Process for producing z-1, 1, 1, 4, 4, 4-hexafluoro-2-butene intermediates and compositions thereof

Abstract

Provided are methods of synthesizing intermediates, such as 2-chloro-1, 1, 1, 4, 4, 4-hexafluoro-2-butene and 2, 3-dichloro-1, 1, 1, 4, 4, 4-hexafluoro-2-butene, which are useful in the production of fluorinated olefins, such as 1, 1, 1, 4, 4, 4-hexafluoro-2-butene, from hexafluorobutadiene.

Description

TECHNICAL FIELD

[0001] The present disclosure relates generally to methods of synthesis of fluorinated olefins. More specifically, the present invention relates to methods and systems for making intermediates such as 2-chloro-1,1,1,4,4,4-hexafluorobut-2-ene and 2,3-dichloro-1,1,1,4,4,4-hexafluorobut-2-ene, which can be used to make fluorinated olefins such as 1,1,1,4,4,4-hexafluoro-2-butene from hexachlorobutadiene. BACKGROUND

[0002] The fluorocarbon industry has been working for the past several decades to find replacement refrigerants for the ozone-depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) that are being phased out by the Montreal Protocol. The solution for many applications has been the commercialization of hydrofluorocarbon (HFC) compounds for use as refrigerants, solvents, fire extinguishants, blowing agents, and propellants. These currently most widely used new compounds, such as HFC refrigerants, HFC-134a and HFC-125, have zero ozone depletion potential and are therefore not affected by the current Montreal Protocol phase-out provisions.

[0003] In addition to the problem of ozone depletion, global warming is another environmental problem for many of these applications. Therefore, there is a need for compositions that meet low ozone depletion standards and also have low global warming potential. Certain hydrofluoroolefins are believed to meet both of these goals. Therefore, there is a need for a manufacturing process that provides hydrofluoroolefins that are free of chlorine and also have a lower global warming potential.

[0004] (Z)-1,1,1,4,4,4-hexafluoro-2-butene (Z-HFO-1336mzz) is an example of such a hydrofluoroolefin. The present invention provides an economical system and method for making intermediate compounds from hexachlorobutadiene (HCBD), which can then be converted to form the desired Z-HFO-1336mzz hydrofluoroolefin.

[0005] HCBD is produced primarily in chlorofluorination plants as a byproduct in the production of carbon tetrachloride and tetrachloroethylene. Both of these commodities are produced on a large scale, so generally sufficient HCBD is available to meet industrial demand. Therefore, HCBD can constitute a low cost and available starting material for a manufacturing process to provide halogenated hydrocarbons and fluoroolefins.

[0006] Furthermore, as a byproduct in the production of carbon tetrachloride and tetrachloroethylene, HCBD constitutes a waste material that must be disposed of to prevent environmental pollution. Therefore, the manufacturing process of the present invention utilizes HCBD as a starting material for the production of hydrofluoroolefins, converting a potential environmental pollutant waste into an environmentally friendly product. SUMMARY

[0007] Any of the embodiments of the application discussed herein can be used alone or in combination with each other. Those skilled in the art will appreciate that different embodiments discussed herein can be combined and form part of the application. Those skilled in the art will also appreciate that certain aspects of different embodiments discussed herein can be combined and form part of the application.

[0008] Embodiment 1 : A method of making a compound of the formula CF3CR=CCICF3, wherein R is H or CI, the method comprising reacting a composition comprising hexachlorobutadiene (HCBD) and one or more additional compounds selected from 1,1,3,3,4,4-hexachloro-1-butene (C4H2CI6), carbon tetrachloride (CC14), pentachloroethane (C2HCI5, HCC-120), tetrachloroethylene (CO-1110), hexachloroethane (C2CI6, CC-110), pentachloropyridine (C5CI5N), 1,1,2,3,3-pentachloroprop-1-ene (C3HCl5, CCI2=CHCCI3, HCCO-1220az), 1,1,1,2,2,3,3-heptachloropropane (C2CI5CHCI2), pentachlorocyclopropane (C3HCl5), 1,2,3,3-tetrachloro-1-propene (C3H2CI4), pentachlorobutadiene isomers (CCI2=CH-CCI=CCI2, Z / E-CHCI=CCI-CCI=CCI2), tetrachlorothiophene (C4CI4S), and trichloroethylene in the presence of a catalyst to obtain a product mixture comprising a compound of the formula CF3CR=CCICF3.

[0009] Embodiment 2: The method of embodiment 1, wherein the compound of the formula CF3CR=CCICF3 is 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene.

[0010] Embodiment 3: The method of any one of embodiments 1 to 2, alone or in any combination thereof, the method comprising reacting the composition comprising HCBD and one or more additional compounds with HF in the presence of a fluorination catalyst to produce a product mixture comprising 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene.

[0011] Embodiment 4: The method of any one of embodiments 2 to 3, wherein greater than about 99 mole % of the produced 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene is (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene.

[0012] Embodiment 5: The process of any one of embodiments 2 to 4, individually or any combination thereof, wherein the fluorination catalyst is a transition metal catalyst selected from a tantalum catalyst, a niobium catalyst, or a tantalum-niobium catalyst.

[0013] Embodiment 6: The process of embodiment 5, wherein the transition metal catalyst is selected from tantalum (V) chloride, niobium (V) chloride, niobium (IV) chloride, and combinations of two or more.

[0014] Embodiment 7: The process of any one of embodiments 2 to 4, individually or any combination thereof, wherein the fluorination catalyst is a metal halide selected from an antimony halide, a tin halide, a thallium halide, an iron halide, and combinations of two or more.

[0015] Embodiment 8: The process of embodiment 7, wherein the metal halide catalyst is selected from SbCl5, SbCl3, SbF5, SnCl4, TiCl4, NiF5, FeCl3, and combinations of two or more, and preferably the metal halide catalyst is SbCl5or SbF5.

[0016] Embodiment 9: The process of any one of embodiments 3 to 8, individually or any combination thereof, wherein a molar excess of HF is used based on 1 mole equivalent of hexachlorobutadiene.

[0017] Embodiment 10: The process of any one of embodiments 3 to 8, individually or any combination thereof, wherein the process is conducted at a temperature of about 80 °C to about 150 °C.

[0018] Embodiment 11: The process of any one of embodiments 2 to 8, individually or any combination thereof, wherein the 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene of the product mixture is Z-chloro-1,1,1,4,4,4-hexafluoro-2-butene.

[0019] HCFC-336maf (2,2-dichloro-1,1,1,4,4,4-hexafluorobutane); HCFC-336lbf (1,2-dichloro-1,1,2,4,4,4-hexafluorobutane); HCFC-337mbf (2-chloro-1,1,1,2,4,4,4-heptafluorobutane); HCFC-337mde (2-chloro-1,1,1,3,4,4,4-heptafluorobutane); HFC-356mff (1,1,1,4,4,4-hexafluorobutane); HCFC-346mdf (2-chloro-1,1,1,4,4,4-hexafluorobutane); HFC-338mf (1,1,1,2,2,4,4,4-octafluorobutane); HCFC-1122 (2-chloro-1,1-difluoroethene); HCFC-124 (2-chloro-1,1,1,2-tetrafluoroethane); CFC-114 (1,2-dichloro-1,1,2,2-tetrafluoroethane); CFC-113 (1,1,2-trichloro-1,2,2-trifluoroethane); CFC-133a (2-chloro-1,1,1-trifluoroethane); HCFC-123 (2,2-dichloro-1,1,1-trifluoroethane); HCFC-123a (1,2-dichloro-1,1,2-trifluoroethane); HCFC-122 (1,2,2-trichloro-1,1-difluoroethane); CFC-112a (1,1,1,2-tetrachloro-2,2-difluoroethane); HCFC-224db (1,1,1,3-tetrafluoro-2,3,3-trichloropropane); 33 dichloro-1,1,3,3,3-pentafluoropropane); HCFC-235da (2-chloro-1,1,1,3,3-pentafluoropropane); CFC-235fa (1-chloro-1,1,3,3,3-pentafluoropropane); and HFC-236fa (1,1,1,3,3,3-hexafluoropropane).

[0020] Embodiment 13: The process of any one of embodiments 2 to 11, individually or any combination thereof, wherein the product mixture further comprises one or more additional compounds selected from the group consisting of E-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene, E-CFO-1317mx (E-2-chloro-1,1,1,3,4,4,4-heptafluorobut-2-ene), Z-CFO-1317mx (Z-2-chloro-1,1,1,3,4,4,4-heptafluorobut-2-ene), and HCFC-336mdd (2,3-dichloro-1,1,1,4,4,4-hexafluorobutane).

[0021] Embodiment 14: The process of any one of embodiments 2 to 11, individually or any combination thereof, wherein the product mixture further comprises HCFC-336mdd (2,3-dichloro-1,1,1,4,4,4-hexafluorobutane).

[0022] Embodiment 15: The process of any one of embodiments 2 to 14, individually or any combination thereof, further comprising continuously dehydrochlorinating the Z-chloro-1,1,1,4,4,4-hexafluorobut-2-ene to produce hexafluoro-2-butyne, and then hydrogenating the hexafluoro-2-butyne to produce (Z)-1,1,1,4,4,4-hexafluoro-2-butene.

[0023] Embodiment 16: The process of any one of embodiments 2 to 14, individually or any combination thereof, further comprising continuously dechlorinating a mixture of the Z-chloro-1,1,1,4,4,4-hexafluorobut-2-ene and 2,3-dichloro-1,1,1,4,4,4-hexafluorobutane to produce hexafluoro-2-butyne, and then hydrogenating the hexafluoro-2-butyne to produce (Z)-1,1,1,4,4,4-hexafluoro-2-butene.

[0024] Embodiment 17: The process of any one of embodiments 2 to 14, individually or any combination thereof, wherein the process is conducted in the liquid phase.

[0025] Embodiment 18: The process of embodiment 1, wherein the compound of the formula CF3CR=CClCF3 is 2,3-dichloro-1,1,1,4,4,4-hexafluorobut-2-ene.

[0026] Embodiment 19: The process of any one of embodiments 1 and 18, individually or any combination thereof, comprising reacting the composition comprising HCBD and one or more additional compounds with HF and chlorine in the presence of a metal oxide or metal halide catalyst to produce a product mixture comprising 2,3-dichloro-1,1,1,4,4,4-hexafluorobut-2-ene.

[0027] Embodiment 20: The method of any one of embodiments 1, 18, and 19, individually or any combination thereof, wherein the 2,3-dichloro-1,1,1,4,4,4-hexafluorobut-2-ene comprises Z isomer and E isomer.

[0028] Embodiment 21: The method of any one of embodiments 19 and 20, wherein the metal halide catalyst is selected from the group consisting of nickel halide, chromium halide, iron halide, scandium halide, yttrium halide, lanthanum halide, titanium halide, zirconium halide, hafnium halide, vanadium halide, molybdenum halide, tungsten halide, manganese halide, rhenium halide, ruthenium halide, osmium halide, cobalt halide, palladium halide, copper halide, zinc halide, antimony halide, tantalum halide, aluminum halide, tin halide, lead halide, and mixtures thereof.

[0029] Embodiment 22: The method of embodiment 21, wherein the metal halide catalyst is unsupported or supported on activated carbon.

[0030] Embodiment 23: The method of embodiment 22, wherein the activated carbon is optionally acid washed or base washed.

[0031] Embodiment 24: The method of any one of embodiments 19 to 20, wherein the metal oxide catalyst is selected from the group consisting of chromium oxide, aluminum oxide, and mixtures thereof.

[0032] Embodiment 25: The method of embodiment 24, wherein the metal oxide catalyst is unsupported or supported on activated carbon.

[0033] Embodiment 26: The method of embodiment 25, wherein the activated carbon is optionally acid washed or base washed.

[0034] Embodiment 27: The method of any one of embodiments 19 to 26, wherein the catalyst comprises a chloride source for the method of embodiment 19.

[0035] Embodiment 28: The method of any one of embodiments 19 to 27, wherein a molar excess of HF is used based on 1 molar equivalent of hexachlorobutadiene.

[0036] Embodiment 29: The method of any one of embodiments 19 to 28, wherein a molar excess of chlorine is used based on 1 molar equivalent of hexachlorobutadiene.

[0037] Embodiment 30: The method of any one of embodiments 1 and 18 to 29, wherein the method is carried out at a temperature of about 230 °C to about 480 °C.

[0038] Embodiment 31 : The method of any one of embodiments 1 and 18 to 30, wherein the product mixture comprises E-2,3-dichloro-1,1,1,4,4,4-hexafluorobut-2-ene and Z-2,3-dichloro-1,1,1,4,4,4-hexafluorobut-2-ene.

[0039] Embodiment 32: The method of any one of embodiments 1 and 18 to 31, wherein the product mixture further comprises one or more additional compounds selected from the group consisting of Z-2-chloro-1,1,1,4,4,4-hexafluorobut-2-ene (Z-HCFO-1326mxz); E-2-chloro-1,1,1,4,4,4-hexafluorobut-2-ene (E-HCFO-1326mxz); E-2-chloro-1,1,1,3,4,4,4-hexafluoro-2-butene (E-CFO-1317mx); Z-2-chloro-1,1,1,3,4,4,4-hexafluoro-2-butene (Z-CFO-1317mx); E-1,2,3-trichloro-1,1,4,4,4-pentafluoro-2-butene (E-CFO-1315lxx); Z-1,2,3-trichloro-1,1,4,4,4-pentafluoro-2-butene (Z-CFO-1315lxx); E-1,1,2,3-tetrachloro-1,4,4,4-tetrafluoro-2-butene (E-CFO-1314kxx); Z-1,1,2,3-tetrachloro-1,4,4,4-tetrafluoro-2-butene (Z-CFO-1314kxx); HCFC-2-chloro-1,1,1,4,4,4-hexafluorobutane (HFC-346mdf); and 1,1,1,3,3,3-hexafluoropropane (HFC-236fa).

[0040] Embodiment 33: The method of any one of embodiments 1 and 18 to 32, wherein the product mixture further comprises one or more additional compounds selected from the group consisting of Z-2-chloro-1,1,1,4,4,4-hexafluorobut-2-ene (Z-HCFO-1326mxz) and E-2-chloro-1,1,1,4,4,4-hexafluorobut-2-ene (E-HCFO-1326mxz).

[0041] Embodiment 34: The method of any one of embodiments 1 and 18 to 33, wherein the product mixture further comprises Z-2-chloro-1,1,1,4,4,4-hexafluorobut-2-ene (Z-HCFO-1326mxz).

[0042] Embodiment 35: The method of any one of embodiments 18-34, further comprising continuously dechlorinating the 2,3-dichloro-1,1,1,4,4,4-hexafluorobut-2-ene to produce hexafluoro-2-butyne, and then hydrogenating the hexafluoro-2-butyne to produce (Z)-1,1,1,4,4,4-hexafluoro-2-butene.

[0043] Embodiment 36: The method of any one of embodiments 18-35, wherein the method is conducted in the gas phase.

[0044] Embodiment 37: A composition comprising hexachlorobutadiene and one or more additional compounds selected from 1,1,3,3,4,4-hexachloro-1-butene (C4H2Cl6), carbon tetrachloride (CC14), pentachloroethane (C2HCl5, HCC-120), tetrachloroethylene (CO-1110), hexachloroethane (C2Cl6, CC-110), pentachloropyridine (C5Cl5N), 1,1,2,3,3-pentachloroprop-1-ene (C3HCl5, CCl2=CHCCl3, HCCO-1220az), 1,1,1,2,2,3,3-heptachloropropane (C2Cl5CHCl2), pentachlorocyclopropane (C3HCl5), 1,2,3,3-tetrachloro-1-propene (C3H2Cl4), pentachlorobutadiene isomers (CCl2=CH-CCl=CCl2, Z / E-CHCl=CCl-CCl=CCl2), tetrachlorothiophene (C4Cl4S), and trichloroethylene.

[0045] Embodiment 38: The composition of embodiment 37, wherein the one or more additional compounds are present in an amount less than about 10 wt%, preferably less than about 5 wt%, more preferably less than about 1 wt%, most preferably less than about 0.5 wt%.

[0046] HCFC-1122 (2-chloro-1,1-difluoroethene); HCFC-124 (2-chloro-1,1,1,2- tetrafluoroethane); CFC-114 (1,2-dichloro-1,1,2,2-tetrafluoroethane); CFC-113 (1,1,2- trichloro-1,2,2-trifluoroethane); CFC-133a (2-chloro-1,1,1-trifluoroethane); HCFC-123 (2,2- dichloro-1,1,1-trifluoroethane); HCFC-123a (1,2-dichloro-1,1,2-trifluoroethane); HCFC-122 (1,2,2-trichloro-1,1-difluoroethane); CFC-112a (1,1,1,2-tetrachloro-2,2- difluoroethane); HCFC-224db (1,1,1,3-tetrafluoro-2,3,3-trichloropropane); E-CFO-1317mx (E-2- chloro-1,1,1,3,4,4,4-heptafluorobut-2-ene); Z-CFO-1317mx (Z-2-chloro-1,1,1,3,4,4,4- heptafluorobut-2-ene); HCFC-225da (1,2-dichloro-1,1,3,3,3-pentafluoropropane); HCFC-235da (2- chloro-1,1,1,3,3-pentafluoropropane);CFC-235fa (1-chloro-1,1,3,3,3-pentafluoropropane); and HFC-236fa (1,1,1,3,3,3-hexafluoropropane).

[0047] Embodiment 40: The composition of embodiment 39, wherein the one or more additional compounds are present in an amount less than about 10 wt%, preferably less than about 5 wt%, more preferably less than about 1 wt%, most preferably less than about 0.5 wt%.

[0048] Embodiment 41 : A composition comprising Z-chloro-1,1,1,4,4,4-hexafluorobut-2-ene and one or more additional compounds selected from E-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene and HCFC-336mdd (2,3-dichloro-1,1,1,4,4,4-hexafluorobutane).

[0049] Embodiment 42: The composition of embodiment 41, wherein the one or more additional compounds are present in an amount less than about 10 wt%, preferably less than about 5 wt%, more preferably less than about 1 wt%, most preferably less than about 0.5 wt%.

[0050] Embodiment 43: A composition comprising Z-chloro-1,1,1,4,4,4-hexafluorobut-2-ene and HCFC-336mdd (2,3-dichloro-1,1,1,4,4,4-hexafluorobutane), wherein the HCFC-336mdd is present in an amount less than about 10 wt%, preferably less than about 5 wt%, more preferably less than about 1 wt%, most preferably less than about 0.5 wt%.

[0051] Embodiment 44: A composition comprising E-2,3-dichloro-1,1,1,4,4,4- hexafluorobut-2-ene; Z-2,3-dichloro-1,1,1,4,4,4-hexafluorobut-2-ene; and one or more additional compounds selected from the group consisting of: Z-2-chloro-1,1,1,4,4,4- hexafluorobut-2-ene (Z-HCFO-1326mxz); E-2-chloro-1,1,1,4,4,4-hexafluorobut-2-ene (E-HCFO-1326mxz); E-2-chloro-1,1,1,3,4,4,4-hexafluoro-2-butene (E-CFO-1317mx); Z-2-chloro-1,1,1,3,4,4,4-hexafluoro-2-butene (Z-CFO-1317mx); E-1,2,3-trichloro-1,1,4,4,4-pentafluoro-2-butene (E-CFC-1315lxx); Z-1,2,3-trichloro-1,1,4,4,4-pentafluoro-2-butene (Z-CFC-1315lxx); E-1,1,2,3-tetrachloro-1,4,4,4-tetrafluoro-2-butene (E-CFC-1314kxx); Z-1,1,2,3-tetrachloro-1,4,4,4-tetrafluoro-2-butene (Z-CFC-1314kxx); 2-chloro-1,1,1,4,4,4-hexafluorobutane (HFC-346mdf); and 1,1,1,3,3,3-hexafluoropropane (HFC-236fa).

[0052] Embodiment 45: The composition of embodiment 44, wherein the one or more additional compounds are present in an amount less than about 10 wt%, preferably less than about 5 wt%, more preferably less than about 1 wt%, most preferably less than about 0.5 wt%.

[0053] Embodiment 46: The method of any one of embodiments 1 to 36, individually or any combination thereof, wherein the composition comprising HCBD is supplied from a reactor without storage.

[0054] Implementation Scheme 47: An integrated system for preparing compounds of the formula CF3CR=CClCF3, wherein R is H or Cl, the system comprising: a first reactor configured to produce, in the presence of a catalyst, a composition comprising hexachlorobutadiene (HCBD) and one or more additional compounds to obtain a product mixture comprising a compound of the formula CF3CR=CClCF3, wherein the one or more additional compounds are selected from 1,1,3,3,4,4-hexachloro-1-butene (C4H2Cl6), carbon tetrachloride (CCl4), pentachloroethane (C2HCl5, HCC-120), tetrachloroethylene (CO-11), etc. 10) Hexachloroethane (C2Cl6, CC-110), pentachloropyridine (C5Cl5N), 1,1,2,3,3-pentachloroprop-1-ene (C3HCl5, CCl2=CHCCl3, HCCO-1220az), 1,1,1,2,2,3,3-heptachloropropane (C2Cl5CHCl2), pentachlorocyclopropane (C3HCl5), 1,2,3,3-tetrachloro-1-propene (C3H2Cl4), pentachlorobutadiene isomers (CCl2=CH-CCl=CCl2, Z / E-CHCl=CCl-CCl=CCl2), tetrachlorothiophene (C4Cl4S), and trichloroethylene. A second reactor, connected to the first reactor, is configured to convert the composition containing HCBD into a compound of the formula CF3CR=CClCF3.

[0055] Implementation Scheme 48: The integrated system according to Implementation Scheme 47, wherein the composition containing HCBD is supplied from the first reactor to the second reactor without storage.

[0056] Implementation Scheme 49: The integrated system according to Implementation Scheme 47 or 48, wherein the compound of the formula CF3CR=CClCF3 is 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene.

[0057] Implementation Scheme 50: An integrated system according to any one of Implementation Schemes 47 to 49, alone or in any combination thereof, wherein in the second reactor, a composition comprising HCBD and one or more additional compounds is reacted with HF in the presence of a fluorination catalyst to produce a product mixture comprising 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene.

[0058] Implementation Scheme 51: The integrated system according to any one of Implementation Schemes 49 to 50, wherein more than about 99 mol% of the produced 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene is (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene.

[0059] Embodiment 52: The integrated system according to any one of embodiments 49-51, individually or any combination thereof, wherein the fluorination catalyst is a transition metal catalyst selected from a tantalum catalyst, a niobium catalyst, or a tantalum-niobium catalyst.

[0060] Embodiment 53: The integrated system according to embodiment 52, wherein the transition metal catalyst is selected from tantalum (V) chloride, niobium (V) chloride, niobium (IV) chloride, and combinations of two or more.

[0061] Embodiment 54: The integrated system according to any one of embodiments 49-51, individually or any combination thereof, wherein the fluorination catalyst is a metal halide selected from antimony halide, tin halide, thallium halide, iron halide, and combinations of two or more.

[0062] Embodiment 55: The integrated system according to embodiment 54, wherein the metal halide catalyst is selected from SbCl5, SbCl3, SbF5, SnCl4, TiCl4, NiF5, FeCl3, and combinations of two or more, and preferably the metal halide catalyst is SbCl5or SbF5.

[0063] Embodiment 56: The integrated system according to any one of embodiments 50-55, individually or any combination thereof, wherein a molar excess of HF is used based on 1 mole equivalent of hexachlorobutadiene.

[0064] Embodiment 57: The integrated system according to any one of embodiments 50-55, individually or any combination thereof, wherein the second reactor is operated at a temperature of about 80 °C to about 150 °C.

[0065] Embodiment 58: The integrated system according to any one of embodiments 49-55, individually or any combination thereof, wherein the 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene of the product mixture is Z-chloro-1,1,1,4,4,4-hexafluoro-2-butene.

[0066] HCFC-337mde (2-chloro-1,1,1,3,4,4,4-heptafluorobutane); HFC-356mff (1,1,1,4,4,4-hexafluorobutane); HCFC-346mdf (2-chloro-1,1,1,4,4,4-hexafluorobutane); HFC-338mf (1,1,1,2,2,4,4,4-octafluorobutane); HCFC-1122 (2-chloro-1,1-difluoroethene); HCFC-124 (2-chloro-1,1,1,2-tetrafluoroethane); CFC-114 (1,2-dichloro-1,1,2,2-tetrafluoroethane); CFC-113 (1,1,2-trichloro-1,2,2-trifluoroethane); CFC-133a (2-chloro-1,1,1-trifluoroethane); HCFC-123 (2,2-dichloro-1,1,1-trifluoroethane); HCFC-123a (1,2-dichloro-1,1,2-trifluoroethane); HCFC-122 (1,2,2-trichloro-1,1-difluoroethane); CFC-112a (1,1,1,2-tetrachloro-2,2-difluoroethane); HCFC-224db (1,1,1,3-tetrafluoro-2,3,3-trichloropropane); 33 dichloro-1,1,3,3,3-pentafluoropropane); HCFC-235da (2-chloro-1,1,1,3,3-pentafluoropropane); CFC-235fa (1-chloro-1,1,3,3,3-pentafluoropropane); and HFC-236fa (1,1,1,3,3,3-hexafluoropropane).

[0067] Embodiment 60: The integrated system according to any one of embodiments 49 to 58, individually or any combination thereof, wherein the product mixture further comprises one or more additional compounds selected from the group consisting of E-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene, E-CFO-1317mx (E-2-chloro-1,1,1,3,4,4,4-heptafluorobut-2-ene), Z-CFO-1317mx (Z-2-chloro-1,1,1,3,4,4,4-heptafluorobut-2-ene), and HCFC-336mdd (2,3-dichloro-1,1,1,4,4,4-hexafluorobutane).

[0068] Embodiment 61: The integrated system according to any one of embodiments 49 to 58, individually or any combination thereof, wherein the product mixture further comprises HCFC-336mdd (2,3-dichloro-1,1,1,4,4,4-hexafluorobutane).

[0069] Embodiment 62: The integrated system according to any one of embodiments 49 to 61, individually or any combination thereof, wherein the second reactor is a liquid phase reactor.

[0070] Embodiment 63: The integrated system according to embodiment 47, wherein the compound of the formula CF3CR=CClCF3 is 2,3-dichloro-1,1,1,4,4,4-hexafluorobut-2-ene.

[0071] Embodiment 64: The integrated system according to any one of embodiments 47 and 63, individually or any combination thereof, wherein in the second reactor, the composition comprising HCBD and one or more additional compounds is reacted with HF and chlorine in the presence of a metal oxide or metal halide catalyst to produce a product mixture comprising 2,3-dichloro-1,1,1,4,4,4-hexafluorobut-2-ene.

[0072] Embodiment 65: The integrated system according to any one of embodiments 47, 63, and 64, individually or any combination thereof, wherein the 2,3-dichloro-1,1,1,4,4,4-hexafluorobut-2-ene comprises Z and E isomers.

[0073] Embodiment 66: The integrated system according to any one of embodiments 64 and 65, wherein the metal halide catalyst is selected from the group consisting of nickel halides, chromium halides, iron halides, scandium halides, yttrium halides, lanthanum halides, titanium halides, zirconium halides, hafnium halides, vanadium halides, molybdenum halides, tungsten halides, manganese halides, rhenium halides, ruthenium halides, osmium halides, cobalt halides, palladium halides, copper halides, zinc halides, antimony halides, tantalum halides, aluminum halides, tin halides, lead halides, and mixtures thereof.

[0074] Embodiment 67: The integrated system of embodiment 66, wherein the metal halide catalyst is unsupported or supported on activated carbon.

[0075] Embodiment 68: The integrated system of embodiment 67, wherein the activated carbon is optionally acid or base washed.

[0076] Embodiment 69: The integrated system of any one of embodiments 64 to 65, wherein the metal oxide catalyst is selected from the group consisting of chromium oxide, aluminum oxide, and mixtures thereof.

[0077] Embodiment 70: The integrated system of embodiment 69, wherein the metal oxide catalyst is unsupported or supported on activated carbon.

[0078] Embodiment 71 : The integrated system of embodiment 70, wherein the activated carbon is optionally acid or base washed.

[0079] Embodiment 72: The integrated system of any one of embodiments 64 to 71, wherein the catalyst comprises a chloride source for the system of embodiment 64.

[0080] Embodiment 73: The integrated system of any one of embodiments 63 to 72, wherein the second reactor is operated at a temperature of about 230 °C to about 480 °C.

[0081] Embodiment 74: The integrated system of any one of embodiments 63 to 73, wherein the product mixture comprises E-2,3-dichloro-1,1,1,4,4,4-hexafluorobut-2-ene and Z-2,3-dichloro-1,1,1,4,4,4-hexafluorobut-2-ene.

[0082] Embodiment 75: The integrated system according to any of Embodiments 63-74, wherein the product mixture further comprises one or more additional compounds selected from the group consisting of Z-2-chloro-1,1,1,4,4,4-hexafluorobut-2-ene (Z-HCFO-1326mxz); E-2-chloro-1,1,1,4,4,4-hexafluorobut-2-ene (E-HCFO-1326mxz); E-2-chloro-1,1,1,3,4,4,4-hexafluoro-2-butene (E-CFO-1317mx); Z-2-chloro-1,1,1,3,4,4,4-hexafluoro-2-butene (Z-CFO-1317mx); E-1,2,3-trichloro-1,1,4,4,4-pentafluoro-2-butene (E-CFO-1315lxx); Z-1,2,3-trichloro-1,1,4,4,4-pentafluoro-2-butene (Z-CFO-1315lxx); E-1,1,2,3-tetrachloro-1,4,4,4-tetrafluoro-2-butene (E-CFO-1314kxx); Z-1,1,2,3-tetrachloro-1,4,4,4-tetrafluoro-2-butene (Z-CFO-1314kxx); HCFC-2-chloro-1,1,1,4,4,4-hexafluorobutane (HFC-346mdf); and 1,1,1,3,3,3-hexafluoropropane (HFC-236fa).

[0083] Embodiment 76: The integrated system according to any of Embodiments 63-74, wherein the product mixture further comprises one or more additional compounds selected from the group consisting of Z-2-chloro-1,1,1,4,4,4-hexafluorobut-2-ene (Z-HCFO-1326mxz) and E-2-chloro-1,1,1,4,4,4-hexafluorobut-2-ene (E-HCFO-1326mxz).

[0084] Embodiment 77: The integrated system according to any of Embodiments 63-74, wherein the product mixture further comprises Z-2-chloro-1,1,1,4,4,4-hexafluorobut-2-ene (Z-HCFO-1326mxz).

[0085] Embodiment 78: The integrated system according to any of Embodiments 63-77, wherein the second reactor is a gas phase reactor. BRIEF DESCRIPTION OF DRAWINGS

[0086] The following detailed description of preferred embodiments of the application will better be understood when read in connection with the accompanying drawings, wherein:

[0087] Figure 1is a schematic of an integrated system and method for preparing a compound of formula CF3CR=CCICF3 from hexachlorobutadiene according to an embodiment of the application. DETAILED DESCRIPTION

[0088] The present application generally relates to methods and intermediates for preparing compounds of formula CF3CR=CCICF3 (where R is CI or H) using hexachlorobutadiene (HCBD) as a starting material.

[0089] In some embodiments, the reactors and related equipment used to carry out these methods to convert HCBD to compounds of formula CF3CR=CCICF3 (where R is CI or H) can be integrated with, coupled to, or built on-site with chlorocarbon facilities, such as those used to produce carbon tetrachloride and tetrachloroethylene. Thus, the byproduct HCBD would not need to be disposed of or otherwise handled and / or transported, but can be used directly in these methods. More specifically, a HCBD waste stream from a first system and method, such as one used to produce carbon tetrachloride and tetrachloroethylene, can be supplied directly from the first system / method to a second system or method for producing compounds of formula CF3CR=CCICF3 (where R is CI or H). As described in greater detail herein, the second method can include fluorinating or chlorofluorinating HCBD to produce compounds of formula CF3CR=CCICF3. Such an integrated system would eliminate the need for additional material storage, handling, and transportation of HCBD, and the risks associated therewith, thereby greatly minimizing human and environmental exposure to HCBD.

[0090] As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but can include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus. Further, unless expressly stated to the contrary, "or" refers to an inclusive or and not to an exclusive or. For example, 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).

[0091] The transitional phrase "consisting of limits the claim to the specified materials to exclude addition of unrecited materials except for impurities ordinarily associated therewith. The transitional phrase "consisting of excludes any element, step, or ingredient not specified in the claim. When the phrase "consisting of appears in the body of a claim, it should be given its plain meaning consistent with its ordinary usage. That is, the phrase "consisting of should limit the claim to the specified elements, steps, or ingredients, to the exclusion of anything not specified.

[0092] The transitional phrase "consisting essentially of" is used to define compositions, methods, features, components, or elements that include those that are explicitly recited, plus additional materials, steps, features, components, or elements that do not materially affect the basic and novel characteristics of the claimed invention, especially the mode of action of any of the methods of the invention to achieve the desired result. The term "consisting essentially of" occupies a middle ground between "comprising" and "consisting of."

[0093] Where the applicant has defined the invention or a part thereof with open-ended language such as "comprising" or "including", it should be readily understood that unless otherwise restricted the description expressly sets out alternatives that include the use of the terms "consisting essentially of" or "consisting of" the invention.

[0094] Also, the use of "a" or "an" is employed to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the application. This description should be read to include one or at least one and the singular also includes the plural, unless it is obvious that it is meant otherwise.

[0095] As used herein, the term "about" is intended to account for variations in, for example, experimental error, and is meant to encompass a value that is ±10% of the stated value. Unless otherwise clear from context, all measurements reported herein are understood to be modified by the term "about," regardless of whether the term is actually used.

[0096] Where a range of values or other parameters is given, or preferred ranges or preferred upper and / or lower limits are stated, it is understood that all ranges formed from any of the stated range limits, or preferred values, are contemplated, whether or not the ranges are expressly stated. Where a range of values is given herein, the range is intended to include both the endpoints and all integers and fractions within the range, unless otherwise indicated.

[0097] As used herein, the term "compound" refers to all stereoisomers, geometric isomers, tautomers, and isotopes of the described structure or chemical. Unless otherwise specified, a compound identified herein by name or structure is intended to include other tautomers.

[0098] As used herein, the term "catalyst" refers to a substance that speeds up a chemical reaction but is not consumed by the reaction; thus it can be recovered at the end of the reaction without having undergone a chemical change.

[0099] Disclosed are methods for preparing a compound represented by the formula CF3CR=CClCF3 (where R is CI or H) from a reactant composition comprising, consisting of, or consisting essentially of hexachlorobutadiene (HCBD).

[0100] In one embodiment, the reactant composition comprising HCBD is supplied directly from a facility that produces HCBD, for example, as a waste stream or as a byproduct.

[0101] In some embodiments, the reactant composition comprises HCBD and one or more additional compounds selected from Table 1.

[0102]

[0103] In some embodiments, the reactant composition comprises HCBD and more than one additional compound of Table 1 (e.g., two or more; three or more; five or more; ten or more; etc.). In some embodiments, the reactant composition comprises HCBD and each of the additional compounds of Table 1. In some embodiments, the reactant composition comprises HCBD and one to ten of the additional compounds of Table 1. In some embodiments, the reactant composition comprises HCBD and one to five of the additional compounds of Table 1. In some embodiments, the reactant composition comprises HCBD and one to four of the additional compounds of Table 1. In some embodiments, the reactant composition comprises HCBD and one to three of the additional compounds of Table 1. In some embodiments, the reactant composition comprises HCBD and one to two of the additional compounds of Table 1.

[0104] In some embodiments, the present application provides a method comprising reacting a composition comprising HCBD to produce a compound of the formula CF3CR=CClCF3, where R is H or CI. In some embodiments, the reactant composition comprises HCBD and one or more additional compounds selected from Table 1.

[0105] In some embodiments, when R is H in the formula CF3CR=CClCF3, the compound prepared from HCBD according to the present application is E-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene and / or Z-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (E-HCFO-1326mxz and / or Z-HCFO-1326mxz) (CF3-CCl=CH-CF3), preferably Z-HCFO-1326mxz, as shown below:

[0106] In some embodiments, the present application is directed to a process for preparing E-HCFO-1326mxz and / or Z-HCFO-1326mxz, preferably Z-HCFO-1326mxz, from HCBD. The process comprises fluorinating a composition comprising HCBD and one or more additional compounds of Table 1 in the presence of a fluorination catalyst to obtain a product mixture comprising Z-HCFO-1326mxz. The additional compounds of the HCBD starting composition are selected from 1,1,3,3,4,4-hexachloro-1-butene (C4H2Cl6), carbon tetrachloride (CCl4), pentachloroethane (C2HCl5, HCC-120), tetrachloroethylene (CO-1110), hexachloroethane (C2Cl6, CC-110), pentachloropyridine (C5Cl5N), 1,1,2,3,3-pentachloroprop-1-ene (C3HCl5, CCl2=CHCCl3, HCCO-1220az), 1,1,1,2,2,3,3-heptachloropropane (C2Cl5CHCl2), pentachlorocyclopropane (C3HCl5), 1,2,3,3-tetrachloro-1-propene (C3H2Cl4), pentachlorobutadiene isomers (CCl2=CH-CCl=CCl2, Z / E-CHCl=CCl-CCl=CCl2), tetrachlorothiophene (C4Cl4S), and trichloroethylene.

[0107] The reaction for this process embodiment is as follows:

[0108] While not shown in the above reaction, one skilled in the art will appreciate that while the additional compounds of Table 1 are not shown in the above reaction, the feed material for the catalytic hydrofluorination reaction of HCBD can also comprise one or more additional compounds selected from 1,1,3,3,4,4-hexachloro-1-butene (C4H2Cl6), carbon tetrachloride (CCl4), pentachloroethane (C2HCl5, HCC-120), tetrachloroethylene (CO-1110), hexachloroethane (C2Cl6, CC-110), pentachloropyridine (C5Cl5N), 1,1,2,3,3-pentachloroprop-1-ene (C3HCl5, CCl2=CHCCl3, HCCO-1220az), 1,1,1,2,2,3,3-heptachloropropane (C2Cl5CHCl2), pentachlorocyclopropane (C3HCl5), 1,2,3,3-tetrachloro-1-propene (C3H2Cl4), pentachlorobutadiene isomers (CCl2=CH-CCl=CCl2, Z / E-CHCl=CCl-CCl=CCl2), tetrachlorothiophene (C4Cl4S), and trichloroethylene.

[0109] In some embodiments, a reactant or raw material composition comprising HCBD and one or more additional compounds of Table 1 is introduced into a reactor. Anhydrous hydrogen fluoride (HF) is also introduced into the reactor. In some embodiments, an oxidizing agent can be fed into the reactor. Those skilled in the art will appreciate that an oxidizing agent need not be used in all cases. In the reactor, the HCBD is subjected to fluorination in the presence of a catalytically effective amount of a catalyst to produce a product mixture comprising Z-HCFO-1326mxz.

[0110] In some embodiments, fluorination of HCBD is carried out in a reactor and process conditions are set in accordance with the disclosure of International Application Publication No. WO 2019 / 023572, the entire disclosure of which is incorporated herein by reference.

[0111] In some embodiments, the reaction train and associated equipment for the fluorination process to convert HCBD to HCFO-1326mxz can be integrated or built on-site with a chlorocarbon plant, such as a plant that produces carbon tetrachloride and tetrachloroethylene. Thus, the byproduct HCBD will not need to be disposed of or otherwise handled and / or transported, but can be used directly in the fluorination process.

[0112] In some embodiments, the methods provided herein for making 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene are carried out as liquid phase processes. In some embodiments, the methods for making 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (e.g., liquid phase processes) are carried out in the absence of an additional solvent component.

[0113] In some embodiments, the fluorination process is carried out by flowing HF, HCBD, one or more of the additional compounds of Table 1, and optionally an oxidizing agent into a catalyst bed in a reactor at a specified temperature. In some embodiments, the method is carried out by flowing HF, HCBD, one or more of the additional compounds of Table 1, optionally an oxidizing agent, and a carrier gas into a catalyst bed in a reactor. Examples of carrier gases include inert gases such as nitrogen, argon, and helium.

[0114] The desired reaction results can be achieved by appropriate selection of operating conditions such as temperature, contact time, and ratio of HF to HCBD.

[0115] In some embodiments, the reaction zone temperature for liquid-phase catalytic fluorination of HCBD is in the range of about 30°C to about 150°C, or about 50°C to about 150°C, about 50°C to about 140°C, about 70°C to about 140°C, or about 90°C to about 130°C. In some embodiments, the method is carried out at a temperature of about 80°C to about 150°C. By maintaining the reaction temperature within these ranges, the formation of byproducts can be reduced, and catalyst deactivation can be suppressed. However, those skilled in the art will understand that the catalytic fluorination of HCBD is an exothermic reaction, and temperatures exceeding the range of about 30°C to about 150°C may occur locally within the reactor or catalyst.

[0116] In some implementations, the contact time (CT) between the reactants and the catalyst within the reactor is determined by the following formula:

[0117] VR is the volume of the reactor in cubic meters (m³). 3 ), and VF is the total liquid volumetric flow rate of the reactor feed (m). 3 / h). In one embodiment, the contact time is in the range of about 0.1 hours to about 10 hours, including all values ​​and ranges therein. Those skilled in the art will understand that the contact time can affect the selectivity and conversion rate of HCBD, and therefore the contact time can be adjusted to a target time in the range of about 0.1 hours to about 10 hours, or to a target time shorter or longer than that range, as needed to achieve the desired reaction results.

[0118] In some embodiments, the reaction in the reactor is typically carried out at atmospheric pressure, or at a pressure below atmospheric pressure, or at a pressure above atmospheric pressure. That is, the reaction pressure in the reactor used for the fluorination reaction is not critical and can be adjusted as needed to achieve the desired reaction outcome. In one embodiment, the catalytic fluorination reaction in the reactor is carried out at a pressure above atmospheric pressure, for example, because the increased pressure reduces the size of the equipment used for the reaction. In one embodiment, the pressure within the reactor is in the range of about 0 MPaG to 2.0 MPaG (gauge pressure).

[0119] In some implementations, greater than about 90 mol%, or greater than about 95 mol%, greater than about 97 mol%, greater than about 99 mol%, greater than about 99.5 mol%, or greater than about 99.9 mol% of HCBD is converted into HCFO-1326mxz.

[0120] In some embodiments, greater than about 99 mole %, greater than about 99.5 mole %, or greater than about 99.7 mole % or greater than about 99.9 mole % of the 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene produced by the methods provided herein is Z-HCFO-1326mxz.

[0121] In some embodiments, the catalytic fluorination methods of the present disclosure produce the desired product with high selectivity. In some embodiments of the present invention, the product selectivity for a compound of the formula CF3CR=CCICF3, such as HCFO-1326mxz, is at least 90 mole % (1:1 ratio of Z to E), preferably at least 95 mole %, more preferably at least 99 mole %.

[0122] In some embodiments, the method can be carried out in a batch process or a continuous process.

[0123] In some embodiments, greater than about 90 mole %, or greater than about 95 mole %, or greater than about 97 mole %, or greater than about 99 mole %, or greater than about 99.5 mole %, or greater than about 99.9 mole % of hexachlorobutadiene is converted to 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene in a reaction of less than about 10 hours (e.g., less than about 8 hours, less than about 6 hours, less than about 5 hours of reaction).

[0124] In some embodiments, the catalyst used to effect fluorination of HCBD is a transition metal catalyst, and more preferably a Group V transition metal catalyst. In some embodiments, the Group V transition metal is niobium or tantalum. In some embodiments, the transition metal catalyst is selected from a tantalum catalyst, a niobium catalyst, or a tantalum-niobium catalyst.

[0125] In some embodiments, the transition metal catalyst is a tantalum catalyst. In some embodiments, the transition metal catalyst is a tantalum halide catalyst. In some embodiments, the transition metal catalyst is tantalum (V) chloride. In some embodiments, the transition metal catalyst is a niobium catalyst. In some embodiments, the transition metal catalyst is a niobium halide catalyst. In some embodiments, the transition metal catalyst is selected from niobium (IV) chloride, niobium (V) chloride, or mixtures thereof. In some embodiments, the transition metal catalyst is tantalum (V) chloride, niobium (IV) chloride, niobium (V) chloride, or any mixture thereof.

[0126] In some embodiments, the transition metal catalyst is a mixture of a tantalum catalyst and a niobium catalyst. In some embodiments, the transition metal catalyst is a mixture of a tantalum halide catalyst and a niobium halide catalyst. In some embodiments, the transition metal catalyst is a mixture of tantalum chloride and niobium chloride.

[0127] In some embodiments, the transition metal catalyst is a mixture of tantalum (V) chloride and niobium (IV) chloride. In some embodiments, the transition metal catalyst is a mixture of tantalum (V) chloride and niobium (V) chloride. In some embodiments, the transition metal catalyst is a mixture of tantalum (V) chloride, niobium (IV) chloride, and niobium (V) chloride.

[0128] In some embodiments, the catalyst for fluorination of HCBD is a Lewis acid catalyst, such as a metal halide catalyst, including but not limited to antimony halides, tin halides, thallium halides, iron halides, and combinations of two or more. In certain embodiments, metal chlorides and metal fluorides are used, including but not limited to SbCl5, SbCl3, SbF5, SnCl4, TiCl4, NiF5, FeCl3, and combinations of two or more of these.

[0129] In some embodiments, examples of liquid phase fluorination catalysts include, but are not limited to, antimony halides, tin halides, tantalum halides, titanium halides, niobium halides, molybdenum halides, iron halides, fluorinated chromium halides, fluorinated chromium oxides, or combinations thereof. In some embodiments, examples of liquid phase fluorination catalysts include, but are not limited to, SbCl5, SbCl3, SbF5, SnCl4, TaCl5, TiCl4, NbCl5, MoCl6, FeCl3, fluorinated versions of SbCl5, fluorinated versions of SbCl3, fluorinated versions of SnCl4, fluorinated versions of TaCl5, fluorinated versions of TiCl4, fluorinated versions of NbCl5, fluorinated versions of MoCl6, fluorinated versions of FeCl3, or combinations thereof. If these catalysts become deactivated, the catalysts can be readily regenerated by any means known in the art.

[0130] In one embodiment, the liquid phase fluorination catalyst is selected from the group consisting of SbF5, SnCl4, TaCl5, TiCl4, NbCl5, and fluorinated versions thereof. In another embodiment, the liquid phase fluorination catalyst is selected from the group consisting of SbF5, SnCl4, TaCl5, TiCl4, and / or fluorinated versions thereof. In another embodiment, the liquid phase fluorination catalyst is SbF5or SbCl5.

[0131] In some embodiments, a molar excess of HF is used based on 1 molar equivalent of hexachlorobutadiene, for example, greater than 1 molar equivalent, greater than 2 molar equivalents, greater than 5 molar equivalents, greater than 10 molar equivalents, greater than 20 molar equivalents, greater than 50 molar equivalents, or greater than 100 molar equivalents of HF are used based on 1 molar equivalent of hexachlorobutadiene.

[0132] In some embodiments, about 10 molar equivalents to about 50 molar equivalents of HF are used, e.g., about 10 molar equivalents to about 40 molar equivalents, about 10 molar equivalents to about 30 molar equivalents, about 10 molar equivalents to about 20 molar equivalents, about 20 molar equivalents to about 50 molar equivalents, about 20 molar equivalents to about 40 molar equivalents, about 20 molar equivalents to about 30 molar equivalents, about 30 molar equivalents to about 50 molar equivalents, about 30 molar equivalents to about 40 molar equivalents, or about 40 molar equivalents to about 50 molar equivalents of HF, based on 1 molar equivalent of hexachlorobutadiene. In some embodiments, about 15 molar equivalents to about 20 molar equivalents of HF are used, based on 1 molar equivalent of hexachlorobutadiene.

[0133] In some embodiments, a catalytic amount of transition metal catalyst is used, e.g., less than 0.85 molar equivalents, less than 0.6 molar equivalents, less than 0.4 molar equivalents, less than 0.2 molar equivalents of transition metal catalyst, based on 1 molar equivalent of hexachlorobutadiene.

[0134] In some embodiments, about 0.05 molar equivalents to about 0.5 molar equivalents of metal halide catalyst are used, e.g., about 0.05 molar equivalents to about 0.3 molar equivalents, about 0.05 molar equivalents to about 0.2 molar equivalents, about 0.05 molar equivalents to about 0.1 molar equivalents, about 0.1 molar equivalents to about 0.5 molar equivalents, about 0.1 molar equivalents to about 0.3 molar equivalents, or about 0.1 molar equivalents to about 0.2 molar equivalents, about 0.2 molar equivalents to about 0.5 molar equivalents, about 0.2 molar equivalents to about 0.3 molar equivalents, or about 0.3 molar equivalents to about 0.5 molar equivalents of metal halide catalyst, based on 1 molar equivalent of hexachlorobutadiene. In some embodiments, about 0.1 molar equivalents to about 0.3 molar equivalents of metal halide catalyst are used, based on 1 molar equivalent of hexachlorobutadiene.

[0135] In some embodiments, the method can include adding a fluorination catalyst to the HF to form a first mixture, and adding the hexachlorobutadiene to the first mixture to form a second mixture, and then introducing the second mixture to a reactor for fluorination of the HCBD to occur.

[0136] In one embodiment, the fluorination reaction is conducted in the absence of water. In some embodiments, if water is present, in one embodiment, the water is present at less than 1000 ppm, or in another embodiment, less than 500 ppm by weight. In some embodiments, if water is present, the water is present at less than about 50 ppm, or less than about 25 ppm, or preferably less than about 15 ppm.

[0137] In some embodiments, the composition produced by fluorination of the HCBD composition disclosed above by the system and method comprises: i) (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (Z-HCFO-1326mxz); and ii) one or more additional compounds selected from the group consisting of: E-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene, E-HFO-1316mxx (E-2,3-dichloro-1,1,1,4,4,4-hexafluorobut-2-ene), Z-HFO-1316mxx (Z-2,3-dichloro-1,1,1,4,4,4-hexafluorobut-2-ene), HFO-1327mz (1,1,1,2,4,4,4-heptafluorobut-2-ene), HFO-1325lxz (1,2-dichloro-1,1,4,4,4-pentafluorobut-2-ene), HFO-1325dx (1,2-dichloro-3,3,4,4,4-pentafluorobut-1-ene), HCFC-336mdd (2,3-dichloro-1,1,1,4,4,4-hexafluorobutane), HFC-336maf (2,2-dichloro-1,1,1,4,4,4-hexafluorobutane), HFC-336lbf (1,2-dichloro-1,1,2,4,4,4-hexafluorobutane), HFC-337mbf (2-chloro-1,1,1,2,4,4,4-heptafluorobutane), HFC-337mde (2-chloro-1,1,1,3,4,4,4-heptafluorobutane), HFC-356mff (1,1,1,4,4,4-hexafluorobutane), HFC-346mdf (2-chloro-1,1,1,4,4,4-hexafluorobutane), HFC-338mf (1,1,1,2,2,4,4,4-octafluorobutane), HCFC-1122 (2-chloro-1,1-difluoroethene), HCFC-124 (2-chloro-1,1,1,2-tetrafluoroethane), CFC-114 (1,2-dichloro-1,1,2,2-tetrafluoroethane), CFC-113 (1,1,2-trichloro-1,2,2-trifluoroethane), CFC-133a (2-chloro-1,1,1-trifluoroethane), CFC-123 (2,2-dichloro-1,1,1-trifluoroethane), CFC-123a (1,2-dichloro-1,1,2-trifluoroethane), CFC-122 (1,2,2-trichloro-1,1-difluoroethane), CFC-112a (1,1,1,2-tetrachloro-2,2-difluoroethane), HCFC-224db (1,1,1,3-tetrafluoro-2,3,3-trichloropropane), HFC-225da (1,2-dichloro-1,1,3,3,3-pentafluoropropane), HFC-235da (2-chloro-1,1,1,3,3-pentafluoropropane), HFC-235fa (1-chloro-1,1,3,3,3-pentafluoropropane), HFC-236fa (1,1,1,3,3,3-hexafluoropropane), and E-CFO-1317mx and Z-CFO-1317mx (2-chloro-1,1,1,3,4,4,4-heptafluorobut-2-ene). wherein the composition comprises greater than about 95 mole % of Z-HCFO-1326mxz.

[0138] In some embodiments, the one or more additional compounds of the composition comprising Z-HCFO-1326mxz are selected from the compounds of Table 2.

[0139]

[0140] In some embodiments, the composition produced by the fluorination of the HCBD composition disclosed above by the system and method comprises Z-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene; and one or more additional compounds selected from the group consisting of E-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene and HCFC-336mdd (2,3-dichloro-1,1,1,4,4,4-hexafluorobutane), E-CFO-1317mx and Z-CFO-1317mx (2-chloro-1,1,1,3,4,4,4-heptafluorobut-2-ene). Wherein the composition comprises greater than about 95 mole % of Z-HCFO-1326mxz.

[0141] In some embodiments, the composition produced by fluorination of the HCBD composition disclosed above by the system and method comprises Z-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene and HCFC-336mdd (2,3-dichloro-1,1,1,4,4,4-hexafluorobutane), wherein the composition comprises greater than about 95 mole % of Z-HCFO-1326mxz, or greater than about 96 mole % of Z-HCFO-1326mxz, greater than about 97 mole % of Z-HCFO-1326mxz, greater than about 98 mole % of Z-HCFO-1326mxz, greater than about 99 mole % of Z-HCFO-1326mxz, greater than about 99.2 mole % of Z-HCFO-1326mxz, greater than about 99.5 mole % of Z-HCFO-1326mxz, greater than about 99.7 mole % of Z-HCFO-1326mxz, or greater than about 99.9 mole % of Z-HCFO-1326mxz, the balance being HCFC-336mdd.

[0142] In some embodiments, the composition produced by fluorination of the HCBD composition disclosed above by the system and method comprises: i) (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene; and ii) one or more additional compounds selected from: 1,1,1,3,3,3-hexafluoropropane; 1,1,1,2,2,4,4,4-octafluorobutane; 1,1,1,4,4,4-hexafluorobutane; 1,2-dichloro-1,1,2,2-tetrafluoroethane; 2-chloro-1,1,1-trifluoroethane; 2-chloro-1,1,1,2,4,4,4-heptafluorobutane; 2-chloro-1,1,1,3,4,4,4-heptafluorobutane; 2-chloro-1,1,1,3,3-pentafluoropropane; 1-chloro-1,1,3,3,3-pentafluoropropane; (E)-2-chloro-1,1,1,4,4,4-hexafluorobut-2-ene; 1,2-dichloro-3,3,4,4-tetrafluorocyclobut-1-ene; 2-chloro-1,1,1,4,4,4-hexafluorobutane; 2,2-dichloro-1,1,1-trifluoroethane; 1,2-dichloro-1,1,2-trifluoroethane; 1,2-dichloro-1,1,3,3,3-pentafluoropropane; (E)-2,3-dichloro-1,1,1,4,4,4-hexafluorobut-2-ene; 1,1,2-trichloro-1,2,2-trifluoroethane; (Z)-2,3-dichloro-1,1,1,4,4,4-hexafluorobut-2-ene; 1,2-dichloro-3,3,3-trifluoroprop-1-ene; (Z)-1,2-dichloro-1,1,4,4,4-pentafluorobut-2-ene; 2,2-dichloro-1,1,1,4,4,4-hexafluorobutane; dl-2,3-dichloro-1,1,1,4,4,4-hexafluorobutane; meso-2,3-dichloro-1,1,1,4,4,4-hexafluorobutane; 1,2-dichloro-3,3,4,4,4-pentafluorobut-1-ene; 2,3-dichloro-1,1,1,3-tetrafluoropropane; 1,2-dichloro-1,1,2,4,4,4-hexafluorobutane; 1,2,2-trichloro-1,1-difluoroethane; 1,1,1-trichloro-2,2-difluoroethane; 1,1,2,2-tetrachloro-1,2-difluoroethane; 1,1,1,2-tetrachloro-2,2-difluoroethane; 1,2,3-trichloro-1,1,4,4,4-pentafluorobutane; and 1,1,2,3-tetrachloro-4,4,4-trifluorobut-1-ene; wherein the composition comprises greater than about 95 mole % of Z-HCFO-1326mxz.

[0143] In some embodiments, the composition comprises Z-HCFO-1326mxz and one of the additional compounds of Table 2. In some embodiments, the composition comprises Z-HCFO-1326mxz and more than one of the additional compounds of Table 2 (e.g., two or more; three or more; five or more; ten or more; etc.). In some embodiments, the composition comprises Z-HCFO-1326mxz and each of the additional compounds of Table 2. In some embodiments, the composition comprises Z-1326mxz and one to twenty-five of the additional compounds of Table 2. In some embodiments, the composition comprises Z-HCFO-1326mxz and one to twenty of the additional compounds of Table 2. In some embodiments, the composition comprises Z-HCFO-1326mxz and one to ten of the additional compounds of Table 2. In some embodiments, the composition comprises Z-HCFO-1326mxz and one to five of the additional compounds of Table 2. In some embodiments, the composition comprises Z-HCFO-1326mxz and one to four of the additional compounds of Table 2. In some embodiments, the composition comprises Z-HCFO-1326mxz and one to three of the additional compounds of Table 2. In some embodiments, the composition comprises Z-HCFO-1326mxz and one to two of the additional compounds of Table 2.

[0144] In some embodiments, the composition comprises greater than about 97 mole % Z-HCFO-1326mxz, with the remainder being one or more of the additional compounds of Table 2. In some embodiments, the composition comprises greater than about 98 mole % Z-HCFO-1326mxz, with the remainder being one or more of the additional compounds of Table 2. In some embodiments, the composition comprises greater than about 99 mole % Z-HCFO-1326mxz, with the remainder being one or more of the additional compounds of Table 2. In some embodiments, the composition comprises greater than about 99.5 mole % Z-HCFO-1326mxz, with the remainder being one or more of the additional compounds of Table 2. In some embodiments, the composition comprises greater than about 99.9 mole % Z-HCFO-1326mxz, with the remainder being one or more of the additional compounds of Table 2.

[0145] In some embodiments, the composition consists essentially of, or consists of, Z-HCFO-1326mxz and one or more additional compounds of Table 2.

[0146] In one embodiment, Z-HCFO-1326mxz is of sufficient purity after the batch or continuous fluorination process is complete that no further purification steps are required.

[0147] In another embodiment, upon completion of the batch or continuous fluorination process, the Z-HCFO-1326mxz can be purified and recovered by any conventional method, including, for example, fractional distillation.

[0148] The process according to the present application can also include continuously dehydrochlorinating the Z-HCFO-1326mxz to produce hexafluoro-2-butyne (HFB), and then hydrogenating the HFB to produce Z-HFO-1336mzz, as disclosed in International Application Publication No. WO 2019 / 023572, the entire disclosure of which is incorporated herein by reference.

[0149] In one embodiment, the additional compound HCFC-336mdd can be retained in the product mixture with the Z-1326mxz without further purification, and the process can include continuously dehydrochlorinating the Z-1326mxz / HCFC-336mdd composition to form HFB, and then hydrogenating the HFB to produce Z-HFO-1336mzz, as disclosed in International Application Publication No. WO 2019 / 023572, the entire disclosure of which is incorporated herein by reference.

[0150] In some embodiments, when R is Cl in the formula CF3CR=CClCF3, the compound prepared from HCBD according to the present application is E-2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene and / or Z-2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene (E-CFO-1316mxx and / or Z-CFO-1316mxx), as shown below:

[0151] In some embodiments, the present application relates to a process for preparing E-CFO-1316mxz and / or Z-CFO-1316mxz from HCBD. Preferably, the process according to the present application forms E-CFO-1316mxz and Z-CFO-1316mxz from HCBD. The process comprises reacting a composition comprising HCBD and one or more additional compounds with HF and chlorine in the presence of a catalyst to obtain a product mixture comprising Z-CFO-1316mxx and E-CFO-1316mxx. The additional compounds of the HCBD starting composition are listed in Table 1 and are selected from the group consisting of 1,1,3,3,4,4-hexachloro-1-butene (C4H2Cl6), carbon tetrachloride (CCl4), pentachloroethane (C2HCl5, HCC-120), tetrachloroethylene (CO-1110), hexachloroethane (C2Cl6, CC-110), pentachloropyridine (C5Cl5N), 1,1,2,3,3-pentachloroprop-1-ene (C3HCl5, CCl2=CHCCl3, HCCO-1220az), 1,1,1,2,2,3,3-heptachloropropane (C2Cl5CHCl2), pentachlorocyclopropane (C3HCl5), 1,2,3,3-tetrachloro-1-propene (C3H2Cl4), pentachlorobutadiene isomers (CCl2=CH-CCl=CCl2, Z / E-CHCl=CCl-CCl=CCl2), tetrachlorothiophene (C4Cl4S), and trichloroethylene.

[0152] The reaction of this process embodiment is as follows:

[0153] While not shown in the above reaction, one skilled in the art will appreciate that while the additional compounds are not shown in the above reaction, the feed material for the catalytic chlorofluorination reaction of HCBD can also comprise one or more additional compounds selected from the group consisting of 1,1,3,3,4,4-hexachloro-1-butene (C4H2Cl6), carbon tetrachloride (CCl4), pentachloroethane (C2HCl5, HCC-120), tetrachloroethylene (CO-1110), hexachloroethane (C2Cl6, CC-110), pentachloropyridine (C5Cl5N), 1,1,2,3,3-pentachloroprop-1-ene (C3HCl5, CCl2=CHCCl3, HCCO-1220az), 1,1,1,2,2,3,3-heptachloropropane (C2Cl5CHCl2), pentachlorocyclopropane (C3HCl5), 1,2,3,3-tetrachloro-1-propene (C3H2Cl4), pentachlorobutadiene isomers (CCl2=CH-CCl=CCl2, Z / E-CHCl=CCl-CCl=CCl2), tetrachlorothiophene (C4Cl4S), and trichloroethylene.

[0154] In some embodiments, the reactant composition comprises HCBD and more than one additional compound of Table 1 (e.g., two or more; three or more; five or more; ten or more; etc.). In some embodiments, the reactant composition comprises HCBD and each of the additional compounds of Table 1. In some embodiments, the reactant composition comprises HCBD and one to ten of the additional compounds of Table 1. In some embodiments, the reactant composition comprises HCBD and one to five of the additional compounds of Table 1. In some embodiments, the reactant composition comprises HCBD and one to four of the additional compounds of Table 1. In some embodiments, the reactant composition comprises HCBD and one to three of the additional compounds of Table 1. In some embodiments, the reactant composition comprises HCBD and one to two of the additional compounds of Table 1.

[0155] In some embodiments, a reactant or raw material composition comprising HCBD and one or more additional compounds of Table 1 is introduced into a reactor. Anhydrous HF and chlorine gas (CI2) are also introduced into the reactor. In some embodiments, an oxidizing agent can be fed into the reactor. Those skilled in the art will appreciate that an oxidizing agent need not be used in all cases. In the reactor, the HCBD is subjected to fluorination and chlorination in the presence of a catalytically effective amount of a catalyst to produce a product mixture comprising Z-CFO-1316mxx and E-CFO-1316mxx.

[0156] In some embodiments, the reactor and related equipment for the chlorofluorination process to convert HCBD to CFO-1316mxx can be integrated or built on-site with a chlorocarbon plant (e.g., a plant that produces carbon tetrachloride and tetrachloroethylene). Thus, the byproduct HCBD would not need to be disposed of or otherwise handled and / or transported, but can be used directly in the chlorofluorination process.

[0157] In some embodiments, the methods provided herein for making CFO-1316mxx (E and Z) are carried out as a gas phase process.

[0158] In some embodiments, the reaction to produce Z-CFO-1316mxx and E-CFO-1316mxx is carried out by flowing HF, CI2, HCBD, one or more of the additional compounds of Table 1, and optionally an oxidizing agent into a catalyst bed in a reactor at a specified temperature. In some embodiments, the process is carried out by flowing HF, CI2, HCBD, one or more of the additional compounds of Table 1, an optional oxidizing agent such as an oxygen-containing gas

[0159] and a carrier gas into a catalyst bed in a reactor. Examples of carrier gases include inert gases, such as nitrogen, argon, and helium.

[0160] The desired reaction result can be achieved by appropriately selecting operating conditions such as temperature, contact time, and the ratio of HF, Cl2, and HCBD.

[0161] In some embodiments, the reaction zone temperature for catalytic fluorination / chlorination of HCBD is in the range of about 200°C to about 500°C, or about 210°C to about 490°C, about 220°C to about 480°C, or about 230°C to about 480°C. In some embodiments, the method is carried out at a temperature of about 230°C to about 480°C. By maintaining the reaction temperature within these ranges, the formation of byproducts can be reduced, and catalyst deactivation can be suppressed. However, those skilled in the art will understand that the catalytic fluorination / chlorination of HCBD is an exothermic reaction, and temperatures exceeding the range of about 230°C to about 480°C may occur locally within the reactor or catalyst.

[0162] In some implementations, the contact time (CT) between the reactants and the catalyst within the reactor is determined by the following formula:

[0163] VR is the volume of the reactor in cubic meters (m³). 3 ), and VF is the total liquid volumetric flow rate of the reactor feed (m). 3 / h). In one embodiment, the contact time is in the range of about 1 second to about 60 seconds, including all values ​​and ranges therebetween. Those skilled in the art will understand that the contact time can affect the selectivity and conversion rate of HCBD, and therefore the contact time can be adjusted to a target time in the range of about 1 second to about 60 seconds, or to a target time shorter or longer than that range, as needed to achieve the desired reaction results.

[0164] In some embodiments, the reaction in the reactor is typically carried out at atmospheric pressure, or at a pressure below atmospheric pressure, or at a pressure above atmospheric pressure. That is, the reaction pressure in the reactor used for the fluorination reaction is not critical and can be adjusted as needed to achieve the desired reaction outcome. In one embodiment, the catalytic fluorination reaction in the reactor is carried out at a pressure above atmospheric pressure, for example, because the increased pressure reduces the size of the equipment used for the reaction. In one embodiment, the pressure within the reactor is in the range of about 0 MPaG to 2.0 MPaG (gauge pressure).

[0165] In some implementations, greater than about 90 mol%, or greater than about 95 mol%, greater than about 97 mol%, greater than about 99 mol%, greater than about 99.5 mol%, or greater than about 99.9 mol% of HCBD is converted to CFO-1316mxx (E and Z) (the ratio of Z to E is 1:9 to 9:1, or the ratio of Z to E is 3:7 to 7:3).

[0166] In some embodiments, greater than about 99 mole %, greater than about 99.5 mole %, or greater than about 99.7 mole %, or greater than about 99.9 mole % of the 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene produced by the methods provided herein is CFO-1316mxx (E and Z) (ratio of Z to E is 1:9 to 9:1, or ratio of Z to E is 3:7 to 7:3).

[0167] In some embodiments, the catalytic chlorofluorination methods of the present disclosure produce the desired product with high selectivity. In some embodiments of the present invention, the product selectivity to a compound of the formula CF3CR=CCICF3, such as CFO-1316mxx (E and Z), is at least 90 mole % (ratio of Z to E is 1:9 to 9:1, or ratio of Z to E is 3:7 to 7:3), preferably at least 95 mole %, more preferably at least 99 mole %.

[0168] In some embodiments, the method can be carried out in a batch process or a continuous process.

[0169] In some embodiments, greater than about 90 mole %, or greater than about 95 mole %, or greater than about 97 mole %, or greater than about 99 mole %, or greater than about 99.5 mole %, or greater than about 99.9 mole % of hexachlorobutadiene is converted to Z-CFO-1316mxx and E-CFO-1316mxx in a reaction of less than about 60 seconds hour.

[0170] In some embodiments, the catalyst used to chlorofluorinate HCBD is a catalyst comprising at least one metal halide, metal oxide, or metal oxyhalide. As used herein, the term “halide” refers to fluoride, chloride, and bromide.

[0171] Examples of suitable metals include nickel, chromium, iron, scandium, yttrium, lanthanum, titanium, zirconium, hafnium, vanadium, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, cobalt, palladium, copper, zinc, tantalum, antimony, aluminum, tin, and lead. It should be noted that, as defined herein, antimony is a metal.

[0172] Examples of metal halides include nickel halides, chromium halides, iron halides, scandium halides, yttrium halides, lanthanum halides, titanium halides, zirconium halides, hafnium halides, vanadium halides, molybdenum halides, tungsten halides, manganese halides, rhenium halides, ruthenium halides, osmium halides, cobalt halides, palladium halides, copper halides, zinc halides, antimony halides, tantalum halides, aluminum halides, tin halides, and lead halides. In one embodiment, the metal halide is a nickel halide, an iron halide, or a chromium halide, or a combination thereof, which is used as a catalyst with or without an activated carbon support. In another embodiment, the metal halide is a bromide or a chloride. In another embodiment, the halide is a chloride. In another embodiment, the metal halide is a nickel chloride, an iron chloride, or a chromium chloride, or a combination thereof.

[0173] Examples of metal oxides include chromium oxide, aluminum oxide, and the like. Metal oxyhalides can also be used as chlorofluorination catalysts.

[0174] The chlorofluorination catalyst can be unsupported or supported on activated carbon. The activated carbon can be unwashed, or it can be acid washed or base washed.

[0175] The term "activated carbon" includes any carbon having a relatively high surface area, such as about 50 m 2 to about 3000 m 2 or about 100 m 2 to about 2000 m 2 (e.g., about 200 m 2 to about 1500 m 2 or about 300 m 2 to about 1000 m 2 . The activated carbon can be derived from any carbonaceous material, such as coal (e.g., charcoal), nut shells (e.g., coconut), and wood. Any form of activated carbon can be used, such as powdered, granular, and pelletized activated carbon.

[0176] In some embodiments, the activated carbon has been washed with at least one basic solution to remove silicates. For example, the activated carbon is washed with an alkali metal hydroxide, or an alkaline earth metal hydroxide, or ammonium hydroxide. Examples of basic solutions that have been used to wash activated carbon include sodium hydroxide, ammonium hydroxide, potassium hydroxide, and the like.

[0177] The chlorofluorination process is conducted in the presence of a chlorine source. In some embodiments, the chlorine source can be selected from (i) a catalyst comprising a metal chloride or a metal oxychloride, such as a catalyst comprising chromium chloride (CrCl3) in the form of a metal chloride or in the form of chromium chloride supported on carbon, or (ii) chlorine gas (Cl2), which is added to the process when the fluorination catalyst comprises a metal halide or a metal oxyhalide, wherein the halide is a fluoride or a bromide, or when the catalyst is a metal oxide. Optionally, chlorine gas (Cl2) is added when the catalyst is a metal chloride or a metal oxychloride.

[0178] In one embodiment, the chlorofluorination catalyst comprises a metal chloride or a metal oxychloride. In another embodiment, the chlorofluorination catalyst does not comprise a metal chloride or a metal oxychloride, and the process is conducted in the presence of chlorine gas (Cl2).

[0179] In other embodiments, the chlorine is present in a gaseous state. Chlorine gas is used or chlorine gas is generated in situ from the reaction of gaseous hydrogen chloride with oxygen.

[0180] In one embodiment, the chlorofluorination reaction is conducted in the absence of water. If water is present, in one embodiment, the water is present in less than 1% by weight, or in another embodiment, less than 0.5% by weight.

[0181] In some embodiments, a molar excess of HF is used based on 1 mole equivalent of hexachlorobutadiene, for example, greater than 1 mole equivalent, greater than 2 mole equivalents, greater than 5 mole equivalents, greater than 10 mole equivalents, greater than 20 mole equivalents, greater than 50 mole equivalents, or greater than 100 mole equivalents of HF based on 1 mole equivalent of hexachlorobutadiene.

[0182] In some embodiments, about 10 mole equivalents to about 50 mole equivalents of HF is used based on 1 mole equivalent of hexachlorobutadiene, for example, about 10 mole equivalents to about 40 mole equivalents, about 10 mole equivalents to about 30 mole equivalents, about 10 mole equivalents to about 20 mole equivalents, about 20 mole equivalents to about 50 mole equivalents, about 20 mole equivalents to about 40 mole equivalents, about 20 mole equivalents to about 30 mole equivalents, about 30 mole equivalents to about 50 mole equivalents, about 30 mole equivalents to about 40 mole equivalents, or about 40 mole equivalents to about 50 mole equivalents of HF based on 1 mole equivalent of hexachlorobutadiene. In some embodiments, about 20 mole equivalents to about 30 mole equivalents of HF is used based on 1 mole equivalent of hexachlorobutadiene.

[0183] In some embodiments, a molar excess of chlorine is used based on 1 mole equivalent of hexachlorobutadiene, for example, greater than 1 mole equivalent, greater than 2 mole equivalents, greater than 5 mole equivalents, greater than 10 mole equivalents, greater than 20 mole equivalents, greater than 50 mole equivalents, or greater than 100 mole equivalents of chlorine based on 1 mole equivalent of hexachlorobutadiene.

[0184] In some embodiments, the composition produced by the fluorination and chlorination of the HCBD composition disclosed above by the systems and methods comprises: i) Z-HFO-1316mxx (Z-2,3-dichloro-1,1,1,4,4,4-hexafluorobut-2-ene); ii) E-HFO-1316mxx (E-2,3-dichloro-1,1,1,4,4,4-hexafluorobut-2-ene); and iii) one or more additional compounds selected from the group consisting of: Z-2-chloro-1,1,1,4,4,4-hexafluorobut-2-ene (Z-HCFO-1326mxz); E-2-chloro-1,1,1,4,4,4-hexafluorobut-2-ene (E-HCFO-1326mxz); E-2-chloro-1,1,1,3,4,4,4-hexafluoro-2-butene (E-CFO-1317mx); Z-2-chloro-1,1,1,3,4,4,4-hexafluoro-2-butene (Z-CFO-1317mx); E-1,2,3-trichloro-1,1,4,4,4-pentafluoro-2-butene (E-CFC-1315lxx); Z-1,2,3-trichloro-1,1,4,4,4-pentafluoro-2-butene (Z-CFC-1315lxx); E-1,1,2,3-tetrachloro-1,4,4,4-tetrafluoro-2-butene (E-CFC-1314kxx); Z-1,1,2,3-tetrachloro-1,4,4,4-tetrafluoro-2-butene (Z-CFC-1314kxx); 2-chloro-1,1,1,4,4,4-hexafluorobutane (HFC-346mdf); and 1,1,1,3,3,3-hexafluoropropane (HFC-236fa). wherein the composition comprises greater than about 95 mole %, or greater than about 96 mole %, greater than about 97 mole %, greater than about 98 mole %, greater than about 99 mole %, greater than about 99.2 mole %, greater than about 99.5 mole %, greater than about 99.7 mole %, or greater than about 99.9 mole % of Z-CFO-1316mxx and E-CFO-1316mxx, with the balance being one or more of the additional compounds.

[0185] In some embodiments, the one or more additional compounds of the composition comprising Z-HCFO-1316mxx are selected from the group consisting of the compounds of Table 3.

[0186]

[0187] In some embodiments, the composition produced by fluorination and chlorination of the HCBD composition disclosed above by the system and method comprises Z-HFO-1316mxx (Z-2,3-dichloro-1,1,1,4,4,4-hexafluorobut-2-ene); E-HFO-1316mxx (E-2,3-dichloro-1,1,1,4,4,4-hexafluorobut-2-ene); and one or more of the additional compounds selected from the group consisting of Z-2-chloro-1,1,1,4,4,4-hexafluorobut-2-ene (Z-HCFO-1326mxz), E-2-chloro-1,1,1,4,4,4-hexafluorobut-2-ene (E-HCFO-1326mxz), E-2-chloro-1,1,1,3,4,4,4-hexafluoro-2-butene, and Z-2-chloro-1,1,1,3,4,4,4-hexafluoro-2-butene, wherein the composition comprises greater than about 95 mole%, or greater than about 96 mole%, greater than about 97 mole%, greater than about 98 mole%, greater than about 99 mole%, greater than about 99.2 mole%, greater than about 99.5 mole%, greater than about 99.7 mole%, or greater than about 99.9 mole% of Z-CFO-1316mxx and E-CFO-1316mxx, with the balance being one or more of these additional compounds.

[0188] In some embodiments, the composition produced by fluorination and chlorination of the HCBD composition disclosed above by the system and method comprises Z-HFO-1316mxx (Z-2,3-dichloro-1,1,1,4,4,4-hexafluorobut-2-ene); E-HFO-1316mxx (E-2,3-dichloro-1,1,1,4,4,4-hexafluorobut-2-ene); Z-2-chloro-1,1,1,4,4,4-hexafluorobut-2-ene (Z-HCFO-1326mxz); E-2-chloro-1,1,1,3,4,4,4-hexafluoro-2-butene, and Z-2-chloro-1,1,1,3,4,4,4-hexafluoro-2-butene, wherein the composition comprises greater than about 95 mole%, or greater than about 96 mole%, greater than about 97 mole%, greater than about 98 mole%, greater than about 99 mole%, greater than about 99.2 mole%, greater than about 99.5 mole%, greater than about 99.7 mole%, or greater than about 99.9 mole% of Z-CFO-1316mxx and E-CFO-1316mxx, with the balance being E-HCFO-1326mxz.

[0189] In some embodiments, the composition comprises one of Z-CFO-1316mxx and E-CFO-1316mxx and an additional compound. In some embodiments, the composition comprises Z-CFO-1316mxx and E-CFO-1316mxx and more than one additional compound of Table 3 (e.g., two or more; three or more; five or more; ten or more; etc.). In some embodiments, the composition comprises Z-CFO-1316mxx and E-CFO-1316mxx and each of the additional compounds of Table 3. In some embodiments, the composition comprises Z-CFO-1316mxx and E-CFO-1316mxx and one to twenty-five of the additional compounds of Table 3. In some embodiments, the composition comprises Z-CFO-1316mxx and E-CFO-1316mxx and one to twenty of the additional compounds of Table 3. In some embodiments, the composition comprises Z-CFO-1316mxx and E-CFO-1316mxx and one to ten of the additional compounds of Table 3. In some embodiments, the composition comprises Z-CFO-1316mxx and E-CFO-1316mxx and one to five of the additional compounds of Table 3. In some embodiments, the composition comprises Z-CFO-1316mxx and E-CFO-1316mxx and one to four of the additional compounds of Table 3. In some embodiments, the composition comprises Z-CFO-1316mxx and E-CFO-1316mxx and one to three of the additional compounds of Table 3. In some embodiments, the composition comprises Z-CFO-1316mxx and E-CFO-1316mxx and one to two of the additional compounds of Table 3.

[0190] In some embodiments, the composition comprises greater than about 97 mole percent of Z-CFO-1316mxx and E-CFO-1316mxx, with the balance being one or more of the additional compounds of Table 3. In some embodiments, the composition comprises greater than about 98 mole percent of Z-CFO-1316mxx and E-CFO-1316mxx, with the balance being one or more of the additional compounds of Table 3. In some embodiments, the composition comprises greater than about 99 mole percent of Z-CFO-1316mxx and E-CFO-1316mxx, with the balance being one or more of the additional compounds of Table 3. In some embodiments, the composition comprises greater than about 99.5 mole percent of Z-CFO-1316mxx and E-CFO-1316mxx, with the balance being one or more of the additional compounds of Table 3. In some embodiments, the composition comprises greater than about 99.9 mole percent of Z-CFO-1316mxx and E-CFO-1316mxx, with the balance being one or more of the additional compounds of Table 3.

[0191] In some embodiments, the composition consists essentially of, or consists of, Z-CFO-1316mxx and E-CFO-1316mxx and one or more additional compounds of Table 3.

[0192] In some embodiments, the composition produced by chlorofluorination of HCBD has a moisture content of about 100 ppm or less.

[0193] In one embodiment, Z-CFO-1316mxx and E-CFO-1316mxx are of sufficient purity after completion of the batch or continuous chlorination and fluorination process that no further purification steps are required.

[0194] In another embodiment, Z-CFO-1316mxx and E-CFO-1316mxx can be purified and recovered by any conventional method, including, for example, fractional distillation, after completion of the batch or continuous fluorination process.

[0195] The process according to the present application can further comprise continuously hydrodechlorinating Z-CFO-1316mxx and / or E-CFO-1316mxx to produce Z-HCFO-1326mxz; dehydrochlorinating Z-HCFO-1326mxz to produce hexafluoro-2-butyne (HFB), and then hydrogenating HFB to produce Z-HFO-1336mzz, as disclosed in International Application Publication No. WO 2015 / 120250, the entire disclosure of which is incorporated herein by reference.

[0196] Alternatively, in one embodiment, Z-CFO-1316mxx and / or E-CFO-1316mxx can be converted to Z-HCFO-1326mxz and / or E-HCFO-1326mxz by Zn in liquid phase in an organic solvent such as DMF, ethylene glycol, or diglyme, or by ZnCl2 in liquid phase in an organic solvent such as DMF, ethylene glycol, or diglyme. 2 In gas phase on a carbon support or an alumina support, undergo dichlorination to HFB.

[0197] In one embodiment, additional compound Z-HCFO-1326mxz can be retained in the product mixture with Z-CFO-1316mxx and / or E-CFO-1316mxx without further purification, and the method can include continuously hydrodechlorinating the Z-CFO-1316mxx / E-CFO-1316mxx / Z-HCFO-1326mxz mixture to produce Z-HCFO-1326mxz, dehydrochlorinating Z-1326mxz to form HFB, and hydrogenating HFB to produce Z-HFO-1336mzz.

[0198] The present application also provides an integrated system for making a compound of the formula CF3CR=CClCF3, where R is H or Cl. See Figure 1 The system includes a first reactor 10 and a second reactor 20 coupled to the first reactor 10. The first reactor 10 is configured to produce a composition comprising HCBD and one or more additional compounds selected from Table 1. In some embodiments, the composition comprising HCBD is a waste stream or byproduct that has been separated from desired products (e.g., carbon tetrachloride and tetrachloroethylene), for example, by a distillation column 30 disposed downstream of the first reactor 10 and upstream of the second reactor 20. The second reactor 20 receives the composition comprising HCBD and, in the presence of a catalyst, converts it to a product mixture comprising a compound of the formula CF3CR=CClCF3.

[0199] The present application also provides a composition comprising a combination of a major component of a compound of the formula CF3CR=CClCF3, where R is Cl or H (e.g., E-HCFO-1326mxz or Z-HCFO-1326mxz or E-CFO-1316mxx or Z-CFO-1316mxx) and one or more additional compounds. In some embodiments, the composition is made according to one or more of the methods described herein.

[0200] The compositions provided herein (i.e., the compositions of the present application) can be used as intermediates for producing Z-HFO-1336mzz.

[0201] Z-HFO-1336mzz compositions can be used, for example, in a wide range of applications, including their use as refrigerants, in high temperature heat pumps, in organic Rankine cycles, as fire extinguishing agents / suppressants, propellants, blowing agents, solvents, and / or cleaning fluids.

[0202] Z-HFO-1336mzz compositions can also be used as low global warming potential (GWP) heat transfer compositions, refrigerants, power cycle working fluids, aerosol propellants, blowing agents, bubble forming agents, solvents, cleaners, carrier fluids, displacement drying agents, polishing abrasives, polymerization media, expansion agents for polyolefins and polyurethanes, gas dielectrics, fire extinguishing agents, and fire-suppressing agents in liquid or gaseous form. In one embodiment, the Z-HFO-1336mzz compositions can be used as a working fluid for carrying heat from a heat source to a heat sink. Such heat transfer compositions can also be used as refrigerants in cycles in which the fluid undergoes a phase change (e.g., from liquid to gas, and vice versa, or vice versa).

[0203] Examples of 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, heat pumps, mobile refrigerators, mobile air conditioning units, and combinations thereof.

[0204] In some embodiments, the Z-HFO-1336mzz compositions can be used in mobile heat transfer systems, including refrigeration, air conditioning, or heat pump systems or equipment. In some embodiments, the Z-HFO-1336mzz compositions can be used in stationary heat transfer systems, including refrigeration, air conditioning, or heat pump systems or equipment.

[0205] As used herein, mobile heat transfer systems refer to any refrigeration, air conditioner, or heating equipment incorporated into a highway, railroad, marine, or airborne transport unit. In addition, mobile refrigeration or air conditioner units include those devices that are independent of any mobile carrier and are referred to as "unitary" systems. Such unitary systems include "containers" (sea / land combined transport) as well as "drop-frame trailers" (highway / railroad combined transport).

[0206] As used herein, a fixed heat transfer system is a system that is fixed in one location during operation. Fixed heat transfer systems can be incorporated into or attached to any kind of building, or can be a freestanding device located outside a door, such as a soft drink vending machine. These fixed applications can be fixed air conditioning and heat pump (including but not limited to chillers, high temperature heat pumps, including transcritical heat pumps (e.g., where the condenser temperature is above 50°C, above 70°C, above 80°C, above 100°C, above 120°C, above 140°C, above 160°C, above 180°C, or above 200°C), residential, commercial or industrial air conditioning systems, and including window chillers, ductless chillers, ducted chillers, packaged terminal chillers, and those outside the building but connected to the building such as rooftop systems). In fixed refrigeration applications, the compositions provided herein can be used in high, medium, and / or low temperature refrigeration equipment, including commercial, industrial or residential refrigerators and freezers, ice machines, standalone chillers and freezers, flooded evaporator chillers, direct expansion chillers, walk-in and reach-in chillers and freezers, and combined systems. In some embodiments, the disclosed compositions can be used in supermarket refrigeration system.

[0207] Thus, in accordance with the present application, the Z-HFO-1336mzz compositions that can be produced from the reactive intermediates disclosed herein can be used in methods of producing cooling, producing heating, and transferring heat.

[0208] In some embodiments, the present application provides a method of producing cooling comprising evaporating a Z-HFO-1336mzz composition produced from the reactive intermediates disclosed herein in the vicinity of a body to be cooled, and then condensing the composition.

[0209] In some embodiments, the present application provides a method for producing heating comprising condensing a Z-HFO-1336mzz composition produced from the reactive intermediates disclosed herein in the vicinity of a body to be heated, and then evaporating the composition.

[0210] In some embodiments, the present application provides a method of using a Z-HFO-1336mzz composition produced from the reactive intermediates disclosed herein as a heat transfer fluid composition. In some embodiments, the method comprises transferring the composition from a heat source to a heat sink.

[0211] Z-HFO-1336mzz compositions produced from the reactive intermediates disclosed herein can also be used as low global warming potential (GWP) replacements for currently used refrigerants including, but not limited to, R-123 (i.e., HFC-123, 2,2-dichloro- 1,1,1-trifluoroethane), R-11 (i.e., CFC-11, trichlorofluoromethane), R-245fa (i.e., HFC-245fa, 1,1,1,3,3-pentafluoropropane), R-114 (i.e., CFC-114, 1,2-dichloro-1,1,2,2-tetrafluoroethane), R-236fa (i.e., HFC-236a, 1,1,1,3,3,3-hexafluoropropane), R-236ea (i.e., HFC-236ea, 1,1,1,2,3,3-hexafluoropropane), R-124 (i.e., HCFC-124, 2-chloro-1,1,1,2-tetrafluoroethane), and the like.

[0212] In some embodiments, Z-HFO-1336mzz compositions produced from the reactive intermediates disclosed herein can be used as refrigerants and provide at least comparable cooling performance (i.e., cooling capacity and energy efficiency) to the refrigerants sought to be replaced. In addition, Z-HFO-1336mzz compositions produced from the reactive intermediates disclosed herein can provide comparable heating performance (i.e., heating capacity and energy efficiency) to the refrigerants being replaced.

[0213] In some embodiments, the present application provides a method for recharging a heat transfer system containing a refrigerant to be replaced and a lubricant, the method comprising removing the refrigerant to be replaced from the heat transfer system while retaining a majority of the lubricant in the system, and introducing a Z-HFO-1336mzz composition produced from the reactive intermediates disclosed herein into the heat transfer system. In some embodiments, the lubricant in the system is partially replaced (e.g., a portion of a mineral oil lubricant used with HCFC-123 is replaced with a POE lubricant).

[0214] In some embodiments, Z-HFO-1336mzz compositions produced from the reactive intermediates disclosed herein can be used to supplement the refrigerant charge in a chiller. For example, if a chiller using HCFC-123 has degraded in performance due to a leak of refrigerant, a Z-HFO-1336mzz composition produced from the reactive intermediates disclosed herein can be added to bring the performance back to specification.

[0215] The present application also provides heat exchange systems containing any of the Z-HFO- 1336mzz compositions produced from the reactive intermediates disclosed herein, wherein the system is selected from the group consisting of air conditioners, freezers, refrigerators, heat pumps, water chillers, flooded evaporator chillers, direct expansion chillers, walk-in coolers, heat pumps, mobile refrigerators, mobile air conditioning units, and systems having combinations thereof. Further, the Z-HFO-1336mzz compositions produced from the reactive intermediates disclosed herein can be used in secondary loop systems, wherein the compositions are used as a primary refrigerant, thus providing cooling for a secondary heat transfer fluid, thereby cooling a remote location.

[0216] Vapor compression refrigeration, air conditioning or heat pump systems include an evaporator, a compressor, a condenser and an expansion device. The vapor compression cycle repeatedly uses a refrigerant in multiple steps, producing a cooling effect in one step and a heating effect in a different step. The cycle can be simply described as follows: liquid refrigerant enters the evaporator through the expansion device and the liquid refrigerant boils at a low temperature in the evaporator to form a vapor and produce cooling by extracting heat from the environment. The low pressure vapor enters the compressor where the vapor is compressed to increase its pressure and temperature. The high pressure (compressed) vapor refrigerant then enters the condenser where the refrigerant condenses and discharges its heat to the environment. The refrigerant returns to the expansion device through which the liquid expands from the higher pressure level in the condenser to the low pressure level in the evaporator, thus repeating the cycle.

[0217] The present application also provides foam blowing agent compositions comprising Z-HFO-1336mzz compositions produced from the reactive intermediates disclosed herein for making foams. In some embodiments, the present application provides foamable compositions, including but not limited to, thermoset (e.g., polyurethane, polyisocyanurate or phenolic) foam compositions, thermoplastic (e.g., polystyrene, polyethylene or polypropylene) foam compositions and methods of making foams. In some embodiments, one or more of the Z-HFO-1336mzz compositions produced from the reactive intermediates disclosed herein can be included as a foam blowing agent in the foamable composition, wherein the foamable composition can include one or more additional components capable of reacting and / or mixing and foaming under appropriate conditions to form a foam or porous structure.

[0218] The present application also provides a method of forming a foam, comprising: (a) adding a Z-HFO-1336mzz composition produced from the reactive intermediates disclosed herein to a foamable composition; and (b) treating the foamable composition under conditions effective to form a foam.

[0219] The present application also provides the use of the Z-HFO-1336mzz composition produced from the reactive intermediates disclosed herein as a propellant in a sprayable composition. In addition, the present application provides a sprayable composition of the present application. Active ingredients to be sprayed can also be present in the sprayable composition along with inert ingredients, solvents, and other materials. In some embodiments, the sprayable composition is an aerosol. The Z-HFO-1336mzz composition produced from the reactive intermediates disclosed herein can also be used to formulate various industrial aerosols or other sprayable compositions, such as contact cleaners, dusting agents, lubricant sprays, mold release sprays, pesticides, and the like, as well as consumer aerosols, such as personal care products (e.g., hair sprays, deodorants, and perfumes), household products (e.g., waxes, polishes, pot sprays, room fresheners, and household pesticides), and automotive products (e.g., cleaners and polishes), as well as pharmaceuticals such as anti-asthmatic and anti-oral malodor medications. Examples include, but are not limited to, metered dose inhalers (MDIs) for the treatment of asthma and other chronic obstructive pulmonary diseases and for the delivery of medications to accessible mucous membranes or intranasally.

[0220] The present application also provides a method for producing an aerosol product comprising the step of adding the Z-HFO-1336mzz composition produced from the reactive intermediates disclosed herein to a formulation in an aerosol container, wherein the composition is used as a propellant. In addition, the present application also provides a method for producing an aerosol product comprising the step of adding the Z-HFO-1336mzz composition produced from the reactive intermediates disclosed herein to a barrier aerosol package (e.g., a bag-on-valve or a piston can), wherein the composition of the present application is kept separate from other formulation ingredients in the aerosol container, and wherein the composition is used as a propellant. In addition, the present application also provides a method for producing an aerosol product comprising the step of adding only the Z-HFO-1336mzz composition produced from the reactive intermediates disclosed herein to an aerosol package, wherein the composition is used as an active ingredient (e.g., a dusting agent, or a cooling or freezing spray).

[0221] The present application also provides a method for converting heat from a heat source into mechanical energy comprising heating a working fluid comprising the Z-HFO-1336mzz composition produced from the reactive intermediates disclosed herein, and then expanding the heated working fluid. In this method, the heating of the working fluid uses heat supplied from the heat source; and the expansion of the heated working fluid produces mechanical energy as the pressure of the working fluid is reduced.

[0222] The method for converting heat can be a subcritical cycle, a transcritical cycle, or a supercritical cycle. In a transcritical cycle, the working fluid is compressed to a pressure above its critical pressure before being heated, and then the working fluid pressure is lowered below its critical pressure during expansion. In a supercritical cycle, the working fluid remains above its critical pressure throughout the cycle (e.g., compression, heating, expansion, and cooling).

[0223] The heat source can include, for example, low pressure steam, industrial waste heat, solar energy, geothermal hot water, low pressure geothermal steam (primary or secondary arrangements), or a distributed power plant that utilizes a fuel cell or a prime mover such as a turbine, microturbine, or internal combustion engine. One source of low pressure steam can be a process known as binary geothermal Rankine cycle. Large amounts of low pressure steam can be found in many places, such as in power plants that are fossil fuel powered. Other heat sources include waste heat recovered from the exhaust of a mobile internal combustion engine (e.g., a truck or railroad diesel engine or a ship), waste heat from the exhaust of a stationary internal combustion engine (e.g., a stationary diesel engine generator), waste heat from a fuel cell, heat obtained at a combined heating, cooling, and power or district heating and cooling plant, waste heat from a biomass fuel engine, waste heat from a natural gas or methane gas burner or boiler that burns methane or a methane fuel cell (e.g., a distributed power facility) that operates with methane from various sources including biogas, landfill gas, and coal bed gas, heat from the combustion of tree bark and lignin at a paper / pulp mill, heat from an incinerator, heat from low pressure steam from a conventional steam power plant (to drive a "bottoming" Rankine cycle), and geothermal heat.

[0224] In some embodiments, a heat conversion process is performed using an organic Rankine power cycle. Heat obtained at relatively low temperatures can be used to generate mechanical power by using a Rankine cycle of a working fluid described herein, as compared to a steam (inorganic) power cycle. In some embodiments, the working fluid is compressed before being heated. Compression can be provided by a pump that pumps the working fluid to a heat transfer unit (e.g., a heat exchanger or evaporator), where heat from a heat source is used to heat the working fluid. The heated working fluid is then expanded, reducing its pressure. Mechanical energy is generated during expansion of the working fluid using an expander. Examples of expanders include, but are not limited to, turboexpanders or dynamic expanders (such as turbines), as well as positive displacement expanders (such as screw expanders, scroll expanders, and piston expanders). Examples of expanders also include vane expanders.

[0225] The mechanical power can be used directly (e.g., to drive a compressor) or converted to electrical power by using an electric power generator. In a power cycle that reuses the working fluid, the expanded working fluid is cooled. The cooling can be accomplished in a working fluid cooling unit (e.g., a heat exchanger or condenser). The cooled working fluid can then be used in a repeated cycle (i.e., compression, heating, expansion, etc.). The same pump used for compression can be used to transfer the working fluid from the cooling stage.

[0226] The present application also provides a method for detecting a leak from a container, the method comprising sampling air in the vicinity of the container and detecting at least one additional compound of the composition provided herein with a device for detecting a leak, wherein the container contains a composition of the present application within the container. By "in the vicinity" is meant within 12 inches of the outer surface of the container. Alternatively, in the vicinity can be within 6 inches, within 3 inches, or within 1 inch of the outer surface of the container.

[0227] The container can be any known container or system or device filled with a composition comprising a compound of formula CF3CR=CClCF3, wherein R is CI or H, such as Z-HCFO-1326mxz or E-HCFO-1326mxz and Z-CFO-1316mxx or E-CFO-1316mxx. The container can include, but is not limited to, a storage container, a transport container, an aerosol can, a fire suppression system, a chiller device, a heat pump device, a heat transfer container, and a power cycle device (e.g., an organic Rankine cycle system).

[0228] The device for detecting a leak can be performed using any known sensor designed to detect a leak. In particular, the device for detecting a leak includes, but is not limited to, electrochemical, corona discharge, and mass spectrometry leak detectors.

[0229] Aspects and embodiments have been described above and are merely what are exemplary and not limiting. After reading this description, skilled artisans appreciate that other aspects and embodiments are possible without departing from the scope of the application.

[0230] Examples

[0231] The present application will be described in greater detail by way of specific examples. The following examples are provided for purposes of illustration only and are not intended to be limiting.

[0232] Example 1: Liquid phase production of HCFO-1326mxz

[0233] SbCl5(10.5 g) was added to a 210 mL Hastelloy C reactor followed by the addition of HF (49 g). The reaction mixture was heated at 100 °C for 1 hour and then cooled to 0 °C. Hexachlorobutadiene (30 g) and one or more additional compounds selected from the group consisting of 1,1,3,3,4,4-hexachloro-1-butene (C4H2Cl6), carbon tetrachloride (CCl4), pentachloroethane (C2HCl5, HCC-120), tetrachloroethylene (CO-1110), hexachloroethane (C2Cl6, CC-110), pentachloropyridine (C5Cl5N), 1,1,2,3,3-pentachloroprop-1-ene (C3HCl5, CCl2=CHCCl3, HCCO-1220az), 1,1,1,2,2,3,3-heptachloropropane (C2Cl5CHCl2), pentachlorocyclopropane (C3HCl5), 1,2,3,3-tetrachloro-1-propene (C3H2Cl4), pentachlorobutadiene isomers (CCl2=CH-CCl=CCl2, Z / E-CHCl=CCl-CCl=CCl2), tetrachlorothiophene (C4Cl4S), and trichloroethylene were added to the reactor and the reaction mixture was heated to 100 °C. The rate of reaction was indicated by the increase in pressure and stabilization of the pressure indicated completion of the reaction. Similar reactions were also performed using TaCl5 catalyst or NbCl5 catalyst. The reaction stereoselectivity produced a product mixture comprising (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene:(E)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene in a ratio of greater than about 99:1 of (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene. The product mixture also contained about 5 mole % or less of one or more additional compounds selected from the group consisting of: E-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene, E-HFO-1316mxx (E-2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene), Z-HFO-1316mxx (Z-2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene), HFO-1327mz (1,1,1,2,4,4,4-heptafluoro-2-butene), HFO-1325lxz (1,2-dichloro-1,1,4,4,4-pentafluoro-2-butene), HFO-1325dx (1,2-dichloro-3,3,4,4,4-pentafluoro-2-butene), HCFC-336mdd (2,3-dichloro-1,1,1,4,4,4-hexafluorobutane), HFC-336maf (2,2-dichloro-1,1,1,4,4,4-hexafluorobutane), HFC-336lbf (1,2-dichloro-1,1,2,4,4,4-hexafluorobutane), HFC-337mbf (2-chloro-1,1,1,2,4,4,4-heptafluorobutane), HFC-337mde (2-chloro-1,1,1,3,4,4,4-heptafluorobutane), HFC-356mff (1,1,1,4,4,4-hexafluorobutane), HFC-346mdf (2-chloro-1,1,1,4,4,4-hexafluorobutane), 338mf (1,1,1,2,2,4,4,4-octafluorobutane) HCFC-1122 (2-chloro-1,1-difluoroethene), HCFC-124 (2-chloro-1,1,1,2-tetrafluoroethane), CFC-114 (1,2-dichloro-1,1,2,2-tetrafluoroethane), CFC-113 (1,1,2-trichloro-1,2,2-trifluoroethane), CFC-133a (2-chloro-1,1,1-trifluoroethane), CFC-123 (2,2-dichloro-1,1,1-trifluoroethane), CFC-123a (1,2-dichloro-1,1,2-trifluoroethane), CFC-122 (1,2,2-trichloro-1,1-difluoroethane), CFC-112a (1,1,1,2-tetrachloro-2,2-difluoroethane), HCFC-224db (1,1,1,3-tetrafluoro-2,3,3-trichloropropane), HFC-225da (1,2-dichloro-1,1,3,3,3-pentafluoropropane), HFC-235da (2-chloro-1,1,1,3,3-pentafluoropropane), HFC-235fa (1-chloro-1,1,3,3,3-pentafluoropropane), and HFC-236fa (1,1,1,3,3,3-hexafluoropropane).

[0234] Example 2: Gas phase production of Z-CFO-1316mxx and E-CFO-1316mxx from HCBD

[0235]

[0236] An InConel tube was filled with 12 cc (6.45 g) of 10% chromium chloride on carbon catalyst ® (0.5 inch OD, 16 inch length, 0.34 inch wall thickness). The catalyst was activated with anhydrous HF at 300 °C. The reactor was heated to 400 °C in a Lindberg furnace and HCBD was fed at 0.16 ml / hour, HF gas was fed at 8.2 sccm (standard cubic centimeters / minute) through a vaporizer controlled at 220 °C, and then chlorine was fed at 2.0 sccm. The feed also included one or more additional compounds selected from the group consisting of 1,1,3,3,4,4-hexachloro-1-butene (C4H2Cl6), carbon tetrachloride (CCl4), pentachloroethane (C2HCl5, HCC-120), tetrachloroethylene (CO-1110), hexachloroethane (C2Cl6, CC-110), pentachloropyridine (C5Cl5N), 1,1,2,3,3-pentachloroprop-1-ene (C3HCl5, CCl2=CHCCl3, HCCO-1220az), 1,1,1,2,2,3,3-heptachloropropane (C2Cl5CHCl2), pentachlorocyclopropane (C3HCl5), 1,2,3,3-tetrachloro-1-propene (C3H2Cl4), pentachlorobutadiene isomers (CCl2=CH-CCl=CCl2, Z / E-CHCl=CCl-CCl=CCl2), tetrachlorothiophene (C4Cl4S), and trichloroethylene. The experiment was conducted at 1 psig to 2 psig. An Agilent ® 6890 GC / 5973 MS and Restek ® PC2618 5% Krytox ® CBK-D / 60 / 80 6 meter x 2 mm ID 1 / 8" OD packed column, purged with helium at 30 seem, and the effluent of the reactor was analyzed on-line. The data showed 100% HCBD conversion with a CFO-1316mxx selectivity of 70% (1:1 ratio of Z to E). In addition to E-CFO-1316mxx and Z-CFO-1316mxx, the product mixture also included about 5 mole% or less of one or more additional compounds selected from the group consisting of: Z-2-chloro-1,1,1,4,4,4-hexafluorobut-2-ene (Z-HCFO-1326mxz); E-2-chloro-1,1,1,4,4,4-hexafluorobut-2-ene (E-HCFO-1326mxz); E-2-chloro-1,1,1,3,4,4,4-hexafluoro-2-butene (E-CFO-1317mx); Z-2-chloro-1,1,1,3,4,4,4-heptafluoro-2-butene (Z-CFO-1317mx); E-1,2,3-trichloro-1,1,4,4,4-pentafluoro-2-butene (E-CFC-1315lxx); Z-1,2,3-trichloro-1,1,4,4,4-pentafluoro-2-butene (Z-CFC-1315lxx); E-1,1,2,3-tetrachloro-1,4,4,4-tetrafluoro-2-butene (E-CFC-1314kxx); Z-1,1,2,3-tetrachloro-1,4,4,4-tetrafluoro-2-butene (Z-CFC-1314kxx); 2-chloro-1,1,1,4,4,4-hexafluorobutane (HFC-346md); and 1,1,1,3,3,3-hexafluoropropane (HFC-236fa).

[0237] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present application, suitable methods and materials are described below. All publications, patent applications, patents and other references mentioned herein are incorporated by reference in their entirety, unless a particular passage is cited. In case of conflict between the present specification and the incorporated references, the present specification will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.

Claims

1. A method of making a compound of the formula CF3CR=CCICF3, wherein R is H or CI, the method comprising reacting a composition comprising hexachlorobutadiene (HCBD) and one or more additional compounds selected from the group consisting of 1,1,3,3,4,4-hexachloro-1-butene (C4H2CI6), carbon tetrachloride (CC14), pentachloroethane (C2HCI5, HCC-120), tetrachloroethylene (CO-1110), hexachloroethane (C2CI6, CC-110), pentachloropyridine (C5CI5N), 1,1,2,3,3-pentachloroprop-1-ene (C3HCI5, CCI2=CHCCI3, HCCO-1220az), 1,1,1,2,2,3,3-heptachloropropane (C2CI5CHCI2), pentachlorocyclopropane (C3HCI5), 1,2,3,3-tetrachloro-1-propene (C3H2CI4), pentachlorobutadiene isomers (CCI2=CH-CCI=CCI2, Z / E-CHCI=CCI-CCI=CCI2), tetrachlorothiophene (C4CI4S), and trichloroethylene, in the presence of a catalyst to obtain a product mixture comprising the compound of the formula CF3CR=CCICF3.

2. The method of claim 1, wherein the compound of the formula CF3CR=CCICF3 is 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene.

3. The method of claim 2, the method comprising reacting the composition comprising HCBD and one or more additional compounds with HF in the presence of a fluorination catalyst to produce a product mixture comprising 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene.

4. The method of any one of claims 2-3, wherein greater than about 99 mole % of the 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene produced is (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene.

5. The method of any one of claims 3-4, wherein the fluorination catalyst is a transition metal catalyst selected from the group consisting of a tantalum catalyst, a niobium catalyst, or a tantalum-niobium catalyst.

6. The method of claim 5, wherein the transition metal catalyst is selected from the group consisting of tantalum (V) chloride, niobium (V) chloride, niobium (IV) chloride, and combinations of two or more.

7. The method of any one of claims 3-4, wherein the fluorination catalyst is a metal halide selected from the group consisting of an antimony halide, a tin halide, a thallium halide, an iron halide, and combinations of two or more.

8. The process of claim 7, wherein the metal halide catalyst is selected from the group consisting of SbCl5, SbCl3, SbF5, SnCl4, TiCl4, NiF5, FeCl3, and combinations of two or more, and preferably the metal halide catalyst is SbCl5or SbF5.

9. The process of claim 3, wherein a molar excess of HF is used based on 1 mole equivalent of hexachlorobutadiene.

10. The process of claim 3, wherein the process is conducted at a temperature of about 80 °C to about 150 °C.

11. The process of claim 2, wherein the 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene of the product mixture is Z-chloro-1,1,1,4,4,4-hexafluoro-2-butene.

12. The method of any one of claims 2-11, wherein the product composition further comprises one or more additional compounds selected from the group consisting of: E-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene; E-CFO-1316mxx (E-2,3-dichloro-1,1,1,4,4,4-hexafluorobut-2-ene); Z-CFO-1316mxx (Z-2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene); HFO-1327mz (1,1,1,2,4,4,4-heptafluoro-2-butene), HCFO-1325lxz (1,2-dichloro-1,1,4,4,4-pentafluoro-2-butene); HCFO-1325dx (1,2-dichloro-3,3,4,4,4-pentafluoro-2-butene); HCFC-336mdd (2,3-dichloro-1,1,1,4,4,4-hexafluorobutane); HCFC-336maf (2,2-dichloro-1,1,1,4,4,4-hexafluorobutane); HCFC-336lbf (1,2-dichloro-1,1,2,4,4,4-hexafluorobutane); HCFC-337mbf (2-chloro-1,1,1,2,4,4,4-heptafluorobutane); HCFC-337mde (2-chloro-1,1,1,3,4,4,4-heptafluorobutane); HFC-356mff (1,1,1,4,4,4-hexafluorobutane); HCFC-346mdf (2-chloro-1,1,1,4,4,4-hexafluorobutane); HFC-338mf (1,1,1,2,2,4,4,4-octafluorobutane); HCFC-1122 (2-chloro-1,1 -difluoroethene); HCFC-124 (2-chloro-1,1,1,2-tetrafluoroethane); CFC-114 (1,2-dichloro-1,1,2,2-tetrafluoroethane); CFC-113 (1,1,2-trichloro-1,2,2-trifluoroethane); CFC-133a (2-chloro-1,1,1 -trifluoroethane); HCFC-123 (2,2-dichloro-1,1,1 -trifluoroethane); HCFC-123a (1,2-dichloro-1,1,2-trifluoroethane); HCFC-122 (1,2,2-trichloro-1,1 -difluoroethane); CFC-112a (1,1,1,2-tetrachloro-2,2-difluoroethane); HCFC-224db (1,1,1,3-tetrafluoro-2,3,3-trichloropropane); E-CFO-1317mx (E-2-chloro-1,1,1,3,4,4,4-heptafluorobut-2-ene); Z-CFO-1317mx (Z-2-chloro-1,1,1,3,4,4,4-heptafluorobut-2-ene); HCFC-225da (1,2-dichloro-1,1,3,3,3-pentafluoropropane); HCFC-235da (2-chloro-1,1,1,3,3-pentafluoropropane);CFC-235fa (1-chloro-1, 1, 3, 3, 3-pentafluoropropane); and HFC-236fa (1, 1, 1, 3, 3, 3-hexafluoropropane).

13. The process of claim 11, wherein the product mixture further comprises one or more additional compounds selected from the group consisting of E-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene, E-CFO-1317mx (2-chloro-1,1,1,3,4,4,4-heptafluoro-2-butene), Z-CFO-1317mx (2-chloro-1,1,1,3,4,4,4-heptafluoro-2-butene), and HCFC-336mdd (2,3-dichloro-1,1,1,4,4,4-hexafluorobutane).

14. The process of claim 11, wherein the product mixture further comprises HCFC-336mdd (2,3-dichloro-1,1,1,4,4,4-hexafluorobutane).

15. The process of any one of claims 11 to 14, further comprising continuously dehydrochlorinating the Z-chloro-1,1,1,4,4,4-hexafluorobut-2-ene to produce hexafluoro-2-butyne, and then hydrogenating the hexafluoro-2-butyne to produce (Z)-1,1,1,4,4,4-hexafluoro-2-butene.

16. The process of any one of claims 12 to 14, further comprising continuously dechlorinating a mixture of the Z-chloro-1,1,1,4,4,4-hexafluorobut-2-ene and 2,3-dichloro-1,1,1,4,4,4-hexafluorobutane to produce hexafluoro-2-butyne, and then hydrogenating the hexafluoro-2-butyne to produce (Z)-1,1,1,4,4,4-hexafluoro-2-butene.

17. The process of claim 2, wherein the process is conducted in a liquid phase.

18. The process of claim 1, wherein the compound of the formula CF3CR=CClCF3 is 2,3-dichloro-1,1,1,4,4,4-hexafluorobut-2-ene.

19. The process of claim 18, comprising reacting the composition comprising HCBD and one or more additional compounds with HF and chlorine in the presence of a metal oxide or metal halide catalyst to produce a product mixture comprising 2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene.

20. The method of any one of claims 18-19, wherein the 2,3-dichloro-1,1,1,4,4,4- hexafluorobut-2-ene comprises a Z isomer and an E isomer.

21. The method of any one of claims 19-20, wherein the metal halide catalyst is selected from the group consisting of nickel halide, chromium halide, iron halide, scandium halide, yttrium halide, lanthanum halide, titanium halide, zirconium halide, hafnium halide, vanadium halide, molybdenum halide, tungsten halide, manganese halide, rhenium halide, ruthenium halide, osmium halide, cobalt halide, palladium halide, copper halide, zinc halide, antimony halide, tantalum halide, aluminum halide, tin halide, lead halide, and mixtures thereof.

22. The method of claim 21, wherein the metal halide catalyst is unsupported or supported on activated carbon.

23. The method of claim 22, wherein the activated carbon is optionally acid or base washed.

24. The method of any one of claims 19-20, wherein the metal oxide catalyst is selected from the group consisting of chromium oxide, aluminum oxide, and mixtures thereof.

25. The method of claim 24, wherein the metal oxide catalyst is unsupported or supported on activated carbon.

26. The method of claim 25, wherein the activated carbon is optionally acid or base washed.

27. The method of any one of claims 19-26, wherein the catalyst comprises a chloride source for the method of claim 19.

28. The method of claim 19, wherein a molar excess of HF is used based on 1 molar equivalent of hexachlorobutadiene.

29. The method of claim 19, wherein a molar excess of chlorine is used based on 1 molar equivalent of hexachlorobutadiene.

30. The method of claim 19, wherein the method is conducted at a temperature of about 230 °C to about 480 °C.

31. The method of claim 19, wherein the product mixture comprises E-2,3-dichloro-1,1,1,4,4,4- hexafluorobut-2-ene and Z-2,3-dichloro-1,1,1,4,4,4-hexafluorobut-2-ene.

32. The method of claim 31, wherein the product mixture further comprises one or more additional compounds selected from the group consisting of Z-2-chloro- 1,1,1,4,4,4-hexafluorobut-2-ene (Z-HCFO-1326mxz); E-2-chloro- 1,1,1,4,4,4-hexafluorobut-2-ene (E-HCFO-1326mxz); E-2-chloro- 1,1,1,3,4,4,4-hexafluoro-2-buten (E-CFO-1317mx); Z-2-chloro- 1,1,1,3,4,4,4-hexafluoro-2-buten (Z-CFO-1317mx); E- 1,2,3-trichloro- 1,1,4,4,4-pentafluoro-2-buten (E-CFC-1315lxx); Z- 1,2,3-trichloro- 1,1,4,4,4-pentafluoro-2-buten (Z-CFC-1315lxx); E- 1,1,2,3-tetrachloro- 1,4,4,4-tetrafluoro-2-buten (E-CFC-1314kxx); Z- 1,1,2,3-tetrachloro- 1,4,4,4-tetrafluoro-2-buten (Z-CFC-1314kxx); 2-chloro- 1,1,1,4,4,4-hexafluorobutane (HFC-346mdf); and 1,1,1,3,3,3-hexafluoropropane (HFC-236fa).

33. The method of claim 31, wherein the product mixture further comprises one or more additional compounds selected from the group consisting of Z-2-chloro- 1,1,1,4,4,4-hexafluorobut-2-ene (Z-HCFO-1326mxz) and E-2-chloro- 1,1,1,4,4,4-hexafluorobut-2-ene (E-HCFO-1326mxz).

34. The method of claim 31, wherein the product mixture further comprises Z-2-chloro- 1,1,1,4,4,4-hexafluorobut-2-ene (Z-HCFO-1326mxz).

35. The method of claim 19, further comprising continuously dechlorinating the 2,3-dichloro- 1,1,1,4,4,4-hexafluorobut-2-ene to produce hexafluoro-2-butyne, and then hydrogenating the hexafluoro-2-butyne to produce (Z)- 1,1,1,4,4,4-hexafluoro-2-buten.

36. The method of claim 19, wherein the method is conducted in the gas phase.

37. A composition comprising hexachlorobutadiene and one or more additional compounds selected from the group consisting of 1,1,3,3,4,4-hexachloro-1-butene (C4H2Cl6), carbon tetrachloride (CC14), pentachloroethane (C2HCl5, HCC-120), tetrachloroethylene (CO-1110), hexachloroethane (C2Cl6, CC-110), pentachloropyridine (C5Cl5N), 1,1,2,3,3-pentachloroprop-1-ene (C3HCl5, CCl2=CHCC13, HCCO-1220az), 1,1,1,2,2,3,3-heptachloropropane (C2Cl5CHCl2), pentachlorocyclopropane (C3HCl5), 1,2,3,3-tetrachloro-1-propene (C3H2Cl4), pentachlorobutadiene isomers (CC12=CH-CC1=CC12, Z / E-CHCl=CC1-CC1=CC12), tetrachlorothiophene (C4Cl4S), and trichloroethylene.

38. The composition of claim 37, wherein the one or more additional compounds are present in an amount less than about 10 wt%, preferably less than about 5 wt%, more preferably less than about 1 wt%, most preferably less than about 0.5 wt%.

39. A composition comprising Z-chloro-1,1,1,4,4,4-hexafluorobut-2-ene and one or more additional compounds selected from the group consisting of: E-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene; E-CFO-1316mxx (E-2,3-dichloro-1,1,1,4,4,4-hexafluorobut-2-ene); Z-CFO-1316mxx (Z-2,3-dichloro-1,1,1,4,4,4-hexafluorobut-2-ene); HFO-1327mz (1,1,1,2,4,4,4-heptafluorobut-2-ene); HCFO-1325lxz (1,2-dichloro-1,1,4,4,4-pentafluorobut-2-ene); HCFO-1325dx (1,2-dichloro-3,3,4,4,4-pentafluorobut-1-ene); HCFC-336mdd (2,3-dichloro-1,1,1,4,4,4-hexafluorobutane); HCFC-336maf (2,2-dichloro-1,1,1,4,4,4-hexafluorobutane); HCFC-336lbf (1,2-dichloro-1,1,2,4,4,4-hexafluorobutane); HCFC-337mbf (2-chloro-1,1,1,2,4,4,4-heptafluorobutane); HCFC-337mde (2-chloro-1,1,1,3,4,4,4-heptafluorobutane); HFC-356mff (1,1,1,4,4,4-hexafluorobutane); HCFC-346mdf (2-chloro-1,1,1,4,4,4-hexafluorobutane); HFC-338mf (1,1,1,2,2,4,4,4-octafluorobutane); HCFC-1122 (2-chloro-1,1-difluoroethene); HCFC-124 (2-chloro-1,1,1,2-tetrafluoroethane); CFC-114 (1,2-dichloro-1,1,2,2-tetrafluoroethane); CFC-113 (1,1,2-trichloro-1,2,2-trifluoroethane); CFC-133a (2-chloro-1,1,1-trifluoroethane); HCFC-123 (2,2-dichloro-1,1,1-trifluoroethane); HCFC-123a (1,2-dichloro-1,1,2-trifluoroethane); HCFC-122 (1,2,2-trichloro-1,1-difluoroethane); CFC-112a (1,1,1,2-tetrachloro-2,2-difluoroethane); HCFC-224db (1,1,1,3-tetrafluoro-2,3,3-trichloropropane); CFO-1317mx (2-chloro-1,1,1,3,4,4,4-heptafluorobut-2-ene); HCFC-225da (1,2-dichloro-1,1,3,3,3-pentafluoropropane); HCFC-235da (2-chloro-1,1,1,3,3-pentafluoropropane); CFC-235fa (1-chloro-1,1,3,3,3-pentafluoropropane);and HFC-236fa (1,1,1,3,3,3-hexafluoropropane).

40. The composition of claim 39, wherein the one or more additional compounds are present in an amount less than about 10 wt%, preferably less than about 5 wt%, more preferably less than about 1 wt%, most preferably less than about 0.5 wt%.

41. A composition comprising Z-chloro-1,1,1,4,4,4-hexafluorobut-2-ene and one or more additional compounds selected from the group consisting of E-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene and HCFC-336mdd (2,3-dichloro-1,1,1,4,4,4-hexafluorobutane).

42. The composition of claim 41, wherein the one or more additional compounds are present in an amount less than about 10 wt%, preferably less than about 5 wt%, more preferably less than about 1 wt%, most preferably less than about 0.5 wt%.

43. A composition comprising Z-chloro-1,1,1,4,4,4-hexafluorobut-2-ene and HCFC-336mdd (2,3-dichloro-1,1,1,4,4,4-hexafluorobutane), wherein the HCFC-336mdd is present in an amount less than about 10 wt%, preferably less than about 5 wt%, more preferably less than about 1 wt%, most preferably less than about 0.5 wt%.

44. A composition comprising E-2,3-dichloro-1,1,1,4,4,4-hexafluorobut-2-ene; Z-2,3-dichloro-1,1,1,4,4,4-hexafluorobut-2-ene; and one or more additional compounds selected from the group consisting of Z-2-chloro-1,1,1,4,4,4-hexafluorobut-2-ene (Z-HCFO-1326mxz); E-2-chloro-1,1,1,4,4,4-hexafluorobut-2-ene (E-HCFO-1326mxz); E-2-chloro-1,1,1,3,4,4,4-hexafluoro-2-butene (E-CFO-1317mx); Z-2-chloro-1,1,1,3,4,4,4-hexafluoro-2-butene (Z-CFO-1317mx); E-1,2,3-trichloro-1,1,4,4,4-pentafluoro-2-butene (E-CFC-1315lxx); Z-1,2,3-trichloro-1,1,4,4,4-pentafluoro-2-butene (Z-CFC-1315lxx); E-1,1,2,3-tetrachloro-1,4,4,4-tetrafluoro-2-butene (E-CFC-1314kxx); Z-1,1,2,3-tetrachloro-1,4,4,4-tetrafluoro-2-butene (Z-CFC-1314kxx); 2-chloro-1,1,1,4,4,4-hexafluorobutane (HFC-346mdf); and 1,1,1,3,3,3-hexafluoropropane (HFC-236fa).

45. The composition of claim 44, wherein the one or more additional compounds are present in an amount less than about 10 wt%, preferably less than about 5 wt%, more preferably less than about 1 wt%, most preferably less than about 0.5 wt%.

46. The method of any one of claims 1 to 36, wherein the composition comprising HCBD is supplied from a reactor without storage.

47. An integrated system for making a compound of the formula CF3CR=CCICF3, wherein R is H or CI, the system comprising: a first reactor configured to produce a composition comprising hexachlorobutadiene (HCBD) and one or more additional compounds in the presence of a catalyst to obtain a product mixture comprising the compound of the formula CF3CR=CCICF3, wherein the one or more additional compounds are selected from the group consisting of 1,1,3,3,4,4-hexachloro-1-butene (C4H2Cl6), carbon tetrachloride (CC14), pentachloroethane (C2HCl5, HCC-120), tetrachloroethylene (CO-1110), hexachloroethane (C2Cl6, CC-110), pentachloropyridine (C5Cl5N), 1,1,2,3,3-pentachloropropene (C3HCl5, CCl2=CHCC13, HCCO-1220az), 1,1,1,2,2,3,3-heptachloropropane (C2Cl5CHCl2), pentachlorocyclopropane (C3HCl5), 1,2,3,3-tetrachloro-1-propene (C3H2Cl4), pentachlorobutadiene isomers (CC12=CH-CC1=CC12, Z / E-CHCl=CC1-CC1=CC12), tetrachlorothiophene (C4Cl4S), and trichloroethylene, the first reactor having a discharge line for the composition comprising HCBD; and a second reactor coupled to the first reactor and configured to convert the composition comprising HCBD to the compound of the formula CF3CR=CCICF3.

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