is determined by the relative temperature difference between the device and the heat transfer mechanism. Also included as provided apparatus are refrigeration systems, cooling systems, test apparatuses, and machining apparatuses. In some embodiments, the provided apparatus can be a constant temperature bath or a thermal shock test chamber.

[0034] In some embodiments, the present disclosure relates to a cleaning composition comprising one or more compounds of the present disclosure and one or more co-solvents.

[0035] In some embodiments, the compound of the present disclosure may be present in an amount greater than 50 wt%, greater than 60 wt%, greater than 70 wt%, or greater than 80 wt% based on the total weight of the compound and co-solvent of the present disclosure.

[0036] In various embodiments, the cleaning composition may further comprise a surfactant. Suitable surfactants include, in particular, surfactants that are sufficiently soluble in hydrofluoroethers and surfactants that promote the removal of dirt by dissolving, dispersing or removing the dirt. One useful class of surfactants is nonionic surfactants having a hydrophilic-lipophilic balance (HLB) value of less than about 14. Examples include ethoxylated alcohols, ethoxylated alkylphenols, ethoxylated fatty acids, alkylary sulfonates, glycerol esters, ethoxylated fluoroalcohols, and fluorinated sulfonamides. A mixture of surfactants with complementary properties may be used, where one surfactant is added to the cleaning composition to promote the removal of oily dirt and another surfactant is added to promote the removal of water-soluble dirt. When used, the surfactant can be added in an amount sufficient to promote dirt removal. Typically, the surfactant is added in an amount of about 0.1 wt% to 5.0 wt% of the cleaning composition, preferably in an amount of about 0.2 wt% to 2.0 wt%.

[0037] In an exemplary embodiment, the co-solvent may include alcohol, ether, alkane, alkene, haloalkene, perfluorocarbon, perfluorinated tertiary amine, perfluoroether, cycloalkane, ester, ketone, oxirane, aromatic, haloaromatic, siloxane, hydrochlorocarbon, hydrochlorofluorocarbon, hydrofluorocarbon, hydrofluoroolefin, hydrochloroolefin, hydrochlorofluoroolefin, or a mixture thereof. Representative examples of co-solvents that can be used in the cleaning composition include methanol, ethanol, isopropanol, t-butyl alcohol, methyl t-butyl ether, methyl t-amyl ether, 1,2-dimethoxyethane, cyclohexane, 2,2,4-trimethylpentane, n-decane, terpene (e.g., a-pinene, camphene, and limonene), trans-1,2-dichloroethylene, cis-1,2-dichloroethylene, methylcyclopentane, decalin, methyl decanoate, t-butyl acetate, ethyl acetate, diethyl phthalate, 2-butanone, methyl isobutyl ketone, naphthalene, toluene, p-chlorobenzotrifluoride, trifluorotoluene, bis(trifluoromethyl)benzene, hexamethyldisiloxane, octamethyltrisiloxane, perfluorohexane, perfluoroheptane, perfluorooctane, perfluorotributylamine, perfluoro-N-methylmorpholine, perfluoro-2-butyloxacyclopentane, methylene chloride, chlorocyclohexane, 1-chlorobutane, 1,1-dichloro-1-fluoroethane, 1,1,1-trifluoro-2,2-dichloroethane, 1,1,1,2,2-pentafluoro-3,3-dichloropropane, 1,1,2,2,3-pentafluoro-1,3-dichloropropane, 2,3-dihydroperfluoropentane, 1,1,1,2,2,4-hexafluorobutane, 1-trifluoromethyl-1,2,2-trifluorocyclobutane, 3-methyl-1,1,2,2-tetrafluorocyclobutane, 1-hydroperfluoropentadecaneheptane, or a mixture thereof.

[0038] In some embodiments, the present disclosure relates to a process for cleaning a substrate. The cleaning process can be carried out by contacting the contaminated substrate with the cleaning composition described above. The compounds of the present disclosure can be used alone, as mixtures with each other or with other commonly used cleaning solvents (e.g., alcohols, ethers, alkanes, alkenes, haloalkenes, perfluorocarbons, perfluorinated tertiary amines, perfluoroethers, cycloalkanes, esters, ketones, oxiranes, aromatics, haloaromatics, siloxanes, hydrochlorocarbons, hydrochlorofluorocarbons, hydrofluorocarbons, hydrofluoroolefins, hydrochloroolefins, hydrochlorofluorooletins, or mixtures thereof). Such co-solvents can be selected to modify or improve the dissolution properties of the cleaning composition for a particular application and can be used in a ratio (ratio of co-solvent to hydrofluoroolefin compound) such that the resulting composition is non-flammable. If desired for a particular application, the cleaning composition can further contain one or more dissolved or dispersed gaseous, liquid or solid additives (e.g., carbon dioxide gas, surfactant, stabilizer, antioxidant or activated carbon).

[0039] In some embodiments, the present disclosure relates to a cleaning composition comprising one or more compounds of the present disclosure and optionally one or more surfactants. Suitable surfactants include surfactants that are sufficiently soluble in the compounds of the present disclosure and surfactants that promote the removal of dirt by dissolving, dispersing or removing the dirt. One useful classification of surfactants is nonionic surfactants having a hydrophilic-lipophilic balance (HLB) value of less than about 14. Examples include ethoxylated alcohols, ethoxylated alkylphenols, ethoxylated fatty acids, alkylaryl sulfonates, glycerol esters, ethoxylated fluoroalcohols and fluorinated sulfonamides. A mixture of surfactants with complementary properties may be used, where one surfactant is added to the cleaning composition to promote the removal of oily dirt and another surfactant is added to promote the removal of water-soluble dirt. When used, the surfactant can be added in an amount sufficient to promote dirt removal. Typically, the surfactant may be added in an amount of 0.1 wt% to 5.0 wt% or 0.2 wt% to 2.0 wt% of the cleaning composition.

[0040] Most contaminants can also be dissolved or removed from the surface of a substrate using the cleaning process of the present disclosure. For example, substances such as light hydrocarbon contaminants; high molecular weight hydrocarbon contaminants such as mineral oil and grease; fluorocarbon contaminants such as perfluoropolyethers, bromotrifluoroethylene oligomers (gyroscope fluids), and chlorotrifluoroethylene oligomers (hydraulic oils, lubricants); silicone oils and greases; solder fluxes; particulates; water; and other contaminants encountered in the cleaning of precision, electronic, metal, and medical devices can be removed.

[0041] The cleaning composition can be used in either the gaseous state or the liquid state (or both), and can employ any known or future technique for "contacting" with a substrate. For example, a liquid cleaning composition can be sprayed or brushed onto a substrate, a gaseous cleaning composition can be sprayed over the entire substrate, or the substrate can be exposed to either a gaseous or a liquid composition. High temperature, ultrasonic energy, and / or agitation can be used to facilitate the cleaning. Various different solvent cleaning techniques are described by B. N. Ellis in Cleaning and Contamination of Electronics Components and Assemblies, Electrochemical Publications Limited, Ayr, Scotland, 182 - 94 (1986).

[0042] Both organic and inorganic substrates can be cleaned by the process of the present disclosure. Representative examples of substrates include metals, ceramics, glass, polycarbonate, polystyrene, acrylonitrile - butadiene - styrene copolymer, natural fibers (and fabrics derived from natural fibers), such as cotton, silk, fur, suede, leather, linen, and wool, synthetic fibers (and fabrics), such as polyester, rayon, acrylic, nylon, or blends thereof, fabrics including blends of natural and synthetic fibers, and composites of the aforementioned materials. In some embodiments, this process can be used for precision cleaning of electronic components (e.g., circuit boards), optical or magnetic media, or medical devices.

[0043] Electrochemical cells (e.g., lithium-ion batteries) are widely used worldwide in a vast number of electronic and electrical devices ranging from hybrid and electric vehicles to power tools, portable computers, and mobile devices. Lithium-ion batteries are generally safe and reliable energy storage devices, but under certain conditions, they can undergo catastrophic failures known as thermal runaway. Thermal runaway is a series of self-heating reactions caused by heat. The generation of excessive heat can be caused by overcharging, overheating, or internal electrical short circuits. Internal short circuits are typically caused by manufacturing defects or impurities, dendritic lithium formation, and mechanical damage. Typically, charge devices and battery packs have protection circuits that disable the battery in the event of overcharging or overheating, but these cannot protect the battery from internal short circuits caused by internal defects or mechanical damage.

[0044] Thermal management systems for packs of electrochemical cells (e.g., lithium-ion battery packs) are often required to maximize the cycle life of the cells within the pack. This type of system maintains each cell within the pack at a uniform temperature. High temperatures can increase the rate of capacity fade and impedance of lithium-ion batteries while decreasing their lifespan. Ideally, each individual cell within the battery pack is at the same ambient temperature.

[0045] Direct contact fluid immersion of the battery can reduce the probability of sudden thermal runaway events to a low level, while also achieving continuous thermal management required for the efficient normal operation of a lithium-ion battery pack. This type of application provides thermal management when using a fluid with a heat exchange system to maintain a desired operating temperature range. However, in the event of mechanical damage or internal short circuit of any cell, the fluid also prevents the propagation or cascading of a thermal runaway event to adjacent cells within the pack via evaporative cooling, thereby significantly reducing the risk of a sudden thermal runaway event involving multiple cells. Immersion cooling and thermal management of the battery can be achieved using a system designed for single-phase or two-phase immersion cooling. In either scenario, the fluid is disposed in thermal communication with the battery to maintain increases and decreases in the temperature of the battery (i.e., heat can be transferred to or from the battery via the fluid).

[0046] In some embodiments, the present disclosure is directed to a thermal management system for a pack of electrochemical cells (e.g., a lithium-ion battery pack). The system may include a lithium-ion battery pack and a working fluid in thermal communication with the lithium-ion battery pack. The working fluid may include one or more of the compounds or working fluids of the present disclosure.

[0047] The compounds of the present disclosure, alone or in combination, can be employed as fluids for transferring heat from various electronic components (e.g., server computers) by direct contact to provide thermal management and maintain optimal component performance under extreme operating conditions.

[0048] In some embodiments, the present disclosure describes the use of the compounds or working fluids of the present disclosure as a two-phase immersion cooling fluid for electronic devices, including computer servers. Large-scale computer server systems execute significant workloads and can generate large amounts of heat during their operation. A substantial portion of the heat is generated by the operation of these servers. Due to the large amount of heat generated, these servers are typically rack-mounted and air-cooled via internal fans and / or fans attached to the rear of the rack or other locations within the server ecosystem. As the need for access to ever more processing and storage resources continues to grow, the density of server systems (i.e., the amount of processing power and / or storage placed in a single server, the number of servers placed in a single rack, and / or the number of servers and / or racks deployed in a single server farm) continues to increase. The resulting thermal challenges remain a significant obstacle due to the desire to increase the processing or storage density in these server systems. Conventional air-cooling systems (e.g., fan-based) require large amounts of power, and the cost of the power required to drive such systems increases exponentially with increasing server density. Therefore, there is a need for an efficient low-power usage system for cooling servers while enabling the desired increase in processing and / or storage density in modern server systems.

[0049] Two-phase immersion cooling is a new cooling technology for the high-performance server computing market that relies on the heat absorbed (i.e., the heat of vaporization) in the process of vaporizing a liquid (cooling fluid) into a gas. The fluid used in this application must meet certain requirements in order to be viable for the application. For example, the boiling temperature during operation should be in the range of, for example, 45°C to 75°C. Generally, this range corresponds to maintaining the server components at a sufficiently cold temperature while allowing the heat to be efficiently dissipated to the final heat sink (e.g., the outside air). The fluid needs to be inert so as to be compatible with the materials of the components and electrical components. The fluid should be stable so as not to react with normal contaminants such as water or with reagents such as activated carbon or alumina that can be used to scrub the fluid during operation. The global warming potential (GWP, 100-year ITH) and ozone depletion potential (ODP) of the parent compound and its decomposition products should be below the tolerance limits, for example, GWP less than 2000, 1000, 800, 600 respectively, and ODP less than 0.01. The compounds of the present disclosure generally meet these requirements.

[0050] In another embodiment, the present disclosure describes the use of the compounds or working fluids of the present disclosure as single-phase immersion cooling fluids for electronic devices. Single-phase immersion cooling has a long history in the cooling of computer servers. There is no phase transition in single-phase immersion. Instead, the liquid is warmed and cooled as it flows or is pumped through the computer hardware and the heat exchanger respectively, thereby transferring heat from the server. The fluid used for single-phase immersion cooling of servers must generally meet the same requirements as outlined above, except that it typically has a high boiling temperature above about 75°C to limit evaporation losses.

[0051] In some embodiments, the present disclosure may be directed to an immersion cooling system that includes a compound or working fluid of the present disclosure. Generally, an immersion cooling system may operate as a two-phase vaporization condensation cooling vessel for cooling one or more heat-generating components. In some embodiments, the two-phase immersion cooling system may include a housing having an internal space. A liquid phase of a working fluid having an upper liquid surface (i.e., the uppermost level of the liquid phase) may be disposed within a lower volume of the internal space. The internal space may also include an upper volume that extends from the liquid surface to the top of the housing.

[0052] In some embodiments, the heat-generating component may be disposed within the internal space such that it is at least partially immersed (and until fully immersed) in the liquid phase of the working fluid. In some embodiments, the heat-generating component may include one or more electronic devices such as a computer server.

[0053] In various embodiments, a heat exchanger (e.g., a condenser) may be disposed within the upper volume. Generally, the heat exchanger may be configured to be able to condense the vapor phase of the working fluid that is generated as a result of the heat generated by the heat-generating element. For example, the heat exchanger may have an external surface that is maintained at a temperature lower than the condensation temperature of the vapor phase of the working fluid. In this regard, when the rising vapor phase of the working fluid contacts the heat exchanger, the heat exchanger can re-condense the rising vapor phase into a liquid phase or condensate by releasing the latent heat to the heat exchanger. The resulting condensate can then be returned to the liquid phase disposed in the lower volume.

[0054] In some embodiments, the present disclosure can be directed to an immersion cooling system that operates by single-phase immersion cooling. Generally, a single-phase immersion cooling system can include a heat-generating component disposed within an internal space of a housing such that it is at least partially (and until fully) immersed in the liquid phase of the working fluid, similar to the case of a two-phase system in this regard. The single-phase system may further include a pump and a heat exchanger, where the pump operates to move the working fluid to and from the heat-generating component and the heat exchanger, and the heat exchanger operates to cool the working fluid. The heat exchanger may be disposed inside or outside the housing.

[0055] In some embodiments, the present disclosure can be directed to a method for cooling an electronic component. Generally, the method can include at least partially immersing an electronic component (e.g., a computer server) that generates heat in a liquid containing a compound or a working fluid of the present disclosure. The method may further include transferring heat from the heat-generating electronic component using the compound or the working fluid of the present disclosure.

[0056] In some embodiments, the present disclosure is directed to a fire extinguishing composition. The composition may include one or more compounds of the present disclosure and one or more co-extinguishing agents.

[0057] In exemplary embodiments, co-extinguishing agents may include hydrofluorocarbons, hydrochlorofluorocarbons, perfluorocarbons, perfluoropolyethers, hydrofluoroethers, hydrofluoropolyethers, chlorofluorocarbons, bromofluorocarbons, bromochlorofluorocarbons, hydrobromocarbons, iodofluorocarbons, fluorinated ketones, hydrofluorocarbons, hydrochlorofluorocarbons, perfluorocarbons, perfluoropolyethers, hydrofluoroethers, hydrofluoropolyethers, chlorofluorocarbons, bromofluorocarbons, bromochlorofluorocarbons, iodofluorocarbons, hydrobromofluorocarbons, fluorinated ketones, hydrobromocarbons, fluorinated olefins, hydrofluoroolefins, fluorinated sulfones, fluorinated vinyl ethers, unsaturated fluoroethers, bromofluoroolefins, chlorofluoroolefins, iodofluoroolefins, fluorinated vinyl amines, fluorinated aminopropenes, and mixtures thereof.

[0058] Such co-extinguishing agents can be selected to enhance the extinguishing ability or to modify the physical properties of the fire extinguishing composition for a particular type (or scale or location) of fire (e.g., by functioning as a propellant to change the introduction rate), and preferably can be utilized in a ratio (the ratio of the co-extinguishing agent to the hydrofluoroolefin compound) such that the resulting composition does not form a flammable mixture in air.

[0059] In some embodiments, the compounds and co-extinguishing agents of the present disclosure may be present in the fire extinguishing composition in an amount sufficient to extinguish or suppress a fire. The compounds and co-extinguishing agents of the present disclosure may be in a weight ratio of about 9:1 to about 1:9.

Examples

[0060] The objectives and advantages of the present disclosure are further illustrated by the following exemplary embodiments. Unless otherwise specified, all parts, percentages, ratios, etc. in the embodiments and other parts of this specification are by weight, and all reagents used in the embodiments were obtained from common chemical suppliers such as Sigma-Aldrich Corp. (Saint Louis, MO, US), or were available, or could be synthesized by conventional methods.

[0061] The following abbreviations are used in this specification: mL = milliliter, L = liter, mol = mole, mmol = millimole, min = minute, h or hr = hour, sec = second, g = gram, °C = degree Celsius, mp = melting point, cSt = centistokes. "RT" or "room temperature" refers to an ambient temperature of approximately 20 - 25 °C, with an average of 23 °C.

[0062] [Table 1-1] [Table 1-2]

[0063] Sample Preparation Example 1: 1,1,1,2,2,4,4,4 - Octafluoro - 3 - methoxy - 3 - (trifluoromethyl)butane) [Chemical formula] Test Method A: A 4 L (net volume 7.42 L) stainless steel kettle was charged with diglyme (994 g, 7.4 mol; contained according to titration in the sense of 70 ppm moisture by the Karl Fischer method), cesium fluoride (184 g, 1.2 mol), and α - pinene (1 g, 0.01 mol). While stirring at 400 rpm, within 114 hours, TFE (180 g, 1.8 mol) and hexafluoroacetone (206 g, 1.2 mol) were reacted at 90 °C until a constant pressure plateau (8.1 bar → 1.8 bar) was observed. Then, the temperature was cooled to room temperature, and the resulting stirred mixture was N 2The mixture was sparged with gas to remove any excess TFE. The reactor was then discharged to obtain a solution of Cs[(CF 3 ) 2 (C 2 F 5 )CO] (356 g, 0.85 mol, 71% yield), which was confirmed by 19 F NMR and by GC-MS via acidification with H 2 SO 4 of the cesium salt. Cs[(CF 3 ) 2 (C 2 F 5 )CO] was used in the next step without further purification.

[0064] A three-necked flask equipped with a magnetic stir bar and a reflux condenser was charged with cesium 1,1,1,3,3,4,4,4-octafluoro-2-(trifluoromethyl)butan-2-olate (33 wt% solution in 300 g of diglyme, 237 mmol). The resulting reaction mixture was heated to 70 °C, and subsequently iodomethane (17 mL, 273 mmol) was added dropwise. The reaction mixture was stirred at the same temperature overnight. After cooling to room temperature, H 2 O (400 mL) was added and the mixture was transferred to a 2 L separatory funnel. The bottom fluorochemical layer was then separated and analyzed by GC-FID, showing a 58% yield of the title compound. By distillation, the desired 1,1,1,2,2,4,4,4-octafluoro-3-methoxy-3-(trifluoromethyl)butane (77 °C, 740 mm / Hg, 32.1 g, 45% isolated yield) was obtained as a colorless liquid. GC-MS analysis confirmed the identification information of the purified composition. Toxicity screening studies in rats showed that the 4-hour inhalation LC50 of this compound was >1,840 ppm.

[0065] Test Method B: A 600 mL stainless steel reaction vessel was charged with tetraglyme (120 mL), potassium fluoride (24.1 g, 415 mmol), and 18-crown-6 (15 g, 57 mmol). The sealed reaction vessel was then evacuated under reduced pressure, and subsequently 2,2,3,3,3-pentafluoropropionyl fluoride (65 g, 390 mmol) was added. Then, trifluoromethyltrimethylsilane (114 g, 803 mmol) was added to the stirred mixture over 1 hour at a rate that avoided an increase in the reaction temperature above 45 °C. After the addition was complete, the resulting reaction mixture was stirred overnight without heating. The reaction mixture was then transferred to a 500 mL three-neck round-bottom flask equipped with a stir bar, reflux condenser, and temperature probe. While stirring, dimethyl sulfate (49.4 g, 392 mmol) was slowly added to the heated (45 °C) mixture. Salt formation was observed 15 minutes after the addition was complete. The reaction mixture was stirred overnight at the same temperature. The resulting reaction mixture was then cooled to room temperature, and subsequently H 2 O (100 mL) and ammonium hydroxide (50% solution in 100 mL of H 2 O) were added. The contents were transferred to a 1 L separatory funnel, and the fluorochemical layer was collected and analyzed by GC-FID, which showed the formation of the desired 1,1,1,2,2,4,4,4-octafluoro-3-methoxy-3-(trifluoromethyl)butane (60% GC-FID yield). The identification information of the desired composition in the fluorochemical layer was confirmed by GC-MS analysis.

[0066] Example 2: 2-Ethoxy-1,1,1,3,3,4,4,4-octafluoro-2-(trifluoromethyl)butane

Chemical formula

[0067] Example 3: 1,1,1,2,2,4,4,5,5,5-decafluoro-3-methoxy-3-(1,1,2,2,2-pentafluoroethyl)pentane

Chemical formula

[0068] A round-bottom three-necked flask equipped with a magnetic stir bar, a reflux condenser, and a temperature probe was charged with cesium 1,1,1,2,2,4,4,5,5,5-decafluoro-3-(1,1,2,2,2-pentafluoroethyl)pentane-3-olate (400 g, a 31 wt% solution in diglyme, 239 mmol) and sodium carbonate (24.3 g, 229 mmol). The resulting mixture was heated to 70 °C, and then iodomethane (40.8 g, 287 mmol) was added dropwise. After stirring overnight at the same temperature, the reaction mixture was cooled to room temperature, and then H 2O (400 mL) was added. Subsequently, the contents were transferred to a 2 L separatory funnel, and the fluorochemical layer was collected and analyzed by GC-FID. The formation of the desired 1,1,1,2,2,4,4,5,5,5-decafluoro-3-methoxy-3-(1,1,2,2,2-pentafluoroethyl)pentane (59% GC-FID yield) was shown. By concentric tube distillation (126 °C, 740 mmHg, 32.1 g, 34% isolated yield), the desired 1,1,1,2,2,4,4,5,5,5-decafluoro-3-methoxy-3-(1,1,2,2,2-pentafluoroethyl)pentane was obtained. The identification information of the isolated composition was confirmed by GC-MS analysis.

[0069] Example 4: 3-Ethoxy-1,1,1,2,2,4,4,5,5,5-decafluoro-3-(1,1,2,2,2-pentafluoroethyl)pentane

Chemical formula

[0070] A round-bottom three-necked flask equipped with a magnetic stir bar, a reflux condenser, and a temperature probe was charged with cesium 1,1,1,2,2,4,4,5,5,5-decafluoro-3-(1,1,2,2,2-pentafluoroethyl)pentane-3-olate (200 g, a 33 wt% solution in diglyme, 127 mmol) and sodium carbonate (5.4 g, 51 mmol). The resulting mixture was heated to 70 °C, and then iodomethane (21.9 g, 140 mmol) was added dropwise. After stirring overnight at the same temperature, the reaction mixture was cooled to room temperature, and then H 2 O (150 mL) was added. The contents were transferred to a 1 L separatory funnel, and the fluorochemical layer was collected and purified via concentric tube distillation (138 °C, 740 mmHg) to obtain the desired 3-ethoxy-1,1,1,2,2,4,4,5,5,5-decafluoro-3-(1,1,2,2,2-pentafluoroethyl)pentane (25.6 g, 49% isolated yield) as a colorless liquid.

[0071] Example 5: 1,1,1,2,2,3,3,4,4,6,6,6-dodecafluoro-5-methoxy-5-(trifluoromethyl)hexane

Chemical formula

[0072] Example 6: 1,1,2,2,3,3,4,4-octafluoro-5-methoxy-5-(trifluoromethyl)cyclopentane

Chemical formula

[0073] Example 7: 1,1,1,2,2,4,5,5,5-nonafluoro-3-methoxy-3,4-bis(trifluoromethyl)pentane

Chemical formula

[0074] Example 8: 1,1,2,2,3,3,5,5,5-Nonafluoro-4-methoxy-N,N-bis(perfluoropropyl)-4-(trifluoromethyl)pentan-1-amine

Chem.

[0075] Example 9: 2,2,3,3,5,5,6,6-Octafluoro-4-(1,1,2,2,4,4,5,5,5-nonafluoro-3-methoxy-3-(perfluoroethyl)pentyl)morpholine

Chem.

[0076] Example 10: 2,2,3,3,5,5,6,6-octafluoro-4-(1,1,3,3,3-pentafluoro-2-methoxy-2-(trifluoromethyl)propyl)morpholine

Chem.

[0077] Example 11: 1,1,1,3,3,4,4-Heptafluoro-2-methoxy-4-(trifluoromethoxy)-2-(trifluoromethyl)butane [Chemical formula] A round-bottom flask equipped with a magnetic stir bar, a Claisen head adapter, and a dry ice reflux condenser was charged with 18-crown-6 (9.1 g, 34 mmol), potassium fluoride (13.0 g, 224 mmol), and DMF (75 mL). The resulting mixture was then stirred and 2,2,3,3-tetrafluoro-3-(trifluoromethoxy)propanoyl fluoride (40.1 g, 173 mmol) was charged through a plastic line at a rate to avoid temperature spikes above 30 °C. Then, trifluoromethyltrimethylsilane (51.5 g, 362 mmol) was slowly added to the heated resulting reaction mixture over 20 minutes, avoiding the temperature rising above 40 °C. After the addition was complete, the reaction mixture was stirred at room temperature overnight. Then, iodomethane (25.8 g, 181 mmol) was added to the resulting reaction mixture and the mixture was subsequently stirred at 40 °C for 3 hours. The mixture was then cooled to room temperature and subsequently water (100 mL) was added. Removal of the aqueous layer gave a crude fluorochemical layer, and GC-FID analysis thereof showed the desired 1,1,1,3,3,4,4-heptafluoro-2-methoxy-4-(trifluoromethoxy)-2-(trifluoromethyl)butane in 55% yield. Distillation of the crude fluorochemical material (103.6 °C, 740 mm / Hg) gave the desired 1,1,1,3,3,4,4-heptafluoro-2-methoxy-4-(trifluoromethoxy)-2-(trifluoromethyl)butane (20.8 g, 33% isolated yield) as a colorless liquid. GC-MS analysis confirmed the identification information of the isolated material.

[0078] Example 12: 1,1,1,3,3,4,4,5,5-Nonafluoro-2-methoxy-5-(perfluoroethoxy)-2-(trifluoromethyl)pentane [Chemical formula] A three-neck round-bottom flask equipped with a magnetic stir bar, a reflux condenser, and a temperature probe was charged with 18-crown-6 (4.8 g, 18 mmol), potassium fluoride (6.3 g, 110 mmol), and DMF (40 mL). The flask was then evacuated and N 2It was backfilled three times. Then, 2,2,3,3,4,4-hexafluoro-4-(perfluoroethoxy)butanoyl fluoride (30.0 g, 90.4 mmol) was slowly added to the stirred mixture at a rate that avoided a temperature spike above 30 °C. Then, trifluoromethyltrimethylsilane (27.0 g, 190 mmol) was slowly added to the mixture over 20 minutes, avoiding the temperature rising above 40 °C. After the addition was complete, the reaction mixture was stirred at room temperature overnight. Then, dimethyl sulfate (11.4 g, 90.4 mmol) was added to the resulting reaction mixture, followed by stirring at 40 °C for 3 hours. Then, the mixture was cooled to room temperature, followed by the addition of saturated ammonium hydroxide (50 mL). Removal of the aqueous layer gave a crude fluorochemical layer, and GC-FID analysis of this showed the desired 1,1,1,3,3,4,4,5,5-nonafluoro-2-methoxy-5-(perfluoroethoxy)-2-(trifluoromethyl)pentane in 61.6% yield. Distillation of the crude fluorochemical material (150.7 °C, 740 mm / Hg) gave the desired 1,1,1,3,3,4,4,5,5-nonafluoro-2-methoxy-5-(perfluoroethoxy)-2-(trifluoromethyl)pentane (25 g, 58% isolated yield) as a colorless liquid. GC-MS analysis confirmed the identification information of the isolated substance.

[0079] Example 13: 1,1,1,3,3,4,4,5,5-Nonafluoro-2-methoxy-5-(perfluoropropoxy)-2-(trifluoromethyl)pentane

Chemical formula

[0080] Example 14: 1,1,1,2,2,4,4,5,5,5-decafluoro-3-methoxy-3-(1,1,2,2-tetrafluoro-2-(trifluoromethoxy)ethyl)pentane [Chemical formula] A three-neck round-bottom flask equipped with a magnetic stir bar, a reflux condenser, and a temperature probe was charged with cesium fluoride (10.8 g, 71.1 mmol) and tetraglyme (30 mL). Then, 2,2,3,3-tetrafluoro-3-(trifluoromethoxy)propanoyl fluoride (15 g, 65 mmol) was slowly added to the stirred mixture at a rate that avoided temperature spikes above 30 °C. Then, (pentafluoroethyl)trimethylsilane (24.9 g, 130 mmol) was slowly added to the mixture over 20 minutes to avoid the temperature rising above 30 °C. After completion of the addition, the reaction mixture was stirred at room temperature overnight. Then, dimethyl sulfate (8.2 g, 65 mmol) was added to the resulting reaction mixture, followed by stirring at 30 °C for 3 hours. Then, the resulting reaction mixture was cooled to room temperature, and saturated ammonium hydroxide (50 mL) was added. The aqueous layer was removed, and the desired 1,1,1,2,2,4,4,5,5,5-decafluoro-3-methoxy-3-(1,1,2,2-tetrafluoro-2-(trifluoromethoxy)ethyl)pentane (16.2 g, 54% isolated yield) was obtained as a colorless liquid by distillation of the crude fluorochemical layer (148 °C, 740 mm / Hg). The identity information of the isolated substance was confirmed by GC-MS analysis.

[0081] Example 15: 1,1,1,2,2,4,4,4-octafluoro-3-(2,2,2-trifluoroethoxy)-3-(trifluoromethyl)butane [Chemical formula] Procedure 1: In a 600 mL stainless steel reaction vessel equipped with an overhead stirrer, add tetraglyme (100 mL), potassium fluoride (16.1 g, 277 mmol), and 18-crown-6 (10.5 g, 39.7 mmol). Seal and evacuate the reaction vessel. Then, add 2,2,3,3,3-pentafluoropropanoyl fluoride (43.0 g, 259 mmol) to the vessel all at once. Next, charge trimethyl(trifluoromethyl)silane (77.3 g, 544 mmol) to the stirred mixture over 1 hour at a rate that avoids the temperature rising above 45 °C. After stirring overnight without heating, transfer the resulting mixture to a two-neck round-bottom flask equipped with a magnetic stir bar and a reflux condenser. Sweep the headspace of the flask with N 2 2 flow to remove trimethylsilyl fluoride (TMS-F). Use the resulting mixture in subsequent synthetic transformations without purification.

[0082] Procedure 2a: Transfer half of the mixture from Procedure 1 to a 250 mL round-bottom flask equipped with a magnetic stir bar and a reflux condenser. While stirring, slowly heat the reaction mixture to 60 °C and then add 2,2,2-trifluoroethyl nonafluorobutanesulfonate (49.7 g, 130 mmol) dropwise. After stirring overnight at the same temperature, dilute the resulting reaction mixture with water (150 mL) and then transfer it to a separatory funnel. Remove the aqueous layer to obtain a crude fluorochemical layer, and GC-FID analysis of this showed approximately 99% conversion of the 2,2,2-trifluoroethyl nonafluorobutanesulfonate starting material.

[0083] Step 2b: Half of the mixture from Step 1 was transferred to a 250 mL round-bottom flask equipped with a magnetic stir bar and a reflux condenser. While stirring, the reaction mixture was slowly heated to 60 °C, and then 2,2,2-trifluoroethyl trifluoromethanesulfonate (30.5 g, 130 mmol) was added dropwise. After stirring overnight at the same temperature, the resulting reaction mixture was diluted with water (150 mL) and then transferred to a separatory funnel. The aqueous layer was removed to obtain a crude fluorochemical layer, and GC-FID analysis of this showed about 97% conversion of the 2,2,2-trifluoroethyl trifluoromethanesulfonate starting material.

[0084] The crude fluorochemical product mixtures from Steps 2a and 2b were combined and purified via fractional distillation (90.9 °C, 740 mmHg) to obtain the desired 1,1,1,2,2,4,4,4-octafluoro-3-(2,2,2-trifluoroethoxy)-3-(trifluoromethyl)butane (58.4 g, 61% isolated yield) as a colorless liquid. The identification information of the desired 1,1,1,2,2,4,4,4-octafluoro-3-(2,2,2-trifluoroethoxy)-3-(trifluoromethyl)butane was confirmed by GC-MS analysis.

[0085] Example 16: 1,1,1,2,2,4,4,4-octafluoro-3-(2,2,3,3,3-pentafluoropropoxy)-3-(trifluoromethyl)butane

Chemical formula

[0086] Procedure 2: Transfer one-third of the product mixture from Procedure 1 to a three-neck round-bottom flask equipped with a magnetic stir bar, a temperature probe, and a reflux condenser. While stirring, add 2,2,3,3,3-pentafluoropropyl trifluoromethanesulfonate (25 g, 89 mmol) dropwise to the heated (45 °C) mixture over 30 minutes. After stirring for 2 days, dilute the resulting mixture with water (100 mL) and then transfer it to a separatory funnel. Removal of the aqueous layer gives a crude fluorochemical layer, and GC-FID analysis of this shows complete conversion of the 2,2,3,3,3-pentafluoropropyl trifluoromethanesulfonate starting material and a 79% yield of the desired 1,1,1,2,2,4,4,4-octafluoro-3-(2,2,3,3,3-pentafluoropropoxy)-3-(trifluoromethyl)butane. Fractional distillation (109 °C, 740 mm / Hg) gives the desired 1,1,1,2,2,4,4,4-octafluoro-3-(2,2,3,3,3-pentafluoropropoxy)-3-(trifluoromethyl)butane (18.4 g, 50% isolated yield). GC-MS analysis confirms the identification information of the desired 1,1,1,2,2,4,4,4-octafluoro-3-(2,2,3,3,3-pentafluoropropoxy)-3-(trifluoromethyl)butane.

[0087] Example 17: 1,1,1,2,2,4,4,4 - Octafluoro - 3-(2,2,3,3,4,4,4 - heptafluorobutoxy)-3-(trifluoromethyl)butane [Chemical formula] Step 1: Tetraglyme (100 mL), potassium fluoride (16.1 g, 277 mmol), and 18 - crown - 6 (10.5 g, 39.7 mmol) were added to a 600 mL stainless - steel reaction vessel equipped with an overhead stirrer. The reaction vessel was sealed and evacuated. Then, 2,2,3,3,3 - pentafluoropropanoyl fluoride (43.0 g, 259 mmol) was added to the vessel all at once. Next, trimethyl(trifluoromethyl)silane (77.3 g, 544 mmol) was charged to the stirred mixture over 1 hour at a rate that avoided the temperature rising above 45 °C. After stirring overnight without heating, the resulting mixture was transferred to a two - neck round - bottom flask equipped with a magnetic stir bar and a reflux condenser. The headspace of the flask was swept with N 2 2 flow to remove trimethylsilyl fluoride (TMS - F). The resulting mixture was used in the subsequent synthetic transformation without purification.

[0088] Procedure 2a: Half of the mixture from Procedure 1 was transferred to a 250 mL round-bottom flask equipped with a magnetic stir bar and a reflux condenser. While stirring, the reaction mixture was slowly heated to 60 °C, and subsequently 1H,1H-heptafluorobutyl nonafluorobutanesulfonate (62.7 g, 130 mmol) was added dropwise. After stirring overnight at the same temperature, the reaction mixture was cooled to room temperature and then diluted with water (150 mL). The mixture was transferred to a separatory funnel, and by removing the aqueous layer, a crude fluorochemical mixture was obtained, for which GC-FID showed the desired 1,1,1,2,2,4,4,4-octafluoro-3-(2,2,3,3,4,4,4-heptafluorobutoxy)-3-(trifluoromethyl)butane in about 73% yield. The crude fluorochemical mixture was purified by fractional distillation (134 °C, 740 mmHg) to obtain the desired 1,1,1,2,2,4,4,4-octafluoro-3-(2,2,3,3,4,4,4-heptafluorobutoxy)-3-(trifluoromethyl)butane (28.6 g, 47% isolated yield) as a colorless liquid. The identification information of the desired 1,1,1,2,2,4,4,4-octafluoro-3-(2,2,3,3,4,4,4-heptafluorobutoxy)-3-(trifluoromethyl)butane was confirmed by GC-MS analysis.

[0089] Example 18: 1,1,1,3,3,3-Hexafluoro-2-(2,2,3,3,3-pentafluoropropoxy)-2-(trifluoromethyl)propane

Chemical formula

[0090] Procedure 2: Half of the mixture from Procedure 1 was transferred to a 250 mL three-necked round-bottom flask equipped with a magnetic stir bar, a temperature probe, and a reflux condenser. While stirring, the reaction mixture was slowly heated to 45 °C, and then 2,2,3,3,3-pentafluoropropyl 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate (65.1 g, 150.6 mmol) was added dropwise. The resulting mixture was stirred at 60 °C overnight. The reaction mixture was cooled to room temperature, diluted with water (150 mL), and then transferred to a separatory funnel. Removal of the aqueous layer gave a crude fluorochemical mixture, which was purified by fractional distillation (85 °C, 740 mmHg) to give the desired 1,1,1,3,3,3-hexafluoro-2-(2,2,3,3,3-pentafluoropropoxy)-2-(trifluoromethyl)propane (29.1 g, 53% isolated yield) as a colorless liquid. The identification information of the desired 1,1,1,3,3,3-hexafluoro-2-(2,2,3,3,3-pentafluoropropoxy)-2-(trifluoromethyl)propane was confirmed by GC-MS analysis.

[0091] Example 19: 1,1,1,2,2,3,3-Heptafluoro-4-((1,1,1,3,3,3-hexafluoro-2-(trifluoromethyl)propan-2-yl)oxy)butane [Chemical formula] Step 1: N,N-Dimethylformamide (105 mL) and potassium fluoride (20.1 g, 355 mmol) were added to a 600 mL stainless steel reaction vessel equipped with an overhead stirrer. The reactor was then sealed, evacuated, and subsequently 1,1,1,3,3,3-hexafluoropropan-2-one (50.1 g, 302 mmol) was slowly added. The reaction mixture was returned to 25 °C, and then trimethyl(trifluoromethyl)silane (47.2 g, 332 mmol) was added at a rate that avoided the temperature of the reaction mixture rising above 30 °C. After the addition was complete, the resulting mixture was stirred at 25 °C overnight. The mixture was then transferred to a 250 mL three-necked round-bottom flask, slowly heated to 70 °C, and the headspace of the flask was swept with N 2 flow to remove trimethylsilyl fluoride (TMS-F). The resulting mixture was used in the subsequent synthetic transformation without purification.

[0092] Procedure 2: Half of the mixture from Procedure 1 was transferred to a 250 mL three-necked round-bottom flask equipped with a magnetic stir bar, a temperature probe, and a reflux condenser. While stirring, the reaction mixture was slowly heated to 45 °C, and then 1H,1H-heptafluorobutyl nonafluorobutanesulfonate (72.5 g, 150 mmol) was added dropwise. The resulting mixture was stirred at 60 °C overnight. The reaction mixture was cooled to room temperature, diluted with water (150 mL), and then transferred to a separatory funnel. Removal of the aqueous layer gave a crude fluorochemical mixture, which was purified by fractional distillation (108 °C, 740 mmHg) to give the desired 1,1,1,2,2,3,3-heptafluoro-4-((1,1,1,3,3,3-hexafluoro-2-(trifluoromethyl)propan-2-yl)oxy)butane (30.2 g, 48% isolated yield) as a colorless liquid. Identification information of the desired 1,1,1,2,2,3,3-heptafluoro-4-((1,1,1,3,3,3-hexafluoro-2-(trifluoromethyl)propan-2-yl)oxy)butane was confirmed by GC-MS analysis.

[0093] Test Method Atmospheric Lifetime: The atmospheric lifetime of the hydrofluoroether of Example 1 was determined from its reaction rate with hydroxyl radicals. The pseudo-first-order reaction rate of gaseous 1,1,1,2,2,4,4,4-octafluoro-3-methoxy-3-(trifluoromethyl)butane with hydroxyl radicals relative to reference compounds such as chloromethane and ethane was measured in a series of experiments. The measurements were carried out in a 5.7 L heated FTIR gas cell equipped with a polished semiconductor-grade quartz window. Ozone was photolyzed in the presence of water vapor using an Oriel Instruments UV Lamp, Model 66921 equipped with a 480 W mercury-xenon bulb to generate hydroxyl radicals. The concentrations of the hydrofluoroether and reference compounds were measured as a function of reaction time using an I-Series FTIR from Midac Corporation. The atmospheric lifetime was calculated as follows from the reaction rate of the hydrofluoroether relative to the reference compounds and the reported lifetimes of the reference compounds

Number

[0094] Global warming potential (GWP): Using the measured IR cross-section and the method of Pinnock et al. described in J. Geophys. Res. 1995, 100, 23227-23238, the radiative forcing value for Example 1 (1,1,1,2,2,4,4,4-octafluoro-3-methoxy-3-(trifluoromethyl)butane) was calculated. The GWP (100-year iterative measurement period (ITH)) is calculated using the radiative forcing value and the experimentally determined atmospheric lifetime using the equations and methods described hereinabove.

[0095] Specific heat capacity (C p ): C p was measured using a TA Instruments Model Q2000 DSC (differential scanning calorimeter) instrument. A sapphire reference was run before and after the sample measurement, and the measured heat capacity of the sample was corrected using the average value of the measured heat capacity of the sapphire relative to the theoretical heat capacity of the sapphire.

[0096] Kinematic viscosity: The kinematic viscosity was measured using a Schott-Ubbelohde viscometer (glass capillary viscometer). The viscometer was timed using a viscosity timer available under the trade name AVS-350 from SI Analytics (College Station, TX, USA). The viscometer measurement stand and the glass viscometer were immersed in a temperature-controlled liquid bath filled with NOVEC 7500 fluid available from 3M Company, Maplewood, MN, USA. A copper tube coil for liquid nitrogen cooling with fine temperature control provided by the tank's electronic temperature control heater was attached to the temperature-controlled liquid bath available from Lawler Manufacturing Corporation, Edison, NJ, USA. The fluid was mechanically stirred to provide a uniform temperature within the bath. The bath was controlled to within ±0.1 °C of the temperature measured by the built-in RTD temperature sensor. The sample liquid was added to the viscometer between two filling lines etched on the viscometer. The viscosity timer automatically pumped the sample fluid above the upper timing mark and then released the fluid, measuring the outflow time between the upper and lower timing marks. The fluid meniscus was detected by an optical sensor as it passed each timing mark. The sample was removed and measured repeatedly, and the results were provided as the average of multiple measurements. The glass viscometer was calibrated using a certified kinematic viscosity standard fluid available from Cannon Instrument Company (State College, PA, USA), and a calibration constant (cSt / second) was obtained for each viscometer. The kinematic viscosity in centistokes (cSt) was calculated as the product of the viscometer calibration constant (cSt / second) and the average outflow time (seconds).

[0097] Pour point: The pour point was determined visually and defined as the lowest temperature at which flow of the sample was observed after tilting horizontally for 5 seconds. A 1 - 2 milliliter sample was placed in a vial and cooled in the bath until it solidified. The sample was then slowly warmed in the bath and observed every 3 - 5 °C.

[0098] Largest Soluble Hydrocarbon (LSH): The LSH of each compound was determined by mixing the compound with hydrocarbons of various molecular weights (C n H 2n+2 [where n = 9 - 14]) at a weight ratio of approximately 1:1 to 1:2 of hydrofluoroether:hydrocarbon at room temperature (25 °C) and 50 °C. The LSH value was reported as the value of n for the longest hydrocarbon that was compatible with the hydrofluoroether without showing haze to the naked eye for the formula C n H 2n+2 . In this specification, it is interpreted that the higher the value of n, the higher the ability of the hydrofluoroether to wash the hydrocarbon.

[0099] Chemical Stability: The stability of the compounds in the presence of the base triethylamine (TEA), 1,4-diazabicyclo[2.2.2]octane (DABCO), and N,N,N,N-tetramethylethylenediamine (TMEDA) was tested as follows. Substances of the examples and comparative examples were added to a 20 mL vial equipped with a magnetic stir bar in the following starting amounts: Example 1 - 0.30 g (1.0 mmol), CE4 - 0.30 g (1.0 mmol), and CE5 - 0.30 g (1.0 mmol). Since it is known to be stable in the presence of the base substances tested in this specification, FC-770 (0.40 g, 1.0 mmol) was added as an internal standard. One of triethylamine (0.10 g, 1.0 mmol), DABCO (0.10 g, 0.89 mmol), or TMEDA (0.12 g, 1.0 mmol) was added to this mixture. The resulting mixture was stirred at 50 °C for 24 hours. GC-FID analysis was performed at specific time intervals to monitor the remaining hydrofluoroethers and comparative substances present in the mixture.

[0100] In the presence of N-methylpyrrolidinone (NMP), the stability of the compound was tested as follows. In a 20 mL glass vial equipped with a magnetic stir bar, 0.66 g of NMP (6.7 mmol) and the substances of the following Examples or Comparative Examples were added in the following starting amounts: Example 1 - 2.0 g (6.7 mmol); CE4 - 2.0 g (6.7 mmol); CE5 - 2.0 g (6.7 mmol), or CE6 - 2.40 g (6.7 mmol). The mixture was then stirred at 50 °C for 144 hours. H 2 O (6.0 mL) was added to the resulting mixture, and the aqueous layer was evaluated for fluoride ion content. Samples were analyzed using an Orion EA940 meter equipped with an Orion 9609BNWB fluoride-ISE. The meter was calibrated using an Orion Ionplus fluoride standard.

[0101] Results The atmospheric lifetime of Example 1 was determined from the reaction rate with hydroxyl radicals as described above, and a calculated atmospheric lifetime of 2.3 years was obtained. Using this value, it was found that the GWP (100-year integrated time horizon (ITH)) for Example 1 is 170. This is much lower than the GWP of PFCs (perfluorinated hydrocarbons, perfluorinated amines, and perfluorinated ethers, or polyethers), and lower than other closely related hydrofluoromethyl ethers.

[0102] Table 2 compares the specific heat capacity of Example 3 with commercially available heat transfer fluids. Considering the similarity of the materials with respect to specific heat capacity, the compositions of the present disclosure may also function as heat transfer fluids.

[0103]

Table 2

[0104] The measured kinematic viscosities for Example 3 at various temperatures are shown in Table 3. The pour point of -62 °C was measured for Example 3. These results indicate that the hydrofluoroethers of the present invention are suitable fluids for heat transfer and cleaning applications.

[0105]

Table 3

[0106] The maximum soluble hydrocarbon (LSH) values for Examples 1 and 2 at 25 °C and 50 °C are provided in Table 4. The results in Table 4 indicate that the hydrofluoroether of the present invention is a fluid suitable for cleaning applications.

[0107]

Table 4

[0108] The results of the stability tests for Examples 1, CE4, and CE5 in the presence of TEA, DABCO, and TMEDA are presented in Tables 5, 6, and 7, respectively. Tables 5 - 7 list the remaining percentage (on a molar basis) of each material after various exposure times, based on the initial amount. The low consumption of Example 1 in TEA, DABCO, and TMEDA indicates that the hydrofluoroether of the present invention has excellent stability in the presence of bases and is a fluid suitable for cleaning applications.

[0109]

Table 5

[0110]

Table 6

[0111]

Table 7

[0112] The results of the stability tests of Example 1, CE4, CE5, and CE6 in the presence of NMP are summarized in Table 8. A small amount of fluoride is interpreted to mean that the test substance is relatively stable. The results in Table 8 show that, compared with CE4 - CE6, the hydrofluoroether of the present invention has excellent stability in the presence of a base such as NMP and is a suitable fluid for cleaning applications.

[0113]

Table 8

[0114] Those skilled in the art will appreciate various modifications and changes to the present disclosure that do not depart from the scope and spirit of the present disclosure. The present disclosure is not intended to be unduly limited by the exemplary embodiments and examples described herein, and such embodiments and examples are presented only as illustrations within the scope of the present disclosure, which is intended to be limited only by the following claims as described herein. All references cited in the present disclosure are hereby incorporated by reference in their entirety. The present invention includes the following aspects. (1) A compound having the structural formula (II):

Chemical formula

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Claims

1. A compound having the structural formula (II): 【Chemical 1】 [wherein, R ２ is H, CH ３ , CF ３ , CH ２ CF ２ CF ２ H, or CH ２ CF ２ CF ２ CF ２ CF ２ H, and R ２ f is a perfluoroalkyl group having 1 to 4 carbon atoms and optionally contains either or both of a nitrogen heteroatom linked in a chain and an oxygen heteroatom linked in a chain. R ２ f' is CF ３ or CF ２ CF ３ and R ２ f” is CF ２ CF ３ and However, when R ２ is H or CH ３ , R ２ f is not CF ３ .

2. R ２ is H or CH ３ The compound according to claim 1, wherein

3. An apparatus for heat transfer, comprising: a device; and a mechanism for transferring heat to or from the device, the mechanism comprising a compound having the structural formula (I): [Chemical 2] [wherein, R Ｈ is CH ３ or CH ２ CH ３ and Rf is a perfluoroalkyl group having 1 to 9 carbon atoms, optionally containing either or both a nitrogen heteroatom linked in a chain and an oxygen heteroatom linked in a chain, and optionally containing a 5- or 6-membered ring; Rf' and Rf'' are independently perfluoroalkyl groups having 1 to 2 carbon atoms, and at least one of Rf' and Rf'' has 2 carbon atoms; and an operating fluid containing the same, the apparatus.

4. A method for transferring heat, comprising: providing a device; and using a heat transfer fluid containing a compound having the structural formula (I): 【Chemical Formula 3】 [wherein, R Ｈ is CH ３ or CH ２ CH ３ and Rf is a perfluoroalkyl group having 1 to 9 carbon atoms, optionally containing either or both a nitrogen heteroatom linked in a chain and an oxygen heteroatom linked in a chain, and optionally containing a 5- or 6-membered ring; Rf' and Rf'' are independently perfluoroalkyl groups having 1 to 2 carbon atoms, and at least one of Rf' and Rf'' has 2 carbon atoms; to transfer heat to or from the device.

5. A cleaning composition comprising a compound having the structural formula (I): [Chemical Formula 4] [wherein, R Ｈ is CH ３ or CH ２ CH ３ and is Rf is a perfluoroalkyl group having 1 to 9 carbon atoms, optionally containing either or both a nitrogen heteroatom linked in a chain and an oxygen heteroatom linked in a chain, and optionally containing a 5- or 6-membered ring; Rf' and Rf'' are independently perfluoroalkyl groups having 1 to 2 carbon atoms, and at least one of Rf' and Rf'' has 2 carbon atoms; and a co-solvent.

6. A compound having the structural formula (I): [Chemical Formula 5] (I) [wherein, R Ｈ is CH ３ or CH ２ CH ３ and is Rf is a perfluoroalkyl group having 1 to 9 carbon atoms, optionally containing either or both a nitrogen heteroatom linked in a chain and an oxygen heteroatom linked in a chain, and optionally containing a 5- or 6-membered ring; Rf' and Rf'' are independently perfluoroalkyl groups having 1 to 2 carbon atoms, and at least one of Rf' and Rf'' has 2 carbon atoms; A cleaning composition comprising a surfactant and...

7. A process for removing contaminants from a substrate, the process comprising contacting the contaminated substrate with the cleaning composition according to claim 5 or 6.

8. An immersion cooling system comprising... A housing having an internal space, A component generating heat disposed within the internal space, A working fluid disposed within the internal space such that the component generating heat is in contact therewith, The working fluid comprises a compound having the structural formula (I): [Chemical Formula 6] [wherein, R Ｈ is CH ３ or CH ２ CH ３ and is Rf is a perfluoroalkyl group having 1 to 9 carbon atoms, optionally containing either or both of a nitrogen heteroatom and an oxygen heteroatom linked in a chain, and optionally containing a 5- or 6-membered ring. Rf' and Rf" are independently perfluoroalkyl groups having 1 to 2 carbon atoms, and at least one of Rf' and Rf" has 2 carbon atoms. An immersion cooling system comprising...

9. The immersion cooling system according to claim 8, wherein the component generating heat comprises an electronic device.

10. The immersion cooling system according to claim 9, wherein the electronic device comprises a computer server.

11. A thermal management system for a lithium-ion battery pack, comprising... A lithium-ion battery pack, A working fluid in thermal communication with the lithium-ion battery pack, The working fluid comprises a compound having the structural formula (I): 【Chemical Formula 7】 [wherein, R Ｈ is CH ３ or CH ２ CH ３ and is Rf is a perfluoroalkyl group having 1 to 9 carbon atoms, optionally containing either or both of a nitrogen heteroatom and an oxygen heteroatom linked in a chain, and optionally containing a 5- or 6-membered ring. Rf' and Rf" are independently perfluoroalkyl groups having 1 to 2 carbon atoms, and at least one of Rf' and Rf" has 2 carbon atoms. A thermal management system comprising...

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