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• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
  • C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
  • C07C17/278—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of only halogenated hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C21/00—Acyclic unsaturated compounds containing halogen atoms
  • C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
  • C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
  • C09K5/02—Materials undergoing a change of physical state when used
  • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
  • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
  • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
  • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
  • C09K5/08—Materials not undergoing a change of physical state when used
  • C09K5/10—Liquid materials
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
  • C09K2205/10—Components
  • C09K2205/12—Hydrocarbons
  • C09K2205/126—Unsaturated fluorinated hydrocarbons

Definitions

• the present disclosure is directed to the production of fluorinated alkene compounds. More specifically, the present disclosure is directed to the production of the hydrofluoroolefins (HFOs) E'-l,l,l,2,2,5,5,6,6,6-decafluoro-3-hexene (HFO-153- lOmczz; C2F5CFHCHCF2CF3) and l,l,l,4,4,5,5,6,6,6-decafluoro-2-hexene (HFO-153- lOmzz; C3F7CHCHCF3).
• HFOs hydrofluoroolefins
• the first catalyst comprises a palladium catalyst.
• the second catalyst comprises aluminum chlorofluoride.
• the aluminum chlorofluoride has the formula A1C1 X F3- X , wherein x is in the range of 0.05 to 0.3.
• CFC-113a 1, 1, l-trichloro-2,2,2-trifluoroethane
• the second catalyst comprises SbFv
• the second catalyst comprises Sb .
• compositions formed by any of the foregoing methods are also disclosed herein.
• the compound of formula (2) comprises E- C3FCH-CHC2F5 (E-l,l,l,2,2,5,5,6,6,6-decafluoro-3-hexene; E-HFO-153-10mczz).
• composition for use as a working fluid or heat exchange fluid comprises one or more of the compounds identified in Table 1, alone or in combination with one another, optionally including other HFCs, HFOs, and HCFOs.
• Embodiments of the present disclosure provide methods for the production of fluorinated alkenes. More specifically, the present disclosure provides methods for the production of fluorinated alkenes having a perfluorinated alkyl chain.
• the resulting fluorinated alkenes are environmentally friendly, exhibiting a low GWP and low ozone depletion potential (ODP), non-flammable, non-conductive, and exhibit low liquid viscosities.
• Methods and compositions of the present disclosure may include one or more of a compound of formula (1) and a compound of formula (2). Each of these compounds has an E isomeric form and a Z isomeric form. As used herein, when the form is unspecified, the composition may include the E isomer, the Z isomer, or any combination thereof.
• the E isomer is preferred.
• starting materials and/or method conditions are selected to increase formation of the E isomer over the Z isomer.
• the method includes separating the E isomer from the Z isomer.
• the reaction occurs in the vapor phase.
• the first catalyst includes palladium.
• the compounds of formulas (1) and (2) are unbranched.
• the temperature and pressure of the reactor are maintained at levels sufficient to effect, in the presence of the second catalyst, the formation of a composition including a compound of formula (1).
• the reaction occurs in the vapor phase.
• the second catalyst includes aluminum chlorofluoride.
• the aluminum chlorofluoride has the formula AlCkFs-x, wherein x is in the range of 0.05 to 0.3.
• the ruthenium catalyst is supported on SiC.
• n 1 and Xi is H
• the temperature and pressure of the reactor are maintained at levels sufficient to effect, in the presence of the second catalyst, the formation of a composition including a compound of formula (1).
• the reaction occurs in the vapor phase.
• the second catalyst includes SbF
• the catalyst comprising copper 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.
• n 2 and Xi is Cl
• C2F5CCI3 is charged to a reactor and heated. The temperature and pressure of the reactor are maintained at levels sufficient to effect coupling of the C2F5CCI3, the formation of a composition including a compound of formula (I).
• 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 levels sufficient to effect, in the presence of the second catalyst, the formation of a composition including C2F5CCI3.
• the reaction occurs in the vapor phase.
• the second catalyst includes SbFs.
• the compound of formula (1) comprises CF3CCM2HC3F7 (2-chloro-l,l,l,4,4,5,5,6,6,6-decafluoro-2-hexene).
• the compound of formula (1) comprises CF3COCCIC3F7 (2, 3 -di chloro- 1, 1 , 1 ,4,4,5,5,6,6,6-decafluoro-2-hexene).
• the compound of formula (1) comprises ChFjCCI ⁇ CCIChF, (3,4-dichloro-l,l,l,2,2,5,5,6,6,6-decafluoro-3-hexene; CFO-151- lOmcxx).
• the compound formed by hydrodechlorinating a compound of formula (1) comprises C2F5-COCCIC2F5 (CFO-151-10mcxx).
• the compound formed by hydrodechlorinating a compound of formula (1) comprises a mixture of HCFO-152-10mcxz, CFO-151- lOmcxx, and HFO-153-10mczz.
• a reaction step is conducted in a closed system.
• the catalyst for a reaction step is a Lewis acid.
• the Lewis acid is a strong Lewis acid.
• the catalyst is, aluminum chloride (Aids), or antimony pentafluoride (SbFs), or aluminum chlorofluoride AlClxFs-x or a compound of formula (4), SbCLFs-x.
• x may be an integer from 1 to 3.
• x may be 0.01 to 0.5.
• x may be 0.05 to 0.3. Additional suitable strong Lewis acids may be found in Krespan et al., “The Chemistry of Highly Fluorinated Carbocations”, Chemical Reviews, Vol. 96, pp. 3269- 3301, 1996, which is incorporated by reference herein.
• the process may be conducted in any reactor suitable for a vapor phase fluorination reaction.
• the reactor is made of a material that is resistant to the reactants employed.
• the reactor may be constructed from materials which are resistant to the corrosive effects of hydrogen fluoride such as stainless steel, a Hastelloy® alloy, an Inconel® alloy, a Monel® alloy, gold, gold-lined, or quartz.
• the reactions may be conducted batchwise, continuous, semi-continuous or combinations thereof. Suitable reactors include batch reactor vessels and tubular reactors.
• a reaction mixture is heated to a sub-ambient, ambient, or super-ambient temperature. In some embodiments, the reaction mixture is heated to a temperature of -50°C to 50°C. In some embodiments, the reaction mixture is heated to a temperature of -50°C to 25°C. In some embodiments, the reaction mixture is heated to a temperature of 50°C to I00°C. In some embodiments, the reaction mixture is heated to a temperature of 100°C to 150°C.
• a reaction step is performed at a reactor pressure of 0. 1 pound per square inch gauged (psig) (690 Pa) to 300 pounds per square inch gauged (psig) (2.07 MPa). In some embodiments, the reaction step is performed under autogenic pressure.
• a reaction step is conducted in the presence of a solvent.
• the solvent is a perfluorinated saturated compound.
• the perfluorinated saturated compound may include perfluoropentane, perfluorohexane, cyclic dimer of hexafluoropropene, (mixture of perfluoro- 1,2- and perfluoro-1,3- dimethylcyclobutanes), and combinations thereof.
• hydrodechlonnation is conducted in the presence of a catalyst.
• hydrodechlorination is conducted in the presence of a Pd containing catalyst.
• the hydrodechlorination is conducted in the presence of Pd-Cu supported on activated carbon catalyst.
• the compound of formula (2) may be isolated and optionally purified prior to use. Suitable uses of a compound of formula (2) may include, but are not limited to, a working fluid in a system utilizing a thermodynamic cycle, a cooling medium, a specialty fluid for thermal management, an immersion cooling fluid, a reactive intermediate, a refrigerant, a heat transfer fluid with or without phase change, a carrier fluid, or a solvent.
• the properties of a compound of formula (2) yield benefits in carrier fluid applications.
• a compound of formula (2) exhibits good characteristics to enable it to provide traditional carrier fluid behavior for the deposition or removal of soluble compounds, where it readily dissolves, transports, and/or deposits specified media.
• a compound of formula (2) is used as a solvent for any of a number of various applications.
• the properties of a compound of formula (2) may yield benefits in solvent cleaning applications.
• Additional solventbased of applications for a compound of formula (2) include as a fluid for removal of particulates, greases, oils, and contamination, a compound of formula (2) may also be used as solvents in various applications such as for cleaning (vapor degreasing, flux removal).
• a compound of formula (2) serves as a specialty fluid for thermal management, with slightly elevated boiling temperature ranges, where the product is environmentally friendly (low GWP and ODP), non-flammable, non- conductive, and has low liquid viscosities.
• a 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.
• Two-phase immersion cooling is an emerging cooling technology for the high- performance cooling market as applied to high performance server systems. It relies on the heat absorbed in the process of vaporizing a liquid immersion cooler fluid to a gas.
• the fluids used in this application must meet certain requirements to be viable in use.
• the boiling temperature of the fluid should be in the range between 30- 75°C. Generally, this range accommodates maintaining the server components at a sufficiently cool temperature while allowing generated heat to be dissipated sufficiently to an external heat sink.
• the operating temperature of the server, and the immersion cooling system could be raised or lowered, by using an enclosed system and raising or lowering the pressure within the system to raise or lower the boiling point of a given fluid.
• Single phase immersion cooling has a long history in computer server cooling. There is no phase change in single phase immersion cooling. Instead, the liquid warms as it circulates through the computer server and or heat exchanger, and then is circulated with a pump to a heat exchanger for cooling prior to returning to the server, thus transferring heat away from the computer server. Fluids used for single phase immersion cooling have the same requirements as those for two-phase immersion cooling, except that the boiling temperatures are typically higher than 30-75°C, to reduce loss by evaporation.
• a compound of formula (2) serves as an immersion cooling fluid having an operating temperature range near ambient temperatures.
• Embodiments of the present disclosure for example, in comparison to concepts failing to include one or more of the features disclosed herein, provide an immersion cooling fluid for thermal management which is environmentally friendly (i.e., have a low global warming potential (GWP) and low ozone depletion potential (ODP)).
• GWP global warming potential
• ODP ozone depletion potential
• the immersion cooling fluid cools a heat generating component by at least partially immersing the heat generating component of a device into the immersion cooling fluid in a liquid state such that heat is transferred from the heat generating component 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.
• Appropriate devices may include, but are not limited to, microprocessors, wafers used to manufacture semiconductor devices, power control semiconductors, electrical distribution switch gear, power transformers, circuit boards, multi-chip modules, packaged and unpackaged semiconductor devices, laser, fuel cells, electrochemical cells and energy storage devices such as batteries.
• cooling power electronics such as, for example, televisions, cell phones, monitors, drones, and avionics devices
• 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; telecommunication infrastructure; 5G network; displays; military electronics; high temperature mechanical compression heat pumps (HTHPs); Organic Rankine Cycles (ORCs); and anywhere a working fluid provides a medium to transport heat or in applications where passive evaporative cooling exists, such as, for example, heat pipes.
• a compound of formula (2) may be used in numerous applications for the transfer of heat, such as, heat transfer fluids or refrigerants.
• a compound of formula (2) may be used to transfer heat from an article.
• the article may be contacted with a heat transfer media including a compound of formula (2).
• a compound of formula (2) may be used in various applications including as working fluids.
• Working fluids provide the medium to transport heat or produce power by mechanical means by expansion.
• Working fluids are typically in the liquid state at a first region.
• the working fluid absorbs heat in the first region, vaporizes, and migrates 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 be repeated.
• Working fluids may be used in conjunction with compression, expansion systems, pumps, or in passive evaporative cooling such as heat pipes or thermosyphons.
• the working fluid in a first region is exposed to an elevated (first) temperature causing the working fluid to vaporize, thus absorbing thermal energy.
• the vaporized working fluid migrates to a second region, which is at a lower (second) temperature than the first region.
• the working fluid condenses in the second region, releasing the thermal energy, which is transported external to the system.
• the working fluid is subsequently returned to the first region.
• the working fluid typically cyclically moves between the first region and the second region, transporting thermal energy between the first region and the second region.
• Working fluids are selected to undergo a phase transition from the liquid to the gaseous state over the desired operational temperature range of a system, such as a heat pipe or thermosyphon.
• the composition of the working fluids includes a compound of formula (2).
• the operational 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.
• a compound of formula (2) may exhibit a heat of vaporization of at least 35 kilojoules per mole (kJ/mol).
• Working fluids may also be selected based at least partially on additional material properties. As the working fluids condense and return to the first region workings fluids having a lower viscosity more easily flow between the regions.
• a compound of formula (2) may exhibit a viscosity less than water of the same temperature, over the operational temperature range. In some embodiments, a compound of formula (2) may exhibit a viscosity of less than 0.5 centipoise at 55°C.
• a compound of fonnula (2) as a working fluid for heat transfer applications may be selected based at least partially on the surface tension exhibited by the material. For example, in heat pipe applications, working fluids exhibiting high surface tensions may be more easily transported between the hot region and the cool region. In some embodiments, the selection of the wick materials may enhance the rate at which the condensed working fluid is returned to the hot region of the heat pipe. In some embodiments, the working fluids may exhibit a surface tension less than water of the same temperature, over the operational temperature range.
• a compound of formula (2) may exhibit a surface tension of less than 64.5 dyne/cm at 70°C, less than 66.3 dyne/cm at 60°C, and/or less than 67.9 dyne/cm at 50°C.
• the working fluids may also be selected based at least partially on other thermodynamic properties of the materials.
• Working fluids exhibiting a lower specific heat and/or a lower thermal conductivity than water at the same temperature may enhance energy transport between the hot region and the cool region of a heat pipe.
• the working fluids may exhibit a specific heat of less than 4.2 Joules per gram Kelvin degree.
• a compound of formula (2) may exhibit a thermal conductivity of less than 0.6 watts per meter Kelvin degree at 20°C.
• the working fluids may also be selected to exhibit a dielectric constant suitable for electrical applications.
• materials exhibiting a low dielectric constant provide increased electrical isolation of the electrical components immersed therein.
• the dielectric constant of the working fluids is less than about 8 over the operational frequency range (0 to 20 GHz).
• Suitable dielectric working fluids include a compound of formula (2) having a dielectric constant over the operational frequency range (0 to 20 GHz) of less than 7.3, or less than 5.5, or less than 5.0, or less than 4.0, or less than 3.5, or less than 2.7, or less than 2.5, or less than 2.0, or less than 1.9, or less than 1.8, or less than 1.5.
• Other embodiments include compounds and mixtures having a dielectric constant greater than 1.0 and less than 8.0 or greater than 2.0 and less than 7.3 or greater than 2.5 and less than 5.5 or greater than 3.5 and less than 5.0.
• Table 1 shows certain properties relevant for working fluids for a compound of formula (2) compared to other similar compounds.
• 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.
• 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), methyl cyclobutane (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 163702-07-6), C4F9OCH2CH3 (CAS 163702-05-4); i-C 4 F 9 OCH 2 CH3 (CAS 163702-06-5), and C3F7OCH3 (CAS 375-03-1), as well as fluids including (CF3)2CFCF(OCH 3 )CF 2 CF3 (73DE, CAS 132182-92-4);
• HFO-153-10mzz was formed by a reaction of CFO-1316mxx with tetrafluoroethylene (TFE) to form 2,3-dichloro-l,l,l,4,4,5,5,6,6,6-decafluoro-2-hexene followed by a hydrodechlorination of 2,3-dichloro-l,l,l,4,4,5,5,6,6,6-decafluoro-2- hexene to form HFO-153-10mzz.
• TFE tetrafluoroethylene
• CFO-1316 TFE [0098]
• CFO-1316mxx is combined with TFE in a vapor phase reaction catalyzed by aluminum chlorofluoride to form 2,3-dichloro-l,l,l,4,4,5,5,6,6,6- decafluoro-2-hexene with a yield of at least 48%.
• 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 by reference herein.
• HFO-153-10mzz can be formed by a vapor phase reaction of HCFO-1326mxz with TFE to form 2-chloro-l,l,l,4,4,5,5,6,6,6-decafluoro-2-hexene followed by a vapor phase hydrodechlorination of 2-chloro-l,l,l,4,4,5,5,6,6,6-decafluoro-2-hexene to form HFO- 153-10mzz.
• SbFs antimony pentafluoride
• HFO-153-10mczz can be formed by a chlorination of HFC-245cb to form CFC- 215cb followed by a coupling reaction of CFC-215cb to form 3,4-dichloro- l,l,1.2,2,5,5,6,6,6-decafluoro-3-hexene followed by a hydrodechlorination of 3,4-dichloro- l,l,1.2,2,5,5,6,6,6-decafluoro-3-hexene to form HFO-153-10mczz.
• HFC-245cb is chlorinated in a vapor phase reaction to form CFC-215cb.
• CFC-215cb couples at 130°C in a vapor phase reaction in the presence of a 2% Ru/SiC catalyst to form 3,4-dichloro-l,l,l,2,2,5,5,6,6,6-decafluoro-3- hexene in a yield of at least 86%.
• Liquid CFC-51-10mcaa (CF3-CF2-CCI2-CCI2-CF2-CF3) was fed into a heated chamber at temperature where it is vaporized and mixed with H2 to form a CFC-51 - lOmcaa/FL reaction mixture.

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