Compositions of chlorofluorinated compounds

Abstract

The present disclosure relates to compositions of chlorofluorinated compounds that can be used as intermediates in chemical processes, particularly for the production of 1336 mzZ.

Description

Technical Field

[0001] This invention relates to compositions comprising chlorofluorocarbons, including chlorofluoroalkanes and chlorofluoroolefins. These compositions provide improved results in the preparation of unsaturated fluorinated compounds, including hexafluorobutene. Background Technology

[0002] Increased public awareness of the environmental impacts of fossil fuel extraction, transportation, and use is prompting a shift towards new forms of environmental sustainability, exemplified by regulations and reductions in atmospheric CO2 equivalent emissions. In particular, new environmental regulations for refrigerants have forced the refrigeration and air conditioning industry to seek new refrigerants with low global warming potential (GWP). For both existing and new applications in thermal management, alternative refrigerants with low GWP and ozone depletion potential (ODP) will need to comply with these new regulations.

[0003] Z-1,1,1,4,4,4-Hexafluoro-2-butene (Z-HFO-1336mzz) can be used as a refrigerant, heat transfer fluid, foam expander, power circulation working fluid, and other applications. It has also been advantageously found that Z-HFO-1336mzz has a low global warming potential (GWP) of 32. Therefore, fluorobutene compositions containing Z-HFO-1336mzz could be good candidates for replacing higher GWP saturated compounds such as CFCs (chlorofluorocarbons), HCFCs (hydrochlorofluorocarbons), or HFCs (hydrofluorocarbons) in many applications.

[0004] Methods for preparing Z-HFO-1336mzz are disclosed, for example, in WO 2015 / 120250 A1, WO2014 / 052695A1, US2013 / 0158304 A1, CN 103193586, CN 106008147, and CN106966856 (Seabiscuit case, red). For example, WO 2015 / 120250 A1 discloses that Z-HFO-1336mzz can be prepared starting from CFC-113a (1,1,1-trichloro-2,2,2-trifluoroethane). For example, US2013 / 0158304 A1 discloses that Z-HFO-1336mzz can be prepared starting from hexachlorobutadiene (CCl2=CCl-Cl=CCl2). It has been found that the materials and intermediates used in these methods may contain compounds that negatively impact downstream processes and equipment used in the manufacture of Z-HFO-1336mzz.

[0005] This invention solves these problems. Summary of the Invention

[0006] It has been found that certain chlorofluorinated compositions disclosed herein provide improved results for the manufacture of Z-HFO-1336mzz, including the use of such chlorofluorinated compositions as intermediates to manufacture Z-HFO-1336mzz. The improved results include better yields and fewer byproducts, which facilitates purification and increases product purity.

[0007] The present invention provides a composition comprising 1,1,1-trichloro-2,2,2-trifluoroethane (CFC-113a), 2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene (CFO-1316mxx) or 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (HCFO-1326mxz), and at least one of 113, 122, 123 and 1122 in total not more than 0.5% (in molar percentage).

[0008] In one embodiment, the present invention provides a composition comprising 1,1,1-trichloro-2,2,2-trifluoroethane (CFC-113a) and at least one of 113, 122, 123 and 1122 in total not exceeding 0.5%.

[0009] In one embodiment, the present invention provides a composition comprising 2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene (CFO-1316mxx) and at least one of 113, 122, 123 and 1122 in total not exceeding 0.5%.

[0010] In one embodiment, the present invention provides a composition comprising 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (HCFO-1326mxz) and at least one of 113, 122, 123 and 1122 in total not more than 0.5%.

[0011] Compositions comprising at least one of 1,1,1-trichloro-2,2,2-trifluoroethane (CFC-113a), 2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene (CFO-1316mxx), or 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (HCFO-1326mxz), and a total of not more than 0.5% (by weight or molar percentage) of 113, 122, 123, and 1122, may further comprise one or more additional compounds selected from HCFC-2,2-dichloro-1,1,1-trifluoroethane (CFC-113a), 2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene (CFO-1316mxx), and 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (HCFO-1326mxz), and at least 0.5% (by weight or molar percentage) of 113, 122, 123, and 1122. Fluoroethane (HCFC-142b), HFC-1,1,1-trifluoroethane (HFC-143a), HCFC-2-chloro-1,1,1,4,4,4-hexafluorobutane (HCFC-346mdf), HFC-1,1,1,4,4,4-hexafluorobutane (HFC-356mff), Z-1,1,1,4,4,4-hexafluoro-2-butene (Z-HFO-1336mzz), E-1,1,1,4,4,4-hexafluoro-2-butene (E-HFO-1336mzz), and HFO-pentafluorobutene (HFO-1345czf).

[0012] In one embodiment, the composition comprises at least 95% by weight (or mol)%, such as at least 98% by weight (or mol)%, or at least 99% by weight (or mol)%, or at least 99.5% by weight (or mol)%, of 1,1,1-trichloro-2,2,2-trifluoroethane (CFC-113a), 2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene (CFO-1316mxx), or 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (HCFO-1326mxz).

[0013] In one embodiment, the composition comprises 113a or 1316mxx or 1326mxz and one or more of 113, 122, 123 and 1122, wherein the total amount of 113, 122, 123 and 1122 does not exceed 0.5% by weight (or moles)%, for example, not more than 0.2% by weight (or moles)% or not more than 0.1% by weight (or moles). Preferably, the total amount of 113, 122, 123 and 1122 does not exceed 0.1% by weight (or moles)% or not more than 0.01% by weight (or moles).

[0014] In one embodiment, the compositions disclosed herein comprise one or more of 1,1,1-trichloro-2,2,2-trifluoroethane (CFC-113a), 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113), HCFC-1,2,2-trichloro-1,1-difluoroethane (HCFC-122), HCFC-2,2-dichloro-1,1,1-trifluoroethane (HCFC-123), and HCFO-2-chloro-1,1-difluoroethylene (HCFO-1122).

[0015] In one embodiment, the compositions disclosed herein comprise 1,1,1-trichloro-2,2,2-trifluoroethane (CFC-113a) and 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113).

[0016] In one embodiment, the compositions disclosed herein comprise 1,1,1-trichloro-2,2,2-trifluoroethane (CFC-113a) and HCFC-1,2,2-trichloro-1,1-difluoroethane (HCFC-122).

[0017] In one embodiment, the compositions disclosed herein comprise one or more of 2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene and 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113), 1,1,1-trichloro-2,2,2-trifluoroethane (CFC-113a), HCFC-1,2,2-trichloro-1,1-difluoroethane (HCFC-122), HCFC-2,2-dichloro-1,1,1-trifluoroethane (HCFC-123), and HCFO-2-chloro-1,1-difluoroethylene (HCFO-1122).

[0018] In one embodiment, the compositions disclosed herein comprise 2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene and HCFC-2,2-dichloro-1,1,1-trifluoroethane (HCFC-123).

[0019] In one embodiment, the compositions disclosed herein comprise 1,1,1-trichloro-2,2,2-trifluoroethane (CFC-113a) and HCFO-2-chloro-1,1-difluoroethylene (HCFO-1122).

[0020] In one embodiment, the compositions disclosed herein comprise 2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene (CFO-1316mxx) and 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113).

[0021] In one embodiment, the compositions disclosed herein comprise 2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene (CFO-1316mxx) and HCFC-1,2,2-trichloro-1,1-difluoroethane (HCFC-122).

[0022] In one embodiment, the compositions disclosed herein comprise 2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene (CFO-1316mxx) and HCFC-2,2-dichloro-1,1,1-trifluoroethane (HCFC-123).

[0023] In one embodiment, the compositions disclosed herein comprise 2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene (CFO-1316mxx) and HCFO-2-chloro-1,1-difluoroethylene (HCFO-1122).

[0024] In one embodiment, the compositions disclosed herein comprise one or more of 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (HCFO-1326mxz) and 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113), 1,1,1-trichloro-2,2,2-trifluoroethane (CFC-113a), HCFC-1,2,2-trichloro-1,1-difluoroethane (HCFC-122), HCFC-2,2-dichloro-1,1,1-trifluoroethane (HCFC-123), and HCFO-2-chloro-1,1-difluoroethylene (HCFO-1122).

[0025] In one embodiment, the compositions disclosed herein comprise 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (HCFO-1326mxz) and 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113).

[0026] In one embodiment, the compositions disclosed herein comprise 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (HCFO-1326mxz) and 1,1,1-trichloro-2,2,2-trifluoroethane (CFC-113a).

[0027] In one embodiment, the compositions disclosed herein comprise 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (HCFO-1326mxz) and HCFC-1,2,2-trichloro-1,1-difluoroethane (HCFC-122).

[0028] In one embodiment, the compositions disclosed herein comprise 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (HCFO-1326mxz) and HCFC-2,2-dichloro-1,1,1-trifluoroethane (HCFC-123).

[0029] In one embodiment, the compositions disclosed herein comprise 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (HCFO-1326mxz) and HCFO-2-chloro-1,1-difluoroethylene (HCFO-1122). Detailed Implementation

[0030] As used herein, the terms “comprising,” “including,” “having,” or any other variations thereof are intended to cover non-exclusive inclusion. For example, a composition, process, method, article of manufacture, or apparatus that includes a list of elements is not necessarily limited to those elements, but may include other elements not expressly listed or inherent to such composition, process, method, article of manufacture, or apparatus. Furthermore, unless expressly stated otherwise, “or” refers to an inclusive or non-exclusive or. For example, conditions A or B satisfy one of the following: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); and both A and B are true (or exist).

[0031] The transitional phrase "composed of..." does not include any unspecified elements, steps, or components. If in a claim, it will not include protection for materials other than those described, except for impurities typically associated with them. When the phrase "composed of..." appears in a clause of the body of a claim, rather than immediately following the preamble, it only limits the elements described in that clause; other elements as a whole are not excluded from the claim.

[0032] The transitional phrase "consistently composed of..." is used to define compositions or methods that include materials, steps, features, components, or elements in addition to those disclosed in the literature, provided that these additionally included materials, steps, features, components, or elements do not significantly affect one or more essential and novel features of the invention protected by the claims, particularly the mode of action for achieving the desired results of any of the methods of the invention. The term "consistently composed of..." occupies an intermediate position between "comprising" and "composed of...".

[0033] Where the applicant has defined the invention or a part thereof using open-ended terms such as “comprising”, it should be readily understood (unless otherwise stated) that the description should be interpreted as also including inventions using terms such as “substantially composed of” or “composed of”.

[0034] Furthermore, the terms "an" or "a" are used to describe the elements and components described herein. This is for convenience only and to give a general meaning to the scope of the invention. This description should be understood to include one or at least one, and the singular includes the plural, unless it is obvious that it means otherwise.

[0035] As used herein, the term “about” is intended to account for variations due to experimental error (e.g., adding or subtracting approximately 10% of the indicated value). Unless otherwise expressly stated, all measurements reported herein should be understood to be modified by the term “about,” whether or not the term is explicitly used.

[0036] When quantities, concentrations, or other values ​​or parameters are given as a list of ranges, preferred ranges, or preferred upper and / or preferred lower limits, it should be understood as specifically disclosing all ranges formed by any pair of any upper or preferred range value and any lower or preferred range value, regardless of whether the range is disclosed individually. Wherever a numerical range is given herein, the range is intended to include its endpoints, as well as all integers and fractions within that range, unless otherwise indicated.

[0037] As used herein, the term "compound" means all stereoisomers, geometric isomers, tautomers, and isotopes that include the structure or chemical described. Unless otherwise stated, compounds identified herein by name or structure as a particular tautomer are intended to include other tautomers.

[0038] As used in this article, the term "catalyst" refers to a substance that accelerates a chemical reaction but is not consumed by the reaction; therefore, it can be recovered without undergoing a chemical change at the end of the reaction.

[0039] Composition

[0040] The compositions containing chlorofluoro compounds disclosed herein can be used as starting materials and / or intermediates in the manufacture of usable molecules. While not intended to be limiting, the compositions are illustrated herein as being suitable for the manufacture of Z-1,1,1,4,4,4-hexafluoro-2-butene (1336mzzZ). Table 1 provides a list of the compounds discussed herein.

[0041]

[0042] This invention provides a composition comprising 1,1,1-trichloro-2,2,2-trifluoroethane (CFC-113a), 2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene (CFO-1316mxx), or 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (HCFO-1326mxz), and at least one of 113, 122, 123, and 1122 in total not exceeding 0.5% (by weight or molar percentage). It should be understood that “0.5%” is equivalent to 5000 ppm, and “0.1%” is equivalent to 1000 ppm, and so on. For the purposes of this document, all amounts expressed as percentages “%” reflect molar percentages.

[0043] In one embodiment, the composition comprises at least 0.5% of one of 113, 122, 123, and 1122 in total. In another embodiment, the composition comprises at least 0.2% of one of 113, 122, 123, and 1122 in total. In another embodiment, the composition comprises at least 0.1% of one of 113, 122, 123, and 1122 in total. In another embodiment, the composition comprises at least 0.05% of one of 113, 122, 123, and 1122 in total. In yet another embodiment, the composition comprises at least 0.01% of one of 113, 122, 123, and 1122 in total.

[0044] Compositions containing 113a

[0045] In one embodiment, the composition provided herein comprises 113a and at least one of 113, 122, 123 and 1122 in total not more than 0.5%.

[0046] The compositions provided herein may comprise 113a, 112, 112a, 113, 114, 114a and 123a, wherein the compositions comprise at least one of 112, 112a, 114, 114a and 123a in total not more than 0.5%.

[0047] In one embodiment, the composition provided herein comprises 113a and at least one of 113, 122, 123 and 1122 in total not more than 0.5%, and further comprises one or more of 122b, 132a, 132b, 142, 142b, 1112, 1112a and PCE in total not more than 0.5%.

[0048] In one embodiment, the composition provided herein comprises 113a and a total of no more than 0.5% of 113, 122, 123 and 1122, and also comprises no more than 0.5% of one or more of 112, 112a, 114, 114a, 115, 215ba, 216, 316, 318 and PCE.

[0049] In one embodiment, the composition provided herein comprises a total of no more than 0.5% of at least one of 111, 214cb, CHCl2CCl3, and CCl3CCl3.

[0050] In one embodiment, the composition provided herein comprises 113a and at least one of 112, 112a, 113, 114a and 318 in total not more than 0.5%.

[0051] Compositions containing 1316mxx

[0052] In one embodiment, the composition provided herein comprises 1316mxx and at least one of 113, 122, 123 and 1122 in total not more than 0.5%.

[0053] For all compositions comprising 1316mxx disclosed herein, the composition comprises Z-1316mxx or E-1316mxx or a mixture of Z-1316mxx and E-1316mxx. The designation “Z” or “E” is provided when referring to a particular isomer.

[0054] Preferably, the composition containing 1316mxx comprises a mixture of Z-1316mxx and E-1316mxx. The ratio of Z-1316mxx to E-1316mxx (Z / E) is in the range of 1 to 99, or 5 to 95, or 10 to 90, or 15 to 85, or 20 to 80, or 25 to 75, or 30 to 70, or 35 to 65, or 40 to 60, or 45 to 55, or 50 to 50, or 55 to 45, or 60 to 40, or 65 to 35, or 70 to 30, or 75 to 25, or 80 to 20, or 85 to 15, or 90 to 10, or 95 to 5, or 99 to 1. The ratio of Z-1316mxx to E-1316mxx (Z / E) is preferably within the range of 10:90, or 15:85, or 20:80, or 25:75, or 30:70, or 35:65, or 40:60, or 45:55, or 50:50, or 55:45, or 60:40, or 65:35, or 70:30, or 75:25, or 80:20, or 85:15, or 90:10. More preferably, the ratio of Z-1316mxx to E-1316mxx (Z / E) is within the range of 65, or 40:60, or 45:55, 50:50, or 55:45, or 60:40, or 65:35.

[0055] In one embodiment, the composition comprises 1316mxx and at least one of 113, 122, 123 and 1122 in total not exceeding 0.5%, wherein the ratio of Z-1316mxx to E-1316mxx (Z / E) is in the range of 10 to 90, or 15 to 85, or 20 to 80, or 25 to 75, or 30 to 70, or 35 to 65, or 40 to 60, or 45 to 55, or 50 to 50, or 55 to 45, or 60 to 40, or 65 to 35, or 70 to 30, or 75 to 25, or 80 to 20, or 85 to 15, or 90 to 10. In one embodiment, the composition comprises 1316mxx and at least 0.5% of one of 113, 122, 123 and 1122, wherein the ratio of Z-1316mxx to E-1316mxx (Z / E) is in the range of 65, or 40 to 60, or 45 to 55, or 50 to 50, or 55 to 45, or 60 to 40, or 65 to 35.

[0056] In one embodiment, the composition comprises 1316mxx and 113, wherein 113 is present in an amount not exceeding 0.5%, or not exceeding 0.2%, or not exceeding 0.1%, or not exceeding 0.05%, or not exceeding 0.01%. In one embodiment, the composition comprises 1316mxx and 122, wherein 122 is present in an amount not exceeding 0.5%, or not exceeding 0.2%, or not exceeding 0.1%, or not exceeding 0.05%, or not exceeding 0.01%. In one embodiment, the composition comprises 1316mxx and 123, wherein 123 is present in an amount not exceeding 0.5%, or not exceeding 0.2%, or not exceeding 0.1%, or not exceeding 0.05%, or not exceeding 0.01%. In one embodiment, the composition comprises 1316mxx and 1122, wherein 1122 is present in an amount not exceeding 0.5%, or not exceeding 0.2%, or not exceeding 0.1%, or not exceeding 0.05%, or not exceeding 0.01%.

[0057] In one embodiment, the composition comprising 1316mxx comprises 113 and 122, wherein the total amount of 113 and 122 is not more than 0.5%, or not more than 0.2%, or not more than 0.1%, or not more than 0.05%, or not more than 0.01%. In one embodiment, the composition comprising 1316mxx comprises 113 and 123, wherein the total amount of 113 and 123 is not more than 0.5%, or not more than 0.2%, or not more than 0.1%, or not more than 0.05%, or not more than 0.01%. In one embodiment, the composition comprising 1316mxx comprises 113 and 1122, wherein the total amount of 113 and 1122 is not more than 0.5%, or not more than 0.2%, or not more than 0.1%, or not more than 0.05%, or not more than 0.01%. In one embodiment, the composition containing 1316mxx comprises 122 and 123, wherein the total amount of 122 and 123 does not exceed 0.5%, or 0.2%, or 0.1%, or 0.05%, or 0.01%. In one embodiment, the composition containing 1316mxx comprises 122 and 1122, wherein the total amount of 122 and 1122 does not exceed 0.5%, or 0.2%, or 0.1%, or 0.05%, or 0.01%. In one embodiment, the composition containing 1316mxx comprises 123 and 1122, wherein the total amount of 123 and 1122 does not exceed 0.5%, or 0.2%, or 0.1%, or 0.05%, or 0.01%.

[0058] In one embodiment, the composition comprising 1316mxx comprises 113, 122, and 123, wherein the total amount of 113, 122, and 123 does not exceed 0.5%, or 0.2%, or 0.1%, or 0.05%, or 0.01%. In one embodiment, the composition comprises 1316mxx, 122, and 1122, wherein the total amount of 113, 122, and 1122 does not exceed 0.5%, or 0.2%, or 0.1%, or 0.05%, or 0.01%. In one embodiment, the composition comprises 1316mxx, 122, 123, and 1122, wherein the total amount of 122, 123, and 1122 does not exceed 0.5%, or 0.2%, or 0.1%, or 0.05%, or 0.01%.

[0059] In one embodiment, the composition comprises 1316mxx, 113, 122, 123 and 1122, wherein the total amount of 113, 122, 123 and 1122 does not exceed 0.5%, or 0.2%, or 0.1%, or 0.05% or 0.01%.

[0060] Composition containing 1326mxz

[0061] For all compositions comprising 1326mxz disclosed herein, the composition may comprise Z-1326mxz or E-1326mxz or a mixture of Z-1326mxz and E-1326mxz. The designation “Z” or “E” is provided when referring to a particular isomer.

[0062] Preferably, the composition containing 1326mxz comprises a mixture of Z-1326mxz and E-1326mxz. The ratio of Z-1326mxz to E-1326mxz (Z / E) is in the range of 1 to 99, or 5 to 95, or 10 to 90, or 15 to 85, or 20 to 80, or 25 to 75, or 30 to 70, or 35 to 65, or 40 to 60, or 45 to 55, or 50 to 50, or 55 to 45, or 60 to 40, or 65 to 35, or 70 to 30, or 75 to 25, or 80 to 20, or 85 to 15, or 90 to 10, or 95 to 5, or 99 to 1. The ratio of Z-1326mxz to E-1326mxz (Z / E) is preferably within the range of 10:90, 15:85, 20:80, 25:75, 30:70, 35:65, 40:60, 45:55, 50:50, 55:45, 60:40, 65:35, 70:30, 75:25, 80:20, 85:15, or 90:10. More preferably, the ratio of Z-1326mxz to E-1326mxz (Z / E) is within the range of 65, 40:60, 45:55, 50:50, 55:45, 60:40, or 65:35.

[0063] In one embodiment, the composition comprises 1326mxz and at least one of 113, 122, 123 and 1122 in total not exceeding 0.5%, wherein the ratio of Z-1326mxz to E-1326mxz (Z / E) is in the range of 10 to 90, or 15 to 85, or 20 to 80, or 25 to 75, or 30 to 70, or 35 to 65, or 40 to 60, or 45 to 55, or 50 to 50, or 55 to 45, or 60 to 40, or 65 to 35, or 70 to 30, or 75 to 25, or 80 to 20, or 85 to 15, or 90 to 10. In one embodiment, the composition comprises 1326mxz and at least 0.5% of one of 113, 122, 123 and 1122, wherein the ratio of Z-1316mxx to E-1326mxz (Z / E) is in the range of 65, or 40 to 60, or 45 to 55, or 50 to 50, or 55 to 45, or 60 to 40, or 65 to 35.

[0064] In one embodiment, the composition comprises 1326mxz and 113, wherein 113 is present in an amount not exceeding 0.5%, or not exceeding 0.2%, or not exceeding 0.1%, or not exceeding 0.05%, or not exceeding 0.01%. In one embodiment, the composition comprises 1326mxz and 122, wherein 122 is present in an amount not exceeding 0.5%, or not exceeding 0.2%, or not exceeding 0.1%, or not exceeding 0.05%, or not exceeding 0.01%. In one embodiment, the composition comprises 1326mxz and 123, wherein 123 is present in an amount not exceeding 0.5%, or not exceeding 0.2%, or not exceeding 0.1%, or not exceeding 0.05%, or not exceeding 0.01%. In one embodiment, the composition comprises 1326mxz and 1122, wherein 1122 is present in an amount not exceeding 0.5%, or not exceeding 0.2%, or not exceeding 0.1%, or not exceeding 0.05%, or not exceeding 0.01%.

[0065] In one embodiment, the composition containing 1326mxz comprises 113 and 122, wherein the total amount of 113 and 122 does not exceed 0.5%, or 0.2%, or 0.1%, or 0.05%, or 0.01%. In one embodiment, the composition containing 1326mxz comprises 113 and 123, wherein the total amount of 113 and 123 does not exceed 0.5%, or 0.2%, or 0.1%, or 0.05%, or 0.01%. In one embodiment, the composition containing 1326mxz comprises 113 and 1122, wherein the total amount of 113 and 1122 does not exceed 0.5%, or 0.2%, or 0.1%, or 0.05%, or 0.01%. In one embodiment, the composition containing 1326mxz comprises 122 and 123, wherein the total amount of 122 and 123 is not more than 0.5%, or not more than 0.2%, or not more than 0.1%, or not more than 0.05%, or not more than 0.01%. In one embodiment, the composition containing 1326mxz comprises 122 and 1122, wherein the total amount of 122 and 1122 is not more than 0.5%, or not more than 0.2%, or not more than 0.1%, or not more than 0.05%, or not more than 0.01%. In one embodiment, the composition containing 1326mxz comprises 123 and 1122, wherein the total amount of 123 and 1122 is not more than 0.5%, or not more than 0.2%, or not more than 0.1%, or not more than 0.05%, or not more than 0.01%.

[0066] In one embodiment, the composition comprising 1326mxz contains 113, 122, and 123, wherein the total amount of 113, 122, and 123 is not more than 0.5%, or not more than 0.2%, or not more than 0.1%, or not more than 0.05%, or not more than 0.01%. In another embodiment, the composition comprises 1326mxz, 122, and 1122, wherein the total amount of 113, 122, and 1122 is not more than 0.5%, or not more than 0.2%, or not more than 0.1%, or not more than 0.05%, or not more than 0.01%. In yet another embodiment, the composition comprises 1326mxz, 122, 123, and 1122, wherein the total amount of 122, 123, and 1122 is not more than 0.5%, or not more than 0.2%, or not more than 0.1%, or not more than 0.05%, or not more than 0.01%.

[0067] In one embodiment, the composition comprises 1326mxz, 113, 122, 123 and 1122, wherein the total amount of 113, 122, 123 and 1122 does not exceed 0.5%, or 0.2%, or 0.1%, or 0.05% or 0.01%.

[0068] In one embodiment, the composition comprises 1326mxz and at least one of 113, 122, 123, and 1122 in a total of no more than 0.5%, and further comprises one or more of 113a, 142b, 143a, 346mdf, 356mff, E-1336mzz, and 1345czf. In one embodiment, the composition comprises 1326mxz and at least one of 113, 122, 123, and 1122 in a total of no more than 0.5%, and further comprises 113a. In one embodiment, the composition comprises 1326mxz and at least one of 113, 122, 123, and 1122 in a total of no more than 0.5%, and further comprises 142b. In one embodiment, the composition comprises 1326mxz and at least one of 113, 122, 123, and 1122 in a total of no more than 0.5%, and further comprises 143a. In one embodiment, the composition comprises 1326mxz and at least 0.5% of one of 113, 122, 123, and 1122, and further comprises 346mdf. In one embodiment, the composition comprises 1326mxz and at least 0.5% of one of 113, 122, 123, and 1122, and further comprises 356mff. In one embodiment, the composition comprises 1326mxz and at least 0.5% of one of 113, 122, 123, and 1122, and further comprises E-1336mzz. In one embodiment, the composition comprises 1326mxz and at least 0.5% of one of 113, 122, 123, and 1122, and further comprises 1345czf.

[0069] In one embodiment, the composition comprises 1326mxz and at least one of 113, 122, 123 and 1122 in total not more than 0.5%, and also comprises one or more of 113a, 142b, 143a, 346mdf, 356mff, E-1336mzz and 1345czf.

[0070] In one embodiment, the composition comprises 1326mxz and at least one of 113, 122, 123, and 1122 in total not exceeding 0.5%, and further comprises 113a and 142b. In one embodiment, the composition comprises 1326mxz and at least one of 113, 122, 123, and 1122 in total not exceeding 0.5%, and further comprises 113a and 143a. In one embodiment, the composition comprises 1326mxz and at least one of 113, 122, 123, and 1122 in total not exceeding 0.5%, and further comprises 113a and 346mdf. In one embodiment, the composition comprises 1326mxz and at least one of 113, 122, 123, and 1122 in total not exceeding 0.5%, and further comprises 113a and 356mff. In one embodiment, the composition comprises 1326mxz and at least one of 113, 122, 123 and 1122 in total not more than 0.5%, and also comprises 113a and 1345czf.

[0071] In one embodiment, the composition comprises 1326mxz and at least one of 113, 122, 123, and 1122 in total not exceeding 0.5%, and further comprises 142b and 143a. In one embodiment, the composition comprises 1326mxz and at least one of 113, 122, 123, and 1122 in total not exceeding 0.5%, and further comprises 142b and 356mff. In one embodiment, the composition comprises 1326mxz and at least one of 113, 122, 123, and 1122 in total not exceeding 0.5%, and further comprises 142b and E-1336mzz. In one embodiment, the composition comprises 1326mxz and at least one of 113, 122, 123, and 1122 in total not exceeding 0.5%, and further comprises 142b and 1345czf.

[0072] In one embodiment, the composition comprises 1326mxz and at least one of 113, 122, 123, and 1122 in total not exceeding 0.5%, and further comprises 143a and 346mdf. In one embodiment, the composition comprises 1326mxz and at least one of 113, 122, 123, and 1122 in total not exceeding 0.5%, and further comprises 143a and 356mff. In one embodiment, the composition comprises 1326mxz and at least one of 113, 122, 123, and 1122 in total not exceeding 0.5%, and further comprises 143a and E-1336mzz. In one embodiment, the composition comprises 1326mxz and at least one of 113, 122, 123, and 1122 in total not exceeding 0.5%, and further comprises 143a and 1345czf.

[0073] In one embodiment, the composition comprises 1326mxz and at least 0.5% of one of 113, 122, 123, and 1122, and further comprises 346mdf and 356mff. In one embodiment, the composition comprises 1326mxz and at least 0.5% of one of 113, 122, 123, and 1122, and further comprises 346mdf and E-1336mzz. In one embodiment, the composition comprises 1326mxz and at least 0.5% of one of 113, 122, 123, and 1122, and further comprises 346mdf and 1345czf.

[0074] In one embodiment, the composition comprises 1326mxz and at least one of 113, 122, 123, and 1122 in total not exceeding 0.5%, and further comprises 356mff and E-1336mzz. In another embodiment, the composition comprises 1326mxz and at least one of 113, 122, 123, and 1122 in total not exceeding 0.5%, and further comprises 356mff and 1345czf.

[0075] In one embodiment, the composition comprises 1326mxz and at least one of 113, 122, 123 and 1122 in total not more than 0.5%, and also comprises E-1336mzz and 1345czf.

[0076] In one embodiment, the composition comprises 1326mxz and at least 0.5% of one of 113, 122, 123, and 1122, and further comprises 113a, 142b, and 143a. In one embodiment, the composition comprises 1326mxz and at least 0.5% of one of 113, 122, 123, and 1122, and further comprises 113a, 142b, and 346mdf. In one embodiment, the composition comprises 1326mxz and at least 0.5% of one of 113, 122, 123, and 1122, and further comprises 113a, 142b, and 356mff. In one embodiment, the composition comprises 1326mxz and at least 0.5% of one of 113, 122, 123, and 1122, and further comprises 113a, 142b, and E-1336mzz. In one embodiment, the composition comprises 1326mxz and at least one of 113, 122, 123 and 1122 in total not more than 0.5%, and also comprises 113a, 142b and 1345czf.

[0077] In one embodiment, the composition comprises 1326mxz and at least 0.5% of one of 113, 122, 123, and 1122, and further comprises 113a, 143a, and 346mdf. In one embodiment, the composition comprises 1326mxz and at least 0.5% of one of 113, 122, 123, and 1122, and further comprises 113a, 143a, and 356mff. In one embodiment, the composition comprises 1326mxz and at least 0.5% of one of 113, 122, 123, and 1122, and further comprises 113a, 143a, and E-1336mzz. In one embodiment, the composition comprises 1326mxz and at least 0.5% of one of 113, 122, 123 and 1122 in total, and also comprises 113a, 143a and 1345czf.

[0078] In one embodiment, the composition comprises 1326mxz and at least one of 113, 122, 123, and 1122 in total not exceeding 0.5%, and further comprises 113a, 346mdf, and 356mff. In one embodiment, the composition comprises 1326mxz and at least one of 113, 122, 123, and 1122 in total not exceeding 0.5%, and further comprises 113a, 346mdf, and E-1336mzz. In one embodiment, the composition comprises 1326mxz and at least one of 113, 122, 123, and 1122 in total not exceeding 0.5%, and further comprises 113a, 346mdf, and 1345czf.

[0079] In one embodiment, the composition comprises 1326mxz and at least one of 113, 122, 123, and 1122 in total not exceeding 0.5%, and further comprises 113a, 356mff, and E-1336mzz. In another embodiment, the composition comprises 1326mxz and at least one of 113, 122, 123, and 1122 in total not exceeding 0.5%, and further comprises 113a, 356mff, and 1345czf.

[0080] In one embodiment, the composition comprises 1326mxz and at least one of 113, 122, 123 and 1122 in total not more than 0.5%, and also comprises 113a, E-1336mzz and 1345czf.

[0081] In one embodiment, the composition comprises 1326mxz and at least one of 113, 122, 123, and 1122 in total not exceeding 0.5%, and further comprises 113a, 142b, 143a, and 346mdf. In one embodiment, the composition comprises 1326mxz and at least one of 113, 122, 123, and 1122 in total not exceeding 0.5%, and further comprises 113a, 142b, 143a, and 356mff. In one embodiment, the composition comprises 1326mxz and at least one of 113, 122, 123, and 1122 in total not exceeding 0.5%, and further comprises 113a, 142b, 143a, and E-1336mzz. In one embodiment, the composition comprises 1326mxz and at least one of 113, 122, 123 and 1122 in total not more than 0.5%, and also comprises 113a, 142b, 143a and 1345czf.

[0082] In one embodiment, the composition comprises 1326mxz and at least 0.5% of one of 113, 122, 123, and 1122, and further comprises 113a, 143a, 346mdf, and 356mff. In one embodiment, the composition comprises 1326mxz and at least 0.5% of one of 113, 122, 123, and 1122, and further comprises 113a, 143a, 346mdf, and E-1336mzz. In one embodiment, the composition comprises 1326mxz and at least 0.5% of one of 113, 122, 123, and 1122, and further comprises 113a, 143a, 346mdf, and 1345czf.

[0083] In one embodiment, the composition comprises 1326mxz and at least one of 113, 122, 123, and 1122 in total not exceeding 0.5%, and further comprises 113a, 346mdf, 356mff, and E-1336mzz. In another embodiment, the composition comprises 1326mxz and at least one of 113, 122, 123, and 1122 in total not exceeding 0.5%, and further comprises 113a, 346mdf, E-1336mzz, and 1345czf.

[0084] In one embodiment, the composition comprises 1326mxz and at least one of 113, 122, 123 and 1122 in total not more than 0.5%, and also comprises 113a, 356mff, E-1336mzz and 1345czf.

[0085] In one embodiment, the composition comprises 1326mxz and at least 0.5% of one of 113, 122, 123 and 1122 in total, and further comprises 142b, 143a, 346mdf, 356mff, E-1336mzz and 1345czf.

[0086] In one embodiment, the composition comprises 1326mxz and at least 0.5% of one of 113, 122, 123 and 1122 in total, and also comprises 113a, 142b, 143a, 346mdf, 356mff, E-1336mzz and 1345czf.

[0087] method

[0088] The present invention provides compositions that can be used as intermediates for the production of fluoroolefins (particularly 1336mzzZ).

[0089] In one embodiment of the present invention, a method for generating 1336mzzZ is also provided, the method comprising the following steps.

[0090] One step (a) includes providing a composition comprising 113a and at least 0.5% of one of 113, 122, 123 and 1122 in total, or at least 0.2% of one of 113, 122, 123 and 1122 in total, or at least 0.1% of one of 113, 122, 123 and 1122 in total, or at least 0.05% of one of 113, 122, 123 and 1122 in total, or at least 0.01% of one of 113, 122, 123 and 1122 in total.

[0091] The method further includes step (b) of contacting the composition containing 113a with hydrogen in the presence of a catalyst in step (b) to produce a first product mixture containing 1316mxx and at least one of 113, 122, 123 and 1122, wherein the composition containing 113a contains at least one of 113, 122, 123 and 1122 in total not more than 0.5%.

[0092] The catalyst in step (b) contains a transition metal. The transition metal may be selected from ruthenium, rhodium, palladium, and platinum. The catalyst in step (b) may contain a support. The support may be selected from silicon carbide (SiC), tungsten carbide (WC), and alumina.

[0093] Typical reaction conditions for step (b) are as follows. The reaction can be carried out at temperatures ranging from 90°C to 200°C. The reaction pressure in step (b) is typically in the range of 80 psig to 200 psig (0.55 MPa to 1.38 MPa). Step (b) can be carried out with a contact time ranging from 30 seconds to 100 seconds (30 s to 100 s), such as a contact time of 70 seconds (70 s).

[0094] In some embodiments, the composition comprising 113a in step (b) comprises 113. In some embodiments, the composition comprising 113a in step (b) comprises 122. In some embodiments, the composition comprising 113a in step (b) comprises 123. In some embodiments, the composition comprising 113a in step (b) comprises 1122.

[0095] In some embodiments, the composition comprising 113a in step (b) comprises 113 and 122. In some embodiments, the composition comprising 113a in step (b) comprises 113 and 123. In some embodiments, the composition comprising 113a in step (b) comprises 113 and 1122. In some embodiments, the composition comprising 113a in step (b) comprises 122 and 123. In some embodiments, the composition comprising 113a in step (b) comprises 122 and 1122. In some embodiments, the composition comprising 113a in step (b) comprises 123 and 1122. In some embodiments, the composition comprising 113a in step (b) comprises 113, 122, 123, and 1122.

[0096] In some embodiments, the composition comprising 113a and at least one of 113, 122, 123, and 1122 in steps (a) and (b) further comprises at least one of 112, 112a, 114, 114a, 115, 215ba, 216, 316, 318, and PCE in a total of no more than 0.5%. In some embodiments, the composition comprising 113a and at least one of 113, 122, 123, and 1122 in step (a) or (b) further comprises at least one of 111, 214cb, CHCl2CCl3, and CCl3CCl3 in a total of no more than 0.5%. In some embodiments, the composition comprising 113a and at least one of 113, 122, 123 and 1122 in total not more than 0.5% comprises at least one of 112, 112a, 113, 114a and 318 in total not more than 0.5%.

[0097] The method further includes step (c) of purifying a first product mixture comprising 1316mxx and at least one of 113, 122, 123 and 1122 by fractionation at a ratio not exceeding 1:1, 2:1 or 3:1, to provide a composition comprising 1316mxx and at least one of 113, 122, 123 and 1122 in total not exceeding 0.5%.

[0098] This step (c) is typically performed at a pressure of 200 psig or lower, or 150 psig (1.03 MPa) or lower, or 80 psig (0.55 MPa) or lower, which is within the range of ambient pressure up to 200 psig (1.38 MPa).

[0099] The composition provided by purifying a mixture of first products comprising 1316mxx and at least one of 113, 122, 123, and 1122 by fractionation in step (c) using a reflux ratio not exceeding 1:1, 2:1, or 3:1 comprises 1316mxx and at least one of 113, 122, 123, and 1122 in total not exceeding 0.5%. The composition provided in step (c) may comprise Z-1316mxx or E-1316mxx, or a mixture of Z-1316mxx and E-1316mxx. When the composition provided in step (c) comprises a mixture of Z-1316mxx and E-1316mxx, the ratio of Z-1316mxx to E-1316mxx (Z / E) is in the range of 1:99, or 5:95, or 10:90, or 15:85, or 20:80, or 25:75, or 30:70, or 35:65, or 40:60, or 45:55, or 50:50, or 55:45, or 60:40, or 65:35, or 70:30, or 75:25, or 80:20, or 85:15, or 90:10, or 95:5, or 99:1. The ratio of Z-1316mxx to E-1316mxx (Z / E) is preferably within the range of 10:90, or 15:85, or 20:80, or 25:75, or 30:70, or 35:65, or 40:60, or 45:55, or 50:50, or 55:45, or 60:40, or 65:35, or 70:30, or 75:25, or 80:20, or 85:15, or 90:10. More preferably, the ratio of Z-1316mxx to E-1316mxx (Z / E) is within the range of 65, or 40:60, or 45:55, 50:50, or 55:45, or 60:40, or 65:35.

[0100] In step (c), when purifying a first product mixture comprising 1316mxx and at least one of 113, 122, 123, and 1122 by fractionation using a reflux ratio not exceeding 1:1, 2:1, or 3:1, the first product mixture fed to this step may contain a total of more than 0.5%, or more than 0.2%, or more than 0.1%, or more than 0.05%, or more than 0.01% of at least one of 113, 122, 123, and 1122. Purification step (c) provides a composition comprising 1316mxx and a total of not more than 0.5%, or more than 0.2%, or more than 0.1%, or more than 0.05%, or more than 0.01% of at least one of 113, 122, 123, and 1122.

[0101] In one embodiment, the reflux ratio is at least 1:1. In one embodiment, the reflux ratio is at least 2:1. In one embodiment, the reflux ratio is at least 3:1.

[0102] In one embodiment of step (c) of purifying a first product mixture comprising at least one of 1316mxx and 113, 122, 123 and 1122 by fractionation using a reflux ratio not exceeding 1:1, 2:1 or 3:1, the first product mixture comprises a total of more than 0.1% of at least one of 113, 122, 123 and 1122 to provide a composition comprising 1316mxx and a total of not more than 0.1%, or not more than 0.05%, or not more than 0.01% of at least one of 113, 122, 123 and 1122.

[0103] In one embodiment of step (c), the first product mixture comprising at least one of 1316mxx and 113, 122, 123, and 1122 is purified by fractionation using a reflux ratio not exceeding 1:1, wherein the first product mixture comprises a total of greater than 0.1% of at least one of 113, 122, 123, and 1122. In another embodiment of step (c), the first product mixture comprising at least one of 1316mxx and 113, 122, 123, and 1122 is purified by fractionation using a reflux ratio not exceeding 2:1, wherein the first product mixture comprises a total of greater than 0.1% of at least one of 113, 122, 123, and 1122. In one embodiment, the first product mixture is purified by fractionation using a reflux ratio not exceeding 3:1, wherein the first product mixture contains a total of more than 0.05% of at least one of 113, 122, 123 and 1122.

[0104] In one embodiment, a first product mixture comprising 1316mxx and at least one of 113, 122, 123, and 1122 is purified by fractionation using a reflux ratio not exceeding 1:1, 2:1, or 3:1, wherein the first product mixture comprises a total of more than 0.05% of at least one of 113, 122, 123, and 1122 to provide a composition comprising 1316mxx and a total of not more than 0.05% or not more than 0.01% of at least one of 113, 122, 123, and 1122.

[0105] The method further includes step (d) of contacting the composition containing 1316mxx with hydrogen in the presence of a catalyst selected from the group consisting of carbon-supported copper, carbon-supported nickel, carbon-supported copper and nickel, and carbon-supported copper and palladium, to produce a second product mixture containing 1326mxx and at least one of 113, 122, 123, and 1122, wherein the composition containing 1316mxx comprises a total of no more than 0.5% of at least one of 113, 122, 123, and 1122. The composition containing 1316mxx used in step (d) may comprise a total of no more than 0.2% of at least one of 113, 122, 123, and 1122. The composition containing 1316mxx used in step (d) may comprise a total of no more than 0.1% of at least one of 113, 122, 123, and 1122. The composition containing 1316mxx used in step (d) may contain at least one of 113, 122, 123, and 1122 in total not exceeding 0.05%. The composition containing 1316mxx used in step (d) may contain at least one of 113, 122, 123, and 1122 in total not exceeding 0.01%. Additional compounds may be present in the composition containing 1316mxx used in step (d) as described above.

[0106] In one embodiment, the composition containing 1316mxx used in step (d) comprises 113, 122, 123, and 1122. In one embodiment, the composition containing 1316mxx used in step (d) comprises 113, 122, and 123. In one embodiment, the composition containing 1316mxx used in step (d) comprises 113, 122, and 1122. In one embodiment, the composition containing 1316mxx used in step (d) comprises 122, 123, and 1122. In one embodiment, the composition containing 1316mxx used in step (d) comprises 113 and 122. In one embodiment, the composition containing 1316mxx used in step (d) comprises 113 and 123. In one embodiment, the composition containing 1316mxx used in step (d) comprises 113 and 1122. In one embodiment, the composition containing 1316mxx used in step (d) comprises 122 and 123. In one embodiment, the composition containing 1316mxx used in step (d) comprises 122 and 1122. In one embodiment, the composition containing 1316mxx used in step (d) comprises 123 and 1122. In one embodiment, the composition containing 1316mxx used in step (d) comprises 113. In one embodiment, the composition containing 1316mxx used in step (d) comprises 122. In one embodiment, the composition containing 1316mxx used in step (d) comprises 123. In one embodiment, the composition containing 1316mxx used in step (d) comprises 1122.

[0107] Step (d) is typically performed at temperatures ranging from 150°C to 250°C and pressures ranging from 80 psig to 300 psig (0.55 MPa to 2.07 MPa). The contact time is typically between 50 and 200 seconds.

[0108] The second product mixture containing 1326mxz produced in step (d) may contain a total of more than 0.5% of one or more of 113, 122, 123 and 1122, or a total of more than 0.2% of one or more of 113, 122, 123 and 1122, or a total of more than 0.1% of one or more of 113, 122, 123 and 1122.

[0109] The method further includes the step (e) of purifying a second product mixture containing 1326 mgxz by fractionation using a reflux ratio not exceeding 1:1, 2:1, or 3:1 to provide a composition containing 1326 mgxz and a total of not more than 0.5% (by weight or molar percentage) of at least one of 113, 122, 123, and 1122.

[0110] The second product mixture may contain a total of more than 0.5%, or more than 0.2%, or more than 0.1%, or more than 0.05%, or more than 0.01% of 113, 122, 123, and 1122. Purification of the second product mixture provides a composition comprising 1326mxz and a total of no more than 0.5%, or no more than 0.2%, or no more than 0.1%, or no more than 0.05%, or no more than 0.01% of 113, 122, 123, and 1122.

[0111] In one embodiment, the reflux ratio of step (e) is at least 1:1. In one embodiment, the reflux ratio of step (e) is at least 2:1. In one embodiment, the reflux ratio of step (e) is at least 3:1.

[0112] In one embodiment of step (e) for purifying a second product mixture comprising at least one of 1326mxz and 113, 122, 123, and 1122 by fractionation using a reflux ratio not exceeding 1:1, the second product mixture comprises a total of greater than 0.1% of 113, 122, 123, and 1122. In one embodiment of step (e) for purifying a second product mixture comprising at least one of 1326mxz and 113, 122, 123, and 1122 by fractionation using a reflux ratio not exceeding 2:1, the second product mixture comprises a total of greater than 0.1% of 113, 122, 123, and 1122. In one embodiment of step (e) for purifying a second product mixture comprising at least one of 1326mxz and 113, 122, 123 and 1122 by fractionation using a reflux ratio not exceeding 3:1, the second product mixture comprises a total of greater than 0.1% of 113, 122, 123 and 1122.

[0113] The conditions for step (e) are the same as those for step (c). That is, step (e) is typically performed at a pressure of 200 psig or lower, or 150 psig (1.03 MPa) or lower, or 80 psig (0.55 MPa) or lower, which is within the range of ambient pressure up to 200 psig (1.38 MPa).

[0114] The method further includes step (f) of contacting a composition comprising 1326mxz and a total of no more than 0.5% of 113, 122, 123, and 1122 with an alkali metal hydroxide in an alkaline aqueous solution in the presence of a phase transfer catalyst to produce a third product mixture comprising hexafluoro-2-butyne. The composition comprising 1326mxz used in step (f) may comprise a total of no more than 0.2% of 113, 122, 123, and 1122. The composition comprising 1326mxz used in step (f) may comprise a total of no more than 0.1% of 113, 122, 123, and 1122. The composition comprising 1326mxz used in step (f) may comprise a total of no more than 0.05% of 113, 122, 123, and 1122. The composition comprising 1326mxz used in step (f) may comprise a total of no more than 0.01% of 113, 122, 123, and 1122. Additional compounds may be present in the composition containing 1326mxz used in step (d) as described above.

[0115] In one embodiment, the composition containing 1326mxz used in step (f) comprises 113, 122, 123, and 1122. In one embodiment, the composition containing 1326mxz used in step (f) comprises 113, 122, and 123. In one embodiment, the composition containing 1326mxz used in step (f) comprises 113, 122, and 1122. In one embodiment, the composition containing 1326mxz used in step (f) comprises 122, 123, and 1122. In one embodiment, the composition containing 1326mxz used in step (f) comprises 113 and 122. In one embodiment, the composition containing 1326mxz used in step (f) comprises 113 and 123. In one embodiment, the composition containing 1326mxz used in step (f) comprises 113 and 1122. In one embodiment, the composition containing 1326mxz used in step (f) comprises 122 and 123. In one embodiment, the composition containing 1326mxz used in step (f) comprises 122 and 1122. In one embodiment, the composition containing 1326mxz used in step (f) comprises 123 and 1122. In one embodiment, the composition containing 1326mxz used in step (f) comprises 113. In one embodiment, the composition containing 1326mxz used in step (f) comprises 122. In one embodiment, the composition containing 1326mxz used in step (f) comprises 123. In one embodiment, the composition containing 1326mxz used in step (f) comprises 1122.

[0116] Typical reaction conditions for step (f) are as follows: temperature from 150°C to 250°C, pressure from 80 psig to 300 psig (0.55 MPa to 2.07 MPa), and contact time from 50 seconds to 200 seconds.

[0117] The method further includes the step (g) of purifying a third product mixture containing hexafluoro-2-butyne (PFBY) by fractionation using a reflux ratio not exceeding 1:1, 2:1, or 3:1 to provide a composition containing PFBY and 113, 122, 123, and 1122 in total not exceeding 0.5%, 0.2%, 0.1%, 0.05%, or 0.01%.

[0118] The third product mixture may contain 113, 122, 123, and 1122 in total amounts greater than 0.5%, or greater than 0.2%, or greater than 0.1%, or greater than 0.05%, or greater than 0.01%. Purification of the third product mixture provides a composition comprising PFBY and 113, 122, 123, and 1122 in total amounts not exceeding 0.5%, or not exceeding 0.2%, or not exceeding 0.1%, or not exceeding 0.05%, or not exceeding 0.01%.

[0119] In one embodiment, the reflux ratio of step (g) is at least 1:1. In one embodiment, the reflux ratio of step (g) is at least 2:1. In one embodiment, the reflux ratio of step (g) is at least 3:1.

[0120] In one embodiment of step (g) for purifying a mixture of third products comprising at least one of PFBY and 113, 122, 123, and 1122 by fractionation using a reflux ratio not exceeding 1:1, the third product mixture comprises a total of greater than 0.5%, or greater than 0.2%, or greater than 0.1%, or greater than 0.05%, or greater than 0.01% of 113, 122, 123, and 1122. In one embodiment of step (g) for purifying a mixture of third products comprising at least one of PFBY and 113, 122, 123, and 1122 by fractionation using a reflux ratio not exceeding 2:1, the third product mixture comprises a total of greater than 0.5%, or greater than 0.2%, or greater than 0.1%, or greater than 0.05%, or greater than 0.01% of 113, 122, 123, and 1122. In one embodiment, the third product mixture is purified by fractionation using a reflux ratio not exceeding 3:1, wherein the third product mixture contains a total of greater than 0.5%, or greater than 0.2%, or greater than 0.1%, or greater than 0.05%, or greater than 0.01% of 113, 122, 123, and 1122.

[0121] The conditions for step (g) are the same as those for step (c). That is, step (g) is typically performed at a pressure of 200 psig or lower, or 150 psig (1.03 MPa) or lower, or 80 psig (0.55 MPa) or lower, i.e., an ambient pressure of up to 200 psig (1.38 MPa).

[0122] The method further includes the step (h) of contacting a composition comprising hexafluoro-2-butyne and 113, 122, 123 and 1122 in a total of no more than 0.5%, or no more than 0.2%, or no more than 0.1%, or no more than 0.05%, or no more than 0.01% with a Lindlar's catalyst or a palladium catalyst further comprising lanthanides or silver in the presence of hydrogen to produce a fourth product mixture comprising 1336 mzzz.

[0123] The composition containing PFBY used in step (h) may contain a total of no more than 0.2% of 113, 122, 123, and 1122. The composition containing 1326mxz used in step (f) may contain a total of no more than 0.2% of 113, 122, 123, and 1122. The composition containing PFBY used in step (h) may contain a total of no more than 0.1% of 113, 122, 123, and 1122. The composition containing PFBY used in step (h) may contain a total of no more than 0.05% of 113, 122, 123, and 1122. The composition containing PFBY used in step (h) may contain a total of no more than 0.01% of 113, 122, 123, and 1122.

[0124] In one embodiment, the PFBY-containing composition used in step (h) comprises 113, 122, 123, and 1122. In one embodiment, the PFBY-containing composition used in step (h) comprises 113, 122, and 123. In one embodiment, the PFBY-containing composition used in step (h) comprises 113, 122, and 1122. In one embodiment, the PFBY-containing composition used in step (h) comprises 122, 123, and 1122. In one embodiment, the PFBY-containing composition used in step (h) comprises 113 and 122. In one embodiment, the PFBY-containing composition used in step (h) comprises 113 and 123. In one embodiment, the PFBY-containing composition used in step (h) comprises 113 and 1122. In one embodiment, the PFBY-containing composition used in step (h) comprises 122 and 123. In one embodiment, the PFBY-containing composition used in step (h) comprises 122 and 1122. In one embodiment, the composition containing 1326mxz used in step (f) comprises 123 and 1122. In one embodiment, the composition containing PFBY used in step (h) comprises 113. In one embodiment, the composition containing PFBY used in step (h) comprises 122. In one embodiment, the composition containing PFBY used in step (h) comprises 123. In one embodiment, the composition containing PFBY used in step (h) comprises 1122.

[0125] Typical reaction conditions for step (h) are as follows: temperature in the range of 30°C to 60°C, and pressure in the range of atmospheric pressure to 50 psig (atmospheric pressure to 0.34 MPa). Residence time in the range of 0.5 hours to 5 hours.

[0126] By using steps (a) to (h) of the method disclosed herein, a fourth product containing 1336 mZZ generated in step (h) can be produced in high purity with fewer byproducts and less product yield loss. Therefore, the purification of the fourth product containing 1336 mZZ is simplified.

[0127] Without further explanation, those skilled in the art should be able to make full use of the invention based on the description herein. After reading this specification, those skilled in the art will understand that other aspects and embodiments are possible without departing from the scope of the invention. Therefore, the following specific embodiments should be understood as illustrative only and not as limiting the remainder of this disclosure in any way.

[0128] Example

[0129] Material. The materials used in the preparation examples are commercially available or can be prepared by known methods.

[0130] Example 1. Preparation of 1316mxx from 113a

[0131] A 1 / 2-inch OD chromium-nickel-iron alloy tube was filled with 2 cc (1.07 gm) of 1% Ru / SiC 1 / 8" granules. The catalyst bed temperature was raised to 120 °C and purged with hydrogen (50 sccm) for 60 min, followed by purging at 250 °C for 180 min. The temperature was then lowered to 175 °C for 120 min while maintaining a hydrogen flow rate of 20 sccm. The temperature was then lowered to 160 °C, and the flow rate of CFC-113a without 122 was set to 2.31 ml / h, with hydrogen set at 32 sccm. The reactor effluent was analyzed hourly via online GCMS for 113a, 1316mxx, and 122. For 1316mxx containing 100 ppm of 122, the conversion was 80% and the selectivity was 80%.

[0132] Example 2. Preparation of 1326mxz

[0133] Chromium-nickel-iron alloy pipe ® (0.5-inch OD, 15-inch length, 0.34-inch wall thickness) packed with 3 cc (1.2 gm) of acid-washed carbon-supported Pd / Cu (12-20 mesh). The reactor temperature was raised to 100°C for 30 minutes under a flow of N2 (30 sccm). Then the temperature was increased to 200°C for one hour under a flow of H2. A mixture of the Z- and E-isomers of 1316mxx containing 50 ppm 122 (0.87 g / mL) was fed at 12 sccm H2 at 175°C and 145 psig. The contact time was 90 s. Agilent was used. ® 6890 GC / 5973 MS and Restek ® PC2618 5% Krytox ® CBK-D / 60 / 80 6m × 2mm ID1 / 8" OD packed column (purged with 30sccm of helium) for periodic online analysis of reactor effluent for 1316mxx, 1326mxz, and 1122. The product mixture contains 10ppm to 25ppm of 1122 (CHCl=CF2) and 10% to 15% of 1326mxz (a mixture of the Z and E isomers of 1326mxz).

[0134] Comparative Example 2. Preparation of 1326mxz

[0135] Chromium-nickel-iron alloy pipe ®(0.5-inch OD, 15-inch length, 0.34-inch wall thickness) packed with 3 cc (1.2 gm) of pickled carbon-supported Pd / Cu (12-20 mesh). The reactor temperature was raised to 100°C for 30 minutes under a N2 flow (30 sccm). The temperature was then increased to 200°C for one hour under an H2 flow. 12 sccm of H2 containing 100 ppm 122 (0.87 g / mL) was fed into 1316 mg / mL at 175°C and 145 psig. The contact time was 90 s. Agilent was used. ® 6890 GC / 5973 MS and Restek ® PC2618 5% Krytox ® A CBK-D / 60 / 80 6m × 2mm ID 1 / 8" OD packed column (purged with 30 sccm of helium) was used for periodic online analysis of the reactor effluent for 1316mxx, 1326mxz, and 1122. 20 ppm to 50 ppm of 1122 (CHCl=CF2) formation and 10% to 15% of 1326mxz (a mixture of the Z and E isomers of 1326mxz) formation were observed.

[0136] Example 3. Preparation of pfby

[0137] At 35°C, in Aliquat ® In the presence of 336 (0.53 g, 0.001325 mol), an aqueous solution of NaOH (12 mL, 0.12 mol) was added to a mixture of Z / E-1326mxz containing 100 ppm 1122 (20 g, 0.1 mol) and water (18 mL). After the addition, the reaction temperature was raised to 70 °C, and the reaction was monitored by gas chromatography for 1326mxz, PFBY, and 1122. The reaction was completed after 2.5 hours, and 15.0 g of the product (conversion: 100%; yield: 92%, PFBY, containing 100 ppm 1122) was collected in a dry ice trap.

[0138] Example 4. Preparation of 1336mzzz

[0139] Chromium-nickel-iron alloy pipe ®(0.5-inch OD, 15-inch length, 0.34-inch wall thickness) packed with 2.6 cc (3.2 gm) of 200 ppm Al₂O₃-loaded Pd (12-20 mesh). The reactor temperature was raised to 100°C for 30 minutes under a N₂ flow (30 sccm). Then, the temperature was increased to 200°C for one hour under an H₂ flow. PFBY containing 500 ppm 1122 (2 sccm) was fed together with 25.9 sccm of N₂ containing H₂ (5% H₂) at 95°C and 50 psig. The contact time was 20 s. Agilent was used. ® 6890 GC / 5973 MS and Restek ® PC2618 5% Krytox ® A CBK-D / 60 / 80 6m × 2mm ID 1 / 8" OD packed column (purged with 30 sccm of helium) was used for online analysis of reactor effluent for PFBY, 1326mxz(Z), 1326mxz(E), and 1336mzz(Z). Formation of 10 ppm 1326mxz(Z) and 1 ppm 1326mxz(E), as well as 26% 1336mzz(Z), was observed.

[0140] Comparative Example 4. Preparation of 1336mzzz

[0141] Chromium-nickel-iron alloy pipe ® (0.5-inch OD, 15-inch length, 0.34-inch wall thickness) packed with 2.6 cc (3.2 gm) of 200 ppm Al₂O₃-loaded Pd (12-20 mesh). The reactor temperature was raised to 100°C for 30 minutes under a N₂ flow (30 sccm). Then, the temperature was increased to 200°C for one hour under an H₂ flow. PFBY containing 1000 ppm 1122 (2 sccm) was fed together with 25.9 sccm of N₂ containing H₂ (5% H₂) at 95°C and 50 psig. The contact time was 20 s. Agilent was used. ® 6890 GC / 5973 MS and Restek ® PC2618 5% Krytox ® A CBK-D / 60 / 80 6m × 2mm ID1 / 8" OD packed column (purged with 30 sccm of helium) was used for online analysis of reactor effluent for PFBY, 1326mxz(Z), 1326mxz(E), and 1336mzz(Z). Formation of 25 ppm 1326mxz(Z) and 2 ppm 1326mxz(E), as well as 26% 1336mzzZ, was observed.

[0142] While not wishing to be bound by theory, it is suggested that during the hydrogenation of PFBY to 1336mzz(Z), 1122 present in PFBY is hydrogenated to form 152a plus HCl. Adding HCl to PFBY forms 1326mxzZ and 1326mxzE, with boiling points of 35°C and 42°C, respectively. Since the boiling point of 1336mzzZ is 33°C, the formation of 1326mxz may negatively impact product purity due to separation difficulties (close to its boiling point). Furthermore, the combination of HCl formed during PFBY hydrogenation with any unintentional moisture may lead to equipment corrosion. For these reasons, understanding the concentrations of 1122 and its precursor in the starting materials and intermediates used to produce 1336mzzZ is particularly beneficial.

Claims

1. A composition comprising 1,1,1-trichloro-2,2,2-trifluoroethane (CFC-113a), 2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene (CFO-1316mxx) or 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (HCFO-1326mxz), and at least one of 113, 122, 123 and 1122 in total not exceeding 0.5%.

2. The composition according to claim 1, wherein the composition comprises 113a.

3. The composition of claim 2, wherein the composition comprises at least one of 113, 122, 123 and 1122 in total not more than 0.2%.

4. The composition of claim 2, wherein the composition comprises at least one of 113, 122, 123 and 1122 in total not more than 0.1%.

5. The composition of claim 2, wherein the composition comprises a total of no more than 0.05% of 113, 122, 123 and 1122.

6. The composition of claim 2, wherein the composition comprises at least one of 113, 122, 123 and 1122 in total not more than 0.01%.

7. The composition of claim 2, wherein the composition further comprises, in total, no more than 0.5% of one or more of 112, 112a, 114, 114a and 123a.

8. The composition according to claim 7, wherein the composition comprises 112, 112a, 113, 114, 114a and 123a.

9. The composition of claim 7, wherein the composition further comprises, in total not more than 0.5% of one or more of 122b, 132a, 132b, 142, 142b, 1112, 1112a and PCE.

10. The composition of claim 2, wherein the composition further comprises, in total, no more than 0.5% of one or more of 112, 112a, 114, 114a, 115, 215ba, 216, 316, 318 and PCE.

11. The composition of claim 10, wherein the composition comprises, in total, not more than 0.5% of at least one of 111, 214cb, CHCl2CCl3, and CCl3CCl3.

12. The composition of claim 10, wherein the composition comprises 113a, 112, 112a, 113, 114a and 318.

13. The composition of claim 1, wherein the composition comprises 1316mxx.

14. The composition of claim 13, wherein the composition comprises at least 0.2% in total of one of 113, 122, 123 and 1122.

15. The composition of claim 13, wherein the composition comprises not more than 0.1% of 113, 122, 123 and 1122.

16. The composition of claim 13, wherein the composition comprises at least 0.05% in total of one of 113, 122, 123 and 1122.

17. The composition of claim 13, wherein the composition comprises Z-1316mxx and E-1316mxx, and the ratio of Z-1316mxx to E-1316mxx is from 1 to 99.

18. The composition of claim 13, wherein the composition further comprises, in total, not more than 0.5% of one or more of 113a and 1336mzzZ.

19. The composition of claim 13, wherein the composition comprises 1316mxx, 113, 113a, 122, 123 and 1336mzzZ.

20. The composition according to claim 1, wherein the composition comprises 1326 mxz.

21. The composition of claim 20, wherein the composition comprises at least one of 113, 122, 123 and 1122 in total not more than 0.2%.

22. The composition of claim 20, wherein the composition comprises at least 0.1% of one of 113, 122, 123 and 1122 in total.

23. The composition of claim 20, wherein the composition comprises at least 0.05% of one of 113, 122, 123 and 1122 in total.

24. The composition of claim 20, wherein the composition comprises Z-1326mxz and E-1326mxz, and the ratio of Z-1326mxz to E-1326mxz is from 1 to 99.

25. The composition of claim 20, wherein the composition further comprises, in total, no more than 0.5% of one or more of 113a, 142b, 143a, 346mdf, 356mff and 1345czf.

26. The composition of claim 20, wherein the composition comprises 1326mxz, 113a, 123, 142b, 143a, 346mdf, 356mff, 1122 and 1345czf.

27. A method for preparing 1336mzzZ, the method comprising (a) providing a composition comprising 113a and at least 0.5% in total of at least one of 113, 122, 123, and 1122; (b) contacting the composition comprising 113a and at least 0.5% in total of at least one of 113, 122, 123, and 1122 with hydrogen in the presence of a catalyst comprising ruthenium to produce a first product mixture comprising 1316mxx; and (c) purifying the first product mixture comprising 1316mxx by fractionation at a reflux ratio not exceeding 1:

1. (c) a mixture of substances to produce a composition comprising 1316mxx and at least 0.5% of 113, 122, 123, and 1122; (d) the composition comprising 1316mxx from step (c) and at least 0.5% of 113, 122, 123, and 1122 in total, contacted with hydrogen in the presence of a catalyst selected from the group consisting of carbon-supported copper, carbon-supported nickel, carbon-supported copper and nickel, and carbon-supported copper and palladium, to produce a second product mixture comprising 1326mxz; (e) purification by fractionation at a reflux ratio not exceeding 1:

1. (f) The second product mixture comprising 1326mxz is used to produce a composition comprising 1326mxz and at least one of 113, 122, 123, and 1122 in total not exceeding 0.5%; (g) The composition from step (e) comprising 1326mxz and at least one of 113, 122, 123, and 1122 in total not exceeding 0.5% is contacted with an alkali metal hydroxide in an alkaline aqueous solution in the presence of a phase transfer catalyst to produce a third product mixture comprising hexafluoro-2-butyne; (g) Fractionation is carried out using a reflux ratio not exceeding 1:

1. The third product mixture containing hexafluoro-2-butyne (PFBY) is purified to produce a composition containing hexafluoro-2-butyne (PFBY) and at least one of 113, 122, 123, and 1122 in total not exceeding 0.5%; and (h) the composition from step (g) containing hexafluoro-2-butyne and at least one of 113, 122, 123, and 1122 in total not exceeding 0.5% is contacted with a Lindall catalyst or a palladium catalyst further containing lanthanides or silver in the presence of hydrogen to produce a fourth product mixture containing 1336 mzzz.

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