Compositions and methods for producing HFO-153-10MZZ and HFO-153-10MCZZ

Abstract

The method for producing a fluoroolefin comprises the steps of: n F 2n+1 CH=CHC 4-n F 9-2n in the presence of a sufficient amount of a first catalyst to form a composition comprising a compound of formula (1): n F 2n+1 CX 1 =CClC 4-n F 9-2n wherein n is 1 or 2; X 1 is H or Cl. In some embodiments, the method also includes hydrodechlorinating a compound of formula (1) by reacting CF 3 CCl=CClCF 3 or CF 3 CCl=CHCF 3 CF 2 =CF 2 In other embodiments, the method also includes contacting a compound of formula (1) with C under conditions sufficient to form a composition comprising the compound of formula (1). 2 F 5 CCl 3 In other embodiments, the method comprises coupling 2 F 5 CCl 3 in the presence of a sufficient amount of a second catalyst to form a composition comprising 2 F 5 CH 3 The method further comprises chlorinating

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) This application claims the benefit of priority to U.S. Provisional Application No. 63 / 313,773, filed February 25, 2022, and U.S. Provisional Application No. 63 / 444,716, filed February 10, 2023. The disclosures of the aforementioned commonly-assigned applications are incorporated herein by reference.

[0002] FIELD OF THEINVENTION The present disclosure relates to the production of fluorinated alkene compounds. More specifically, the present disclosure relates to hydrofluoroolefins (HFOs) E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (HFO-153-10mczz, C2F5CH=CHCF2CF3) and 1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene (HFO-153-10mzz, C3F7CH=CHCF3). [Background technology]

[0003] Increasing societal awareness of the environmental impact of fossil fuel extraction, transportation, and use is creating new drivers for environmental sustainability in the form of regulation and reduction of atmospheric CO2 equivalent emissions. New working fluids with low Global Warming Potential (GWP) and Ozone Depletion Potential (ODP) for both existing and new applications in the temperature management segment are required to comply with these new regulations. Summary of the Invention [Means for solving the problem]

[0004] In one embodiment, a method for producing a fluoroolefin comprises the steps of: n F 2n+1 CX1=CClC 4-n F 9-2n(1), wherein n is 1 or 2 and X1 is H or Cl, is reacted with a compound of formula (2): n F 2n+1 CH=CHC 4-n F 9-2n (2) in the presence of a sufficient amount of a first catalyst to form a composition comprising the compound of formula (1).

[0005] The present invention includes the following aspects and embodiments.

[0006] In one embodiment, a method for producing fluoroolefins is disclosed herein. The method described herein includes hydrodechlorinating a compound of formula (1): CnF2n+1CX1=CClC4-nF9-2n(1), where n is 1 or 2 and X1 is H or Cl, in the presence of a first catalyst in an amount sufficient to form a composition comprising a compound of formula (2): CnF2n+1CH=CHC4-nF9-2n(2).

[0007] Also disclosed herein, in accordance with the foregoing embodiments, is a method wherein the hydrodechlorinating occurs in the gas phase.

[0008] Also disclosed herein, according to any of the preceding embodiments, is a method, wherein the first catalyst comprises a palladium catalyst.

[0009] Also disclosed herein is a method, according to any of the preceding embodiments, where n is 1 and X1 is Cl.

[0010] Also disclosed herein, according to any of the preceding embodiments, is a method, wherein the compound of formula (2) is unbranched.

[0011] Also disclosed herein, according to any of the foregoing embodiments, is a method further comprising contacting CF3CCl=CClCF3 with CF2=CF2 in the presence of a sufficient amount of a second catalyst to form a composition comprising a compound of formula (1).

[0012] Also disclosed herein, in accordance with the foregoing embodiments, is a method wherein the contacting occurs in the gas phase.

[0013] Also disclosed herein, according to any of the preceding embodiments, is a method, wherein the second catalyst comprises aluminum chlorofluoride.

[0014] According to any of the foregoing embodiments, the aluminum chlorofluoride has the formula AlCl x F 3-x Also disclosed herein is a method having the formula:

[0015] According to any of the foregoing embodiments, also disclosed herein is a method of forming CF3CCl=CClCF3 as an intermediate in the production of Z-CF3-CH=CH-CF3 by coupling 1,1,1-trichloro-2,2,2-trifluoroethane (CFC-113a) in the presence of a ruthenium catalyst supported on SiC, as disclosed, for example, in WO 2015 / 120250.

[0016] Also disclosed herein is a method, according to any of the preceding embodiments, where n is 1 and X1 is H.

[0017] Also disclosed herein, according to any of the foregoing embodiments, is a method further comprising contacting CF3CCl=CHCF3 with CF2=CF2 in the presence of a sufficient amount of a second catalyst to form a composition comprising a compound of formula (1).

[0018] Also disclosed herein, in accordance with the foregoing embodiments, is a method wherein the contacting occurs in the gas phase.

[0019] Also disclosed herein, according to any of the preceding embodiments, is a method, wherein the second catalyst comprises SbF5.

[0020] According to any of the foregoing embodiments, also disclosed herein is a method of forming CF3CCl=CHCF3 as an intermediate in the production of Z-CF3-CH=CH-CF3 by contacting CF3CCl=CClCF3 with hydrogen in the presence of a catalyst comprising copper, e.g., as disclosed in WO 2015 / 120250.

[0021] Also disclosed herein is a method, according to any of the preceding embodiments, where n is 2.

[0022] Also disclosed herein is a method, according to any of the preceding embodiments, where X1 is Cl.

[0023] Also disclosed herein, according to any of the preceding embodiments, is a method, further comprising coupling C2F5CCl3 under conditions sufficient to form a composition comprising a compound of formula (1).

[0024] Also disclosed herein, in accordance with the foregoing embodiments, is a method wherein the coupling occurs in the gas phase.

[0025] Also disclosed herein is a method, according to any of the preceding embodiments, wherein the coupling is carried out at a temperature of about 130° C.

[0026] Also disclosed herein, according to any of the foregoing embodiments, is a method further comprising chlorinating C2F5CH3 in the presence of a sufficient amount of a second catalyst to form a composition comprising C2F5CCl3.

[0027] Also disclosed herein, according to any of the preceding embodiments, is a method, wherein the second catalyst comprises SbF5.

[0028] Also disclosed herein, according to any of the foregoing embodiments, is a method in which C2F5CH3 is formed as a by-product in the production of CF3-CF=CH2.

[0029] Also disclosed herein are compositions formed by any of the aforementioned methods, according to any of the aforementioned embodiments.

[0030] In some embodiments, the compound of formula (2) includes E-C3FCH=CHC2F5 (E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene, E-HFO-153-10mczz).

[0031] According to certain embodiments, a composition for use as a working fluid or heat exchange fluid comprises one of CF3CCl=CHC3F7 (2-chloro-1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene), CF3CCl=CClC3F7 (2,3-dichloro-1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene), C2F5CCl=CClC2F5 (3,4-dichloro-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene), CF3CH=CHC3F7 (1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene, HFO-153-10mzz), alone or in combination with each other, and optionally other HFCs, HFOs, HCFOs.

[0032] According to other embodiments, compositions for use as working fluids or heat exchange fluids include one or more of the compounds identified in Table 1, alone or in combination with each other, and optionally including other HFCs, HFOs, and HCFOs.

[0033] The embodiments disclosed herein may be used alone or in various combinations with other embodiments. Other features and advantages of the present invention will become apparent from the following more detailed description, illustrating by way of example the principles of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0034] A synthetic method for producing fluorinated alkenes is provided that overcomes the above limitations.

[0035] For example, embodiments of the present disclosure provide a method for producing fluorinated alkenes. More specifically, the present disclosure provides a method for producing fluorinated alkenes having perfluorinated alkyl chains. The resulting fluorinated alkenes are environmentally friendly, exhibit low GWP and low ozone depletion potential (ODP), are non-flammable, non-conductive, and exhibit low liquid viscosity.

[0036] In some embodiments, the compound of formula (1): n F 2n+1 CX1=CClC 4-n F 9-2n A compound of formula (1), where n is 1 or 2 and X1 is H or Cl, is charged to a reactor in the presence of a first catalyst, heated, and contacted with hydrogen gas. The reactor temperature and pressure are adjusted to react with the first catalyst to produce a compound of formula (2): n F 2n+1 CH=CHC 4-n F 9-2n (2) is maintained at a level sufficient to result in the formation of a composition containing the compound.

[0037] In some embodiments, the compound of formula (3): n F 2n+1 CCl2CCl2C 4-n F 9-2n (3), n is 1. The compound has the formula (2): n F 2n+1 CH=CHC 4-n F 9-2n (2) is hydrodechlorinated in the presence of a sufficient amount of a catalyst to form a composition comprising the compound of formula (1).

[0038] The disclosed methods and compositions may include one or more of the compounds of formula (1) and formula (2). Each of these compounds has an E isomer form and a Z isomer form. As used herein, when the form is not specified, the composition may include the E isomer, the Z isomer, or any combination thereof.

[0039] In some embodiments, the E isomer is preferred. In some embodiments, the starting materials and / or process conditions are selected to increase the formation of the E isomer over the Z isomer. In some embodiments, the process includes separating the E isomer from the Z isomer.

[0040] In some embodiments, the reaction occurs in the gas phase.

[0041] In some embodiments, the first catalyst comprises palladium.

[0042] In some embodiments, the compounds of formula (1) and (2) are unbranched.

[0043] In some embodiments, n is 1, X1 is Cl, and CF3CCl=CClCF3 is charged to a reactor, heated, and contacted with CF2=CF2 in the presence of a second catalyst. The reactor temperature and pressure are maintained at levels sufficient to effect the formation of a composition comprising the compound of formula (1) in the presence of the second catalyst.

[0044] In some embodiments, the reaction occurs in the gas phase.

[0045] In some embodiments, the second catalyst comprises aluminum chlorofluoride.

[0046] In some embodiments, the aluminum chlorofluoride has the formula AlCl x F 3-x where x is in the range of 0.05 to 0.3.

[0047] In some embodiments, CF3CCl=CClCF3 is formed as an intermediate in the production of Z-CF3CH=CHCF3 (Z-HFO-1336mzz) by coupling 1,1,1-trichloro-2,2,2-trifluoroethane (CFC-113a) in the presence of a ruthenium catalyst. In some embodiments, the ruthenium catalyst is supported on SiC.

[0048] In some embodiments, n is 1, X1 is H, and CF3CCl=CHCF3 is charged to a reactor, heated, and contacted with CF2=CF2 in the presence of a second catalyst. The reactor temperature and pressure are maintained at levels sufficient to effect the formation of a composition comprising the compound of formula (1) in the presence of the second catalyst.

[0049] In some embodiments, the reaction occurs in the gas phase.

[0050] In some embodiments, the second catalyst comprises SbF5.

[0051] In some embodiments, CF3CCl=CHCF3 is formed as an intermediate in the production of Z-CF3CH=CHCF3 by contacting CF3CCl=CClCF3 with hydrogen in the presence of a copper-containing catalyst, which may be selected from the group consisting of copper on carbon, nickel on carbon, copper and nickel on carbon, and copper and palladium on carbon.

[0052] In some embodiments, n is 2, X1 is Cl, and C2F5CCl3 is charged to a reactor and heated. The temperature and pressure of the reactor are maintained at a level sufficient to effect the coupling of C2F5CCl3 to form a composition comprising the compound of formula (1). In some embodiments, C2F5CH3 is charged to a reactor, heated, and contacted with chlorine gas in the presence of a second catalyst. The temperature and pressure of the reactor are maintained at a level sufficient to effect the formation of a composition comprising C2F5CCl3 in the presence of a second catalyst.

[0053] In some embodiments, the reaction occurs in the gas phase.

[0054] In some embodiments, the second catalyst comprises SbF5.

[0055] In some embodiments, C2F5CH3 is formed as a by-product in the production of CF3-CF=CH2 (HFO-1234yf).

[0056] In some embodiments, the compound of formula (1) includes CF3CCl=CHC3F7 (2-chloro-1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene).

[0057] In some embodiments, the compound of formula (1) includes CF3CCl=CClC3F7 (2,3-dichloro-1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene).

[0058] In some embodiments, the compound of formula (1) includes C2F5CCl=CClC2F5 (3,4-dichloro-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene, CFO-151-10mcxx).

[0059] In some embodiments, the compound of formula (2) comprises CF3CH=CHC3F7 (1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene, HFO-153-10mzz).

[0060] In some embodiments, the compound of formula (2) comprises C2F5CH=CHC2F5(1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene, HFO-153-10mczz). In some embodiments, C2F5CH=CHC2F5 comprises E-C2F5CH=CHC2F5(E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene, E-HFO-153-10mczz).

[0061] In some embodiments, the compound formed by hydrodechlorinating the compound of formula (1) comprises C2F5CCl=CHCF2CF3H (HCFO-152-10mcxz).

[0062] In some embodiments, the compound formed by hydrodechlorinating the compound of formula (1) comprises C2F5-CCl=CClC2F5 (CFO-151-10mcxx).

[0063] In some embodiments, the compound formed by hydrodechlorinating the compound of formula (1) comprises C2F5-CH=CHC2F5 (HFO-153-10mczz).

[0064] In some embodiments, compounds formed by hydrodechlorinating compounds of formula (1) include a mixture of HCFO-152-10mcxz, CFO-151-10mcxx, and HFO-153-10mczz.

[0065] In some embodiments, the reacting step is carried out in a closed system. In some embodiments, the catalyst for the reacting step is a Lewis acid. In some embodiments, the Lewis acid is a strong Lewis acid. In one embodiment, the catalyst is aluminum chloride (AlCl3), or antimony pentafluoride (SbF5), or aluminum chlorofluoride (AlCl4). x F 3-x Or formula (4): SBCl x F5 - x In some embodiments, x can be an integer from 1 to 3. In some embodiments, x can be from 0.01 to 0.5. In some embodiments, x can be from 0.05 to 0.3. Additional suitable strong Lewis acids can be found in Krespan et al., "The Chemistry of Highly Fluorinated Carbocations," Chemical Reviews, Vol. 96, pp. 3269-3301, 1996, which is incorporated herein by reference.

[0066] The process may be carried out in any reactor suitable for gas phase fluorination reactions. The reactor is fabricated from a material that is resistant to the reactants used. The reactor may be constructed from a material that is resistant to the corrosive effects of hydrogen fluoride, such as stainless steel, Hastelloy® alloy, Inconel® alloy, Monel® alloy, gold, gold-plated material, or quartz. The reaction may be carried out batchwise, continuously, semi-continuously, or a combination thereof. Suitable reactors include batch reactors and tubular reactors.

[0067] In some embodiments, the reaction mixture is heated to sub-ambient, ambient, or super-ambient temperatures. In some embodiments, the reaction mixture is heated to a temperature between -50°C and 50°C. In some embodiments, the reaction mixture is heated to a temperature between -50°C and 25°C. In some embodiments, the reaction mixture is heated to a temperature between 50°C and 100°C. In some embodiments, the reaction mixture is heated to a temperature between 100°C and 150°C.

[0068] In some embodiments, the reacting step is carried out at a reactor pressure of 0.1 pounds per square inch gauge (psig) (690 Pa) to 300 pounds per square inch gauge (psig) (2.07 MPa). In some embodiments, the reacting step is carried out under autogenous pressure.

[0069] In some embodiments, the reacting step is carried out in the presence of a solvent. In some embodiments, the solvent is a perfluorinated saturated compound. In some embodiments, the perfluorinated saturated compound may include perfluoropentane, perfluorohexane, cyclic dimers of hexafluoropropene (mixtures of perfluoro-1,2-dimethylcyclobutane and perfluoro-1,3-dimethylcyclobutane), and combinations thereof.

[0070] In some embodiments, the hydrodechlorination is carried out in the presence of a catalyst.

[0071] In some embodiments, the hydrodechlorination is carried out in the presence of a Pd-containing catalyst.

[0072] In some embodiments, the hydrodechlorination is carried out in the presence of a Pd-Cu supported on activated carbon catalyst.

[0073] The compound of formula (2) may be isolated and optionally purified prior to use. Suitable applications of the compound of formula (2) may include, but are not limited to, working fluids in systems utilizing thermodynamic cycles, cooling media, specialty fluids for thermal management, immersion cooling fluids, reactive intermediates, refrigerants, heat transfer fluids with or without phase change, carrier fluids, or solvents.

[0074] The good dielectric properties and suitable boiling point make the compound of formula (2) a potential candidate for use as a cooling medium for Lithium-ion Batteries (LiBs) in automobiles.

[0075] In other exemplary embodiments, the properties of the compounds of formula (2) provide benefits in carrier fluid applications: the compounds of formula (2) exhibit favorable properties that allow them to provide conventional carrier fluid behavior for the deposition or removal of soluble compounds, readily dissolving, transporting, and / or depositing certain media.

[0076] In other exemplary embodiments, the compound of formula (2) is used as a solvent for any of a number of different applications. For example, the properties of the compound of formula (2) may be beneficial in solvent cleaning applications. Additional solvent-based applications of the compound of formula (2) include as a fluid for removing particulates, grease, oil, and contaminants. The compound of formula (2) may also be used as a solvent in a variety of applications, such as cleaning (vapor degreasing, flux removal).

[0077] In an exemplary embodiment, the compounds of formula (2) function as specialty fluids for thermal management with a slightly elevated boiling range, where the products are environmentally friendly (low GWP and low ODP), non-flammable, non-conductive, have low liquid viscosity.

[0078] The compound of formula (2) may also be used as a working fluid for immersion cooling, which may be two-phase immersion cooling or single-phase immersion cooling.

[0079] Two-phase immersion cooling is an emerging cooling technology for the high-performance cooling market as applied to high-performance server systems. Its cooling relies on heat absorbed in the process of vaporizing the immersion cooling fluid into a gas. The fluid used in this application must meet certain requirements to be viable in use. For example, the boiling point of the fluid should be in the range of 30-75°C. In general, this range accommodates maintaining a sufficiently cool temperature for the server components while allowing the generated heat to be sufficiently dissipated to an external heat sink. Alternatively, the operating temperature of the server and immersion cooling system can be increased or decreased by using a closed system and increasing or decreasing the pressure within the system to increase or decrease the boiling point of a given fluid.

[0080] Single-phase immersion cooling has a long history in cooling computer servers. In single-phase immersion cooling, there is no phase change. Instead, the liquid warms as it circulates through the computer server and / or heat exchanger, and is then pumped through the heat exchanger for cooling before returning to the server, thereby transferring heat away from the computer server. Fluids used in single-phase immersion cooling have the same requirements as in two-phase immersion cooling, except that their boiling points are typically higher than 30-75 °C to reduce evaporative losses.

[0081] In an exemplary embodiment, the compound of formula (2) functions as an immersion cooling fluid having an operating temperature range close to ambient temperature. Embodiments of the present disclosure provide an immersion cooling fluid for thermal management that is environmentally friendly (i.e., has a low global warming potential (GWP) and a low ozone depletion potential (ODP)) compared to, for example, concepts that do not include one or more of the features disclosed herein.

[0082] In an exemplary embodiment, the immersion cooling fluid cools the heat generating components of the device by at least partially immersing the heat generating components in the immersion cooling fluid in a liquid state such that heat is conducted away from the heat generating components using the immersion cooling fluid. Such devices may include, but are not limited to, high capacity energy storage devices, electrical components, mechanical components, and optical components. Suitable devices may 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, fuel cells, electrochemical cells, and energy storage devices such as batteries.

[0083] Opportunities for compounds of formula (2) as new working fluids potentially exist in a variety of heat transfer applications including, but not limited to, cooling power electronics, e.g., televisions, cell phones, monitors, drones, and avionics equipment, battery thermal management in both automotive and stationary systems, powertrains for electronic vehicles, Insulated-Gate Bipolar Transistors (IGBTs), electronic devices-data center servers, computer server systems, telecommunications infrastructure, 5G networks, displays, military electronics, High Temperature mechanical compression Heat Pumps (HTHPs), Organic Rankine Cycles (ORCs), and anywhere a working fluid provides a medium for transporting heat or where there is passive evaporative cooling, such as, for example, heat pipes.

[0084] The compounds of formula (2) may be used in many applications for the transfer of heat, for example as heat transfer fluids or refrigerants. In one embodiment, the compounds of formula (2) may be used to transfer heat from an article. The article may be contacted with a heat transfer medium comprising the compound of formula (2).

[0085] The compounds of formula (2) may be used in a variety of applications, for example as working fluids. The working fluid provides a medium for transporting heat or for expanding to generate power through mechanical means. The working fluid is typically in a liquid state in a first region. The working fluid absorbs heat in the first region, vaporizes, and travels to a second region having a lower temperature where it condenses. The working fluid is typically returned to the first region after condensation, allowing the heat transfer cycle to repeat. The working fluid may be used in conjunction with compression systems, expansion systems, pumps, or passive evaporative cooling such as heat pipes or thermosiphons.

[0086] In use, the working fluid in the first region is exposed to a higher (first) temperature and the working fluid is vaporized, absorbing thermal energy. The vaporized working fluid travels to a second region that is at a lower (second) temperature than the first region. The working fluid condenses in the second region, releasing thermal energy that is transported out of the system. The working fluid is then returned to the first region. The working fluid typically travels in a cyclical manner between the first and second regions, transporting thermal energy between the first and second regions.

[0087] The working fluid is selected to undergo a phase transition from a liquid to a gaseous state over a desired operating temperature range of a system, such as, for example, a heat pipe or thermosiphon. In some embodiments, the composition of the working fluid comprises a compound of formula (2). In some embodiments, the operating temperature is at least 0° C., at least 10° C., at least 20° C., at least 30° C., at least 40° C., at least 50° C., at least 60° C., at least 70° C., at least 80° C., at least 90° C., at least 100° C., less than 125° C., less than 120° C., less than 110° C., less than 100° C., less than 90° C., less than 75° C., less than 70° C., less than 65° C., less than 60° C., less than 55° C., and combinations thereof.

[0088] The ability of a working fluid to transport heat is related to the working fluid's heat of vaporization. The greater the working fluid's heat of vaporization, the greater the amount of energy it absorbs, transports across the heat pipe during vaporization, and releases during condensation. In some embodiments, the compound of formula (2) may exhibit a heat of vaporization of at least 35 kilojoules / mole (kJ / mol).

[0089] The working fluid may also be selected based at least in part on additional material properties. A working fluid having a lower viscosity will flow more easily between the two regions because the working fluid will condense and return to the first region. In some embodiments, the compound of formula (2) may exhibit a lower viscosity than water at the same temperature over the operating temperature range. In some embodiments, the compound of formula (2) may exhibit a viscosity of less than 0.5 centipoise at 55° C.

[0090] Compounds of formula (2) as working fluids for heat transfer applications may be selected based at least in part on the surface tension exhibited by the material. For example, in heat pipe applications, working fluids exhibiting high surface tension may be more easily transported between hot and cold regions. In some embodiments, the selection of wick materials may increase the rate at which condensed working fluid is returned to the hot region of the heat pipe. In some embodiments, the working fluid may exhibit a lower surface tension than water at the same temperature over the operating temperature range. In some embodiments, compounds of formula (2) may exhibit a surface tension of less than 64.5 dynes / cm at 70°C, less than 66.3 dynes / cm at 60°C, and / or less than 67.9 dynes / cm at 50°C.

[0091] The working fluid may also be selected based at least in part on other thermodynamic properties of the material. A working fluid that exhibits a lower specific heat and / or a lower heat transfer rate than water at the same temperature may enhance energy transport between the hot and cold regions of the heat pipe. In some embodiments, the working fluid may exhibit a specific heat of less than 4.2 J / gK. In some embodiments, the compound of formula (2) may exhibit a heat transfer rate of less than 0.6 W / mK at 20° C.

[0092] The working fluid may also be selected to exhibit a suitable dielectric constant for electrical applications. Generally, materials exhibiting a low dielectric constant enhance the electrical insulation of electrical components immersed therein. In some embodiments, the dielectric constant of the working fluid is less than about 8 over its operating frequency range (0-20 GHz). Suitable dielectric working fluids include compounds of formula (2) having a dielectric constant of less than 7.3, less than 5.5, less than 5.0, less than 4.0, less than 3.5, less than 2.7, less than 2.5, less than 2.0, less than 1.9, less than 1.8, or less than 1.5 over the operating frequency range (0-20 GHz). Other embodiments include compounds and mixtures thereof having a dielectric constant greater than 1.0 and less than 8.0, greater than 2.0 and less than 7.3, greater than 2.5 and less than 5.5, or greater than 3.5 and less than 5.0.

[0093] Table 1 shows certain properties relevant to working fluids for compounds of formula (2) compared to other similar compounds.

[0094] [Table 1] * Measured using ASTM D924 ** Calculated using conventional methods known in the art

[0095] Additional additives may be added to the working fluid. Suitable additives include linear hydrocarbons, linear halocarbons, cyclic hydrocarbons, cyclic halocarbons, heptafluorocyclopentane, alcohols (e.g., methanol, ethanol, isopropanol), ethers, halogenated ethers, ketones, and halogenated ketones. Examples of suitable additives include pentane (bp 36° C.), hexane (bp 69° C.), heptane (bp 98° C.), octane (bp 125° C.), cyclopentane (bp 49° C.), cyclohexane (bp 80° C.), cycloheptane (bp 118° C.), methylcyclobutane (bp 39° C.), and methylcyclopentane (bp 72° C.). Examples of other suitable additives include diethyl ether (bp 35° C.), diisopropyl ether (bp 69° C.), C4F9OCH3 (CAS Registry No. 163702-07-6), C4F9OCH2CH3 (CAS Registry No. 163702-05-4), i-C4F9OCH2CH3 (CAS Registry No. 163702-06-5), and C3F7OCH3 (CAS Registry No. 375-03-1), as well as fluids containing (CF3)2CFCF(OCH3)CF2CF3 (73DE, CAS Registry No. 132182-92-4) and (CF3)2CFCF(OCH2CH3)CF2CF2CF3 (HFE7500, CAS Registry No. 29 7730-93-9), 1,1,1,2,3,3-hexafluoro-4-(1,1,2,3,3,3-hexafluoropropoxy)pentane (HFE7600, CAS Registry Number 870778-34-0), furan, 2,3,3,4,4-pentafluorotetrahydro-5-methoxy-2,5-bis[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]- (HFE7700, CAS Registry Number 812-05-4), and 1,1,1,2,4,4,5,5,5-nonafluoro-(2-trifluoromethyl)-3-pentanone (Novec™ 1230, CAS Registry Number 756-13-8).

[0096] The following examples illustrate certain embodiments of the invention and are not intended to limit the scope of the appended claims. EXAMPLES

[0097] Illustrative examples of the formation of compounds of formula (2) are provided below.

[0098] Example 1 A two-step reaction to form HFO-153-10mzz starting from CFO-1316mxx HFO-153-10mzz was formed by reacting CFO-1316mxx with tetrafluoroethylene (TFE) to form 2,3-dichloro-1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene, which was subsequently hydrodechlorinated to form HFO-153-10mzz.

[0099] Reaction of CFO-1316mxx with TFE catalyzed by aluminum chlorofluoride (ACF)

[0100] [ka]

[0101] In the first reaction step, CFO-1316mxx is combined with TFE in a gas phase reaction catalyzed by aluminum chlorofluoride to form 2,3-dichloro-1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene in at least 48% yield. In some embodiments, the reaction occurs under conditions described by Krespan et al., "Fluoroolefin condensation catalyzed by aluminum chlorofluoride," Journal of Fluorine Chemistry, Vol. 77, pp. 117-126, 1996, which is incorporated herein by reference.

[0102] Hydrodechlorination of 2,3-dichloro-1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene

[0103] [ka]

[0104] In the second reaction step, 2,3-dichloro-1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene is hydrodechlorinated in a gas phase reaction over a palladium catalyst to form HFO-153-10mzz.

[0105] Example 2 A two-step reaction to form HFO-153-10mzz starting from HCFO-1326mxz HFO-153-10mzz can be formed by gas phase reaction of HCFO-1326mxz with TFE to form 2-chloro-1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene, followed by gas phase hydrodechlorination of 2-chloro-1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene to form HFO-153-10mzz.

[0106] Reaction of HFO-1326mxz with TFE catalyzed by SbF5

[0107] [ka]

[0108] In the first reaction step, HFO-1326mxz was reacted with TFE in the presence of antimony pentafluoride (SbF5) catalyst to form a mixture of CF3CCl=CHCF2C2F5 and C2F5(CF3)CClCH=CFC2F5. A 400 mL Hastelloy® shaker tube was charged with 6 g (0.028 mol) SbF5, the shaker tube was cooled in dry ice, evacuated, and charged with 60 g (0.3 mol) HCFO-1326mxz (CF3CH=CClCF3) and 50 g (0.5 mol) TFE. The tube was placed in a blast-proof wall, warmed to room temperature, and continued to stir for 16 hours. 100 mL water was injected into the shaker tube, the tube was cooled in ice, evacuated, and the contents were removed. The organic layer was separated, dried over MgSO4, and filtered to give 85 g of crude product, which contained 50% HCFO-1326mxz, 37% CF3CCl=CHC3F7, and 13% HCFO-1326 / TFE 1:2 adduct (GC (Gas Chromatography) / MS (Mass Spectrometry)).

[0109] The crude reaction mixture was fractionated to give 39 g of a fraction boiling at 80-86 °C (79% yield of 2-chloro-1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene at 50% conversion of HCFO-1326mxz), which was identified as a mixture of E-CF3CCl=CHCF2CF3 and Z-CF3CCl=CHCF2CF3 in the ratio 65:35, together with 10 g of a higher boiling fraction (1:2 adducts, GC / MS).

[0110] E-CF3CCl=CHC3F7: 19 F NMR (CDCl3): -70.98 (3F, s), -80.67 (3F, t, 8.9Hz), -111.64 (2F, sixt.10.5Hz), -127.16 (2F, q, 4.0Hz)ppm 1 H NMR(CDCl3):6.59(t, 12.3Hz)ppm Z-CF3CCl=CHC3F7: 19 F NMR (CDCl3): -63.64 (3F, tt, 17.7, 4.0Hz), -80.52 (3F, t, 10.5), -107.20(2F, m), -127.76(2F, s)ppm 1 H NMR(CDCl3): 1 H NMR(CDCl3):6.41(t, 14.5Hz)ppm GC / MS (m / z, mixture of isomers): 298 (M + , C6HClF 10 + ) 1:2 -C2F5CF=CHCCl(CF3)CF2CF3 adduct (major isomer): bp 105-109°C (estimated).

[0111] 19 F NMR (CDCl3): -71.83 (3F, dm, 12.1Hz), -78.24 (3F, m), -83.96 (3F, dt, 6.1, 1.8Hz), -108.55 (1F, m), -115.92 (2F, AB quart., J d =296.7Hz), -122.32(2F, ddq, 13.0, 10.8, 2.1Hz)ppm 1 H NMR(CDCl3):5.84(d, 27.6Hz)ppm GC / MS (m / z, mixture of isomers): 398 (M + , CHClF 14 + ).

[0112] Hydrodechlorination of 2-chloro-1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene

[0113] [ka]

[0114] In the second reaction step, 2,3-dichloro-1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene is hydrodechlorinated in a gas phase reaction over a palladium catalyst to form HFO-153-10mzz.

[0115] Example 3 A three-step reaction to form HFO-153-10mczz starting from HFC-245cb HFO-153-10mczz can be formed by chlorination of HFC-245cb to form CFC-215cb, followed by a coupling reaction of CFC-215cb to form 3,4-dichloro-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene, followed by hydrodechlorination of 3,4-dichloro-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene to form HFO-153-10mczz.

[0116] Chlorination of HFC-245cb

[0117] [ka]

[0118] In the first reaction step, HFC-245cb is chlorinated in a vapor phase reaction to form CFC-215cb.

[0119] CFC-215cb coupling

[0120] [ka]

[0121] In the second reaction step, CFC-215cb is coupled in a gas phase reaction at 130° C. in the presence of a 2% Ru / SiC catalyst to form 3,4-dichloro-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene in at least 86% yield.

[0122] Hydrodechlorination of CFO-151-10mcxx

[0123] [ka]

[0124] In the third reaction step, 3,4-dichloro-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (CFO-151-10mcxx) is hydrodechlorinated in a gas phase reaction to form HFO-153-10mczz using a palladium catalyst.

[0125] Although the present invention has been described with reference to one or more embodiments, it will be understood by those skilled in the art that various changes can be made without departing from the scope of the invention and that equivalents can be substituted for the elements. It is to be understood that many modifications can be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope of the invention. Therefore, it is not intended that the invention be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but the invention is intended to include all embodiments falling within the scope of the appended claims. It is to be understood that all numerical values ​​specified in the detailed description should be interpreted as if both exact and approximate values ​​were explicitly specified.

[0126] Example 4 Hydrodechlorination of CFC-51-10mcaa using 1% Ir / C catalyst 10 mL of 1% Ir / C catalyst was loaded into a Monel 400 reactor with a length of 12 inches and an outer diameter of ½ inch. After purging the reactor with N to remove air, the catalyst was activated with H for 8 hours at 250° C. Then, CFC-51-10mcaa and H were fed into the reactor at a pressure of 150 psi, an organic flow rate of 0.86 cc / hr, and an H flow rate of 17.9 sccm.

[0127] [ka]

[0128] The reactor effluent was analyzed by online GC-MS-FID.

[0129] Example 5 Synthesis of HFO-153-10mczz with 0.6% Pd / 5.5% Cu activated carbon

[0130] [ka]

[0131] An Inconel (0.5 inch OD) tubular reactor was loaded with 6 cc of 0.6% Pd / 5.5% Cu (on activated carbon) and pretreated with H2 according to Table 2 below.

[0132] [Table 2]

[0133] Liquid CFC-51-10mcaa (CF3-CF2-CCl2-CCl2-CF2-CF3) was fed into a heated chamber at a temperature where it was vaporized and mixed with H2 to form a CFC-51-10mcaa / H2 reaction mixture. Then, 0.3 ml / hr of the reaction mixture of CFC-51-10mcaa and 5.5 sccm of H2 was passed through a tubular reactor containing the H2-treated Pd-Cu / C catalyst. A portion of the reactor effluent was passed through a series of valves and analyzed by GCMS (Gas Chromatography and Mass Spectroscopy). The reaction conditions and results are listed in Table 3 below.

[0134] [Table 3] * Combined intermediates and by-products

[0135] Legend-CFC-51-10mcaa, CF3-CF2-CCl2-CCl2-CF2-CF3 HCFO-152-10mcxz, CF3-CF2-CCl=CH-CF2-CF3 CFO-151-10mcxx, CF3-CF2-CCl=CCl-CF2-CF3 HFO-153-10mczz, CF3-CF2-CH=CH-CF2-CF3 (1,1,1,2,2,5,5,6,6,6-Decafluorohex-3-ene)

[0136] Other embodiments E-C2F5CF = Working fluid containing CFC2F5 (FO-151-12mcyyE).

[0137] A working fluid containing E-C2F5CH=CHC2F5 (HFO-153-10mczzE).

[0138] A working fluid containing C3F7CH=CHCF3 (HFO-153-10mzz).

[0139] A working fluid containing (CF3)2CFCH=CHCF3 (HFO-153-10mzzy).

[0140] A working fluid containing Z-C2F5CF = CFC2F5 (FO-151-12mcyyZ).

[0141] While certain aspects, embodiments, and principles have been described above, it is understood that this description is made by way of example only and does not limit the scope of the invention or the appended claims. The various aspects, embodiments, and principles described above can be used alone and in combination with each other.

Claims

1. 1. A method for producing fluoroolefins, comprising: Equation (1): C n F 2n+1 CX 1 =CClC 4-n F 9-2n (1) wherein n is 1 and X 1 is H or Cl, Equation (2): C n F 2n+1 CH=CHC 4-n F 9-2n (2) and hydrodechlorinating in the presence of a sufficient amount of a first catalyst to form a composition comprising the compound of said hydrodechlorinating occurring in the gas phase; the first catalyst comprises a palladium catalyst; A method for producing fluoroolefins.

2. X 1 The method of claim 1 , wherein is Cl.

3. A method for producing a catalyst comprising the steps of: (a) reacting a catalyst containing aluminum chlorofluoride with a catalyst having the formula AlCl x F 3-x, where x is in the range of 0.05 to 0.3; CF 3 CCl=CClCF 3 CF 2 =CF 2 3. The method of claim 2, further comprising contacting a compound of formula (1) with a compound of formula (1).

4. X 1 The method of claim 1 , wherein

5. In the presence of a second catalyst comprising antimony pentafluoride (SbF 5 ), CF 3 CCl=CHCF 3 CF 2 =CF 2 5. The method of claim 4, further comprising contacting a compound of formula (1) with a