Chlorinated fluoroaromatic compounds and their use

Abstract

Chlorinated fluoroaromatic compounds having structural formula (I): wherein G is an oxygen or sulfur atom; 1 are independently fluoroalkenyl groups having 2 to 10 carbon atoms and optionally containing one or more catenated heteroatoms; each R 2 are independently (i) a hydrogen atom or a fluorine atom, or (ii) a fluoroalkyl or fluoroalkenyl group having 1 to 9 carbon atoms and optionally containing one or more linearly linked heteroatoms; R 3 is a hydrogen atom or a fluorine atom; a is 1 to 3; x is 1 or 2; y is 1 to 4; and z=6-axy. TIFF2023508543000018.tif32115

Description

[Technical Field]

[0001] This disclosure relates to chlorinated fluoroaromatic compounds, methods for producing and using the same, and working fluids containing the same. [Background technology]

[0002] Various fluoroaromatic compounds are described, for example, in "The Reactions of the Dimers of Hexafluoropropene with O-Nucleophiles," Nobuo, I.; Nagashima, A. Bulletin of the Chemical Society of Japan 1976, 49, 502-505; and "Mode of the nucleophilic reaction of F-2,4-dimethyl-3-heptene and phenol," Maruta, M.; Ishikawa, N. Journal of Fluorine Chemistry 1979, 13, 421-429. Various chlorine-containing fluoroaromatic compounds are described, for example, in "Synthesis of partially fluorinated organic compounds from perfluoro-2-methyl-2-pentene and phenol derivatives," Furin, GG; Zhuzhgov, EL; Chi, K.-V., Kim, N.-A. Russian Journal of General Chemistry 2005, 75, 394-401; and Takeshi, M.; Kazuyuki, O.; Yasunori, O.; Toshiya, I. Perfluoroalkenyl Derivative, Japanese Patent Publication No. 2006335677, December 14, 2006. [Overview of the project]

[0003] In some embodiments, chlorinated fluoroaromatic compounds having structural formula (I) are provided. [ka] In the formula, G is an oxygen or sulfur atom; Each R 1 This is an independent fluoroalkenyl group having 2 to 10 carbon atoms and optionally containing one or more heteroatoms linked in a chain; Each R 2 Each comprises, independently, (i) a hydrogen atom or a fluorine atom, or (ii) a fluoroalkyl group or fluoroalkenyl group having 1 to 9 carbon atoms, and optionally containing one or more heteroatoms linked in a chain. R 3 is a hydrogen atom or a fluorine atom; a is 1 to 3; x is either 1 or 2; y is between 1 and 4; z = 6 - axy.

[0004] The above summary of the disclosure is not intended to describe each embodiment of the disclosure. Details of one or more embodiments of the disclosure are also described below. Other features, purposes, and advantages of the disclosure will become apparent from this specification and the claims. [Modes for carrying out the invention]

[0005] Given the growing demand for environmentally friendly chemical compounds (due to environmental concerns and industry regulations), there is a recognized need for new working fluids that offer reduced environmental impact (e.g., exhibiting low global warming potentials, GWP). In addition to environmental concerns, such compounds need to meet the performance requirements (e.g., non-flammability, solubility, stability, low toxicity, low dielectric constant, and wide operating temperature range) for various applications (e.g., heat transfer, immersion cooling, solvent cleaning, and adhesive coating solvents) and be manufactured in a cost-effective manner. More specifically, there is a need for non-flammable, high-boiling-point working fluids for high-temperature applications (e.g., those defined below) with a wide liquid range (e.g., <-50°C to >180°C at 760 Torr), low dielectric constant (e.g., <3 at 1 kHz), and very low global warming potentials (GWP) (e.g., <100 as defined below).

[0006] Generally, this disclosure relates to certain chlorinated fluoroaromatic compounds that are particularly useful as high-boiling-point heat transfer fluids, dielectric fluids, immersion cooling fluids, or fluids for converting thermal energy into mechanical energy. In particular, the compounds of this disclosure have significantly lower GWP compared to related working fluids used in the industry (e.g., perfluorocarbons (PFCs), perfluoropolyethers (PFPEs), and hydrofluorocarbons (HFCs)). Furthermore, certain compounds exhibit non-flammability, low ozone depletion potential (ODP), and low toxicity.

[0007] Furthermore, the compounds of this disclosure exhibit remarkably favorable dielectric properties (i.e., low dielectric constant and high dielectric strength) and high boiling points. With respect to dielectric properties, preferred embodiments have been found to exhibit a dielectric constant of less than 3 and a dielectric strength greater than 40 kV (2.5 mm gap), making the compound suitable for immersion cooling applications where electronic components are in direct contact with the working fluid.

[0008] The combination of low GWP and favorable dielectric properties exhibited by the compounds of the present disclosure should be emphasized as being surprising for high-boiling fluorinated fluids used in the industry. For example, perfluoropolyethers (PFPEs) having boiling points in the range of about 130 °C to 200 °C generally have excellent dielectric properties (dielectric constant ≈ 1.9, dielectric strength ≈ 40 kV) and also have a very high GWP (about 10,000). Conversely, hydrofluoroethers (HFEs) having boiling points in the range of about 130 °C to 170 °C generally have a lower GWP (<500) than PFPEs but have a higher dielectric constant and a lower dielectric strength (≥5.8 and <30 kV, respectively). Thus, the chlorinated aromatics described herein provide a very low GWP and a slightly higher dielectric strength than PFPEs. Similarly, the chlorinated aromatics have a lower GWP, a lower dielectric constant, and a higher dielectric strength than HFEs.

[0009] With respect to the operating temperature range, it has been discovered that certain chlorinated fluoroaromatic compounds have significantly higher boiling points (>20 °C) than their non-chlorinated analogs and, in some embodiments, have boiling points above 190 °C and excellent thermal stability. Thus, these compounds are particularly useful in high-temperature operating fluid applications. Finally, certain compounds of the present disclosure can be produced cost-effectively, due in part to the relatively low cost of the starting materials.

[0010] As used herein, "chain-linked heteroatoms" means an atom other than carbon (e.g., oxygen, nitrogen, or sulfur) that is bonded to at least two carbon atoms of a carbon chain (linear, branched, or within a ring) so as to form a carbon-heteroatom-carbon bond.

[0011] 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 such that there is at least one carbon-bonded hydrogen atom in addition to carbon-fluorine bonds, or (ii) being fully fluorinated.

[0012] 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 "fully fluorinated" means being fully fluorinated such that there are no carbon-bonded hydrogen atoms replaceable by fluorine, unless otherwise specified.

[0013] 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.

[0014] As used herein, "alkenyl" means a molecular fragment consisting 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.

[0015] As used herein, “fluoroaromatic” or “fluoroaromatic compound” refers to a compound having an aromatic moiety (i.e., a planar ring structure satisfying Hückel’s 4n+2 rule, e.g., benzene and pyridine derivatives), which also contains a carbon-fluorine bond. The aromatic ring may be directly fluorinated with a group bonded to the aromatic ring that also contains a carbon-fluorine bond (e.g., fluoroalkyl, fluoroalkenyl, and derivatives thereof containing chain-linked heteroatoms) (i.e., having an aryl carbon-fluorine bond, e.g., a pentafluorophenol derivative). Alternatively, the aromatic ring may not be fluorinated with a group bonded to it that contains a carbon-fluorine bond (e.g., fluoroalkyl, fluoroalkenyl, and derivatives thereof containing chain-linked heteroatoms) (i.e., not containing an aryl carbon-fluorine bond, e.g., a phenol derivative).

[0016] As used herein, "chlorinated fluoroaromatic" refers to a compound that satisfies the above definition of "fluoroaromatic" and further has one or more chlorine atoms bonded to an aromatic ring.

[0017] As used herein, the singular forms "a," "an," and "the" refer to multiple objects unless explicitly stated otherwise. As used herein and in the accompanying embodiments, the term "or" generally means "and / or" unless explicitly stated otherwise.

[0018] When used herein, a numerical range indicated by an endpoint includes all numbers within that range (for example, 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.8, 4, and 5).

[0019] Unless otherwise indicated, all numbers expressing quantities of ingredients, properties, and so forth used in this specification and the 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 list of examples 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, each numerical parameter should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques, but this is not intended to limit the application of the doctrine of equivalents to the scope of the claimed embodiments.

[0020] In some embodiments, the present disclosure relates to a chlorinated fluoroaromatic compound represented by the following structural formula (I):

Chemical formula

[0021] In some embodiments, either or both of R 1 and R 2 (R 2(When the group is a fluoroalkyl or fluoroalkenyl group), it may be totally fluorinated.

[0022] In some embodiments, the present disclosure relates to chlorinated fluoroaromatic compounds represented by the following structural formula (II): [ka] [In the formula, G' is an oxygen or sulfur atom; R 1’ This is a fluoroalkenyl group having 2 to 10, 3 to 9, or 4 to 9 carbon atoms, and optionally containing one or more heteroatoms linked in a chain; Each R 2’ Each comprises, independently, (i) a hydrogen atom or a fluorine atom, or (ii) a fluoroalkyl group or fluoroalkenyl group having 1 to 9 carbon atoms, and optionally containing one or more heteroatoms linked in a chain; x' is 2 to 4 or 2 to 3; a', b', and c' are independently either 0 or 1.

[0023] In some embodiments, R 1’ and R 2’ Either or both (R 2’ (When the group is a fluoroalkyl or fluoroalkenyl group), it may be totally fluorinated.

[0024] In some embodiments, the fluorine content in the chlorinated fluoroaromatic compounds of this disclosure may be sufficient to make the compounds non-flammable according to the ASTM D-3278-96 e-1 test method ("Flash Point of Liquids by Small Scale Closed Cup Apparatus").

[0025] In various embodiments, typical examples of compounds of general formula I or II include the following: [ka] [ka]

[0026] For the purposes of this disclosure, it should be understood that any chlorinated fluoroaromatic compound, regardless of whether it is represented by a general formula or chemical structure, may include an E isomer, a Z isomer, or a mixture of an E isomer and a Z isomer.

[0027] In some embodiments, the chlorinated fluoroaromatic compounds of the present disclosure may be useful over a wide operating temperature range. In this regard, in some embodiments, the chlorinated fluoroaromatic compounds of the present disclosure may have boiling points of 220, 210, 200, 190, or 180°C or higher.

[0028] In some embodiments, the chlorinated fluoroaromatic compounds of this disclosure may be hydrophobic, relatively chemically unreactive, and thermally stable. The chlorinated fluoroaromatic compounds may have a low environmental impact. In this regard, the chlorinated fluoroaromatic compounds of this disclosure may have a global warming potential (GWP) of 300, 200, 100, 50, less than 10, or less than 1. As used herein, GWP is a relative measure of a compound's global warming potential based on its structure. The GWP of a compound was defined in 1990 by the Intergovernmental Panel on Climate Change (IPCC) and revised in 2007, and is calculated as the warming caused by one kilogram of compound emission versus the warming caused by one kilogram of CO2 emission over a specific integration time horizon (ITH).

number

[0029] In this formula, a iθ is the radiative forcing per unit mass increase of a compound in the atmosphere (the change in radiant 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 typically accepted ITH is 100 years, representing a compromise between short-term effects (20 years) and long-term effects (more than 500 years). The concentration of organic compound i in the atmosphere is assumed to follow pseudo-first-order kinetics (i.e., exponential decay). The concentration of CO2 at the same time interval incorporates a more complex model of CO2 exchange and removal from the atmosphere (the Bern carbon cycle model).

[0030] In some embodiments, the chlorinated fluoroaromatic compounds of this disclosure may be prepared by nucleophilic substitution of a fluoride ion from a fluoroalkene with a chlorophenolate ion (e.g., 4-chlorophenolate or 3,5-dichlorophenolate) using a procedure adapted from the prior art. The chlorophenolate species may be a pre-formed alkali metal salt (e.g., sodium or potassium chlorophenolate). Alternatively, a chlorophenolate may be formed from a chlorophilic chlorophenol in the reaction medium in the presence of a Brønsted base, with suitable bases being amines (e.g., triethylamine), alkali metal carbonates (e.g., sodium carbonate or potassium carbonate), or alkali metal hydroxides (e.g., sodium hydroxide or potassium hydroxide). Suitable media for these reactions include organic solvents such as N,N-dimethylformamide, acetone, and tetrahydrofuran.

[0031] In some embodiments, the disclosure further relates to a working fluid comprising one or more of the above-mentioned chlorinated fluoroaromatic compounds as a main component. For example, the working fluid may contain at least 25% by weight, at least 50% by weight, at least 70% by weight, at least 80% by weight, at least 90% by weight, at least 95% by weight, or at least 99% by weight of the above-mentioned chlorinated fluoroaromatic compounds, based on the total weight of the working fluid. In addition to the chlorinated fluoroaromatic compounds, the working fluid may contain one or more of the following components: alcohols, ethers, alkanes, alkenes, haloalkenes, perfluorocarbons, perfluorotertiary amines, perfluoroethers, cycloalkanes, esters, ketones, oxiranes, aromatics, siloxanes, hydrochlorocarbons, hydrochlorofluorocarbons, hydrofluorocarbons, hydrochloroolefins, hydrochlorofluoroolefins, hydrofluoroethers, sulfones, or mixtures thereof, in total at up to 75% by weight, up to 5% by weight, up to 50 Such additional components can be selected to modify or enhance the properties of the composition for a specific application.

[0032] In some embodiments, the chlorinated fluoroaromatic compounds of the present disclosure (or working heat transfer fluids containing them) can be used as heat transfer agents in a variety of applications (for example, for cooling or heating tools for integrated circuits in the semiconductor industry, including dry etchers, integrated circuit testers, photolithography exposure tools (steppers), ashers, chemical vapor deposition equipment, automated test equipment (probers), physical vapor deposition equipment (e.g., sputtering), and vapor-phase soldering fluids and thermal shock fluids).

[0033] In some embodiments, the disclosure further covers a device for heat transfer, comprising a device and a mechanism for transferring heat to or from the device. The mechanism for heat transfer may include a heat transfer agent or working fluid comprising one or more chlorinated fluoroaromatic compounds of the disclosure.

[0034] The apparatus for heat transfer provided may include devices. A device may be a component, workpiece, 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 devices of this 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, a device may include a cooler, a heater, or a combination thereof.

[0035] In yet another embodiment, the device may include electronic devices such as processors, including microprocessors. As these electronic devices become more powerful, the amount of heat produced per unit time increases. Therefore, the heat transfer mechanism plays a crucial role in the performance of the processor. Heat transfer fluids typically have good heat transfer performance, good electrical compatibility (even when used in "indirect contact" applications such as those employing cooling plates), as well as low toxicity, low flammability (or non-flammability), and low environmental impact. Good electrical compatibility requires that the heat transfer fluid candidate exhibits high dielectric strength, high volume resistivity, and poor solubility in polar materials. In addition, the heat transfer fluid should exhibit good mechanical compatibility, i.e., should not adversely affect typical constituent materials and should have a low pour point and low viscosity to maintain fluidity during low-temperature operation.

[0036] The provided device may include a mechanism for transferring heat. The mechanism may include a heat transfer fluid. The heat transfer fluid may include one or more chlorinated fluoroaromatics of the present disclosure. Heat can be transferred by positioning the heat transfer mechanism in thermal contact with the device. When positioned 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.

[0037] Examples of heat transfer mechanisms, though not limited to those mentioned above, include equipment for managing heat transfer fluids, such as pumps, valves, fluid storage systems, pressure control systems, condensers, heat exchangers, heat sources, heat sinks, cooling systems, active and passive temperature control systems. Suitable examples of heat transfer mechanisms include, but are not limited to, temperature-controlled wafer chucks for plasma chemical vapor deposition (PECVD) tools, temperature-controlled test heads for die performance testing, temperature-controlled operating areas in semiconductor process equipment, thermal shock test chambers, liquid storage containers, and constant temperature baths. In some systems, such as etchers, ashers, 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 220°C.

[0038] Heat can be transferred by arranging a heat transfer mechanism to communicate thermally with the device. When the heat transfer mechanism is arranged to communicate thermally with the device, it 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. Other devices that may be provided include refrigeration systems, cooling systems, testing equipment, and machining equipment. In some embodiments, the devices provided may be a constant temperature bath or a thermal shock test bath.

[0039] In some embodiments, the disclosure relates to a thermal management system for an electrochemical cell pack (e.g., a lithium-ion battery pack). The system may include the electrochemical cell pack and a working fluid that is in thermal communication with the battery pack. The working fluid may include one or more chlorinated fluoroaromatics of the disclosure.

[0040] Electrochemical cells (e.g., lithium-ion batteries) are widely used worldwide in a vast array of electronic and electrical devices, ranging from hybrid and electric vehicles to power tools, portable computers, and mobile devices. While lithium-ion batteries are generally safe and reliable energy storage devices, under certain conditions they can suffer a catastrophic failure known as thermal runaway. Thermal runaway is a series of internal exothermic reactions caused by heat. Excessive heat generation can result from overcharging, overheating, or internal short circuits. Internal short circuits are typically caused by manufacturing defects or impurities, dendritic lithium formation, and mechanical damage. Typically, charging devices and battery packs contain protective 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.

[0041] Thermal management systems for lithium-ion battery packs are often required to maximize the cycle life of lithium-ion batteries. This type of system maintains a uniform temperature for each cell within the battery pack. High temperatures can increase the rate of capacity degradation and impedance of lithium-ion batteries, while also reducing their lifespan. Ideally, each individual cell within a battery pack should be at the same ambient temperature.

[0042] Direct contact fluid immersion of batteries can reduce the probability of sudden thermal runaway events to a low level, while also achieving the continuous thermal management required for the efficient normal operation of lithium-ion battery packs. This type of application provides thermal management when using fluid in conjunction with a heat exchange system to maintain a desired operating temperature range. However, in the event of any mechanical damage or internal short circuit of a lithium-ion battery, the fluid is also considered to prevent the propagation or cascading of the thermal runaway event to adjacent batteries in the pack via evaporative cooling, thereby significantly reducing the risk of sudden thermal runaway events involving multiple batteries. Similar to the immersion cooling of electronic equipment described above, immersion cooling and thermal management of batteries can be achieved using systems designed for single-phase or two-phase immersion cooling, and the requirements for the fluid to cool the batteries are similar to those described above for electronic equipment. In either scenario, the fluid is positioned in thermal communication with the battery to maintain the increase or decrease of the battery temperature (i.e., heat can be transferred to or from the battery via the fluid).

[0043] Direct contact fluid immersion technology has been shown to be useful for providing thermal management and thermal runaway protection for batteries, but there is still a need for improved fluids that can provide better chemical stability and system life while addressing environmental concerns such as high GWP. Hydrofluoroethers and perfluoroketones are two examples of chemicals that have shown usefulness in direct contact fluid immersion heat transfer applications for thermal management and thermal runaway protection for batteries, and also provide acceptable global warming potentials. These applications impose stringent performance requirements on the fluids used, such as non-flammability, acceptable toxicity, small environmental footprint, high dielectric strength, low dielectric constant, high volume resistivity, stability, material compatibility, and excellent thermal properties, in order to maintain high volume resistivity over long periods. In some embodiments, the present disclosure applies to a direct contact fluid immersion thermal management system for electrochemical cell packs. This system may include an electrochemical cell pack and a working fluid that is thermally communicating with the pack. The working fluid may include one or more of the chlorinated fluoroaromatic compounds of the present disclosure.

[0044] In some embodiments, the disclosure relates to the use of one or more chlorinated fluoroaromatic (or chlorinated fluoroaromatic-containing working fluids) as single-phase immersion cooling fluids for electronic devices (e.g., computer servers). There is no phase transition in single-phase immersion. Instead, typically, the fluid is heated and cooled as it flows through the electronic device and heat exchanger, or is pumped, thereby transferring heat from the electronic device.

[0045] In some embodiments, the disclosure may relate to immersion cooling systems operating by single-phase immersion cooling. Generally, a single-phase immersion cooling system may include heat-producing components (e.g., computer servers) positioned within the internal space of a housing so as to be at least partially immersed (and until fully immersed) in the liquid phase of a working fluid. The single-phase system may further include a pump and a heat exchanger, the pump operating to move the working fluid to or from the heat-producing electronic device and heat exchanger, and the heat exchanger operating to cool the working fluid. The heat exchanger may be located inside or outside the housing. [Examples]

[0046] The purposes and advantages of this disclosure are further illustrated by the following comparative examples and examples. Unless otherwise noted, all parts, percentages, ratios, etc., in the examples and the remainder of this specification are by weight, and all reagents used in the examples are obtained or available from common chemical suppliers such as Sigma-Aldrich Corp. (Saint Louis, MO, US) or Oakwood Chemicals (Estill, SC, US). The following abbreviations are used herein: mL = milliliter, L = liter, mm = millimeter, min = minute, h = hour, g = gram, mmol = millimoles, mol = mole, °C = degrees Celsius, bp = boiling point, GC = gas chromatography, FID = flame ionization detector, MS = mass spectrometry, i = iso and n = n (referring to the structural configuration of a carbon-based group, such as in iso- or n-propyl), Ph = phenyl (C6H5), NMR = nuclear magnetic resonance, cSt = centistokes, KHz = kilohertz, kV = kilovolt.

[0047] Sample preparation procedure Note that the following procedures for Examples 1 and 3, and Comparative Examples CE1 and CE3, yielded multiple isomers. The structures shown are the major isomers (>90% by weight).

[0048] Example 1: 4-Cl(C6H4)O(C9F 17 ):(E)-1-chloro-4-((1,1,1,2,2,3,5,6,7,7,7-undecafluoro-4,6-bis(trifluoromethyl)hepta-4-en-3-yl)oxy)benzene + isomer [ka] (E)-Perfluoro-2,4-dimethylhepta-3-ene [(E)-CF(i-C3F7)=C(CF3)(n-C3F7)] was prepared according to the procedure described in KNMakarov, et al., Journal of Fluorine Chemistry 1977, 10, 323-327. 4-chlorophenol (84.7 g, 659 mmol), (E)-perfluoro-2,4-dimethylhepta-3-ene (308 g, 684 mmol), and N,N-dimethylformamide (300 mL) were combined in a 1 L three-necked flask equipped with an addition funnel, temperature probe, and magnetic stirring rod. The slightly yellowish two-phase mixture was cooled to approximately 12°C in an ice bath. Triethylamine (66.7 g, 659 mmol) was added dropwise over 1 hour at a temperature of 10°C–15°C using the addition funnel while vigorously stirring. The two-phase mixture (yellow upper layer, slightly yellow lower layer) was stirred at ambient temperature (21°C-23°C) for 1 hour and 30 minutes. The layers were separated. The lower (fluorocarbon) layer was washed with water (200 mL x 3), dried over magnesium sulfate, and filtered (clear, slightly yellow liquid). This substance was purified by distillation under vacuum (5 Torr, bp ≈ 80°C), followed by filtration through silica (20 g). The combined 4-Cl(C6H4)O(C9F) 17 The yield for the isomer was 238 g (65%), and the purity was >99%, as established by GC-MS and NMR.

[0049] Example 2 4-Cl(C6H4)O(C6F 11 ):1-Chloro-4-((1,1,1,4,4,5,5,5-Octafluoro-2-(trifluoromethyl)penta-2-en-3-yl)oxy)benzene [ka] Acetone (250 mL), powdered potassium carbonate (approximately 325 mesh, 150.2 g, 1087 mmol), and perfluoro-2-(methyl)penta-2-ene [CF(C2F5)=C(CF3)2] (250.4 g, 834.7 mmol) were combined in a 1 L three-necked flask equipped with an addition funnel, temperature probe, and magnetic stirring rod (a slightly yellow suspension). The mixture was cooled to approximately 2°C in an ice bath. A solution of 4-chlorophenol (107.2 g, 833.6 mmol) in acetone (50 mL) was added dropwise over 45 minutes at a temperature of 0°C to 5°C while vigorously stirring. The yellow suspension was stirred at ambient temperature (21°C to 23°C) for 1 hour and 40 minutes. The mixture was filtered, and the solids were washed with acetone (50 mL x 3). These washings were collected along with the remaining yellow filtrate. The filtrate was concentrated under vacuum (approximately 0.5-1.0 Torr) in a water bath maintained at 12°C-20°C (approximately 350 mL of acetone was removed). The concentrated substance was washed with water (200 mL x 3), dried over magnesium sulfate, and filtered (a clear yellow liquid). This substance was purified by distillation under vacuum (6.4 Torr at bp ≈ 61°C), followed by filtration through silica (10 g). 4-Cl(C6H4)O(C6F 11 The yield was 195g (57%), and the purity was >99%, as established by GC-FID and GC-MS.

[0050] Example 3: 3,5-Cl2(C6H3)O(C9F 17 ):(E)-1,3-dichloro-5-((1,1,1,2,2,3,5,6,7,7,7-undecafluoro-4,6-bis(trifluoromethyl)hepta-4-en-3-yl)oxy)benzene + isomer [ka] 3,5-Dichlorophenol (52.5 g, 322 mmol, 100% by mass), N,N-dimethylformamide (170 mL), and (E)-perfluoro-2,4-dimethylhepta-3-ene [(E)-CF(i-C3F7)=C(CF3)(n-C3F7)] (146 g, 324 mmol), prepared using the procedure referenced in Example 1, were combined under a nitrogen atmosphere in a 500 mL three-necked flask equipped with an addition funnel, a temperature probe, and a magnetic stirring rod. The two-phase yellowish-brown mixture was cooled to 5°C in an ice bath. Triethylamine (33.0 g, 326 mmol) was added dropwise over 0.5 hours at a temperature of 5°C to 7°C while vigorously stirring. After 10 minutes at 5°C to 7°C, stirring was stopped and the layers were separated. The lower layer (slightly yellow) was washed with hydrochloric acid (5% by weight, 135 mL x 2) and water (135 mL x 2), dried over magnesium sulfate, and filtered. This substance was purified by distillation under vacuum (5.2 Torr, bp ≈ 88°C). Combined 3,5-Cl2(C6H3)O(C9F 17 The yield for the isomer was 109 g (57%), and the purity was >99%, as established by GC-FID and GC-MS.

[0051] Comparative example CE1 PhO(C9F 17 ):(E)-((1,1,1,2,2,3,5,6,7,7,7-undecafluoro-4,6-bis(trifluoromethyl)hepta-4-en-3-yl)oxy)benzene + isomer [ka] Under a nitrogen atmosphere, triethylamine (210 g, 2080 mmol) was added dropwise over 25 minutes using an addition funnel to a vigorously stirred two-phase mixture of phenol (193 g, 2050 mmol), N,N-dimethylformamide (1100 mL), and (E)-perfluoro-2,4-dimethylhepta-3-ene [(E)-CF(i-C3F7)=C(CF3)(n-C3F7) prepared using the procedure referenced in Example 1] (923 g, 2050 mmol). The internal temperature was maintained at 15°C to 22°C during the addition. The mixture was stirred at ambient temperature for 3 hours. The layers were separated, and the fluoroorganic layer (lower) was washed with 5% by weight hydrochloric acid (1 L x 2) and water (0.5 L x 2), dried over magnesium sulfate, and filtered. The crude substance was purified by vacuum distillation (5.0 Torr, bp approximately 61°C). Combined PhO(C9F 17 The yield for the isomer was 924 g (86%), and the purity was >99%, as established by GC-MS and NMR.

[0052] Comparative example CE2 PhO(C6F 11 ):3,3,3-trifluoro-1-(1,1,2,2,2-pentafluoroethyl)-2-(trifluoromethyl)prop-1-enoxy]benzene [ka] Under a nitrogen atmosphere, triethylamine (120 mL, 861 mmol) was added dropwise through an addition funnel to a vigorously stirred two-phase mixture of phenol (80 g, 850 mol), N,N-dimethylformamide (254 mL), and perfluoro-2-(methyl)penta-2-ene [CF(C2F5)=C(CF3)2] (280.6 g, 935.2 mmol). The internal temperature was maintained at 20°C to 40°C during the addition. The mixture was stirred at ambient temperature (21°C to 23°C) for 1 hour and 15 minutes. The fluoroorganic phase (bottom) was separated, washed with water (300 mL x 3), dried over magnesium sulfate, and filtered. The crude substance was purified by vacuum distillation (6.5 Torr, bp ≈ 55°C). The yield of PhO[C(C2F5)=C(CF3)2] was 655 g (83%), and its purity was 98%, as established by GC-MS and NMR.

[0053] Comparative example CE3 4-F(C6H4)O(C9F 17 ):(E)-1-fluoro-4-((1,1,1,2,2,3,5,6,7,7,7-undecafluoro-4,6-bis(trifluoromethyl)hepta-4-en-3-yl)oxy)benzene + isomer [ka] 4-Fluorophenol (71.2 g, 635 mmol), (E)-Perfluoro-2,4-dimethylhepta-3-ene [(E)-CF(i-C3F7)=C(CF3)(n-C3F7) prepared using the procedure referenced in Example 1] (300.7 g, 668.1 mmol), and N,N-dimethylformamide (300 mL) were combined in a 1 L three-necked flask equipped with an addition funnel, a temperature probe, and a magnetic stirring rod. The slightly yellow two-phase mixture was cooled to approximately 12°C in an ice bath. Triethylamine (64.4 g, 636 mmol) was added dropwise over 45 minutes using the addition funnel at a temperature of 10°C to 15°C while vigorously stirring. The two-phase mixture (yellow upper layer, slightly yellow lower layer) was stirred at ambient temperature (21°C to 23°C) for 1 hour and 30 minutes. The layers were separated. The lower (fluorocarbon) layer was washed with hydrochloric acid (5% by weight) (200 mL x 2) and water (100 mL x 2), dried over magnesium sulfate, and filtered (clear, colorless liquid). This substance was purified by distillation under vacuum (5.1 Torr, bp ≈ 66°C), and then filtered through silica (15 g). The combined 4-F(C6H4)O(C9F 17 The yield for the isomer was 262 g (76%), and the purity was >99%, as established by GC-FID and GC-MS.

[0054] Test method The boiling points reported in Table 1 were determined using the procedure outlined in ASTM E1719-97, "Standard Test Method for Vapor Pressure of Liquids by Ebulliometry." First, the vapor pressure was measured, and then the boiling point was calculated as described in Section 10 of ASTM Method E1719-97.

[0055] The dielectric constant was measured using an Alpha-A High Temperature Broadband Dielectric Spectrometer (Novocontrol Technologies, Montabaur, Germany) according to ASTM D150-11, "Standard Test Methods for AC Loss Characteristics and Permittivity (Dielectric Constant) of Solid Electrical Insulation". A parallel plate electrode configuration was selected for this measurement. The sample cell's parallel plates and an Agilent 16452A liquid test fixture (Keysight Technologies, Santa Rosa, CA, US) consisting of 38 mm diameter parallel plates were connected to the Alpha-A mainframe using a ZG2 dielectric / impedance multi-purpose connector (available from Novocontrol Technologies). Each sample was prepared between parallel plate electrodes spaced d (typically d=1 mm), and the complex dielectric constant (dielectric constant and dielectric loss) was evaluated from phase-sensitive measurements of the electrode voltage difference (Vs) and current (Is). Frequency domain measurements were performed at discrete frequencies from 0.00001 Hz to 1 MHz. From 10 milliohms up to a maximum of 1 x 10 14 The impedance of an ohm was measured up to a maximum of 4.2 volts AC. However, a constant AC voltage of 1.0 volt was used for this experiment. The DC conductivity (reciprocal of the volume resistivity) can also be extracted from an optimized broadband dielectric relaxation adaptation function that includes at least one low-frequency Havrrilak Negami dielectric relaxation function term and one separate frequency-dependent conductivity term.

[0056] Dielectric breakdown strength measurements of liquids were performed according to ASTM D877-87 (1995), "Standard Test Method for Dielectric Breakdown Voltage of Insulating Liquids." A disk electrode with a diameter of 25 mm and a spacing of 2.5 mm (0.10 inches) between electrodes was used, along with a Phenix Technologies Model LD60, specifically designed for testing in the 7–60 kV, 60 Hz (high voltage) breakdown range. Typical conditions were used for this experiment, with a frequency of 60 Hz and a voltage rise rate of 500 volts per second.

[0057] Kinematic viscosity was determined according to ASTM D445-94e1 "Standard Test Method for Kinematic Viscosity of Transparent and Opaque Liquids (the Calculation of Dynamic Viscosity)" using a ViscoSystem AVS350 viscosity timer (Schott Instruments GmbH, Hattenbergstraße 10 55122 Mainz, Germany) and a Hagenbach-corrected 545-03, 545-13, or 545-20 Ubbelohde viscometer (Cannon Instruments Company, Box 812, State College, PA), except that the bath temperature was controlled to ±0.1°C. For temperatures below 0°C, a Lawler temperature-controlled bath was used.

[0058] Density was measured using a DDM 2911 equipped with an automatic density meter. Before measurement, the liquid in the syringe was easily degassed by plugging the tip of the syringe and pulling the plunger to release air bubbles.

[0059] The flash point was measured according to the procedure outlined in ASTM D-3278-96e-1, "Standard Test Methods for Flash Point of Liquids by Small Scale Closed-Cup Apparatus." Materials that did not exhibit a flash point were considered non-flammable according to the ASTM test method.

[0060] Log K OW The value (octanol / water partition coefficient) was measured by HPLC using the method described in the Organisation for Economic Co-operation and Development (OECD) Test Method 117, "Partition Coefficient (n-octanol / water), HPLC Method".

[0061] The atmospheric lifetime of each test substance was determined by relative kinetic studies using chloromethane (CH3Cl) as the reference compound. The pseudo-first-order reaction rates of the reference compound and the test compound with hydroxyl radicals (·OH) were determined in a laboratory chamber system. The atmospheric lifetime of the reference compound is described in the literature. Based on this value and the pseudo-first-order rate measured in the chamber experiment, the atmospheric lifetime of each sample was calculated from the reaction rate of the test compound to the reference compound and the reported lifetime of the reference compound shown below:

number

[0062] The global warming potential (GWP) values ​​were calculated using the method described in the Intergovernmental Panel on Climate Change (IPCC) Fifth Assessment Report (AR5). Gas standards of the substance under evaluation, with known and documented concentrations, were prepared and used to obtain quantitative FTIR spectra of this compound. Using a mass flowmeter, quantitative gas-phase single-component FTIR library reference spectra were generated at two different concentration levels by diluting the sample standards with nitrogen. Flow rates were measured in the FTIR cell exhaust using a certified BIOS DRYCAL flowmeter (Mesa Labs (Butler, NJ, US)). The dilution procedure was also validated using a certified ethylene calibration gas cylinder. Using the method described in AR5, the radiative efficiency was calculated using the FTIR data and combined with the atmospheric lifetime to calculate the GWP value.

[0063] result The properties of Examples 1-3 and Comparative Examples CE1-CE3 are summarized in Table 1. Examples 1 and 2, which have a single chlorine atom bonded to the aromatic ring, have boiling points at least 22°C higher than their non-chlorinated analogs (CE1 and CE2). Example 3, which has two chlorine atoms bonded to the aromatic ring, has a boiling point 35°C higher than its non-chlorinated analog (CE1). For comparison, the 4-fluoro analog CE3 has a boiling point 5°C higher than its non-chlorinated analog (CE1). Therefore, partial chlorination of the aromatic ring significantly increases the boiling point compared to non-chlorinated compounds, which enables higher-temperature applications.

[0064] Replacing aromatic hydrogen atoms with chlorine atoms also affects dielectric properties. Compounds with a chlorine atom at the 4-position of the aromatic ring (Examples 1 and 2) or two chlorine atoms at the 3 and 5-positions (Example 3) exhibit significantly lower dielectric constants compared to the non-chlorinated cases (CE1 and CE2). Furthermore, the dielectric strength of Example 1 (46.6 kV) is considerably higher than that of its non-chlorinated analog, CE1, its 4-fluoro analog, CE3 (both 38.1 kV), and most commercially available fluorinated fluids with comparable boiling points (e.g., 170°C to 270°C), such as hydrofluoroethers (<30 kV), perfluoropolyethers (approximately 40 kV), and perfluorotrialkylamines (≤42 kV). Thus, as shown in the data in Table 1, the presence of even one chlorine atom in the aromatic ring has a surprisingly significant effect on dielectric properties. Interestingly, these effects are more pronounced with respect to chlorine than to fluorine, based on a comparison between Example 1 and its 4-fluoro analog, CE3.

[0065] As shown in Table 1, Example 1 also had a very low global warming potential (<10). [Table 1]

[0066] To evaluate thermal stability, Example 1 [1.0g, 4-Cl(C6H4)O(C9F 17 A flame-sealed borosilicate glass tube (outer diameter 50 mm, wall thickness 0.4 mm) containing an isomer mixture of 4-Cl(C6H4)O(C9F) was completely immersed in a temperature-controlled oil bath at 200±2℃ for 31.5 days. After heating, it was shown that there was no increase in pressure inside the tube and no significant gaseous decomposition products were present. GC-FID data was collected after heating and showed no evidence of decomposition or change in isomer distribution [GC-FID before and after heating showed 99.9±0.1% 4-Cl(C6H4)O(C9F) 17 [Isomers]

[0067] Therefore, the chlorinated fluoroaromatic substances of the present invention are highly suitable for immersion cooling applications due to their high boiling point, excellent thermal stability, low dielectric constant, high dielectric strength, and reduced environmental footprint.

[0068] Those skilled in the art will see that various modifications and changes to this disclosure will not deviate from the scope and spirit of this disclosure. It should be understood that this disclosure is not intended to be unduly limited by the exemplary embodiments and examples described herein, and that such embodiments and examples are presented solely as examples within the scope of this disclosure, intended to be limited only by the claims described herein as follows. All references cited herein are incorporated herein by reference in their entirety. The present invention encompasses the following embodiments. (1) Chlorinated fluoroaromatic compounds having structural formula (I): [ka] [In the formula, G is an oxygen or sulfur atom, Each R 1 This is a fluoroalkenyl group having 2 to 10, 3 to 9, or 4 to 9 carbon atoms, and optionally containing one or more heteroatoms linked in a chain. Each R 2 Each comprises, independently, (i) a hydrogen atom or a fluorine atom, or (ii) a fluoroalkyl group or fluoroalkenyl group having 1 to 9 carbon atoms, and optionally containing one or more heteroatoms linked in a chain. R 3 is a hydrogen atom or a fluorine atom, a is 1-3, 1-2, or 1. x is either 1 or 2, or 1. y is 1-4, 1-3, or 1-2. z = 6 - axy. (2) Each R 1 However, it is a chlorinated fluoroaromatic compound as described in item 1, which is fully fluorinated. (3)Each R 2 However, the chlorinated fluoroaromatic compounds described in item 1 or 2 are fully fluorinated. (4) A chlorinated fluoroaromatic compound as described in any of items 1 to 3, wherein a is 1. (5) A device for heat transfer, The device and An apparatus comprising a mechanism for transferring heat to or from the device, wherein the mechanism includes a working fluid comprising a chlorinated fluoroaromatic compound as described in any of items 1 to 4. (6) The apparatus for heat transfer described in item 5, wherein the device is selected from a microprocessor, a semiconductor wafer used to manufacture a semiconductor device, a power control semiconductor, an electrochemical cell, a battery pack, a power distribution switchgear, a power transformer, a circuit board, a multichip module, a packaged or unpackaged semiconductor device, a fuel cell, and a laser. (7) The apparatus for heat transfer according to item 5 or 6, wherein the mechanism for transferring heat is a component in a system for maintaining the temperature or temperature range of the device. (8) A method of transferring heat, A method comprising providing a device and transferring heat to or from the device using a heat transfer fluid comprising a chlorinated fluoroaromatic compound as described in any of items 1 to 4. (9) Immersion cooling system, A housing having an internal space, A heat-generating component arranged within the aforementioned internal space, The heat-producing components include a working fluid disposed within the internal space such that they are in contact with each other, An immersion cooling system wherein the working fluid contains a chlorinated fluoroaromatic compound as described in any of items 1 to 4. (10) The immersion cooling system according to item 9, wherein the chlorinated fluoroaromatic compound is present in the working fluid in an amount of at least 25% by weight, based on the total weight of the working fluid. (11) The system according to item 9 or 10, wherein the heat-producing component includes an electronic device. (12) The system described in item 11, wherein the electronic device includes a computer server. (13) A thermal management system for lithium-ion battery packs, Lithium-ion battery pack, The lithium-ion battery pack includes a working fluid that is in thermal communication with the lithium-ion battery pack, A thermal management system wherein the working fluid contains a chlorinated fluoroaromatic compound as described in any of items 1 to 4. (14) Chlorinated fluoroaromatic compounds having structural formula (II):

change

Claims

1. Chlorinated fluoroaromatic compounds having structural formula (I): 【Chemistry 1】 [In the formula, G is an oxygen or sulfur atom, Each R １ This is a fluoroalkenyl group having 2 to 10 carbon atoms, and optionally containing one or more heteroatoms linked in a chain. Each R ２ Each is independently (i) a fluorine atom, or (ii) a total fluorinated fluoroalkyl group or total fluorinated fluoroalkenyl group having 1 to 9 carbon atoms, and optionally includes one or more heteroatoms linked in a chain. R ３ is a hydrogen atom or a fluorine atom, a is 1 to 3, x is either 1 or 2, y is between 1 and 4. z = 6 - a - x - y.

2. Each R １ The chlorinated fluoroaromatic compound according to claim 1, wherein it is totally fluorinated.

3. A chlorinated fluoroaromatic compound according to claim 1 or 2, wherein a is 1.

4. A device for heat transfer, The device and The device includes a mechanism for transferring heat to or from the device, wherein the mechanism comprises a chlorinated fluoroaromatic compound having structural formula (I): 【Chemistry 2】 [In the formula, G is an oxygen or sulfur atom, Each R １ This is a fluoroalkenyl group having 2 to 10 carbon atoms, and optionally containing one or more heteroatoms linked in a chain. Each R ２ Each comprises, independently, (i) a hydrogen atom or a fluorine atom, or (ii) a fluoroalkyl group or fluoroalkenyl group having 1 to 9 carbon atoms, and optionally containing one or more heteroatoms linked in a chain. R ３ is a hydrogen atom or a fluorine atom, a is 1 to 3, x is either 1 or 2. y is between 1 and 4. z = 6 - a - x - y A device including a working fluid.

5. The apparatus for heat transfer according to claim 4, wherein the device is selected from a microprocessor, a semiconductor wafer used to manufacture semiconductor devices, a power control semiconductor, an electrochemical cell, a battery pack, a power distribution switchgear, a power transformer, a circuit board, a multichip module, a packaged or unpackaged semiconductor device, a fuel cell, and a laser.

6. The heat transfer apparatus according to claim 4 or 5, wherein the mechanism for transferring heat is a component in a system for maintaining the temperature or temperature range of the device.

7. A method of transferring heat, To provide a device and a chlorinated fluoroaromatic compound having structural formula (I): 【Transformation 3】 [In the formula, G is an oxygen or sulfur atom, Each R １ This is a fluoroalkenyl group having 2 to 10 carbon atoms, and optionally containing one or more heteroatoms linked in a chain. Each R ２ is independently (i) a hydrogen atom or a fluorine atom, or (ii) a fluoroalkyl group or a fluoroalkenyl group having 1 to 9 carbon atoms and optionally containing one or more heteroatoms linked in a chain, R ３ is a hydrogen atom or a fluorine atom, a is 1 to 3, x is either 1 or 2. y is between 1 and 4. z = 6 - a - x - y A method comprising transferring heat to or from a device using a heat transfer fluid containing a heat transfer fluid.

8. Immersion cooling system, A housing having an internal space, A heat-generating component arranged within the aforementioned internal space, The heat-producing components include a working fluid disposed within the internal space such that they are in contact with each other, The working fluid is a chlorinated fluoroaromatic compound having structural formula (I): 【Chemistry 4】 [In the formula, G is an oxygen or sulfur atom, Each R １ This is a fluoroalkenyl group having 2 to 10 carbon atoms, and optionally containing one or more heteroatoms linked in a chain. Each R ２ Each comprises, independently, (i) a hydrogen atom or a fluorine atom, or (ii) a fluoroalkyl group or fluoroalkenyl group having 1 to 9 carbon atoms, and optionally containing one or more heteroatoms linked in a chain. R ３ is a hydrogen atom or a fluorine atom, a is 1 to 3, x is either 1 or 2. y is between 1 and 4. z = 6 - a - x - y An immersion cooling system, including one.

9. The immersion cooling system according to claim 8, wherein the chlorinated fluoroaromatic compound is present in the working fluid in an amount of at least 25% by weight, based on the total weight of the working fluid.

10. The system according to claim 8 or 9, wherein the heat-producing component includes an electronic device.

11. The system according to claim 10, wherein the electronic device includes a computer server.

12. A thermal management system for lithium-ion battery packs, Lithium-ion battery pack, The lithium-ion battery pack includes a working fluid that is in thermal communication with the lithium-ion battery pack, The working fluid is a chlorinated fluoroaromatic compound having structural formula (I): 【Transformation 5】 [In the formula, G is an oxygen or sulfur atom, Each R １ This is a fluoroalkenyl group having 2 to 10 carbon atoms, and optionally containing one or more heteroatoms linked in a chain. Each R ２ Each comprises, independently, (i) a hydrogen atom or a fluorine atom, or (ii) a fluoroalkyl group or fluoroalkenyl group having 1 to 9 carbon atoms, and optionally containing one or more heteroatoms linked in a chain. R ３ is a hydrogen atom or a fluorine atom, a is 1 to 3, x is either 1 or 2. y is between 1 and 4. z = 6 - a - x - y A thermal management system, including

13. Chlorinated fluoroaromatic compounds having structural formula (II): 【Transformation 6】 [In the formula, G' is an oxygen or sulfur atom, R １’ This is a fluoroalkenyl group having 2 to 10 carbon atoms, and optionally containing one or more heteroatoms linked in a chain. Each R ２’ Each is independently (i) a fluorine atom, or (ii) a total fluorinated fluoroalkyl group or total fluorinated fluoroalkenyl group having 1 to 9 carbon atoms. x' is between 2 and 4. a', b', and c' are independently either 0 or 1. However, the aromatic ring has at least one chlorine atom.

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