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KR-102961890-B1 - Method to produce 1,1,1,4,4,4-hexafluorobutyrite-2-en

KR102961890B1KR 102961890 B1KR102961890 B1KR 102961890B1KR-102961890-B1

Abstract

A method for producing E -1,1,1,4,4,4-hexafluorobut-2-ene comprises the step of contacting 1,1,2,4,4-pentachlorobuta-1,3-diene in the vapor phase in the presence of a fluorination catalyst with hydrogen fluoride. A method for producing Z -1,1,1,4,4,4-hexafluorobut-2-ene further comprises the step of contacting E -1,1,1,4,4,4-hexafluoro-2-butene with chlorine in the presence of a catalyst to produce 2,3-dichloro-1,1,1,4,4,4-hexafluorobutane, then reacting with a base to produce 1,1,1,4,4,4-hexafluoro-2-butine, and subsequently hydrogenating hexafluoro-2-butine to produce Z-1,1,1,4,4,4-hexafluoro-2-butene.

Inventors

  • 펭, 셍
  • 시버트, 앨런 카프론

Assignees

  • 더 케무어스 컴퍼니 에프씨, 엘엘씨

Dates

Publication Date
20260508
Application Date
20200403
Priority Date
20190405

Claims (20)

  1. A method for producing E -1,1,1,4,4,4-hexafluorobuta-2-ene, comprising the step of contacting 1,1,2,4,4-pentachlorobuta-1,3-diene in the vapor phase in the presence of a fluorination catalyst with HF to produce a product mixture containing E -1,1,1,4,4,4-hexafluorobuta-2-ene, wherein the method further comprises the step of producing 1,1,2,4,4-pentachlorobuta-1,3-diene by contacting trichloroethylene with an iron-containing dimerization catalyst to produce a product mixture containing 1,1,2,4,4-pentachlorobuta-1,3-diene.
  2. The method of claim 1, wherein the fluorination catalyst is selected from carbon; graphite; alumina; alumina fluoride; aluminum fluoride; alumina supported on carbon; aluminum fluoride supported on carbon; alumina fluoride supported on carbon; magnesium fluoride supported on aluminum fluoride; metal (including elemental metals, metal oxides, metal halides, and/or other metal salts); metal supported on aluminum fluoride; metal supported on alumina fluoride; metal supported on alumina; and metal supported on carbon; and mixtures of metals.
  3. A method according to claim 1, wherein HF is added in an amount of 10 to 30 moles per mole of 1,1,2,4,4-pentachlorobuta-1,3-diene.
  4. A method according to claim 1, performed at a temperature in the range of 300 to 350℃.
  5. A method according to claim 1, performed at a pressure in the range of 0 to 200 psi (0 to 1.4 MPa).
  6. A method according to claim 1, wherein trichloroethylene is contacted with an iron-containing dimerization catalyst and pentachloroethane.
  7. As a method for generating Z -1,1,1,4,4,4-hexafluorobuty-2-en, (a) a step of contacting trichloroethylene with a dimerization catalyst to produce a product mixture containing 1,1,2,4,4-pentachlorobuta-1,3-diene; (b) a step of contacting 1,1,2,4,4-pentachlorobuta-1,3-diene with HF in the presence of a fluorination catalyst to produce a product mixture containing E -1,1,1,4,4,4-hexafluoro-2-butene - said method is a vapor phase process -; (c) a step of contacting E -1,1,1,4,4,4-hexafluoro-2-butene with a chlorine source to produce a product mixture containing 2,3-dichloro-1,1,1,4,4,4-hexafluorobutane; (d) contacting 2,3-dichloro-1,1,1,4,4,4-hexafluorobutane with a base to produce a product mixture containing 1,1,1,4,4,4-hexafluoro-2-butine; and (e) a method comprising the step of contacting 1,1,1,4,4,4-hexafluoro-2-butine with H₂ to produce a product mixture containing Z-1,1,1,4,4,4-hexafluorobut-2-ene.
  8. The method of claim 7 further comprises the step of recovering 1,1,2,4,4-pentachlorobuta-1,3-diene from the product mixture of step (a); or the step of recovering trichloroethylene from the product mixture of step (a); or the step of recovering E -1,1,1,4,4,4-hexafluoro-2-butene from the product mixture of step (b); or the step of recovering 2,3-dichloro-1,1,1,4,4,4-hexafluorobutane from the product mixture of step (c); or the step of recovering 1,1,1,4,4,4-hexafluoro-2-butene from the product mixture of step (d); or the step of recovering Z -1,1,1,4,4,4-hexafluoro-2-butene from the product mixture of step (e).
  9. The method of claim 7 further comprises the steps of: recovering 1,1,2,4,4-pentachlorobuta-1,3-diene from the product mixture of step (a); recovering trichloroethylene from the product mixture of step (a); recovering E -1,1,1,4,4,4-hexafluoro-2-butene from the product mixture of step (b); recovering 2,3-dichloro-1,1,1,4,4,4-hexafluorobutane from the product mixture of step (c); recovering 1,1,1,4,4,4-hexafluoro-2-butene from the product mixture of step (d); and recovering Z -1,1,1,4,4,4-hexafluoro-2-butene from the product mixture of step (e).
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Description

Method to produce 1,1,1,4,4,4-hexafluorobutyrite-2-en The present invention relates particularly to a method for producing E- and Z- 1,1,1,4,4,4-hexafluoro-2-butene from a source material comprising 1,1,2,4,4-pentachlorobuta-1,3-diene. The present invention further provides a method for producing 1,1,2,4,4-pentachlorobuta-1,3-diene. Many industries have been researching for decades to find substitutes for ozone-depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs). CFCs and HCFCs have been used in a wide range of applications, including as refrigerants, cleaning agents, expansion agents for thermoplastic and thermosetting foams, heat transfer media, gas dielectrics, aerosol propellants, fire extinguishers and suppressants, power cycle working fluids, polymerization media, particulate removal fluids, carrier fluids, buffing abrasives, and displacement drying agents. In seeking substitutes for these versatile compounds, many industries have switched to the use of hydrofluorocarbons (HFCs). HFCs have an ozone depletion potential of zero and are therefore not affected by the phase-out under current regulations resulting from the Montreal Protocol. In addition to the problem of ozone depletion, global warming is another environmental issue for many of these applications. Therefore, there is a need for compositions that meet both low ozone depletion standards and low global warming potential. Certain hydrofluoroolefins are considered to satisfy both objectives. Accordingly, there is a need for a manufacturing method that provides a hydrofluoroolefin and an intermediate useful for producing a chlorine-free hydrofluoroolefin. These materials have an ozone depletion potential of 0 and a low global warming potential. Reference inclusion All publications, patents, and patent applications mentioned herein are incorporated herein by reference to the same extent as if each individual publication, patent, or patent application were specifically and individually included by reference. In the event of a conflict, the present application, including any definitions in this specification, shall prevail. The present invention provides a method for producing the hydrofluoroolefin E -1,1,1,4,4,4-hexafluorobut-2-ene ( E - CF3CH = CHCF3 , E -HFO-1336mzz, E -1336mzz). The method comprises the step of contacting 1,1,2,4,4-pentachlorobuta-1,3-diene ( CCl2 =CClCH= CCl2 , HCC-2320az) in the vapor phase in the presence of a fluorination catalyst with hydrogen fluoride (HF) to produce a product mixture comprising E - CF3CH = CHCF3 . In some embodiments, the product mixture further comprises Z-1,1,1,4,4,4-hexafluoro-2-chloro-2-butene (Z- CF3CCl = CHCF3 , Z -HCFO-1326mxz, Z -1326mxz). Includes. In some embodiments, the fluorination catalyst is a chromium-based catalyst. The chromium catalyst may be chromium oxyfluoride or chromium oxide, supported or unsupported. When supported, the chromium oxyfluoride catalyst or chromium oxide catalyst may be supported on activated carbon, graphite, fluorinated graphite, or fluorinated alumina. In some embodiments, the product mixture further comprises Z- 1326mxz. In some embodiments, E -1336mzz is produced with a selectivity of greater than 90%, greater than 95%, or greater than 99% relative to Z-1336mzz. In some embodiments, the product comprises more than 99.5% of E -1336mzz based on gas chromatography analysis. In some embodiments, E- 1336mzz is recovered from the product mixture. In some embodiments, E -1336mzz can be used for other purposes, such as a foaming agent or a heat transfer fluid. In some embodiments, 1,1,2,4,4-pentachlorobuta-1,3-diene (HCC-2320az, 2320az) is produced according to a process involving the dimerization of trichloroethylene (TCE). A method for producing 2320az includes the step of contacting TCE in the presence of a catalyst to produce a product mixture containing 2320az. In some embodiments, the dimerization of TCE is carried out in the presence of pentachloroethane ( CCl₃CHCl₂ , HCC-120) which accelerates the dimerization process. In a given embodiment, 2320az is produced with a selectivity of 80% or more; in some embodiments, the selectivity is greater than 90% or greater than 95% or greater than 99% or greater than 99.5%. In a given embodiment, 2320az is recovered from the product mixture. In some embodiments, unreacted TCE is recovered and recycled. A method for producing E-1336 mzz is provided herein , comprising: (a) contacting trichloroethylene in the presence of a catalyst and optionally pentachloroethane ( CHCl₂CCl₃ ) to produce a product mixture containing 2320az; and (b) contacting 2320az in the vapor phase in the presence of a catalyst to produce a product mixture containing E -1336 mzz. A method for producing Z -1,1,1,4,4,4-hexafluorobutane-2-ene ( Z - CF3CH = CHCF3 , Z -HFO-1336mzz, Z -1336mzz) is further provided. The method comprises the steps of: (a) contacting trichloroethylene in the presence of a catalyst and optionally pentachloroet