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WO2023002341A1 - Hydrofluoro-oléfines et leurs utilisations - Google Patents

Hydrofluoro-oléfines et leurs utilisations Download PDF

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Publication number
WO2023002341A1
WO2023002341A1 PCT/IB2022/056588 IB2022056588W WO2023002341A1 WO 2023002341 A1 WO2023002341 A1 WO 2023002341A1 IB 2022056588 W IB2022056588 W IB 2022056588W WO 2023002341 A1 WO2023002341 A1 WO 2023002341A1
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group
carbon atoms
perfluorinated
contain
group containing
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Sean M. Smith
Markus E. HIRSCHBERG
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3M Innovative Properties Co
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3M Innovative Properties Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/14—Unsaturated ethers
    • C07C43/17—Unsaturated ethers containing halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/14—Unsaturated ethers
    • C07C43/17—Unsaturated ethers containing halogen
    • C07C43/172—Unsaturated ethers containing halogen containing rings other than six-membered aromatic rings
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated

Definitions

  • hydrofluoroolefin ether compounds are disclosed herein.
  • the hydrofluoroolefin ether compound is represented by the general formula (I): where R f 1 is a linear, bra containing 1-5 carbon atoms and may contain up to 2 H atoms, R f 2 is a perfluorinated alkyl group containing 1-6 carbon atoms and may contain one or more catenated heteroatoms selected from O or N, R f 3 is an F atom, a CF3 group, or a CF2CF3 group, or Rf 2 and Rf 3 together form a perfluorinated ring structure with 5-6 carbon atoms, and R f 4 is an F atom, a CF 3 group, or a CF 2 CF 3 group.
  • hydrofluoolefin ether compound described above is present in the working fluid at an amount of at least 25% by weight based on the total weight of the working fluid.
  • Methods for preparing hydrofluoroolefin ether compounds are also disclosed.
  • the method comprises providing a perfluorinated precursor, reacting the perfluorinated precursor with a reaction mixture comprising a fluoride salt in an aprotic organic solvent to form a fluorinated alkoxide salt, quenching the fluorinated alkoxide salt with an electrophile to form a compound of Formula II, and dehydrofluorination of the compound of Formula II with an aqueous solution of a metal hydroxide and a phase transfer catalyst to form a hydrofluoroolefin ether of general Formula I.
  • the electrophile has the general structure R f 1 - CF 2 -CH 2 -X, where R f 1 is a linear, branched, or cyclic fluoroalkyl group containing 1-5 carbon atoms and may contain up to 2 H atoms, and X is a group with the general formula -OSO 2 CF 3 , -OSO 2 CF 2 CF 3 , or -OSO 2 CF 2 CF 2 CF 2 CF 3 .
  • Fluorinated compounds of Formula II have the general structure: (R f 2 )(R f 3 )(R f 4 )-C-O-CH 2 -CF 2 -R f 1 II where R f 1 is a linear, branched, or cyclic fluoroalkyl group containing 1-5 carbon atoms and may contain up to 2 H atoms, R f 2 is a perfluorinated alkyl group containing 1-6 carbon atoms and may contain one or more catenated heteroatoms selected from O or N, R f 3 is an F atom, a CF 3 group, or a CF 2 CF 3 group; or R f 2 and R f 3 together form a perfluorinated ring structure with 5-6 carbon atoms, and R f 4 is an F atom, a CF 3 group, or a CF 2 CF 3 group.
  • the desired working fluid materials have desirable low ozone-depleting features, low global warming potential (GWP), and are thermally, hydrolytically, and base stable.
  • GWP global warming potential
  • the desired working fluid materials must also meet the performance requirements (e.g., nonflammability, solvency, stability, and operating temperature range) of a variety of different applications (e.g., heat transfer, solvent cleaning, deposition coating solvents, and electrolyte solvents and additives).
  • fluorinated fluids such as hydrofluoroethers (HFEs), hydrofluorocarbons (HFCs), perfluorocarbons (PFCs), and hydrochlorofluorocarbons (HCFCs).
  • HFEs hydrofluoroethers
  • HFCs hydrofluorocarbons
  • PFCs perfluorocarbons
  • HCFCs hydrochlorofluorocarbons
  • HFOs oxygen-containing hydrofluoroolefins
  • hydrofluoroolefins of this disclosure have catenated oxygen atoms, and are described in this disclosure as “hydrofluoroolefin ethers”. These hydrofluoroolefin ethers have the desirable combination of properties of high thermal stability, low toxicity, nonflammability, good solvency, and a wide operating temperature range to meet the requirements of various applications.
  • the compounds also have generally low atmospheric lifetimes, are not ozone-depleting, and have low global warming potentials (GWPs).
  • GWPs global warming potentials
  • hydrofluoroolefins” and “HFOs” are used consistent with their commonly understood chemical definitions and refer to unsaturated organic compounds comprising hydrogen, fluorine, and carbon atoms.
  • HFOs are unsaturated comprising an olefin group.
  • “catenated heteroatom” means an atom other than carbon (for example, oxygen, nitrogen, or sulfur) that is bonded to at least two carbon atoms in a carbon chain (linear or branched or within a ring) so as to form a carbon-heteroatom- carbon linkage.
  • fluoro- for example, in reference to a group or moiety, such as in the case of "fluoroalkylene” or “fluoroalkyl” or “fluorocarbon" or “fluorinated” means (i) partially fluorinated such that there is at least one carbon-bonded hydrogen atom, or (ii) perfluorinated.
  • perfluoro- for example, in reference to a group or moiety, such as in the case of "perfluoroalkylene” or “perfluoroalkyl” or “perfluorocarbon" or “perfluorinated” means completely fluorinated such that, except as may be otherwise indicated, there are no carbon-bonded hydrogen atoms replaceable with fluorine.
  • group “-R f ” is used according to common usage in chemical arts and refers to fluoroalkyl group.
  • the group “-Rf -“ refers to a fluoroalkylene group.
  • aqueous refers to a liquid composition that includes at least water as the majority component, but may also contain minor amounts of additional water-miscible components.
  • the present disclosure is directed to hydrofluoroolefin ether compounds represented by the following general Formula I: where R f 1 is a linear, branched, or kyl group containing 1-5 carbon atoms and may contain up to 2 H atoms; Rf 2 is a perfluorinated alkyl group containing 1-6 carbon atoms and may contain one or more catenated heteroatoms selected from O or N; R f 3 is an F atom, a CF 3 group, or a CF 2 CF 3 group; or R f 2 and R f 3 together form a perfluorinated ring structure with 5-6 carbon atoms; R f 4 is an F atom, a CF 3 group, or a CF 2 CF 3 group.
  • R f 1 groups are suitable.
  • R f 1 is a linear fluoroalkyl group containing 1-5 carbon atoms.
  • R f 1 is a linear fluoroalkyl group containing 1-5 carbon atoms and containing 1 H atom.
  • R f 2 , R f 3 , and R f 4 groups and combinations of groups are suitable.
  • R f 2 is a perfluorinated alkyl group containing 1-3 carbon atoms; and Rf 3 and Rf 4 each is an F atom.
  • Rf 2 is a perfluorinated alkyl group containing 1-6 carbon atoms and may contain one or more catenated heteroatoms selected from O or N;
  • R f 3 is a CF 3 group, or a CF 2 CF 3 group; or R f 2 and R f 3 together form a perfluorinated ring structure with 5-6 carbon atoms; and
  • R f 4 is an F atom.
  • R f 2 is a perfluorinated alkyl group containing 1-6 carbon atoms and may contain one or more catenated heteroatoms selected from O or N;
  • R f 3 is a CF 3 group, or a CF 2 CF 3 group; and
  • R f 4 is a CF 3 group, or a CF 2 CF 3 group.
  • the fluorine content in the hydrofluoroolefin compounds of the present disclosure may be sufficient to make the compounds non-flammable according to ASTM D-3278-96 e-1 test method (“Flash Point of Liquids by Small Scale Closed Cup Apparatus”).
  • representative examples of the compounds of general Formula I include the following:
  • disclosure may be hydrophobic, relatively chemically unreactive, and thermally stable.
  • the hydrofluoroolefin ether compounds may have a low environmental impact.
  • the hydrofluoroolefin ether compounds of the present disclosure may have a global warming potential (GWP) of less than 500, 400, 300, 250, 200, 275, 150, 100, 80, or even 50.
  • 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 is calculated as the warming due to the release of 1 kilogram of a compound relative to the warming due to the release of 1 kilogram of CO 2 over a specified integration time horizon (ITH).
  • ITH integration time horizon
  • the concentration of an organic compound, i, in the atmosphere is assumed to follow pseudo first order kinetics (i.e., exponential decay).
  • the concentration of CO2 over that same time interval incorporates a more complex model for the exchange and removal of CO 2 from the atmosphere (the Bern carbon cycle model).
  • the hydrofluoroolefin ether compositions of the present disclosure have a desirable boiling point range. In some embodiments, the boiling point is no lower than 40, 50, or even 60°C and no higher than 150, 140, 130, 120, 110, 100, 90, or even 80°C.
  • the hydrofluoroolefin ether compositions of the present disclosure have desirable low temperature properties as demonstrated by determining the pour point.
  • the desirable low temperature properties are reflected by pour points of less than -40, -50, or even -60°C.
  • the hydrofluoroolefin ether compositions of the present disclosure have desirable heat transfer properties as demonstrated by determining specific heat values.
  • the desirable heat transfer properties are reflected by specific heat values of higher than 900, 1,000, 1,050, 1,100, or even 1,150 J/Kg ⁇ K (Joules per Kilogram Kelvin).
  • the hydrofluoroolefin ether compositions of the present disclosure are expected to provide low acute toxicity based on 4-hour acute inhalation studies in rats following U.S.
  • a compound of the present disclosure has a single dose oral median lethal concentration (LC 50) in male and female Sprague-Dawley rats of greater than 1,000, 1,250, 5,000, 10,000, 12,500, 15,000, 18,000, or even 20,000 ppm.
  • LC 50 oral median lethal concentration
  • the hydrofluoroolefin ether compounds of this disclosure can be prepared following the general reaction schemes shown below in Scheme 1.
  • the perfluorinated precursor is a perfluorinated acid fluoride.
  • the perfluorinated precursor is a perfluorinated ketone.
  • the fluoride salt (represented as [M]F) comprises a metal fluoride salt or a tetraalkylammonium fluoride salt.
  • Suitable fluoride salts include KF (potassium fluoride), RbF (rubidium fluoride), CsF (cesium fluoride), and TBAF (tetrabutylammonium fluoride).
  • the salts are dissolved in one or more aprotic organic solvents.
  • Suitable aprotic organic solvents include glymes (e.g. diglyme, tetraglyme, and DPM (di(propylene glycol) methyl ether)), N,N-dimethylformamide (DMF), N- methylpyrrolidinone (NMP), and N,N-dimethylacetamide (DMA).
  • the fluoride salt and aprotic organic solvent mixture also comprises tetrafluoroethylene (TFE) or perfluoroalkyl trimethyl silane (e.g. TMS-CF 3 or TMS-CF 2 CF 3 ).
  • TFE tetrafluoroethylene
  • perfluoroalkyl trimethyl silane e.g. TMS-CF 3 or TMS-CF 2 CF 3 .
  • Scheme 1C provides a method for preparing compounds of general Formula I where R f 3 and R f 4 are not F atoms.
  • the combination of the perfluorinated precursor and the fluoride salt (and optionally TFE or perfluoroalkyl trimethyl silane) forms a fluorinated alkoxide salt. This fluorinated alkoxide salt is quenched with an electrophile.
  • the electrophile has the general structure: R f 1 -CF 2 CH 2 -X, where R f 1 is a linear, branched, or cyclic fluoroalkyl group containing 1-5 carbon atoms and may contain up to 2 H atoms; and X is -OSO 2 CF 3 , OSO 2 CF 2 CF 3 , or OSO 2 CF 2 CF 2 CF 2 CF 3 ).
  • the reaction of the fluorinated alkoxide salt and electrophile forms a fluorinated compound of general Formula II: (R f 2 )( R f 3 )( R f 4 )-C-O-CH 2 -CF 2 R f 1 II where R f 1 is a linear, branched, or cyclic fluoroalkyl group containing 1-5 carbon atoms and may contain up to 2 H atoms; Rf 2 is a perfluorinated alkyl group containing 1-6 carbon atoms and may contain one or more catenated heteroatoms selected from O or N; R f 3 is an F atom, a CF 3 group, or a CF 2 CF 3 group; or R f 2 and R f 3 together form a perfluorinated ring structure with 5-6 carbon atoms; and R f 4 is an F atom, a CF 3 group, or a CF 2 CF 3 group.
  • the fluorinated compound of general Formula II include: The fluorinated compound of general Formula II undergoes dehydrofluorination with an aqueous solution of a metal hydroxide and a phase transfer catalyst to form a hydrofluoroolefin ether of general Formula I as described above.
  • suitable metal hydroxides represented as [M]OH
  • suitable metal hydroxides include KOH (potassium hydroxide), LiOH (lithium hydroxide), and NaOH (sodium hydroxide).
  • the phase transfer catalyst is a tetraalkylammonium halide phase transfer catalyst such as TBACl, TBAB, ALIQUAT 336, or benzyltriethylammonium chloride.
  • the working fluid comprises the hydrofluoroolefin ether compound of general formula I described above.
  • the hydrofluoroolefin ether compound is present in the working fluid at an amount of at least 25% by weight based on the total weight of the working fluid.
  • the above-described hydrofluoroolefin ether compounds is a major component of the working fluid.
  • the working fluids may include at least 50%, at least 70%, at least 80%, at least 90%, at least 95%, or at least 99% by weight of the above-described hydrofluoroolefin ether compounds based on the total weight of the working fluid.
  • the working fluids may include a total of up to 75%, up to 50%, up to 30%, up to 20%, up to 10%, or up to 5% by weight of one or more of the following components: alcohols, ethers, alkanes, alkenes, haloalkenes, perfluorocarbons, perfluorinated tertiary amines, perfluoroethers, cycloalkanes, esters, ketones, oxiranes, aromatics, siloxanes, hydrochlorocarbons, hydrochlorofluorocarbons, hydrofluorocarbons, hydrofluoroolefins, hydrochloroolefins, hydrochlorofluoroolefins, hydrofluoroethers, or mixtures thereof, based on the total weight of the working fluid.
  • the working fluids are suitable for a wide variety of uses.
  • the working fluid comprises a heat transfer fluid, a coating solvent, a foam blowing agent, an electrolyte solvent, an additive for lithium-ion batteries, or a cleaning fluid.
  • the present disclosure is further directed to an apparatus for heat transfer that includes a device and a mechanism for transferring heat to or from the device.
  • the mechanism for transferring heat may include a heat transfer working fluid that includes a hydrofluoroolefin compounds of the present disclosure.
  • Such devices are described for example in US Patent No.10,717,694.
  • the hydrofluoroolefin ether compounds of this disclosure can be used in a fire extinguishing compositions.
  • the composition may include one or more co-extinguishing agents.
  • the co-extinguishing agent may include hydrofluorocarbons, hydrochlorofluorocarbons, perfluorocarbons, perfluoropolyethers, hydrofluoroethers, hydrofluoropolyethers, chlorofluorocarbons, bromofluorocarbons, bromochlorofluorocarbons, hydrobromocarbons, iodofluorocarbons, fluorinated ketones, hydrofluorocarbons, hydrochlorofluorocarbons, perfluorocarbons, perfluoropolyethers, hydrofluoroethers, hydrofluoropolyethers, chlorofluorocarbons, bromofluorocarbons, bromochlorofluorocarbons, iodofluorocarbons, fluorin
  • the working fluids of the present disclosure can be used in an apparatus for converting thermal energy into mechanical energy in a Rankine cycle.
  • the apparatus may further include a heat source to vaporize the working fluid and form a vaporized working fluid, a turbine through which the vaporized working fluid is passed thereby converting thermal energy into mechanical energy, a condenser to cool the vaporized working fluid after it is passed through the turbine, and a pump to recirculate the working fluid.
  • a heat source to vaporize the working fluid and form a vaporized working fluid
  • a turbine through which the vaporized working fluid is passed thereby converting thermal energy into mechanical energy
  • a condenser to cool the vaporized working fluid after it is passed through the turbine
  • a pump to recirculate the working fluid.
  • the present disclosure relates to the use of the hydrofluoroolefin ether compounds of the present disclosure as nucleating agents in the production of polymeric foams and in particular in the production of polyurethane foams and phenolic foams.
  • the present disclosure is directed to a foamable composition that includes one or more blowing agents, one or more foamable polymers or precursor compositions thereof, and one or more nucleating agents that include a hydrofluoroolefin ether compound of the present disclosure.
  • the hydrofluoroolefin ether compounds of the present disclosure can be used as dielectric fluids in electrical devices (e.g., capacitors, switchgear, transformers, or electric cables or buses) that include such dielectric fluids.
  • dielectric fluid is inclusive of both liquid dielectrics and gaseous dielectrics. The physical state of the fluid, gaseous or liquid, is determined at the operating conditions of temperature and pressure of the electrical device in which it is used.
  • the dielectric fluids include one or more hydrofluoroolefin ether compounds of the present disclosure and, optionally, one or more second dielectric fluids.
  • Suitable second dielectric fluids include, for example, air, nitrogen, helium, argon, and carbon dioxide, or combinations thereof.
  • the second dielectric fluid may be a non- condensable gas or an inert gas.
  • the second dielectric fluid may be used in amounts such that vapor pressure is at least 70 kPa at 25 o C, or at the operating temperature of the electrical device.
  • the hydrofluoroolefin ether compounds of the present disclosure can be used in coating compositions that include a solvent composition and one or more coating materials which are soluble or dispersible in the solvent composition.
  • the coating materials of the coating compositions may include pigments, lubricants, stabilizers, adhesives, anti-oxidants, dyes, polymers, pharmaceuticals, release agents, inorganic oxides, and the like, and combinations thereof.
  • coating materials may include perfluoropolyether, hydrocarbon, and silicone lubricants; amorphous copolymers of tetrafluoroethylene; polytetrafluoroethylene; or combinations thereof.
  • suitable coating materials include titanium dioxide, iron oxides, magnesium oxide, perfluoropolyethers, polysiloxanes, stearic acid, acrylic adhesives, polytetrafluoroethylene, amorphous copolymers of tetrafluoroethylene, or combinations thereof.
  • the hydrofluoroolefin ether compounds of the present disclosure can be used in cleaning compositions that include one or more co-solvents.
  • the hydrofluoroolefin ether compounds may be present in an amount greater than 50 weight percent, greater than 60 weight percent, greater than 70 weight percent, or greater than 80 weight percent based upon the total weight of the hydrofluoroolefin ether compounds and the co-solvent(s).
  • the co-solvent may include alcohols, ethers, alkanes, alkenes, haloalkenes, perfluorocarbons, perfluorinated tertiary amines, perfluoroethers, cycloalkanes, esters, ketones, oxiranes, aromatics, haloaromatics, siloxanes, hydrochlorocarbons, hydrochlorofluorocarbons, hydrofluorocarbons, hydrofluoroolefins, hydrochloroolefins, hydrochlorofluoroolefins, hydrofluoroethers, or mixtures thereof.
  • the cleaning compositions can be used in either the gaseous or the liquid state (or both), and any of known or future techniques for “contacting” a substrate can be utilized.
  • a liquid cleaning composition can be sprayed or brushed onto the substrate, a gaseous cleaning composition can be blown across the substrate, or the substrate can be immersed in either a gaseous or a liquid composition. Elevated temperatures, ultrasonic energy, and/or agitation can be used to facilitate the cleaning.
  • Various different solvent cleaning techniques are described by B. N. Ellis in Cleaning and Contamination of Electronics Components and Assemblies, Electrochemical Publications Limited, Ayr, Scotland, pages 182-94 (1986).
  • the present disclosure further relates to electrolyte compositions that include one or more hydrofluoroolefin ether compounds of the present disclosure.
  • the electrolyte compositions may comprise (a) a solvent composition including one or more of the hydrofluoroolefin ether compounds; and (b) at least one electrolyte salt.
  • the electrolyte compositions of the present disclosure exhibit excellent oxidative stability, and when used in high voltage electrochemical cells (such as rechargeable lithium ion batteries) provide outstanding cycle life and calendar life. For example, when such electrolyte compositions are used in an electrochemical cell with a graphitized carbon electrode, the electrolytes provide stable cycling to a maximum charge voltage of at least 4.5V and up to 6.0V vs.
  • Step 1 To a 600 mL stainless steel pressure reactor were added KF (11.0 g, 190 mmol), 2,2,3,3,4,4,4-heptafluorobutylnonafluorobutane sulfonate (83.1 g, 172 mmol), and DMF (50 mL). The reaction vessel was sealed and was then evacuated, backfilled with N 2 , and then evacuated again.
  • Step 2 To a 3-neck round bottom flask equipped with a magnetic stir bar, reflux condenser, and temperature probe were charged KOH (21.5 g, 326 mmol), TBACl (6.0 g, 21.7 mmol), and H 2 O (25 mL). With stirring, KOH and TBACl were dissolved completely before the addition of 1,1,1,2,3,3,3-heptafluoro-2- (2,2,3,3,4,4,4-heptafluorobutoxy)propane (40.0 g, 109 mmol).
  • Example 2 Preparation of 2,3,3,3-tetrafluoro-1-(perfluoro-iso-propoxy)prop-1-ene.
  • Step 1 To a 300 mL stainless steel pressure reactor were added KF (14.5 g, 250 mmol), 2,2,3,3,3-pentafluoropropyltrifluoromethane sul ate (67.1 g, 238 mmol), and DMF (75 mL). The reaction vessel was sealed and was then evacuated, backfilled with N 2 , and then evacuated again.
  • Step 2 To a 3-neck round bottom flask equipped with a magnetic stir bar, reflux condenser, and temperature probe were charged KOH (3.1 g, 47 mmol), TBPBr (1.6 g, 4.7 mmol), and H 2 O (7 mL).
  • Step 1 To a 300 mL stainless steel pressure reactor were added CsF (28.8 g, 190 mmol), tetraglyme (75 mL), and 2,2,3,3,4,4,4-heptafluorobutylnonafluorobutane sulfonate (87.1 g, 181 mmol). The reaction vessel was sealed and was then evacuated, backfilled with N 2 , and then evacuated again. To the stirring, heated (300C) reaction mixture, perfluoropropionyl fluoride (30.2 g, 182 mmol) was slowly added over the course of 30 min. The resultant reaction mixture was then slowly raised to 700C followed by an overnight stir.
  • Step 2 To a 3-neck round bottom flask equipped with a magnetic stir bar and reflux condenser were charged KOH (16.1 g, 245 mmol), TBACl (9.1 g, 33 mmol), and water (30 mL).
  • the reaction vessel was then evacuated and backfilled with nitrogen three times before adding tetraglyme (150 mL).
  • tetraglyme 150 mL
  • CF 3 CF 2 CH 2 ONf 117.1 g,271 mmol
  • perfluoropropionyl fluoride 45 g, 271 mmol
  • the resultant reaction mixture was diluted with water (50 mL).
  • the diluted mixture was then transferred to a separatory funnel and then further diluted with additional water (450 mL).
  • Step 2 To a 3-neck round bottom flask equipped with a magnetic stir bar, reflux condenser, and temperature probe were charged KOH (6.2 g, 95 mmol), TBPBr (4.3 g, 13 mmol), and H 2 O (10 mL). With stirring, KOH and TBPBr were dissolved completely before the addition of 1,1,1,2,2,3,3-heptafluoro-3-(2,2,3,3,3-pentafluoropropoxy)propane (10.1 g, 31.8 mmol). The reaction mixture was stirred vigorously overnight at elevated temperature (800C) and was then allowed to cool back to room temperature and diluted with H 2 O (20 mL).
  • KOH 6.2 g, 95 mmol
  • TBPBr 4.3 g, 13 mmol
  • H 2 O 10 mL
  • Step 1 To a 1 L 3-neck round bottom flask equipped with a dry ice condenser, magnetic stir bar, and temperature probe were added DCM (500 mL), triethylamine (101 g, 1.0 mol). The resultant mixture was cooled with stirring to 50C followed by the slow addition of 2,2,3,3,4,4,4-heptafluorobutanol (200 g, 1.0 mol). PESF (206 g, 1.0 mol) was then slowly added to the cooled reaction mixture over the course of 30 min at rate which avoided temperature increases above 100C. The resultant mixture was allowed to stir for 1 h at the same temperature before allowing to rise to room temperature.
  • DCM 500 mL
  • triethylamine 101 g, 1.0 mol
  • Step 2 To a 600 mL stainless steel pressure reactor were added added KF (11.2 g, 193 mmol), 2,2,3,3,4,4,4-heptafluorobutylpentafluoroethane sulfonate (67.0 g, 175 mmol), and DMF (100 mL). The reaction vessel was sealed and was then evacuated, backfilled with N 2 , and then evacuated again. To the stirring reaction mixture, perfluorocyclopentanone (40.1 g, 176 mmol) was slowly added at a rate which did not allow for the internal temperature to rise above 280C. The reaction temperature was then slowly raised to 500C followed by an overnight stir. The reaction mixture was then cooled to room temperature followed by the addition of water (150 mL).
  • Step 3 To a 3-neck round bottom flask equipped with a magnetic stir bar, reflux condenser, and temperature probe were charged KOH (2.4 g, 36 mmol), TBPBr (1.6 g, 4.8 mmol), and H 2 O (7 mL). With stirring, KOH and TBPBr were dissolved completely before the addition of 1,1,2,2,3,3,4,4,5-nonafluoro-5-(2,2,3,3,4,4,4- heptafluorobutoxy)cyclopentane (5.0 g, 12 mmol). The reaction mixture was stirred vigorously overnight at elevated temperature (800C) and was then allowed to cool back to room temperature and diluted with H 2 O (20 mL).
  • KOH 2.4 g, 36 mmol
  • TBPBr 1.6 g, 4.8 mmol
  • H 2 O 7 mL
  • Step 1 To a 600 mL stainless steel pressure reactor were added tetraglyme (100 mL), KF (16.1 g, 277 mmol), and 18-crown-6 (10.5 g, 39.7 mmol). The vessel was sealed and then evacuated under reduced pressure, back-filled with N 2 , and then evacuated again. 2,2,3,3,3-Pentafluoropropionyl fluoride (43.0 g, 259 mmol) was then added to the stirring mixture. TMSCF 3 (77.3 g, 544 mmol) was then slowly added to the reaction mixture over the course of 1 hour with observed temperature increases up to 450C.
  • Step 2 A portion of reaction mixture containing approximately 100 mmol of the potassium alkoxide salt from Step 1 was transferred to a round-bottom three-neck flask equipped with a temperature probe and magnetic stir bar. To the heated (600C) mixture, CF 3 CF 2 CH 2 OTf (25.2 g, 89.3 mmol) was added dropwise over the course of 0.5 h.
  • Step 3 To a round-bottom flask equipped with a magnetic stir bar were charged KOH (0.95 g, 14 mmol), TBACl (0.40 g, 1.4 mmol), and H 2 O (2 mL). With stirring, KOH and TBPBr were dissolved completely before the addition of 1,1,1,2,2,4,4,4-octafluoro-3- (2,2,3,3,3-pentafluoropropoxy)-3-(trifluoromethyl)butane (2.0 g, 4.8 mmol). The reaction mixture was stirred vigorously overnight at elevated temperature (800C) and was then allowed to cool back to room temperature and diluted with H 2 O (5 mL).
  • Example 7 Preparation of 1,1,1,2,2,4,4,4-octafluoro-3-(2,3,3,4,4,4-hexafluorobut-1- enoxy)-3-(trifluoromethyl)butane.
  • Step 1 To a 600 mL stainless steel pressure reactor were added tetraglyme (100 F (16.1 g, 277 mmol), and 18-crown-6 (10.5 g, 39.7 mmol). The vessel was sealed and then evacuated under reduced pressure, back-filled with N 2 , and then evacuated again. 2,2,3,3,3-Pentafluoropropionyl fluoride (43.0 g, 259 mmol) was then added to the stirring mixture.
  • TMSCF 3 (77.3 g, 544 mmol) was then slowly added to the reaction mixture over the course of 1 hour with observed temperature increases up to 450C.
  • the resultant reaction mixture was allowed to stir overnight at room temperature and was then transferred to a 250 mL round-bottom flask equipped with a magnetic stir bar, and reflux condenser. With stirring, the TMS-F by-product was removed by sweeping the mixture with a steady stream of N 2 . The resultant mixture was used for the next step without further purification.
  • Step 2 Half of the mixture from Step 1 was transferred to a round-bottom three- neck flask equipped with a temperature probe and magnetic stir bar.
  • Step 3 To a 3-neck round bottom flask equipped with a magnetic stir bar, reflux condenser, and temperature probe were charged KOH (2.1 g, 32 mmol), TBPBr (2.9 g, 8.5 mmol), and H 2 O (5 mL). With stirring, KOH and TBPBr were dissolved completely before the addition of 1,1,1,2,2,4,4,4-octafluoro-3-(2,2,3,3,4,4,4-heptafluorobutoxy)-3- (trifluoromethyl)butane (5.0 g, 10.7 mmol).
  • Step 1 To a 600 mL stainless steel pressure reactor were added KF (2 . g, 355 mmol) and DMF (105 mL). The reactor was sealed and evacuated, backfilled with nitrogen, and then evacuated again. To the stirring mixture, hexafluoroacetone (50.1 g, 302 mmol) was slowly added over the course of 10 min.
  • Step 2 A 250 mL 3-neck round-bottom flask equipped with a magnetic stir bar, reflux condenser, and temperature probe was evacuated and backfilled with nitrogen three times before addition of half of the mixture from Step 1.
  • the diluted mixture was transferred, and removal of the aqueous layer yielded a crude fluorochemical mixture for which purification via fractional distillation produced 1,1,1,3,3,3-hexafluoro-2-(2,2,3,3,4,4,4-heptafluorobutoxy)-2- (trifluoromethyl)propane (1080C, 740 mm/Hg) as a colorless liquid (30.4 g, 48% isolated yield).
  • the purified material was used in the next step. Confirmation of the chemical compound was obtained by conventional proton and fluorine NMR.
  • Step 3 To a 3-neck round bottom flask equipped with a magnetic stir bar, reflux condenser, and temperature probe were charged KOH (1.3 g, 20 mmol), TBPBr (0.91 g, 2.7 mmol), and H 2 O (5 mL). With stirring, KOH and TBPBr were dissolved completely before the addition of 1,1,1,3,3,3-hexafluoro-2-(2,2,3,3,4,4,4-heptafluorobutoxy)-2- (trifluoromethyl)propane (2.8 g, 6.7 mmol). The reaction mixture was stirred vigorously overnight at elevated temperature (800C) and was then allowed to cool back to room temperature and diluted with H 2 O (20 mL).
  • KOH 1.3 g, 20 mmol
  • TBPBr 0.91 g, 2.7 mmol
  • H 2 O 5 mL
  • Example 9 Preparation of 1,1,1,3,3,3-hexafluoro-2-(2,2,3,3,3-pentafluoropropoxy)-2- (trifluoromethyl)propane.
  • Step 1 To a 600 mL stainless steel pressure reactor were added KF (20.6 g, 355 mmol) and DMF (105 mL). The reactor was sealed and evacuated, backfilled with nitrogen, and then evacuated again. To the stirring mixture, hexafluoroacetone (50.1 g, 302 mmol) was slowly added over the course of 10 min.
  • Step 2 A 250 mL 3-neck round-bottom flask equipped with a magnetic stir bar, reflux condenser, and temperature probe was evacuated and backfilled with nitrogen three times before addition of half of the mixture from Step 1.
  • Step 3 To a 3-neck round bottom flask equipped with a magnetic stir bar, reflux condenser, and temperature probe were charged KOH (2.7 g, 40.7 mmol), TBPBr (1.8 g, 5.4 mmol), and H 2 O (5 mL). With stirring, KOH and TBPBr were dissolved completely before the addition of 1,1,1,3,3,3-hexafluoro-2-(2,2,3,3,3-pentafluoropropoxy)-2- (trifluoromethyl)propane (5.0 g, 13.6 mmol).
  • Example 10 Preparation of 2,3,3,4,4,5,5-heptafluoro-1-(perfluoropropoxy)but-1-ene.
  • Step 1 To a 3-neck 500 mL round bottom flask equipped with a dry ice condenser, magnetic stir bar, and temperature probe was added KF (23.5 g, 405 mmol). The reaction vessel was then evacuated and backfilled with nitrogen three times before charging with tetraglyme (225 mL). The stirring mixture was cooled to an internal temperature of -100C and was then charged with perfluoropropionyl fluoride (66.0 g, 398 mmol).
  • Step 2 To a 3-neck round bottom flask equipped with a magnetic stir bar, reflux condenser, and temperature probe were charged KOH (19.8 g, 300 mmol), TBPBr (13.6 g, 40.0 mmol), and H 2 O (45 mL). With stirring, KOH and TBPBr were dissolved completely before the addition of 1,1,2,2,3,3,4,4-octafluoro-5-(1,1,2,2,3,3,3- heptafluoropropoxy)pentane (40.0 g, 100 mmol).
  • Example 10 Purification of the fluorochemical mixture via fractional distillation produced 2,3,3,4,4,5,5-heptafluoro-1- (perfluoropropoxy)but-1-ene (1080C, 740 mm/Hg) as a colorless liquid (18.2 g, 48% isolated yield), Example 10. Confirmation of the chemical compound was obtained by conventional proton and fluorine NMR.
  • Example 11 Preparation of 1,1,1,2,2,3,3-heptafluoro-3-(2,3,3-trifluoroprop-1- enoxy)propane. Step 1: To a 3-neck 500 mL round bottom flask equipped with a dry ice condenser, magnetic stir bar, and temperature probe was added KF (23.5 g, 405 mmol).
  • the reaction vessel was then evacuated and backfilled with nitrogen three times before charging with tetraglyme (225 mL).
  • the stirring mixture was cooled to an internal temperature of -100C and was then charged with perfluoropropionyl fluoride (65.1 g, 392 mmol).
  • perfluoropropionyl fluoride 65.1 g, 392 mmol
  • CF 2 HCF 2 CH 2 ONf 172 g, 415 mmol
  • the resultant reaction mixture was diluted with water (100 mL), transferred to a 1 L separatory funnel, and then diluted with an additional portion of water (300 mL).
  • Step 2 To a 2-neck round bottom flask equipped with a magnetic stir bar, reflux condenser, and temperature probe were charged KOH (9.9 g, 150 mmol), TBPBr (10.1 g, 30.0 mmol), and H 2 O (25 mL). With stirring, KOH and TBPBr were dissolved completely before the addition of 1,1,1,2,2,3,3-heptafluoro-3-(2,2,3,3-tetrafluoropropoxy)propane (15.0 g, 50.0 mmol). The reaction mixture was stirred vigorously for 3 h at elevated temperature (800C). A distillation head was then attached to one of the flask necks and the reflux condenser was removed.
  • KOH 9.9 g, 150 mmol
  • TBPBr 10.1 g, 30.0 mmol
  • H 2 O 25 mL
  • Example 12 Preparation of 1,1,2,2,3,3,4,4-octafluoro-5-(2,3,3-trifluoroprop-1- enoxy)cyclopentane.
  • Step 1 A round-bottom 3-neck flask equipped with a magnetic stir bar, reflux condenser, and temperature probe was charged with KF (12.7 g, 219 mmol).
  • the reaction vessel was evacuated and backfilled with nitrogen three times before the addition of tetraglyme (100 mL).
  • the resultant mixture was then cooled (00C) with stirring followed by the slow addition of perfluorocyclopentanone (50.0 g, 219 mmol) over the course of 10 min.
  • Example 12 Confirmation of the chemical compound was obtained by conventional proton and fluorine NMR. Comparative Example 1 (CE-1). Attempted dehydrofluorination of 1,1,1,2,2,4,4,4- octafluoro-3-(2,2,2-trifluoroethoxy)-3-(trifluoromethyl)butane.
  • Step 1 A 600 mL stainless steel pressure reactor was charged with KF (16.1 g, 277 mmol), 18-Crown-6 (10.5 g, 39.7 mmol), and tetraglyme (100 mL). The reaction vessel was sealed and evacuated under reduced pressure followed by the slow addition of 2,2,3,3,3-pentafluoropropionyl fluoride (43.0 g, 259 mmol) to the stirring mixture via a PTFE line. TMSCF 3 (77.3 g, 544 mmol) was then slowly added via a PTFE line over the course of 1 h to avoid temperature increases above 450C. The resultant reaction mixture was stirred overnight at room temperature.
  • Step 2 Half of the mixture from step 1 was transferred to a 3-neck round bottom flask equipped with a temperature probe, reflux condenser, and magnetic stir bar. To the stirring, heated (600C) mixture, CF 3 CH 2 OTf (30.5 g, 130 mmol) was slowly added.
  • Step 3 A 20 mL glass vial equipped with a magnetic stir bar was charged with KOH (0.36 g, 5.4 mmol), water (0.50 mL), TBACl (0.076 g, 0.27 mmol), and 1,1,1,2,2,4,4,4-octafluoro-3-(2,2,2-trifluoroethoxy)-3-(trifluoromethyl)butane (1.0 g, 2.7 mmol). The resultant mixture was stirred at 800C for 16 hours.
  • Comparative Example 2 (CE-2): Preparation of 1,3,3,3-tetrafluoro-N-(perfluoroethyl)-N- (trifluoromethyl)prop-1-en-1-amine.
  • CE-2 was prepared as described in U.S. Pat. Publ. 2018/0141893, which is incorporated herein by reference in its entirety, Example 1.
  • Comparative Example 3 (CE-3): 3,3,4,4,5,5,6,6,6-nonafluorohex-1-ene.
  • CE-3 was purchase from Synquest Laboratories, Inc., and used as received.
  • Comparative Example 4 (CE-4): 3,3,4,4,5,5-hexafluorocyclopent-1-ene.
  • CE-4 was purchase from Synquest Laboratories, Inc., and used as received.
  • Comparative Example 5 (CE-5): (Z)-1,1,1,4,4,4-hexafluorobut-2-ene.
  • CE-5 was purchase from Synquest Laboratories, Inc., and used as received.
  • Dielectric Constants of Examples 1, Example 3 and CE-2 through CE-5 The dielectric constant was determined using ASTM D150 with the average value reported at 1 KHz. Dielectric constant values were measured for Example 1, Example 3, CE-2, CE-3, CE-4, and CE-5.
  • the concentrations of 2,3,3,4,4,4-hexafluoro-1-(perfluoropropoxy)but-1-ene and the reference compound were measured as a function of reaction time using an I-Series FTIR from Midac Corporation.
  • the atmospheric lifetime was calculated from the reaction rates for 2,3,3,4,4,4-hexafluoro-1-(perfluoropropoxy)but-1-ene relative to the reference compounds and the reported lifetime of the reference compounds as shown below: where ⁇ x is the atmospheric lifetime 4-hexafluoro-1-(perfluoropropoxy)but-1- ene, ⁇ r is the atmospheric lifetime of the reference compound, and kx and kr are the rate constants for the reaction of hydroxyl radical with the test compound and the reference compound, respectively.
  • GWP Global Warming Potential

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Abstract

Les composés d'éther d'hydrofluoro-oléfine sont représentés par la formule générale (I) dans laquelle Rf 1 est un groupe linéaire, ramifié, ou un groupe fluoroalkyle cyclique contenant 1 à 5 atomes de carbone et peut contenir jusqu'à 2 atomes de H, Rf 2 est un groupe alkyle perfluoré contenant 1 à 6 atomes de carbone et peut contenir un ou plusieurs hétéroatomes caténés choisis parmi O ou N, Rf 3 est un atome F, un groupe CF3 ou un groupe CF2CF3, ou Rf 2 et Rf 3 ensemble forment une structure cyclique perfluorée à 5 à 6 atomes de carbone, et Rf 4 est un atome F, un groupe CF3 ou un groupe CF2CF3.
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US20100139274A1 (en) 2008-12-05 2010-06-10 Honeywell International Inc. Chloro- And Bromo-Fluoro Olefin Compounds Useful As Organic Rankine Cycle Working Fluids
EP2693558A1 (fr) * 2011-03-31 2014-02-05 Daikin Industries, Ltd. Batterie rechargeable à lithium-ion et électrolyte non aqueux pour batterie rechargeable à lithium-ion
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