Chlorinated fluorinated aromatics and methods of use thereof

Abstract

A chlorinated fluorinated aromatic compound having the structural formula (I): wherein G is an oxygen atom or a sulfur atom; each R 1 is independently a fluoroalkenyl group having 2 to 10 carbon atoms, and optionally containing one or more catenary heteroatoms; each R 2 R 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 catenary heteroatoms; 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-a-x-y.

Description

Technical Field

[0001] The present disclosure relates to chlorinated fluorine-containing aromatic compounds and methods of making and using the same, and to working fluids containing the chlorinated fluorine-containing aromatic compounds. Background Art

[0002] Various fluorinated aromatic 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; "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 fluorine-containing aromatic 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 derivatives. Japanese Patent Application 2006335677, December 14, 2006. Summary of the invention

[0003] In some embodiments, a chlorinated fluorine-containing aromatic compound having structural formula (I) is provided.

[0004]

[0005] Wherein G is an oxygen atom or a sulfur atom;

[0006] Each R 1 is independently a fluoroalkenyl group having from 2 to 10 carbon atoms, and optionally containing one or more catenary heteroatoms;

[0007] 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 catenary heteroatoms;

[0008] R 3 is a hydrogen atom or a fluorine atom;

[0009] a is 1 to 3;

[0010] x is 1 or 2;

[0011] y is 1 to 4; and

[0012] z=6-axy.

[0013] The above summary of the present disclosure is not intended to describe each embodiment of the present disclosure. The details of one or more embodiments of the present disclosure are also set forth in the following description. Other features, objectives and advantages of the present disclosure will be apparent from the specification and claims. DETAILED DESCRIPTION

[0014] In view of the increasing demand for environmentally friendly chemical compounds (due to environmental issues as well as industry regulation), it is recognized that there is an increasing need for new working fluids that can reduce environmental impact (e.g., exhibiting low global warming potential (GWP)). In addition to environmental issues, such compounds should meet the performance requirements of various applications (e.g., heat transfer, immersion cooling, solvent cleaning, and deposition coating solvents) (e.g., non-flammability, solubility, stability, low toxicity, low dielectric constant, and wide operating temperature range), and be cost-effective to manufacture. More specifically, non-flammable high-boiling working fluids for high temperature applications (such as those discussed below) are needed, which have a wide liquid range (e.g., from <-50°C to >180°C at 760 Torr), a low dielectric constant (e.g., <3 at 1kHz), and an extremely low global warming potential (GWP) (e.g., <100, as described below).

[0015] Generally, the present disclosure relates to certain chlorinated fluorine-containing aromatic compounds that are particularly suitable for high boiling point heat transfer fluids, dielectric fluids, immersion cooling fluids or for converting thermal energy into the fluid of mechanical energy. It is noteworthy that, compared with the relevant working fluids used in the industry (for example, perfluorocarbon (PFC), perfluoropolyether (PFPE) and hydrofluorocarbon (HFC)), the compounds of the present disclosure have significantly lower GWP. In addition, some compounds show non-flammability, low ozone depletion potential (ODP) and low toxicity.

[0016] In addition, the compounds of the present disclosure exhibit surprisingly favorable dielectric properties (i.e., low dielectric constant and high dielectric strength) and high boiling points. With respect to dielectric properties, it was found that preferred embodiments exhibit a dielectric constant of less than 3 and a dielectric strength of greater than 40 kV (2.5 mm gap), making the compounds useful for immersion cooling applications, where electronic components are in direct contact with the working fluid.

[0017] It should be emphasized that the combination of low GWP and favorable dielectric properties exhibited by the compounds of the present disclosure is surprising for high boiling point fluorinated fluids used in industry. For example, perfluoropolyethers (PFPEs) with 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), but also have extremely high GWP (about 10,000). In contrast, hydrofluoroethers (HFEs) with boiling points in the range of about 130°C to 170°C generally have lower GWPs (<500) than PFPEs but have higher dielectric constants and lower dielectric strengths (respectively ≥5.8 and <30 kV). Therefore, the chlorinated aromatics described herein provide much lower GWPs and slightly higher dielectric strengths than PFPEs. Similarly, chlorinated aromatics have lower GWPs, lower dielectric constants, and higher dielectric strengths than HFEs.

[0018] With respect to the operating temperature range, certain chlorinated fluorinated aromatic compounds are found to have boiling points significantly higher than their non-chlorinated analogs (by >20°C), and in some embodiments, have boiling points greater than 190°C and excellent thermal stability. Therefore, these compounds are particularly suitable for high temperature working fluid applications. Finally, certain compounds of the present disclosure can be manufactured cost-effectively due in part to the relatively low cost of the raw / starting materials.

[0019] As used herein, "chain heteroatom" means an atom other than carbon (e.g., oxygen, nitrogen or sulfur) that is bonded to at least two carbon atoms in a carbon chain (linear or branched or in a ring) to form a carbon-heteroatom-carbon chain.

[0020] As used herein, "fluoro-" (e.g., in reference to a group or moiety, such as with respect to "fluoroalkene" or "fluoroalkenyl" or "fluoroalkane" or "fluoroalkyl" or "fluorocarbon") or "fluorinated" means (i) partially fluorinated, such that there is at least one carbon-bonded hydrogen atom in addition to the carbon-fluorine bond, or (ii) perfluorinated.

[0021] As used herein, "perfluoro-" (e.g., in reference to a group or moiety, such as in reference to "fluoroalkene" or "fluoroalkenyl" or "fluoroalkane" or "fluoroalkyl" or "fluorocarbon") or "perfluorinated" means completely fluorinated, such that, unless otherwise indicated, there are no carbon-bonded hydrogen atoms replaceable by fluorine.

[0022] As used herein, "alkyl" means a molecular fragment consisting of a carbon-based backbone (ie, derived from alkanes) whose valences are saturated, which may be linear, branched, or cyclic.

[0023] As used herein, "alkenyl" means a molecular fragment consisting of a carbon-based backbone containing at least one carbon-carbon double bond (ie, derived from an olefin, a diene, etc.); the alkenyl fragment may be linear, branched, or cyclic.

[0024] As used herein, "fluorinated aromatic" or "fluorinated aromatic compound" refers to a compound having an aromatic portion (i.e., a planar ring structure satisfying Hückel's 4n+2 rule; for example, benzene and pyridine derivatives) that also contains a carbon-fluorine bond. The aromatic ring may be directly fluorinated (i.e., having an aromatic carbon-fluorine bond; for example, a pentafluorophenol derivative), wherein one or more groups are attached to an aromatic ring that also contains one or more carbon-fluorine bonds (e.g., fluoroalkyl, fluoroalkenyl, and derivatives thereof containing one or more catenary heteroatoms). Alternatively, the aromatic ring may be non-fluorinated (i.e., without an aromatic carbon-fluorine bond; for example, a phenol derivative), wherein one or more groups are attached to an aromatic ring that contains one or more carbon-fluorine bonds (e.g., fluoroalkyl, fluoroalkenyl, and derivatives thereof containing one or more catenary heteroatoms).

[0025] As used herein, "chlorinated fluorinated aromatic" refers to a compound that meets the above definition of "fluorinated aromatic compound" and further has one or more chlorine atoms attached to the aromatic ring.

[0026] As used herein, the singular forms "a", "an", and "the" include plural references unless the context clearly indicates otherwise. As used in this specification and the accompanying embodiments, the term "or" is generally used with its meaning including "and / or", unless the context clearly provides otherwise.

[0027] As used herein, the recitations of numerical ranges by endpoints include all numbers subsumed within that range (eg, 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.8, 4, and 5).

[0028] Unless otherwise specified, all numerals of the expression amount or composition, characteristic measurement, etc. used in this specification and embodiment should be understood to be modified by the term "about" in all cases. Therefore, unless otherwise specified, the numerical parameters shown in the above specification and the attached embodiment list can vary according to the desired characteristics sought to be obtained by those skilled in the art using the teaching content of the present disclosure. At the lowest level, and without attempting to limit the application of the principle of equivalents to the scope of the embodiment protected by the claims, each numerical parameter should be interpreted according to the reported significant digits and by applying the usual rounding method.

[0029] In some embodiments, the present disclosure relates to a chlorinated fluorine-containing aromatic compound represented by the following structural formula (I):

[0030]

[0031] Wherein G is an oxygen atom or a sulfur atom;

[0032] Each R 1 is independently a fluoroalkenyl group having 2 to 10, 3 to 9, or 4 to 9 carbon atoms, and optionally containing one or more catenary heteroatoms;

[0033] 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 catenary heteroatoms;

[0034] Each R 3 is a hydrogen atom or a fluorine atom;

[0035] a is 1 to 3, 1 to 2, or 1;

[0036] x is 1 or 2 or 1;

[0037] y is 1 to 4, 1 to 3, or 1 to 2; and

[0038] z=6-axy.

[0039] In some embodiments, R 1 and R 2 Either or both (when R 2 fluoroalkyl or fluoroalkenyl groups) may be perfluorinated.

[0040] In some embodiments, the present disclosure relates to a chlorinated fluorine-containing aromatic compound represented by the following structural formula (II):

[0041]

[0042] Wherein G' is an oxygen atom or a sulfur atom;

[0043] R 1' is a fluoroalkenyl group having 2 to 10, 3 to 9, or 4 to 9 carbon atoms, and optionally containing one or more catenary heteroatoms;

[0044] 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 catenary heteroatoms;

[0045] x' is 2 to 4 or 2 to 3; and

[0046] a', b' and c' are independently 0 or 1.

[0047] In some embodiments, R 1' and R 2' Either or both (when R 2' fluoroalkyl or fluoroalkenyl groups) may be perfluorinated.

[0048] In some embodiments, the fluorine content in the chlorinated fluorinated aromatic compounds of the present disclosure may be sufficient to render the compounds nonflammable according to ASTM D-3278-96e-1 test method ("Flash Point of Liquids by Small Scale Closed Cup Apparatus").

[0049] In various embodiments, representative examples of compounds of Formula I or II include the following compounds:

[0050]

[0051]

[0052] For purposes of this disclosure, it is understood that any of the chlorinated fluorinated aromatic compounds may include the E isomer, the Z isomer, or a mixture of the E and Z isomers, regardless of which compound is depicted in any of the general formulas or chemical structures.

[0053] In some embodiments, the chlorinated fluorinated aromatic compounds of the present disclosure may be useful over a wide range of operating temperatures. In this regard, in some embodiments, the chlorinated fluorinated aromatic compounds of the present disclosure may have a boiling point of not less than 220, 210, 200, 190, or 180 degrees Celsius.

[0054] In some embodiments, the chlorinated fluorinated aromatic compounds of the present disclosure may be hydrophobic, relatively chemically inert and thermally stable. The chlorinated fluorinated aromatic compounds may have a lower environmental impact. In this regard, the chlorinated fluorinated aromatic compounds of the present disclosure may have a global warming potential (GWP) of less than 300, 200, 100, 50, 10 or less than 1. As used herein, GWP is a relative measure of the global warming potential of a compound based on the structure of the compound. The GWP of a compound defined in 1990 and updated in 2007 by the Intergovernmental Panel on Climate Change (IPCC) is calculated as the warming caused by releasing 1 kg of the compound within a specified integral time range (ITH), relative to the warming caused by releasing 1 kg of CO2.

[0055]

[0056] In this formula, a i =ITH is the radiative forcing added per unit mass of a compound in the atmosphere (the change in the radiative flux through the atmosphere caused by the IR absorption of the compound), C is the atmospheric concentration of the compound, τ is the atmospheric lifetime of the compound, t is the 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 longer). It is assumed that the concentration of organic compound i in the atmosphere follows pseudo-first-order kinetics (i.e., exponential decay). The CO2 concentration within the same time interval adopts a more complex model (Bern carbon cycle model) that exchanges and removes CO2 from the atmosphere.

[0057] In some embodiments, the chlorinated fluorinated aromatic compounds of the present disclosure can be prepared by nucleophilic displacement of fluoride ions from fluoroolefins with chlorophenolate ions (e.g., 4-chlorophenolate or 3,5-dichlorophenolate) using procedures adapted from the prior art. The chlorophenolate material can be a preformed alkali metal salt (e.g., sodium chlorophenolate or potassium chlorophenolate). Alternatively, the chlorophenolate can be formed from the parent chlorophenol in the reaction medium in the presence of a Bronsted base; suitable bases include 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.

[0058] In some embodiments, the disclosure further relates to a working fluid comprising one or more of the above-mentioned chlorinated fluorinated aromatic compounds as a main component. For example, based on the gross weight of the working fluid, the working fluid may include 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 % of the above-mentioned chlorinated fluorinated aromatic compounds. In addition to the chlorinated fluorinated aromatic compounds, based on the gross weight of the working fluid, the working fluid may also include a total 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 % of the following components One or more: alcohols, ethers, alkanes, olefins, halogenated olefins, perfluorocarbons, perfluorinated tertiary amines, perfluoroethers, cycloalkanes, esters, ketones, oxiranes, aromatics, siloxanes, hydrochlorocarbons, hydrochlorofluorocarbons, hydrofluorocarbons, hydrochloroolefins, hydrochlorofluoroolefins, hydrofluoroethers, sulfones or mixtures thereof. Such additional components may be selected to alter or enhance the properties of the composition for a particular use.

[0059] In some embodiments, the chlorinated fluorinated aromatics of the present disclosure (or working heat transfer fluids containing the same) can be used as heat transfer agents in various applications (e.g., for cooling or heating of integrated circuit tools in the semiconductor industry, including tools such as dry etchers, integrated circuit testers, photolithography exposure tools (steppers), ashers, chemical vapor deposition equipment, automatic test equipment (probes), physical vapor deposition equipment (e.g., sputtering), as well as vapor phase soldering fluids and thermal shock fluids).

[0060] In some embodiments, the present invention also relates to an apparatus for heat transfer, which includes 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 working fluid containing one or more chlorinated fluorinated aromatics of the present disclosure.

[0061] The device provided for heat transfer may include equipment. Equipment may be a component, workpiece, assembly, etc. to be cooled, heated, or maintained at a predetermined temperature or temperature range. Such equipment includes electronic components, mechanical components, and optical components. Examples of equipment disclosed herein include, but are not limited to, microprocessors, wafers for manufacturing semiconductor equipment, power control semiconductors, distribution switch gears, power transformers, circuit boards, multi-chip modules, packaged and unpackaged semiconductor equipment, lasers, chemical reactors, fuel cells, heat exchangers, and electrochemical cells. In some embodiments, equipment may include a cooler, a heater, or a combination thereof.

[0062] In other embodiments, the equipment may include electronic equipment, such as processors (including microprocessors). Because the power of these electronic equipment becomes larger and larger, the amount of heat generated per unit time increases. Therefore, the heat transfer mechanism plays an important role in the performance of the processor. Heat transfer fluids generally have good heat transfer performance, good electrical compatibility (even for "indirect contact" applications, such as those using cooling plates), and low toxicity, low (or non-) flammability and low environmental impact. Good electrical compatibility requires that the heat transfer fluid candidate show high dielectric strength, high volume resistivity and low solubility for polar materials. In addition, the heat transfer fluid should show good mechanical compatibility, that is, it should not affect typical construction materials in an unfavorable manner, and it should have low pour point and low viscosity to maintain fluidity during low temperature operation.

[0063] The provided apparatus may include a mechanism for transferring heat. The mechanism may include a heat transfer fluid. The heat transfer fluid may contain one or more chlorinated fluorinated aromatics of the present disclosure. Heat may be transferred by placing the heat transfer mechanism in thermal contact with the device. When the heat transfer mechanism is placed in thermal contact with the device, the heat transfer mechanism removes heat from the device or provides heat to the device, or maintains the device at a selected temperature or temperature range. The direction of the heat flow (flowing from the device or flowing to the device) is determined by the relative temperature difference between the device and the heat transfer mechanism.

[0064] Heat transfer mechanisms may include facilities for managing heat transfer fluids, including but not limited to pumps, valves, fluid restraint 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: temperature-controlled wafer carriers in plasma enhanced chemical vapor deposition (PECVD) tools, temperature-controlled test heads for die performance testing, temperature-controlled work areas within semiconductor processing equipment, thermal shock test bath reservoirs, and constant temperature baths. In some systems, such as etchers, ashers, PECVD chambers, vapor phase soldering equipment, and thermal shock testers, the desired upper operating temperature limit may be up to 170°C, up to 200°C, or even up to 220°C.

[0065] Heat can be transferred by placing a heat transfer mechanism in thermal communication with the device. When the heat transfer mechanism is placed in thermal communication with the device, the heat transfer mechanism removes heat from the device or provides heat to the device, or maintains the device at a selected temperature or temperature range. The direction of heat flow (flowing from the device or flowing to the device) is determined by the relative temperature difference between the device and the heat transfer mechanism. The provided device may also include a refrigeration system, a cooling system, a test device, and a processing device. In some embodiments, the provided device may be a constant temperature bath or a thermal shock test bath.

[0066] In some embodiments, the present disclosure relates to a thermal management system for an electrochemical battery (e.g., a lithium-ion battery). The system may include an electrochemical battery and a working fluid in thermal communication with the battery. The working fluid may include one or more chlorinated fluorinated aromatics of the present disclosure.

[0067] Electrochemical cells (e.g., lithium-ion batteries) are widely used worldwide in a wide range of electrical and electronic devices, from hybrid and electric vehicles to power tools, portable computers, and mobile devices. Although lithium-ion batteries are generally safe and reliable energy storage devices, lithium-ion batteries can suffer catastrophic failures known as thermal runaway under certain conditions. Thermal runaway is a series of internal exothermic reactions triggered by heat. Excess heat generation can come from electrical overcharge, thermal overheating, or from internal electrical short circuits. Internal short circuits are typically caused by manufacturing defects or impurities, dendritic lithium formation, and mechanical damage. Although there is typically a protection circuit in charging devices and battery packs that will disable the battery in the event of overcharge or overheating, it cannot protect the battery from internal short circuits caused by internal defects or mechanical damage.

[0068] 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 capacity decay rate and impedance of lithium-ion batteries while reducing their life cycle. Ideally, each individual cell within the battery pack would be at the same ambient temperature.

[0069] Direct contact fluid immersion of the battery can mitigate low probability but catastrophic thermal runaway events while also providing the necessary continuous thermal management for the effective normal operation of the lithium-ion battery pack. This type of application provides thermal management when the fluid is used in conjunction with a heat exchange system to maintain the desired operating temperature range. However, in the event of mechanical damage or internal short circuiting of any lithium-ion battery, the fluid will also prevent the thermal runaway event from propagating or cascading to adjacent cells in the group via evaporative cooling, thereby significantly reducing the risk of catastrophic thermal runaway events involving multiple cells. As with the immersion cooling of electronic devices described above, immersion cooling and thermal management of the battery can be achieved using a system designed for single-phase or two-phase immersion cooling, and the fluid requirements for battery cooling are similar to those for electronic devices described above. In either case, the fluid is configured to be thermally connected to the battery to maintain, increase, or reduce the temperature of the battery (i.e., heat can be transferred to or from the battery via the fluid).

[0070] Direct contact fluid impregnation technology has been shown to be useful for thermal management of batteries and for providing thermal runaway protection, but there is still a need for improved fluids that can provide better chemical stability and system life while addressing environmental issues such as high GWP. Hydrofluoroethers and perfluoroketones are two examples of chemicals that have shown utility in direct contact fluid impregnation heat transfer applications, which are used for battery thermal management and thermal runaway protection while also providing acceptable global warming potential. These applications place strict 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 good thermal properties to maintain high volume resistivity for a long period of time. In some embodiments, the present disclosure is applicable to direct contact fluid impregnation thermal management systems for electrochemical batteries. The system may include an electrochemical battery and a working fluid that is thermally connected to the battery. The working fluid may include one or more chlorinated fluorinated aromatics of the present disclosure.

[0071] In some embodiments, the present disclosure relates to the use of one or more chlorinated fluorinated aromatics (or chlorinated fluorinated aromatic-containing working fluids) as single-phase immersion cooling fluids for electronic devices (e.g., computer servers). In single-phase immersion, there is no phase change. Instead, typically, the fluid warms and cools as it flows or is pumped through the electronic device and the heat exchanger, respectively, thereby transferring heat away from the electronic device.

[0072] In some embodiments, the present disclosure may relate to an immersion cooling system operated by single-phase immersion cooling. Generally speaking, the single-phase immersion cooling system may include a heat generating component (e.g., a computer server) disposed in the interior space of the housing so that the heat generating component is at least partially immersed (and at most completely immersed) in the liquid phase of the working fluid. The single-phase system may also include a pump and a heat exchanger, the pump operating to move the working fluid to and from the heat generating electronic device and the heat exchanger, and the heat exchanger operating to cool the working fluid. The heat exchanger may be disposed in the housing or outside the housing.

[0073] Example

[0074] The objects and advantages of the present disclosure are further illustrated by the following comparative and illustrative examples. Unless otherwise indicated, all parts, percentages, ratios, etc. in the examples and the remainder of the specification are by weight, and all reagents used in the examples are obtained from or purchased from general chemical suppliers, such as Sigma-Aldrich Corp. (Saint Louis, MO, US) in St. Louis, Missouri, USA or Oakwood Chemicals (Estill, SC, US) in Estill, South Carolina, USA. The following abbreviations are used herein: mL = milliliter, L = liter, mm = millimeter, min = minute, h = hour, g = gram, mmol = millimole, mol = mole, °C = degrees Celsius, bp = boiling point, GC = gas chromatography, FID = flame ionization detector, MS = mass spectrometry, i = iso and n = normal (with reference to the structural arrangement of a carbon-based group, such as isopropyl or n-propyl), Ph = phenyl (C6H5), NMR = nuclear magnetic resonance, cSt = centistokes, KHz = kilohertz, kV = kilovolt.

[0075] Sample preparation procedure

[0076] It should be noted that the procedures of Examples 1 and 3 and Comparative Examples CE1 and CE3 below produced multiple isomers. The structure shown is the major isomer (>90 wt %).

[0077] Example 1: 4-Cl(C6H4)O(C9F 17 ): (E)-1-chloro-4-((1,1,1,2,2,3,5,6,7,7,7-undecylfluoro-4, 6-Bis(trifluoromethyl)hept-4-en-3-yl)oxy)benzene + isomers

[0078]

[0079] (E)-perfluoro-2,4-dimethylhept-3-ene [(E)-CF(i-C3F7)=C(CF3)(n-C3F7)] was prepared according to the procedure described in KN Makarov et al., Journal of Fluorine Chemistry 1977, 10, 323-327. 4-Chlorophenol (84.7 g, 659 mmol), (E)-perfluoro-2,4-dimethylhept-3-ene (308 g, 684 mmol) and N,N-dimethylformamide (300 mL) were combined in a 1 L 3-necked flask equipped with an addition funnel, a temperature probe and a magnetic stirring bar. The pale yellow two-phase mixture was cooled to about 12° C. in an ice bath. Triethylamine (66.7 g, 659 mmol) was added dropwise through an addition funnel over 1 hour with vigorous stirring, the temperature being between 10° C. and 15° C. The two-phase mixture (yellow top layer, light yellow bottom layer) was stirred at ambient temperature (21°C to 23°C) for 1 hour and 30 minutes. The layers were separated. The bottom (fluorocarbon) layer was washed with water (200 mL x 3), dried over magnesium sulfate and filtered (clear, light yellow liquid). The material was purified by vacuum distillation (bp ≈ 80°C, 5 torr) and then filtered through silica (20 g). The yield was 238 g (65%), and the combined 4-Cl(C6H4)O(C9F 17 ) isomeric purity >99% as established by GC-MS and NMR.

[0080] Example 2: 4-Cl(C6H4)O(C6F 11 ): 1-chloro-4-((1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl) (pent-2-en-3-yl)oxy)benzene

[0081]

[0082] Acetone (250 mL), powdered potassium carbonate (about 325 mesh, 150.2 g, 1087 mmol) and perfluoro-2-(methyl)pent-2-ene [CF(C2F5)=C(CF3)2] (250.4 g, 834.7 mmol) were combined in a 1 L 3-necked flask equipped with an addition funnel, a temperature probe and a magnetic stirring bar (light yellow suspension). The mixture was cooled to about 2°C in an ice bath. Under vigorous stirring, a solution of 4-chlorophenol (107.2 g, 833.6 mmol) in acetone (50 mL) was added dropwise over 45 minutes at a temperature between 0°C and 5°C. The yellow suspension was stirred at ambient temperature (21°C to 23°C) for 1 hour and 40 minutes. The mixture was filtered; the solids were washed with acetone (50 mL×3) and the washings were collected with the remaining yellow filtrate. The filtrate was concentrated under vacuum (about 0.5 to 1.0 torr) in a water bath maintained between 12°C and 20°C (removing about 350 mL of acetone). The concentrated material was washed with water (200 mL x 3), dried over magnesium sulfate and filtered (clear, yellow liquid). The material was purified by vacuum distillation (bp ≈ 61°C, 6.4 torr) and then filtered through silica (10 g). 4-Cl(C6H4)O(C6F 11 ) in a yield of 195 g (57%) with a purity >99% as established by GC-FID and GC-MS.

[0083] 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-decachloro 4,6-Bis(trifluoromethyl)hept-4-en-3-yl)oxy)benzene + isomers

[0084]

[0085] Under nitrogen atmosphere, 3,5-dichlorophenol (52.5 g, 322 mmol, 100 mass %), N,N-dimethylformamide (170 mL) and (E)-perfluoro-2,4-dimethylhept-3-ene [(E)-CF(i-C3F7)=C(CF3)(n-C3F7) prepared using the procedure mentioned in Example 1] (146 g, 324 mmol) were combined in a 500 mL 3-necked flask equipped with an addition funnel, a temperature probe and a magnetic stirring bar. The two-phase yellow-brown mixture was cooled to 5°C in an ice bath. Under vigorous stirring, triethylamine (33.0 g, 326 mmol) was added dropwise over 0.5 hours with a temperature between 5°C and 7°C. After 10 minutes at 5°C to 7°C, stirring was stopped and the layers were separated. The bottom layer (light yellow) was washed with hydrochloric acid (5 wt%, 135 mL x 2) and water (135 mL x 2), dried over magnesium sulfate and filtered. The material was purified by vacuum distillation (bp ≈ 88 °C, 5.2 Torr). The yield was 109 g (57%), and the combined 3,5-Cl2(C6H3)O(C9F 17) isomeric purity >99% as established by GC-FID and GC-MS.

[0086] Comparative Example CE1: PhO(C9F 17 ): (E)-((1,1,1,2,2,3,5,6,7,7,7-undecylfluoro-4,6-bis(trifluoromethyl) 4-(2-(4-en-3-yl)hept-4-en-3-yl)oxy)benzene + isomers

[0087]

[0088] To a vigorously stirred two-phase mixture of phenol (193 g, 2050 mmol), N,N-dimethylformamide (1100 mL) and (E)-perfluoro-2,4-dimethylhept-3-ene [(E)-CF(i-C3F7)=C(CF3)(n-C3F7), prepared using the procedure mentioned in Example 1] (923 g, 2050 mmol) was added triethylamine (210 g, 2080 mmol) dropwise over 25 minutes via an addition funnel under nitrogen atmosphere. During the addition, the internal temperature was maintained between 15°C and 22°C. The mixture was stirred at ambient temperature for 3 hours. The layers were separated; the fluoroorganic layer (bottom) was washed with 5 wt% hydrochloric acid (1 L×2) and water (0.5 L×2), dried over magnesium sulfate, and filtered. The crude material was purified by vacuum distillation (bp about 61°C, 5.0 torr). The yield was 924 g (86%), the combined PhO(C9F 17 ) isomeric purity >99% as established by GC-MS and NMR.

[0089] Comparative Example CE2: PhO(C6F 11 ): 3,3,3-trifluoro-1-(1,1,2,2,2-pentafluoroethyl)-2-(trifluoromethyl)propane- 1-Alkenyloxy]benzene .

[0090]

[0091] Under a nitrogen atmosphere, triethylamine (120 mL, 861 mmol) was added dropwise to a vigorously stirred two-phase mixture of phenol (80 g, 850 mol), N,N-dimethylformamide (254 mL) and perfluoro-2-(methyl)pent-2-ene [CF(C2F5)=C(CF3)2] (280.6 g, 935.2 mmol) through an addition funnel. During the addition, the internal temperature was maintained between 20°C and 40°C. The mixture was stirred at ambient temperature (21°C to 23°C) for 1 hour and 15 minutes. The fluorinated organic phase (bottom) was separated, washed with water (300 mL×3), dried over magnesium sulfate, and filtered. The crude material was purified by vacuum distillation (bp≈55°C, 6.5 torr). . . . The yield of PhO[C(C2F5)=C(CF3)2] was 655 g (83%) with a purity of 98%, as established by GC-MS and NMR.

[0092] Comparative Example CE3: 4-F(C6H4)O(C9F 17 ): (E)-1-fluoro-4-((1,1,1,2,2,3,5,6,7,7,7-undecylfluoro- 4,6-Bis(trifluoromethyl)hept-4-en-3-yl)oxy)benzene + isomers

[0093]

[0094] 4-Fluorophenol (71.2 g, 635 mmol), (E)-perfluoro-2,4-dimethylhept-3-ene [(E)-CF(i-C3F7)=C(CF3)(n-C3F7) prepared using the procedure mentioned in Example 1] (300.7 g, 668.1 mmol) and N,N-dimethylformamide (300 mL) were combined in a 1 L 3-necked flask equipped with an addition funnel, a temperature probe and a magnetic stirring bar. The pale yellow two-phase mixture was cooled to about 12°C in an ice bath. With vigorous stirring, triethylamine (64.4 g, 636 mmol) was added dropwise through an addition funnel over 45 minutes at a temperature between 10°C and 15°C. The two-phase mixture (yellow top layer, light yellow bottom layer) was stirred at ambient temperature (21°C to 23°C) for 1 hour and 30 minutes. The layers were separated. The bottom (fluorocarbon) layer was washed with hydrochloric acid (5 wt%) (200 mL x 2) and water (100 mL x 2), dried over magnesium sulfate and filtered (clear, colorless liquid). The material was purified by vacuum distillation (bp ≈ 66 °C, 5.1 Torr) and then filtered through silica (15 g). The yield was 262 g (76%) of the combined 4-F(C6H4)O(C9F 17 ) isomeric purity >99% as established by GC-FID and GC-MS.

[0095] Test Method

[0096] The boiling points reported in Table 1 were determined using the procedure outlined in ASTM E 1719-97 "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.

[0097] The dielectric constant was measured using an α-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 of the parallel plate (Agilent 16452A liquid test fixture consisting of 38 mm diameter parallel plates (Keysight Technologies, Santa Rosa, CA, US)) was coupled to the α-A mainframe, while the ZG2 dielectric / impedance universal interface (purchased from Novocontrol Technologies, Inc.) was used. As described above, each sample was prepared between parallel plate electrodes separated by a distance d (typically d = 1 mm) and the complex resistivity (dielectric constant and loss) was evaluated based on 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. Measurements were made from 10 milliohms to up to 1×10 14 The impedance of the dielectric constant ...

[0098] Liquid dielectric breakdown strength measurements were performed according to ASTM D877-87 (1995) "Standard Test Method for Dielectric Breakdown Voltage of Insulating Liquids". A 25 mm diameter disk electrode with a 2.5 mm (0.10") spacing between electrodes was used with a Phenix Technologies LD 60 model electrode specifically designed for testing in the 7-60 kV, 60 Hz (higher voltage) breakdown range. For this experiment, a frequency of 60 Hz and a ramp rate of 500 volts / second were typically utilized.

[0099] Kinematic viscosity was determined using a ViscoSystem AVS 350 viscometer (Schott Instruments GmbH, Hattenbergstraße 10 55122 Mainz Germany) and a Hagenbach-calibrated 545-03, 545-13, or 545-20 Ubbelohde viscometer (Cannon Instruments Company, Box 812, State College, PA) according to ASTM D445-94e1 "Standard Test Method for Kinematic Viscosity of Transparent and Opaque Liquids (the Calculation of Dynamic Viscosity)" except that the bath temperature was controlled to ±0.1° C. For temperatures below 0° C., a Lawler temperature-controlled bath was used.

[0100] Density was measured using a DDM 2911plus automatic densitometer. Prior to measurement, the fluid was briefly degassed in the syringe by stopping the syringe tip and pulling the plunger to release air bubbles.

[0101] Flash point is measured according to the procedure outlined in ASTM D-3278-96 e-1 "Standard Test Methods for Flash Point of Liquids by Small Scale Closed-Cup Apparatus." According to the ASTM test method, materials that demonstrate no flash point are considered non-flammable.

[0102] Log K was determined by HPLC using the method described in Organisation for Economic Co-operation and Development (OECD) Test Method 117, “Partition Coefficient (n-Octanol / Water), HPLC Method” OW (octanol / water partition coefficient) value.

[0103] The atmospheric lifetime of each test material was determined from a relative rate study using methyl chloride (CH3Cl) as a reference compound. The pseudo-first order reaction rates of the reference and test compounds with hydroxyl (.OH) were determined in a laboratory chamber system. The atmospheric lifetime of the reference compound is documented 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 relative to the reference compound and the reported lifetime of the reference compound as follows:

[0104]

[0105] where τ x is the atmospheric lifetime of the test material, τ r is the atmospheric lifetime of the reference compound, and k x and k r are the rate constants for the reaction of hydroxyl radicals with the test material and the reference compound, respectively. The gas concentrations in the test chamber were quantified by Fourier transform infrared spectroscopy (FTIR). The atmospheric lifetime values ​​measured for each fluid were subsequently used in the GWP calculation.

[0106] The global warming potential (GWP) value is calculated using the method described in the fifth assessment report (AR5) of the Intergovernmental Panel on Climate Change (IPCC). A gas standard of the material to be evaluated with a known and recorded concentration is prepared and used to obtain a quantitative FTIR spectrum of the compound. The sample standard is diluted with nitrogen using a mass flow controller to generate a quantitative gas phase, single component FTIR library reference spectrum at two different concentration levels. The flow rate is measured under the FTIR cell exhaust port using a certified BIOSDRYCAL flowmeter (Mesa Labs, Butler, NJ, US, Butler, New Jersey, USA). The dilution procedure is also verified using a certified ethylene calibration gas cylinder. Using the method described in AR5, the FTIR data is used to calculate the radiative efficiency, which is then combined with the atmospheric lifetime to calculate the GWP value.

[0107] result

[0108] The properties of Examples 1-3 and Comparative Examples CE1-CE3 are summarized in Table 1. The boiling points of Examples 1 and 2, which have a single chlorine atom attached to the aromatic ring, are at least 22°C higher than their non-chlorinated analogs (CE1 and CE2). The boiling point of Example 3, which has two chlorine atoms attached to the aromatic ring, is 35°C higher than its non-chlorinated analog (CE1). For comparison, the boiling point of the 4-fluoro analog CE3 is only 5°C higher than its non-chlorinated analog (CE1). Therefore, partial chlorination of the aromatic ring significantly increases the boiling point compared to the non-chlorinated compound, which enables higher temperature applications.

[0109] Replacing aromatic hydrogen atoms with chlorine atoms also affects dielectric properties. Compounds with chlorine atoms at the 4-position of the aromatic ring (Examples 1 and 2) or compounds with two chlorine atoms at the 3,5-positions (Example 3) exhibit significantly lower dielectric constants relative to the non-chlorinated cases (CE1 and CE2). In addition, the dielectric strength of Example 1 (46.6 kV) is significantly greater than its non-chlorinated analog CE1, its 4-fluoro analog CE3 (both 38.1 kV), and most commercial fluorinated fluids with comparable boiling points (e.g., 170°C to 270°C), such as hydrofluoroethers (<30 kV), perfluoropolyethers (about 40 kV), and perfluorotrialkylamines (≤42 kV). Therefore, the inclusion of even a single chlorine atom on the aromatic ring has an unexpectedly significant effect on dielectric properties, as shown in the data in Table 1. Interestingly, based on a comparison of Example 1 with its 4-fluoro analog CE3, these effects are more prominent for chlorine than for fluorine.

[0110] As shown in Table 1, Example 1 also has a very low global warming potential (<10).

[0111] Table 1. Properties of Examples 1-3 and Comparative Examples CE1-CE3

[0112]

[0113] In order to evaluate the thermal stability, the sample containing Example 1 [1.0 g, 4-Cl(C6H4)O(C9F 17 )] was completely immersed in a temperature-controlled oil bath at 200±2°C for 31.5 days. After heating, there was no pressure buildup in the tube, indicating the absence of significant gaseous decomposition products. GC-FID data were collected after heating and did not show an isomeric distribution [by GC-FID, 99.9±0.1% 4-Cl(C6H4)O(C9F 17 )isomers, before and after heating] evidence of decomposition or change.

[0114] Therefore, the chlorinated fluorinated aromatic materials of the present invention are well suited for immersion cooling applications due to their high boiling point, excellent thermal stability, low dielectric constant, high dielectric strength and reduced environmental footprint.

[0115] Various modifications and changes made to the present disclosure will become apparent to those skilled in the art without departing from the scope and essence of the present disclosure. It should be understood that the present disclosure is not intended to be unduly limited by the exemplary embodiments and examples shown herein, and such examples and embodiments are presented only by way of example, and the scope of the present disclosure is intended to be limited only by the claims shown below herein. All references cited in the present disclosure are incorporated herein by reference in their entirety.

Claims

1. A chlorinated fluorinated aromatic compound having the structural formula (I): Wherein G is an oxygen atom; Each R 1 is independently a perfluoroalkenyl group having 4 to 10 carbon atoms, wherein the perfluoroalkenyl group is a perfluoro straight-chain alkenyl group or a perfluoro branched-chain alkenyl group; Each R 2 are independently hydrogen atoms; R 3 is a hydrogen atom; a is 1 to 3; x is 1 or 2; y is 1 to 4; z = 6-axy, and The chlorinated fluorine-containing aromatic compound is prepared by nucleophilic displacement of fluoride ions from fluoroolefins using 4-chlorophenolate ions or 3,5-dichlorophenolate ions.

2. The chlorinated fluorine-containing aromatic compound according to claim 1, wherein a is 1.

3. A device for heat transfer, the device comprising: equipment; and A means for transferring heat to or from the device, the means comprising a working fluid comprising a chlorinated fluorinated aromatic compound according to any one of claims 1 to 2.

4. The apparatus for heat transfer of claim 3, wherein the device is selected from a microprocessor, a semiconductor wafer for fabricating a semiconductor device, a power control semiconductor, an electrochemical cell, a battery pack, a power distribution switch gear, a power transformer, a circuit board, a multi-chip module, a packaged or unpackaged semiconductor device, a fuel cell, and a laser.

5. The apparatus for transferring heat according to any one of claims 3 to 4, wherein the mechanism for transferring heat is a component in a system for maintaining a temperature or temperature range of the device.

6. A method of transferring heat, the method comprising: Provide equipment; and transferring heat to or from the device using a heat transfer fluid comprising the chlorinated fluorinated aromatic compound according to any one of claims 1 to 2.

7. An immersion cooling system, comprising: a housing having an inner space; a heat generating component, wherein the heat generating component is arranged in the internal space; and a working fluid liquid, the working fluid liquid being disposed in the internal space so that the heat generating component is in contact with the working fluid liquid; The working fluid comprises the chlorinated fluorine-containing aromatic compound according to any one of claims 1 to 2.

8. The immersion cooling system of claim 7, wherein the chlorinated fluorinated aromatic compound is present in the working fluid in an amount of at least 25 wt. %, based on the total weight of the working fluid.

9. The system of any one of claims 7 to 8, wherein the heat generating component comprises an electronic device.

10. The system of claim 9, wherein the electronic device comprises a computer server.

11. A thermal management system for a lithium-ion battery pack, the thermal management system comprising: Lithium-ion battery pack; and a working fluid in thermal communication with the lithium-ion battery pack; The working fluid comprises the chlorinated fluorine-containing aromatic compound according to any one of claims 1 to 2.

12. A chlorinated fluorinated aromatic compound having the structural formula (II): Where G' is an oxygen atom; R 1' is a perfluoroalkenyl group having 4 to 10 carbon atoms, wherein the perfluoroalkenyl group is a perfluoro straight-chain alkenyl group or a perfluoro branched-chain alkenyl group; Each R 2' are independently hydrogen atoms; x' is 2 to 4; and a', b' and c' are independently 0 or 1, The chlorinated fluorine-containing aromatic compound is prepared by nucleophilic displacement of fluoride ions from fluoroolefins using 4-chlorophenolate ions or 3,5-dichlorophenolate ions.

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