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WO2025160052A1 - Procédé intégré pour fabriquer du 1,1,1,2,2,5,5,6,6,6-décafluoro-3-hexène - Google Patents

Procédé intégré pour fabriquer du 1,1,1,2,2,5,5,6,6,6-décafluoro-3-hexène

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Publication number
WO2025160052A1
WO2025160052A1 PCT/US2025/012380 US2025012380W WO2025160052A1 WO 2025160052 A1 WO2025160052 A1 WO 2025160052A1 US 2025012380 W US2025012380 W US 2025012380W WO 2025160052 A1 WO2025160052 A1 WO 2025160052A1
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WIPO (PCT)
Prior art keywords
glycol
catalyst
product
c2f5ch
chc2f5
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English (en)
Inventor
Xuehui Sun
Viacheslav A. Petrov
Michael F. Vincent
John Joseph Hagedorn
Drew Richard BRANDT
Kerry GRAY
Michael Miller
Jonathan P STEHMAN
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Chemours Co FC LLC
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Chemours Co FC LLC
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Publication of WO2025160052A1 publication Critical patent/WO2025160052A1/fr
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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
    • C07C17/275—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of hydrocarbons and 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
    • C07C17/26—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

Definitions

  • the present application provides new processes for preparing 1,1,1,2,2,5,5,6,6,6-decafluoro-3- hexene.
  • PFEI perfluoroethyl iodide
  • ethylene also referred to herein as 153-10mczz
  • the present invention involves 4 steps as illustrated in Fig.1. All four steps involve liquid phase reactions.
  • Step 1 comprises reacting PFEI with ethylene in the presence of a radical initiator.
  • Step 3 comprises reacting 1345zf with PFEI in the presence of a radical initiator.
  • the initiator can be chosen from an azo initiator or a peroxide.
  • Step 3 is generally performed at a reaction temperature of from about 100°C to about 150°C. Preferred temperatures depend on the selection of radical initiator.
  • Step 3 can be also performed at a reaction temperature of from about 180°C to about 220°C without using an initiator.
  • Step 4 comprises reacting CF3CF2CH2CHICF2CF3 with an alkali metal hydroxide in the presence of an oxygen-containing phase transfer catalyst. In certain embodiments, Step 4 is performed at temperatures between 20-90°C.
  • the oxygen-containing catalyst may be chosen from a glycol having the formula, H(OCH2CH2)nOH where n is ⁇ 1, e.g., 2, 3, 4 or greater; propylene glycol, a mono ether of polyethylene glycol or a mono ether of propylene glycol.
  • the oxygen-containing catalyst may be a crown ether.
  • the oxygen-containing catalyst is a glycol catalyst.
  • n 1, and the glycol catalyst comprises HOCH2CH2OH (ethylene glycol, EG).
  • n 2
  • the glycol catalyst comprises (HOCH2CH2)2O (diethylene glycol, DEG).
  • n 4
  • the glycol catalyst comprises H(OCH2CH2)4OH (tetraethylene glycol, TeEG).
  • n ⁇ 5 and the glycol catalyst comprises H(OCH2CH2)nOH [H(OCH2CH2)nOH is referred to herein as polyethylene glycol, PEG].
  • the glycol catalyst when the oxygen-containing catalyst is a glycol catalyst, the glycol catalyst comprises PEG having the formula HO(CH2CH2O)nCH2CH2OH and the value of n provides a PEG having molecular weight of about 100 to about 10000.
  • the glycol catalyst when the oxygen-containing catalyst is a glycol catalyst, the glycol catalyst comprises polypropylene glycol having the formula HO(C3H6O)nC3H6OH where the value of n provides a molecular weight in the range of about 100 to about 10000.
  • the glycol catalyst when the oxygen-containing catalyst is a glycol catalyst, the glycol catalyst comprises a mono ether of polyethylene glycol having the formula R(OCH2CH2)nCH2CH2OH, wherein R is a C1 to C5 group and the value of n provides a molecular weight up to about 10000.
  • the glycol catalyst when the oxygen-containing catalyst is a glycol catalyst, the glycol catalyst comprises a mono ether of polypropylene glycol having the formula R(OC3H6)nC3H6OH, wherein R is a C1 to C5 group and the value of n provides a molecular weight up to about 10000.
  • the oxygen-containing catalyst comprises a crown ether.
  • the product of Step 4 is suitable for use in high temperature, and/or electrical and/or heat exchange environments.
  • the process is an integrated process and uses excess initiator for Step 1 and/or Step 3 to produce the product iodo-fluoroalkane that is dehydroiodinated with a base in the presence of a phase transfer catalyst (PTC) in Step 2 and Step 4, respectively, to form the corresponding fluoroalkene.
  • PTC phase transfer catalyst
  • the initiator is selected such that it can be thermally decomposed from a crude product to eliminate purification steps prior to a subsequent dehydroiodination, without thermally decomposing the carbon-containing iodide.
  • the process further comprises thermally treating the Step 1 product to eliminate the initiator and using the treated Step 1 product as a starting material for Step 2 without purification.
  • the process further comprises thermally treating the Step 3 product to eliminate the initiator and using the treated Step 3 product as a starting material for Step 4 without purification.
  • the process further comprises thermally treating the Step 1 product to eliminate the initiator and using the treated Step 1 product as a starting material for Step 2 without purification and thermally treating the Step 3 product to eliminate the initiator and using the treated Step 3 product as a starting material for Step 4 without purification.
  • Fig.1 illustrates an integrated reaction process as disclosed herein.
  • Figs.2A and 2B respectively, show the 19F and 1H NMR spectra taken of isolated 153-10mczz (E/Z ratio 89:11) from Example 6.
  • Figs.3A and 3B respectively, show the 19F and 1H NMR spectra taken of crude reaction mixture (organic layer) after 18h at ambient temperature from Example 7.
  • Fig. 4 shows the 1H NMR taken of isolated product from Example 8.
  • Fig. 1 shows the 19F and 1H NMR taken of isolated product from Example 8.
  • Fig. 6 shows the NMR spectra taken of crude 153-10mczz from Example 11.
  • the process involves a first radical initiated reaction to produce a reaction mixture containing a first crude alkyl halide product which is thermally treated to remove the initiator and provide an initiator-free mixture which is the dehydroiodinated to form a first crude fluoroalkene.
  • the first crude fluoroalkene is reacted with one of a catalyst or radical initiator to produce a second crude alkyl halide, and then the second crude alkyl halide is dehydroiodinated with an oxygen-containing catalyst to produce the desired fluoroalkene.
  • the process is integrated and involves a first radical initiated reaction to produce a reaction mixture containing a first crude fluoroiodoalkane which mixture may be thermally treated to remove the initiator and provide an initiator-free product mixture which is directly dehydroiodinated to form a first crude fluoroalkene.
  • the first crude fluoroalkene is reacted with one of a catalyst or radical initiator to produce a second crude fluoroiodoalkane, and then dehydroiodinated with an oxygen-containing phase transfer catalyst (PTC) to produce the desired fluoroalkene.
  • PTC phase transfer catalyst
  • alkane and alkyl shall be understood to include both branched and straight-chain saturated aliphatic hydrocarbon groups having the specified number of carbon atoms.
  • C1-C8, as in “C1-C8 alkyl” is defined to include groups having 1, 2, 3, 4, 5, 6, 7, or 8 carbons in a linear or branched arrangement.
  • C1-C8alkyl specifically includes methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, i-butyl, pentyl, hexyl, heptyl, octyl, and so on.
  • alkyl refers to C1-C8 alkyl and in a further embodiment, “alkyl” refers to C1-C6 alkyl.
  • olefin shall be understood to mean a C3-C8 or higher alkene.
  • fluoroolefin shall be understood to mean a C3-C8 or higher olefin that incorporates at least one CF3 group.
  • aqueous and/or alcoholic base shall be understood to mean an alkali metal base. Non-limiting examples include KOH and NaOH.
  • phase transfer catalyst shall be understood to mean a catalyst that facilitates the migration of a reactant from one phase into another phase where reaction occurs.
  • Ammonium and phosphonium salts, glycol catalysts described herein, and crown ethers can be phase transfer catalysts.
  • the hydrofluoroalkene product of Step 4 can be used as a heat transfer medium, working fluid, along or combined with other components suitable for use as the heat transfer medium or working fluid to carry heat to and from a source.
  • Such heat transfer compositions may also be useful as a refrigerant in a cycle wherein the fluid undergoes a phase change; that is, from a liquid to a gas and back, or vice versa.
  • heat transfer systems include but are not limited to air conditioners, freezers, refrigerators, heat pumps, water chillers, flooded evaporator chillers, direct expansion chillers, walk-in coolers, high temperature heat pumps, mobile refrigerators, mobile air conditioning units, electric storage cooling systems, battery cooling, immersion cooling systems, data-center cooling systems, and combinations thereof.
  • the hydrofluoroalkene product of Step 4 can be used for immersion cooling is used to cool electronic devices, such as datacenter servers, insulated-gate bipolar transistor (IGBT) devices, telecommunication infrastructure, military electronics, televisions (TVs), cell phones, monitors, drones, automotive batteries, powertrains for electric vehicles (EVs), avionics devices, power devices and displays.
  • IGBT insulated-gate bipolar transistor
  • Immersion cooling systems are heat transfer devices wherein there is no compressor, and the heat transfer medium possesses suitable dielectric properties.
  • the object to be cooled is at least partially immersed in (in direct contact with) the heat transfer fluid contained in a vessel.
  • the heat transfer fluid may evaporate and condense in the vessel.
  • a refrigerant is a compound or mixture of compounds (blend) that function as a heat transfer fluid in a cycle wherein the fluid undergoes a phase change from a liquid to a gas and back.
  • compositions comprising, “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion.
  • a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
  • “or” refers to an inclusive or and not to an exclusive or.
  • a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
  • the transitional phrase “consisting of” excludes any element, step, or ingredient not specified. If in the claim such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase “consists of” appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.
  • transitional phrase “consisting essentially of” is used to define a composition, method that includes materials, steps, features, components, or elements, in addition to those literally disclosed provided that these additional included materials, steps, features, components, or elements do not materially affect the basic and novel characteristic(s) of the claimed invention, especially the mode of action to achieve the desired result of any of the processes of the present invention.
  • Step 1 comprises reacting pentafluoroiodoethane (pentafluoroethyliodide, iodopentafluoroethane, PFEI) and ethylene in the presence of a radical initiator to produce 1,1,1,2,2- pentafluoro-4
  • the radical initiator may be any initiator suitable for use. Preferably suitable for use at a temperature above 30°C, preferably suitable for use at a temperature within the range of 30-90°C.
  • the radical initiator is AIBN.
  • the radical initiator is benzoyl peroxide.
  • the radical initiator is di-tert-butyl peroxide.
  • Step 1 comprises using a starting material comprising PFEI and one or more of I2 and IF5.
  • a starting material comprising CF3CF2I is washed with a base or sulfite salt, e.g., KOH and/or Na2SO3 or Na2S2O5.
  • a base or sulfite salt e.g., KOH and/or Na2SO3 or Na2S2O5.
  • an excess amount of a radical initiator is used in Step 1.
  • excess initiator is used when certain additional the starting material for Step 1 comprises PFEI and one or both of I2 and IF5.
  • a starting material comprising PFEI and one or more of I2 and IF5 is washed with a base or sulfite salt, e.g., KOH and/or Na2SO3 and/or Na2S2O3 and/or Na2S2O5.
  • a starting material comprising PFEI and one or more of I2 and IF5 is washed with KOH.
  • a starting material comprising PFEI and one or more of I2 and IF5 is washed with Na2SO3.
  • a starting material comprising PFEI and one or more of I2 and IF5 is washed with KOH and Na2SO3.
  • Step 1 may comprise the following steps: Step 1a. Charge initiator such as solid AIBN to a reactor. Step 1b. Inert the reactor by N2 pressurization / venting, then evacuate. (This step provides low oxygen in the reactor. Step 1c. Charge the reactor with PFEI. Step 1d.
  • Step 1e Heat the reactor to 30-80°C, preferably 50-80°C, such as 60-70°C.
  • Step 1f Add ethylene to maintain reactor pressure less than ⁇ 120 psig.
  • Step 1g Allow the reactor pressure to reduce over time to limit the ethylene partial pressure.
  • Step 1h When a target mass of ethylene has been added, maintain temperature at 30-80°C, preferably 50-80°C, such as 60-70°C for a period of time of 30 minutes to 5 hours, such as for 2 hours.
  • Step 1i Decompose the initiator, by heating the reactor.
  • Step 1 heat the reactor to a temperature of about 80°C or greater for a minimum of about 30 minute such as for 1 hour, then increase heat such as to 85-100°C and hold for a minimum of about 30 minute such as for 1 hour.
  • Step 1j Cool the reactor to ambient temperature.
  • Step 1k Vent the residual pressure from the head space and purge with N2 to remove residual ethylene.
  • Step 1l Cease agitation.
  • the product of Step 1 is used as the starting material for Step 2. No further purification is needed.
  • Step 1 reactor material of construction is capable of tolerating the environment created by the reactants and products, for example, alloys comprising nickel.
  • a starting material comprising CF3CF2I is washed with a base or sulfite salt, e.g., KOH and/or Na2SO3 and/or Na2S2O3 and/or Na2S2O5.
  • a base or sulfite salt e.g., KOH and/or Na2SO3 and/or Na2S2O3 and/or Na2S2O5.
  • Using the washed starting material improves reactivity of PFEI in Step 1. It is believed the washing of the starting material comprising CF3CF2I removes impurities such as I2 and IF5 which are the common impurities in PFEI.
  • the reaction temperature for Step 1 is greater than 50°C, 60°C, 70°C, or 80°C, less than 60°C, 70°C, or 80°C. [0063] In a certain embodiment, the reaction temperature for Step 1 is in the range of 50-80°C. In a certain embodiment, the reaction temperature for Step 1 is in the range of 60-75°C and the initiator is AIBN.
  • thermal decomposition of AIBN as the radical initiator following the reaction of PFEI and ethylene in the presence of a radical initiator may be performed at a temperature of about 80°C or greater for a minimum of about 30 minute such as for 1 hour, then increase heat such as to 85-100°C and hold for a minimum of about 30 minute such as for 1 hour.
  • thermal decomposition of a peroxide radical initiator following the reaction of PFEI and ethylene in the presence of a radical initiator may be performed at a temperature of 160 to 250°C, preferably 180-230°C, more preferably 190-210°C.
  • Step 2 comprises reacting a starting material comprising PFEEI produced in accordance with Step 1 with an alkali metal hydroxide in the presence of a phase transfer catalyst.
  • the phase transfer catalyst may be chosen from ammonium and phosphonium salts. For example, tetraalkyl ammonium halide and tetraalkyl phosphonium halide.
  • the halide may be Cl or Br.
  • examples include tetra-n-butylammonium bromide (TBAB), and trioctylmethylammonium chloride (Aliquat ® 336).
  • the starting material for Step 2 comprises PFEEI produced in accordance with Step 1 wherein the starting material for Step 1 is washed with a base or sodium salt prior to Step 1.
  • the product from Step 1 comprising PFEEI also comprises excess radical initiator and the excess radical initiator is removed by thermal decomposition prior to use of the product from Step 1 as the starting material for Step 2.
  • alkali metal hydroxide (MOH) solution used in Step 2 is an aqueous solution of KOH.
  • the alkali metal hydroxide solutions of LiOH and NaOH may be used.
  • the concentration of alkali metal hydroxide can be in the range of 20-60% or 20-45%.
  • Step 2 following condensing of Step 1 product and water, the vapor comprising 1345zf is vented from the reactor to maintain the reactor pressure at 17 psig.
  • the vapor comprising 1345zf is passed through a molecular sieve dryer, a second condenser at -15°C, and collected as Step 2 product in a receiver held at a pressure of 2 psig.
  • the Step 2 product comprising 1345zf is used in Step 3.
  • Step 2 may comprise the following general operating steps: Step 2a. Set up a reactor fitted with agitation mechanism, a reflux condenser, and a drying and collection system. Step 2b.
  • Step 2c Charge solid tetrabutylammonium bromide phase transfer catalyst to the reactor.
  • Step 2d Inert the reactor by N2 pressurization / venting then partially evacuate.
  • Step 2e Set the drying and collection system tracing to 43°C for collection Step 2 product comprising 1345zf.
  • Step 2f Start the reactor agitation and heat the reactor to 80°C.
  • Step 2g Feed Step 1 product to the reactor.
  • Step 2h Apply coolant to the reactor reflux condenser to maintain the outlet temperature of the reflux condenser at 35°C.
  • Step 2i
  • the amount of PTC used can be from about 0.1% to about 10%, preferably from about 0.5% to about 5%, more preferably from about 0.5% to about 1.5%.
  • the amount of PTC added may be about 0.0075 kg/kg of product produced in Step 1.
  • Step 2 reactor material of construction is capable of tolerating the environment created by the reactants and products, including alloys where needed. For certain upstream and downstream operations of the reactor, stainless steel may be used.
  • Step 3 comprises a process of reacting a starting material comprising 1345zf produced in accordance with Step 2 with PFEI to produce CF3CF2CH2CHICF2CF3 (1,1,1,2,2,5,5,6,6,6-decafluoro-3-iodohexane).
  • the process is performed in the absence of a radical initiator.
  • the temperature of the reaction is greater than 150°C or greater than 175°C or greater than 200°C, such as 200-250°C.
  • the process comprises reacting a starting material comprising 1345zf produced in accordance with Step 2 with PFEI in the presence of a radical initiator to produce CF3CF2CH2CHICF2CF3 (1,1,1,2,2,5,5,6,6,6- decafluoro-3-iodohexane).
  • a radical initiator to produce CF3CF2CH2CHICF2CF3 (1,1,1,2,2,5,5,6,6,6- decafluoro-3-iodohexane.
  • lower temperatures can be used when Step 3 is performed in the presence of a radical initiator.
  • a starting material comprising PFEI may contain I2 and IF5.
  • the I2 and IF5 can be removed from PFEI by washing with a base or sulfite salt, e.g., KOH and/or Na2SO3.
  • a starting material comprising PFEI and one or more of I2 and IF5 is washed with KOH. In one embodiment, a starting material comprising PFEI and one or more of I2 and IF5 is washed with Na2SO3. In one embodiment, a starting material comprising PFEI and one or more of I2 and IF5 is washed with KOH and Na2SO3. Using the washed starting material may improve reactivity of PFEI in Step 3. It is believed the washing of the starting material comprising CF3CF2I removes impurities such as I2 and IF5 which are the common impurities in PFEI. [0085] The radical initiator may be any initiator suitable for use.
  • the radical initiator may be an azo initiator capable of operating at a temperature of 100°C or more or a peroxide, such as benzoyl peroxide or di-tert-butyl peroxide. Peroxides are preferred.
  • the radical initiator is benzoyl peroxide, and the temperature is in the range of 100-150°C, preferably 110-130°C.
  • the radical initiator is t-butyl peroxide
  • the temperature is in the range of 100-150°C, preferably 110-145°C or 120-140°C or 130-145°C.
  • the process of Step 3 comprises reacting PFEI with a starting material comprising 1345zf in the presence or absence of a radical initiator.
  • the process of Step 3 may be performed as a batch process.
  • Step 3 comprises charging a reactor with PFEI, liquid di-tert-butyl peroxide (“DTBP”) initiator, heating the reactor to 130°C, adding liquefied starting material comprising 1345zf, monitoring pressure, which increases (which increase may rise to 300 psig) and then decreases as starting material comprising 1345zf is added.
  • the starting material comprising 1345zf is produced according to the process of Step 2 as disclosed herein.
  • Step 3 may comprise the following steps: Step 3a. Inert the reactor by N2 pressurization / venting, then evacuate. (This step provides low oxygen in the reactor.) Step 3b. Charge PFEI to the reactor. Step 3a.
  • Step 3c Charge liquid DTBP initiator to the reactor.
  • Step 3c Heat the reactor to 130°C.
  • Step 3d Feed liquid starting material comprising 1345zf to the reactor with a metering pump.
  • Step 3e After the feed is complete, maintain reactor conditions to complete the reaction.
  • Step 3f Hold the reactor at 145°C for sufficient time to decompose the DTBP.
  • Step 3g Cool the reactor to ambient temperature.
  • the product of Step 3 comprises CF3CF2CH2CHICF2CF3 (1,1,1,2,2,5,5,6,6,6-decafluoro-3-iodohexane).
  • the product of Step 3 is used as the starting material for Step 4. No further purification is needed.
  • thermal decomposition of radical initiator following the reaction of PFEI and 1345zf in the presence of a radical initiator may be performed at a temperature 130-250°C, such as 140-180°C or 140-160°C or 180-230°C or 190-210°C. Lower temperatures may require longer times for thermal decomposition.
  • Step 4 comprises reacting a starting material comprising CF3CF2CH2CHICF2CF3 (1,1,1,2,2,5,5,6,6,6-decafluoro-3- iodohexane) produced in accordance with Step 3 with an alkali metal hydroxide in the presence of a phase transfer catalyst.
  • the phase transfer catalyst for Step 4 is an oxygen-containing catalyst.
  • the oxygen-containing catalyst may be chosen from a glycol catalyst having the formula, H(OCH2CH2)nOH where n is ⁇ 1, e.g., 2, 3, 4 or greater; propylene glycol, a mono ether of polyethylene glycol or a mono ether of propylene glycol.
  • the oxygen-containing catalyst is a crown ether.
  • n 1, and the glycol catalyst comprises HOCH2CH2OH (ethylene glycol, EG).
  • n 2
  • the glycol catalyst comprises (HOCH2CH2)2O (diethylene glycol, DEG).
  • n 3OH (triethylene glycol, TrEG).
  • n 4 and the glycol catalyst comprises H(OCH2CH2)4OH (tetraethylene glycol, TeEG).
  • n ⁇ 5 and the glycol catalyst comprises H(OCH2CH2)nOH [H(OCH2CH2)nOH is referred to herein as polyethylene glycol, PEG].
  • the glycol catalyst comprises PEG having the formula HO(CH2CH2O)nCH2CH2OH and the value of n provides a PEG having molecular weight of about 100 to about 10000.
  • the glycol catalyst comprises polypropylene glycol having the formula HO(C3H6O)nC3H6OH where the value of n provides a molecular weight in the range of about 100 to about 10000.
  • the glycol catalyst comprises a mono ether of polyethylene glycol having the formula R(OCH2CH2)nCH2CH2OH, wherein R is a C1 to C5 group and the value of n provides a molecular weight up to about 10000.
  • the glycol catalyst comprises a mono ether of polypropylene glycol having the formula R(OC3H6)nC3H6OH, wherein R is a C1 to C5 group and the value of n provides a molecular weight up to about 10000.
  • the amount of alkali metal hydroxide (MOH) used is from about 0.1% to about 10%, preferably from about 0.5% to about 5%, more preferably from about 0.5% to about 1.5%. M is Li, Na or K.
  • the amount of oxygen-containing catalyst added in Step 4 is about 0.05 kg/kg of the CF3CF2CH2CHICF2CF3 in the starting material for Step 4 comprising the product produced in Step 3.
  • the reaction for Step 4 the dehydroiodination reaction is conducted at a temperature of ambient or greater, such as 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, or 100°C, less than 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, or 100°C, and ranges between from 30°C to one of 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, or 100°C, ranges between from 40°C to one of and 50°C, 60°C, 70°C, 80°C, 90°C, or 100°C, ranges between from 50°C to one of 60°C, 70°C, 80°C, 90°C, or 100°C, ranges between from 50°C to one of 60°C, 70°C, 80°C, 90°C, or 100°C, ranges between from 70°C to one of 80°C, 90°C, 100°C, ranges between
  • the base is defined by the formula MOH as an aqueous solution including but are not limited to greater than one of 30% MOH, 35% MOH, 40% MOH, 50% MOH or 60 % MOH, where M is selected from one of Na, Li, or K and all values and ranges therebetween.
  • the alkali metal hydroxide is KOH or NaOH and the KOH or NaOH is used as an aqueous solution.
  • the aqueous solution includes, but is not limited, to greater than one of 30% KOH or NaOH, 35% KOH or NaOH, 40% KOH or NaOH, 50% KOH or NaOH or 60 % KOH or NaOH.
  • the crude product from Step 3 can be charged directly into Step 4 without purification.
  • the absorbent for removing impurities from a desired fluoroalkene comprises a zeolite.
  • Step 4 is a process which comprises charging an aqueous solution of KOH and then adding oxygen-containing catalyst to a reactor.
  • Step 4j Control the receiver pressure at 2.5 psig.
  • Step 4k When the feed is complete, adjust the reactor pressure to 0 psig and the receiver pressure. to -2.5 psig.
  • Step 4l Continue to heat the reactor at 75°C for a time sufficient complete the reaction.
  • the dehydroiodinated compound is 153-10mczz with an E/Z ratio provides wherein E- 153-10mczz of at least 80%, or at least 85%, or at least 90%, or at least 95%, or at least 98%, or at least 99%.
  • the mixture was heated to 65°C with agitation where the pressure increased to 156 psig and then dropped to 108 psig during the reaction time. Then the temperature was maintained at around 65°C and ethylene was continuously charged to maintain the shaker tube pressure around 150 psig until a total 20g of ethylene was charged. After all the ethylene was charged, the shaker tube was heated to 70°C and agitated at 70°C for about 30 min, then cooled to room temperature. GC analysis of the product showed 97% of CF3CF2CH2CH2I (1,1,1,2,2- pentafluoro-4-iodobutane).
  • TBAB tetrabutylammonium bromide
  • the 160g PFEI was transferred into shaker tube and heated to 125°C with agitation, 1345zf was pumped into shaker tube at 0.2ml/min until 86g of HFO-1345zf was added. After all 1345zf was added, the reactor was agitated at 125°C for another 5 hrs.
  • the GC analysis of organic reaction product showed 38.6% of C2F5CHICH2C2F5 in the product.
  • the main by-products are the 2 nd and 3 rd moles of HFO-1345zf inserted into C2F5CH2CHIC2F5 which were labeled as 1345-di-adduct and 1345-tri-adduct in the GC (FID) analysis given in Table 1..
  • Example 6 was repeated using a solution of 3g KOH in 10 ml H2O (23 wt % solution); 0.3 g PEG 400, 3.1 g C2F5CH2CHIC2F5. Only 50% conversion was achieved after 16h at ambient (room) temperature.
  • Example 1 was repeated by adding 3.1 g C2F5CH2CHIC2F5 to a mixture of 10 ml of 45 wt.% KOH solution and 0.2 g of PEG 400, (mildly exothermic reaction). The NMR scan indicated full conversion into 153-10mczz that after 30min.
  • Run 9A 2 g C2F5CH2CHIC2F5, 0.15 g ethylene glycol (EG) and 5 ml of 45% aqueous KOH were reacted at 40°C for 3 hrs. with a 53% conversion. The reaction continued for another 15 hrs. and conversion increased to 75%.
  • Run 9B 2 g C2F5CH2CHIC2F5, 0.2 g of diethylene glycol (DEG) and 5 ml of 45% aqueous KOH were reacted at 40°C and had a 20% conversion after 0.5 hrs.
  • DEG diethylene glycol
  • Fig.6A presents conversion at 10%;
  • Fig. 6B presents conversion at 20%;
  • Fig.6C presents conversion at 100%.
  • Figs.6A presents conversion at 10%;
  • Fig. 6B presents conversion at 20%;
  • Fig.6C presents conversion at 100%.
  • 10 ml 45% KOH solution in water and 0.2 g of 18-crown-6 ether were placed in a 20 ml glass sample vial equipped with a magnetic stir bar.
  • TrEG Triethylene glycol
  • the KOH/TrEG reaction mixture was first preheated to 65°C and C2F5CH2CHIC2F5 was added slowly, over a 1h period and the product (153-10mczz) was distilled simultaneously and collected as a liquid in a receiver cooled using ice bath.
  • the flask temperature was brought up to 65°C and 153-10mczz started to distill over about 2.5 h, with the flask temperature of 65°C to 105°C.
  • the product with a b.p. of 47- 50°C was collected into cold (wet ice) receiver and 43.8g of crude 153-10mczz (expected 52.3g) was isolated.
  • the yield of 153-10mczz was 84% with a purity of 99% (1% C2F5CH2CHIC2F5 + di-adduct).
  • the E/Z isomers of 153-10mczz- ratio was ⁇ 95:5.
  • the reaction was scaled up, using 567 g of crude C2F5CH2CHIC2F5 (purity 79 wt %) starting material.
  • Fig.7 shows the 1H NMR spectra taken of the isolated 153-10mczz produced in this Example 11.
  • the flask was kept above 65°C during the addition so the column was under reflux (started at a pot/flask temperature of 68°C and head temperature of 42°C, respectively) while C2F5CH2CHIC2F5 was still being added.
  • Product was collected as a liquid in a pre- chilled (wet ice) receiver. Collection of the product happened mostly when the pot temperature was 63°C and the head temperature was 43°C. When addition of the C2F5CH2CHIC2F5 was complete the pot temperature was 66°C and the head temperature was 44°C.
  • the product was washed with ice cold water and stored over magnesium sulfate.
  • C2F5CH CHC2F5 (mixture E- and Z- isomers, ratio 97:3).
  • E- C2F5CH CHC2F5
  • Crude product (C2F5CH2CHIC2F5) contained residual perfluoroethyl iodide (PFEI) (up to 45 wt%) and in order to avoid additional steps involving distillation to remove PFEI and other impurities (including acetone, and others), a number of experiments using C2F5CH2CHIC2F5 product containing 35-45 wt% of PFEI and other by-products were performed.
  • Example 13 provides a typical procedure used for these experiments.
  • the temperature of the reflux condenser was set to 14°C, resulting in C2F5I being flash distilled and collected in the cold trap.
  • the addition of 270 g of crude C2F5CH2CHIC2F5 took about 3h.
  • the reaction mixture turned light brown in color and the head temperature during addition (mild reflux) stayed at 20-22°C.
  • the reaction mixture was kept at 55- 62°C, while low boiling material was collected using a -78°C cold trap. A total of 138g material was collected, which was determined by NMR to be a mixture of 13 wt% (16.6g), 153-10mczz and 86 wt.
  • TrPG tripropylene glycol
  • the crude Step 4 product was fed to approximately the center of the first column which has 55 theoretical plates and operates at 25 psig head pressure.
  • PFEI and low boiling compounds were taken off overhead as required to control the column temperature profile, while E-153-10mczz and high boiling compounds were taken off from the reboiler to maintain reboiler level.
  • the stream from the reboiler is sent to the approximate center of a second distillation column that has 94 theoretical plates and was operateed at 5 psig head pressure.
  • E-153-10mczz was taken as a liquid distillate off the top of the column as required to control reboiler level, while high boiling compounds were purged from the reboiler to control the reboiler temperature.
  • Embodiment 1a A process of embodiment 1 further comprising thermally treating the first alkyl iodide product mixture comprising 1,1,1,2,2-pentafluoro-4- iodobutane to remove the initiator and provide an initiator-free product mixture.
  • Embodiment 2 A process of embodiment 1 further comprising thermally treating the first alkyl iodide product mixture comprising 1,1,1,2,2-pentafluoro-4- iodobutane to remove the initiator and provide an initiator-free product mixture.
  • Embodiment 2a A process of embodiment 2 wherein the first radical initiator is an azo initiator or a peroxide.
  • Embodiment 2b A process embodiment 2 further comprising recovering and purifying at least one of the first, second, third or fourth product mixtures of process embodiment 2 to form a purified product mixture of the desired fluoroalkene.
  • a composition comprising C2F5CH2CH(C2F5)CH2CHIC2F5 (isomeric di-adducts) and C2F5[CH2 CH(C2F5)]2CH2CHIC2F5 (isomeric tri-adducts).
  • a composition comprising C2F5CH CHC2F5 having a ratio of E/Z of at least 90% and further comprising C2F5CH2CH(C2F5)CH2CHIC2F5 (isomeric di- adducts).
  • Embodiment 5 A cooling process and system embodiment using the composition of Embodiment 3 or Embodiment 4.
  • Embodiment 8 A process of Embodiment 1 or 2 wherein Step 1 is conducted at a temperature from 50 to 100°C.
  • Embodiment 9. A process of Embodiment 1 or 2 wherein Step 2 is conducted at a temperature from 50 to 120°C.
  • Embodiment 10 A process of Embodiment 1 or 2 wherein Step 3 is conducted at a temperature from 80 to 250°C.
  • Embodiment 12 A process of Embodiment 1 or 2 wherein Step 4 is conducted at a temperature between from 20 to 100°C.
  • Embodiment 12. A composition embodiment comprising the first alkyl iodide product mixture comprising 1,1,1,2,2-pentafluoro-4-iodobutane of process Embodiment 1 or 2.
  • Embodiment 13 A composition embodiment comprising the first fluoroalkene product mixture comprising 3,3,4,4,4-pentafluoro-1-butene of process Embodiment 1 or 2.
  • a composition embodiment comprising the second alkyl iodide product mixture comprising 1,1,1,2,2,5,5,6,6,6-decafluoro-3-iodohexane of process Embodiment 1 or 2.
  • Embodiment 15 A composition embodiment comprising the second fluoroalkene product mixture comprising 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene of process Embodiment 1 or 2.
  • IGBT insulated-gate bipolar transistor
  • Embodiment 18a A system comprising devices in need of cooling selected from one of electronic devices, datacenter servers, insulated-gate bipolar transistor (IGBT) devices, telecommunication infrastructure, military electronics, televisions (TVs), cell phones, monitors, drones, automotive batteries, powertrains for electric vehicles (EVs), avionics devices, power devices and displays capable of direct or indirect contact with a composition comprising at least 99%, 99.5%

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Abstract

L'invention concerne un procédé intégré de production de E-1,1,1,2,2,5,5,6,6,6-décafluoro-3-hexène à partir d'éthylène et d'iodure de perfluoroéthyle.
PCT/US2025/012380 2024-01-22 2025-01-21 Procédé intégré pour fabriquer du 1,1,1,2,2,5,5,6,6,6-décafluoro-3-hexène Pending WO2025160052A1 (fr)

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Citations (6)

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Publication number Priority date Publication date Assignee Title
US6300532B1 (en) * 1998-12-15 2001-10-09 Alliedsignal Inc. Process for addition of haloalkanes to alkenes catalyzed by an organophosphite compound
US20030060670A1 (en) * 2001-09-25 2003-03-27 Nair Haridasan K. Process for producing fluoroolefins
US20050250966A1 (en) * 2002-06-17 2005-11-10 Yoshirou Funakoshi Metallic copper catalyst for polyfluoroalkylethyl iodide production and process for producing polyfluoroalkylethyl iodide
WO2008097638A1 (fr) * 2007-02-09 2008-08-14 E. I. Du Pont De Nemours And Company Gravure assistée au laser utilisant des compositions gazeuses comprenant des hydrocarbures fluorés insaturés
WO2010075354A1 (fr) * 2008-12-23 2010-07-01 E. I. Du Pont De Nemours And Company Acides éthylène-tétrafluoroéthylène carboxyliques et sels correspondants
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US6300532B1 (en) * 1998-12-15 2001-10-09 Alliedsignal Inc. Process for addition of haloalkanes to alkenes catalyzed by an organophosphite compound
US20030060670A1 (en) * 2001-09-25 2003-03-27 Nair Haridasan K. Process for producing fluoroolefins
US20050250966A1 (en) * 2002-06-17 2005-11-10 Yoshirou Funakoshi Metallic copper catalyst for polyfluoroalkylethyl iodide production and process for producing polyfluoroalkylethyl iodide
US20130037279A1 (en) * 2005-11-01 2013-02-14 E I Du Pont De Nemours And Company Fire extinguishing and fire suppression compositions comprising unsaturated fluorocarbons
WO2008097638A1 (fr) * 2007-02-09 2008-08-14 E. I. Du Pont De Nemours And Company Gravure assistée au laser utilisant des compositions gazeuses comprenant des hydrocarbures fluorés insaturés
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IGUMNOV ET AL: "Copper salt-catalysed reaction of perfluoroalkyl halides with olefins", MENDELEEV COMMUNICATIONS, INSTITUTE OF PHYSICS PUBLISHING, BRISTOL, GB, vol. 16, no. 3, 1 January 2006 (2006-01-01), pages 189 - 190, XP022533365, ISSN: 0959-9436, DOI: 10.1070/MC2006V016N03ABEH002344 *
QIU WEIMING ET AL: "Ethylene-tetrafluoroethylene (ETFE) cotelomer iodides and their transformation to surface protection intermediates", JOURNAL OF FLUORINE CHEMISTRY, vol. 169, 1 January 2015 (2015-01-01), NL, pages 12 - 23, XP093272708, ISSN: 0022-1139, DOI: 10.1016/j.jfluchem.2014.10.004 *

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