Compositions of chlorofluorinated compounds

Abstract

The present disclosure relates to compositions of chlorofluorinated compounds that may be useful as intermediates in chemical processes, particularly for producing 1336mzzZ.

Description

COMPOSITIONS OF CHLOROFLUORINATED COMPOUNDSFIELD OF THE INVENTION

[0001] The present invention relates to compositions comprising chlorofluorocontaining compounds including chlorofluoroalkanes and chlorofluoroalkenes. The compositions provide improved results in preparing unsaturated fluorinated compounds, including hexafluorobutenes.BACKGROUND OF THE INVENTION

[0002] A growing public awareness of the environmental impacts from the extraction, transportation and use of fossil fuels are motivating a new environmental sustainability driver in the form of regulations and reduction in output of CO2 equivalence in the atmosphere. In particular, new environmental regulations on refrigerants have forced the refrigeration and air-conditioning industry to look for new refrigerants with low global warming potential (GWP). Replacement refrigerants with low global warming potentials (GWP) and ozone depletion potential (ODP) for both existing and new applications in thermal management segments will need to adhere to 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 expansion agent, power cycle working fluid, among other uses. It has also, advantageously, been found that Z-HFO-1336mzz has a low global warming potential (GWP), GWP=32. Thus, fluorobutene compositions comprising Z-HFO-1336mzz may be good candidates for replacing higher GWP saturated compounds such as CFCs (chlorofluorocarbons), HCFCs (hydrochlorofluorocarbons), or HFCs (hydrofluorocarbons) in many uses.

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

[0005] The present invention addresses these issues.SUMMARY

[0006] It has been found that certain chlorofluorinated compositions disclosed herein provide improved results with respect to the manufacture of Z-HFO-1336mzz, including use of such chlorofluorinated compositions as intermediates to manufacture Z-HFO-1336mzz. Improved results include better yield and few byproducts, which facilitate purification and enhances 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 no more than 0.5% (by mole percent) total of at least one 113, 122, 123 and 1122.

[0008] In one embodiment, the present invention provides a composition comprising 1 ,1,1-trichloro-2,2,2-trifluoroethane (CFC-113a), and no more than 0.5% total of at least one of 113, 122, 123 and 1122.

[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 no more than 0.5% total of at least one of 113, 122, 123 and 1122.

[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 no more than 0.5% total of at least one of 113, 122, 123 and 1122.

[0011] The 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 no more than 0.5% (by weight or mole percent) total of at least one of 113, 122, 123 and 1122 may further comprise one or more additional compounds chosen from HCFC-2,2-dichloro-1,1,1- trifluoroethane (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 embodiement, the composition comprises 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), in an amount of at least 95 wt (or mole) %, for example, at least 98 wt (or mole) %, or at least 99 wt (or mole) %, or at least 99.5 wt (or mole) %.

[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 is no more than 0.5 wt (or mole) %, for example, no more than 0.2 wt (or mole) %, or no more than 0.1 wt (or mole) %. Preferably, the total amount of 113, 122, 123 and 1122 is no more than 0.1 wt (or mole) %, or no more than 0.01 wt (or mole) %.

[0014] In one embodiment, the composition disclosed herein comprises 1 ,1 ,1- trichloro-2,2,2-trifluoroethane (CFC-113a) and one or more of 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 composition disclosed herein comprises 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 composition disclosed herein comprises 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 composition disclosed herein comprises 2,3- dichloro-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene and one or more of 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 composition disclosed herein comprises 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 composition disclosed herein comprises 1 ,1 ,1- trichloro-2,2,2-trifluoroethane (CFC-113a) and HCFO-2-chloro- 1 ,1 -difluoroethylene (HCFO-1122).

[0020] In one embodiment, the composition disclosed herein comprises 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 composition disclosed herein comprises 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 composition disclosed herein comprises 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 composition disclosed herein comprises 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 composition disclosed herein comprises 2-chloro-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene (HCFO-1326mxz) and one or more of 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 composition disclosed herein comprises 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 composition disclosed herein comprises 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 composition disclosed herein comprises 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 composition disclosed herein comprises 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 composition disclosed herein comprises 2-chloro- 1 ,1 ,1 ,4,4,4-hexafluoro-2-butene (HCFO-1326mxz) and and HCFO-2-chloro-1 ,1- difluoroethylene (HCFO-1122).DETAILED DESCRIPTION

[0030] 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 may 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).

[0031] The transitional phrase "consisting of' excludes any element, step, or ingredient not specified. If in the claim, such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase "consists of" appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.

[0032] The transitional phrase "consisting essentially of" is used to define a composition, method that includes materials, steps, features, components, or elements, in addition to those literally disclosed provided that these additional included materials, steps, features, components, or elements do not materially affect the basic and novel characteristic(s) of the claimed invention, especially the mode of action to achieve the desired result of any of the processes of the present invention. The term “consisting essentially of’ occupies a middle ground between “comprising”and “consisting of’.

[0033] Where applicants have defined an invention or a portion thereof with an open-ended term such as “comprising,” it should be readily understood that (unless otherwise stated) the description should be interpreted to also include such an invention using the terms “consisting essentially of’ or “consisting of.”

[0034] Also, use of “a” or “an” are 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 invention. 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.

[0035] As used herein, the term “about” is meant to account for variations due to experimental error (e.g., plus or minus approximately 10% of the indicated value). All measurements reported herein are understood to be modified by the term “about”, whether or not the term is explicitly used, unless explicitly stated otherwise.

[0036] When an amount, concentration, or other value or parameter is given as either a range, preferred range or a list of upper preferable values and / or lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range.

[0037] The term “compound” as used herein is meant to include all stereoisomers, geometric isomers, tautomers, and isotopes of the structures or chemical described. Compounds herein identified by name or structure as one particular tautomeric form are intended to include other tautomeric forms unless otherwise specified.

[0038] As used herein, the term “catalyst”, refers to a substance that speeds up the chemical reaction, but is not consumed by the reaction; thus it can be recovered chemically unchanged at the end of the reaction.COMPOSITIONS

[0039] The compositions disclosed herein comprising chlorofluoro compounds are useful as starting materials and / or intermediates in the manufacture of useful molecules. While not intending to be limited, the compositions are illustrated herein as useful in the manufacture of Z-1,1 ,1 ,4,4,4-hexafluoro-2-butene (1336mzzZ). Table 1 provides a list of compounds discussed herein.TABLE I. COMPOUNDS

[0040] 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 no more than 0.5% (by weight or mole percent) total of at least one of 113, 122, 123 and 1122. It is recognized that “0.5%” is the same as 5000 ppm and “0.1%” is the same as 1000 ppm and so on. For purposes herein, all amounts written as percent, “%” reflect mole percent.

[0041] In one embodiment, the composition comprises no more than 0.5% total of at least one of 113, 122, 123 and 1122. In another embodiment, the composition comprises no more than 0.2% total of at least one of 113, 122, 123 and 1122. In another embodiment, the composition comprises no more than 0.1% total of at least one of 113, 122, 123 and 1122. In another embodiment, the composition comprises no more than 0.05% total of at least one of 113, 122, 123 and 1122. In another embodiment, the composition comprises no more than 0.01% total of at least one of 113, 122, 123 and 1122.Compositions comprising 113a

[0042] In one embodiment, the composition provided herein comprises 113a and no more than 0.5% total of at least one of 113, 122, 123 and 1122.

[0043] The composition provided herein may comprise 113a, 112, 112a, 113, 114, 114a, and 123a wherein the composition comprises no more than 0.5% total of at least one of 112, 112a, 114, 114a, and 123a.

[0044] In one embodiment, the composition provided herein comprises 113a and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises no more than 0.5 % total of one or more of 122b, 132a, 132b, 142, 142b, 1112, 1112a, and PCE.

[0045] In one embodiment, the composition provided herein comprises 113a and no more than 0.5% total of 113, 122, 123 and 1122 and further comprises no more than 0.5% total of one or more of 112, 112a, 114, 114a, 115, 215ba, 216, 316, 318, and PCE.

[0046] In one embodiment, the composition provided herein comprises no more than 0.5% total of at least one of 111 , 214cb, CHCI2CCI3 and CCI3CCI3.

[0047] In one embodiment, the composition provided herein comprises 113a and no more than 0.5% total of at least one of 112, 112a, 113, 114a, and 318.Compositions comprising 1316mxx

[0048] In one embodiment, the composition provided herein comprises 1316mxx and no more than 0.5% total of at least one of 113, 122, 123 and 1122.

[0049] For all compositions disclosed herein comprising 1316mxx, the compositions comprise Z-1316mxx or E-1316mxx or a mixture of Z-1316mxx and E- 1316mxx. Where a particular isomer is meant, there is provided the designation of “Z” or “E”.

[0050] Preferably the compositions comprising 1316mxx comprise 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 in the range 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. More preferably, 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.

[0051] In one embodiment the composition comprises 1316mxx and no more than 0.5% total of at least one of 113, 122, 123 and 1122, 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 no more than 0.5% total of at least 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.

[0052] In one embodiment the composition comprises 1316mxx and 113, wherein 113 is present in an amount 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 %. In one embodiment the composition comprises 1316mxx and 122, wherein 122 is present in an amount 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%. In one embodiment the composition comprises 1316mxx and 123, wherein 123 is present in an amount 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%. In one embodiment the composition comprises 1316mxx and 1122 wherein 1122 is present in an amount of no more than 0.5% or no more than 0.2% or no more than 0.1% orno more than 0.05% or no more than 0.01%.

[0053] In one embodiment the composition comprising 1316mxx comprises 113 and 122, wherein the total amount of 113 and 122 is 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%. In one embodiment the composition comprising 1316mxx comprises 113 and 123, wherein the total amount of 113 and 123 is 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%. In one embodiment the composition comprising 1316mxx comprises 113 and 1122, wherein the total amount of 113 and 1122 is 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%. In one embodiment the composition comprising 1316mxx comprises 122 and 123, wherein the total amount of 122 and 123 is 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%. In one embodiment the composition comprising 1316mxx comprises 122 and 1122, wherein the total amount of 122 and 1122 is 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%. In one embodiment the composition comprising 1316mxx comprises 123 and 1122 wherein the total amount of 123 and 1122 is 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%.

[0054] In one embodiment the composition comprising 1316mxx comprises 113, 122 and 123, wherein the total amount of 113, 122 and 123 is 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%. In one embodiment the composition comprises 1316mxx, 122 and 1122, wherein the total amount of 113, 122 and 1122 is 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%. In one embodiment the composition comprises 1316mxx, 122, 123 and 1122, wherein the total amount of 122, 123 and 1122 is 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%.

[0055] In one embodiment the composition comprises 1316mxx, 113, 122, 123 and 1122, wherein the total amount of 113, 122, 123 and 1122 is 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%.Compositions comprising 1326mxz

[0056] For all compositions disclosed herein comprising 1326mxz, the compositions may comprise Z-1326mxz or E-1326mxz or a mixture of Z-1326mxz and E-1326mxz. Where a particular isomer is meant, there is provided the designation of “Z” or “E”.

[0057] Preferably the compositions comprising 1326mxz comprise 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 in the range 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. More preferably, the ratio of Z-1326mxz 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.

[0058] In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122, 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 no more than 0.5% total of at least 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.

[0059] In one embodiment the composition comprises 1326mxz and 113, wherein 113 is present in an amount 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 %. In one embodiment the composition comprises 1326mxz and 122, wherein 122 is present in an amount 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%. In one embodiment the composition comprises 1326mxz and 123, wherein 123 is present in an amount 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%. In one embodiment the composition comprises 1326mxz and 1122 wherein 1122 is presentin an amount 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%.

[0060] In one embodiment the composition comprising 1326mxz comprises 113 and 122, wherein the total amount of 113 and 122 is 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%. In one embodiment the composition comprising 1326mxz comprises 113 and 123, wherein the total amount of 113 and 123 is 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%. In one embodiment the composition comprising 1326mxz comprises 113 and 1122, wherein the total amount of 113 and 1122 is 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%. In one embodiment the composition comprising 1326mxz comprises 122 and 123, wherein the total amount of 122 and 123 is 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%. In one embodiment the composition comprising 1326mxz comprises 122 and 1122, wherein the total amount of 122 and 1122 is 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%. In one embodiment the composition comprising 1326mxz comprises 123 and 1122 wherein the total amount of 123 and 1122 is 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%.

[0061] In one embodiment the composition comprising 1326mxz comprises 113, 122 and 123, wherein the total amount of 113, 122 and 123 is 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%. In one embodiment the composition comprises 1326mxz, 122 and 1122, wherein the total amount of 113, 122 and 1122 is 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%. In one embodiment the composition comprises 1326mxz, 122, 123 and 1122, wherein the total amount of 122, 123 and 1122 is 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%.

[0062] In one embodiment the composition comprises 1326mxz, 113, 122, 123 and 1122, wherein the total amount of 113, 122, 123 and 1122 is 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 than0.01%.

[0063] In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises one or more of 113a, 142b, 143a, 346mdf, 356mff, E-1336mzz, and 1345czf. In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 113a. In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 142b. In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 143a. In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 346mdf. In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 356mff. In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises E-1336mzz. In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 1345czf.

[0064] In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises one or more of 113a, 142b, 143a, 346mdf, 356mff, E-1336mzz, and 1345czf.

[0065] In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 113a and 142b. In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 113a and 143a. In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 113a and 346mdf. In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 113a and 356mff. In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 113a and 1345czf.

[0066] In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 142b and 143a. In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 142b and 356mff. In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 142b and E-1336mzz. In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 142b and 1345czf.

[0067] In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 143a and 346mdf. In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 143a and 356mff. In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 143a and E-1336mzz. In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 143a and 1345czf.

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

[0069] In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 356mff and E-1336mzz. In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 356mff and 1345czf.

[0070] In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises E-1336mzz and 1345czf.

[0071] In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 113a, 142b, and 143a. In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 113a, 142b, and 346mdf. In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 113a, 142b, and 356mff. In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 113a, 142b, and E-1336mzz. In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 113a, 142b and 1345czf.

[0072] In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 113a, 143a, and 346mdf. In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 113a, 143a, and 356mff. In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 113a, 143a, and E-1336mzz. In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 113a, 143a, and 1345czf.

[0073] In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 113a, 346mdf, and 356mff. In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 113a, 346mdf, and E-1336mzz. In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 113a, 346mdf, and 1345czf.

[0074] In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 113a, 356mff, and E-1336mzz. In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and furthercomprises 113a, 356mff, and 1345czf.

[0075] In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 113a, E- 1336mzz, and 1345czf.

[0076] In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 113a, 142b 143a, and 346mdf. In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 113a, 142b, 143a, and 356mff. In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 113a, 142b, 143a, and E-1336mzz. In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 113a, 142b, 143a, and 1345czf.

[0077] In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 113a, 143a, 346mdf, and 356mff. In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 113a, 143a, 346mdf, and E-1336mzz. In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 113a, 143a, 346mdf, and 1345czf.

[0078] In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 113a, 346mdf, 356mff, and E-1336mzz. In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 113a, 346mdf, E-1336mzz, and 1345czf.

[0079] In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 113a, 356mff, E-1336mzz and 1345czf.

[0080] In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 142b,143a, 346mdf, 356mff, E-1336mzz, and 1345czf.

[0081] In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises 113a, 142b, 143a, 346mdf, 356mff, E-1336mzz, and 1345czf.PROCESSES

[0082] The present invention provides compositions of materials useful as intermediates for producing fluoroolefins, particularly 1336mzzZ.

[0083] In an embodiment of this invention, there is further provided a process to produce 1336mzzZ comprising the following steps.

[0084] One step (a) comprises providing a composition comprising 113a and no more than 0.5% total of at least one of 113, 122, 123 and 1122, or no more than 0.2% total of at least one of 113, 122, 123 and 1122, 0.1% total of at least one of 113, 122, 123 and 1122, or 0.05% total of at least one of 113, 122, 123 and 1122, or 0.01% total of at least one of 113, 122, 123 and 1122.

[0085] The process further comprises a step (b) of contacting a composition comprising 113a with hydrogen in the presence of a step (b) catalyst to produce a first product mixture comprising 1316mxx and at least one of 113, 122, 123 and 1122, wherein the composition comprising 113a comprises no more than 0.5% total of at least one of 113, 122, 123 and 1122.

[0086] The step (b) catalyst comprises a transition metal. The transition metal may be chosen from ruthenium, rhodium, palladium, and platinum. The step (b) catalyst may comprise a support. The support may be chosen from silicon carbide (SiC), tungsten carbide (WC), alumina.

[0087] Typical reaction conditions for step (b) are as follows. The reaction may be conducted at a temperature in the range of 90°C to 200°C. The pressure for the reaction in step (b) is typcially in the rant of 80 to 200 psig (0.55 to 1.38 MPa). Step (b) may be conducted with a contact time in the range of 30 to 100 seconds (30-100 s), such as a contact time of 70 seconds (70 s).

[0088] 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.

[0089] 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.

[0090] In some embodiments, the composition comprising 113a and 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 % total of at least one of 113, 122, 123 and 1122 in step (a) and step (b), further comprises no more than 0.5% total of one or more of 112, 112a, 114, 114a, 115, 215ba, 216, 316, 318, and PCE. In some embodiments, the composition comprising 113a and no more than 0.5% total of at least one of 113, 122, 123 and 1122 in step (a) or step (b), comprises no more than 0.5% total of at least one of111 , 214cb, CHCI2CCI3 and CCI3CCI3. In some embodiments, the composition comprising 113a and no more than 0.5% total of at least one of 113, 122, 123 and 1122 in step (a) or step (b), comprises no more than 0.5% total of at least one of112, 112a, 113, 114a, and 318.

[0091] The process further comprises a step (c) of purifying the first product mixture comprising 1316mxx and at least one of 113, 122, 123 and 1122, by fractional distillation using a no no more than 1 :1 or 2:1 or 3:1 to provide a composition comprising 1316mxx and no more than 0.5% total of at least one of 113, 122, 123 and 1122.

[0092] This step (c) is generally performed at a pressure of 200 psig or less, or 150 psig (1.03 MPa) or less or 80 psig (0.55 MPa) or less, that is a range of ambient pressure up to 200 psig (1.38 MPa).

[0093] The composition provided by purifying the first product mixture comprising1316mxx and at least one of 113, 122, 123 and 1122 in step (c) by fractional distillation using a reflux ratio of no no more than 1 :1 or 2:1 or 3:1 , comprises 1316mxx and no more than 0.5% total of at least one of 113, 122, 123 and 1122. 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 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 in the range 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. More preferably, 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.

[0094] In purifying the first product mixture comprising 1316mxx and at least one of 113, 122, 123 and 1122 in step (c), by fractional distillation using a reflux ratio of no no more than 1 :1 or 2:1 or 3:1 , the first product mixture fed to the step may comprise more than 0.5% or more than 0.2% or more than 0.1% or more than 0.05% or more than 0.01% total of at least one of 113, 122, 123 and 1122. The purifying step (c) provides a composition comprising 1316mxx and 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% total of at least one of 113, 122, 123 and 1122.

[0095] 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.

[0096] In one embodiment for step (c) of purifying the first product mixture comprising 1316mxx and at least one of 113, 122, 123 and 1122, by fractional distillation using a reflux ratio of no no more than 1 :1 or 2:1 or 3:1 , the first product mixture comprises more than 0.1 % total of at least one of 113, 122, 123 and 1122 to provide a composition comprising 1316mxx and no more than 0.1% or no more than 0.05% or no more than 0.01 % total of at least one of 113, 122, 123 and 1122.

[0097] In one embodiment for purifying in step (c) the first product mixturecomprising 1316mxx and at least one of 113, 122, 123 and 1122, by fractional distillation using a reflux ratio of no no more than 1:1, the first product mixture comprises more than 0.1% total of at least one of 113, 122, 123 and 1122. In one embodiment for purifying in step (c) the first product mixture comprising 1316mxx and at least one of 113, 122, 123 and 1122, by fractional distillation using a reflux ratio of no no more than 2:1 , the first product mixture comprises more than 0.1% total of at least one of 113, 122, 123 and 1122. In one embodiment for purifying the first product mixture comprising 1316mxx and at least one of 113, 122, 123 and 1122, by fractional distillation using a reflux ratio of no no more than 3:1, the first product mixture comprises more than 0.05% total of at least one of 113, 122, 123 and 1122.

[0098] In one embodiment for purifying the first product mixture comprising 1316mxx and at least one of 113, 122, 123 and 1122, by fractional distillation using a reflux ratio of no no more than 1:1 or 2:1 or 3:1 , the first product mixture comprises more than 0.05% total of at least one of 113, 122, 123 and 1122 to provide a composition comprising 1316mxx and no more than 0.05% or no more than 0.01% total of at least one of 113, 122, 123 and 1122.

[0099] The process further comprises a step (d) of contacting a composition comprising 1316mxx with hydrogen, in the presence of a catalyst selected from the group consisting of copper on carbon, nickel on carbon, copper and nickel on carbon and copper and palladium on carbon, to produce a second product mixture, comprising 1326mxz and at least one of 113, 122, 123 and 1122, wherein the composition comprising 1316mxx comprises no more than 0.5% total of at least one of 113, 122, 123 and 1122. The composition comprising 1316mxx used in step (d) may comprise no more than 0.2% total of at least one of 113, 122, 123 and 1122. The composition comprising 1316mxx used in step (d) may comprise no more than 0.1% total of at least one of 113, 122, 123 and 1122. The composition comprising 1316mxx used in step (d) may comprise no more than 0.05% total of at least one of 113, 122, 123 and 1122. The composition comprising 1316mxx used in step (d) may comprise no more than 0.01% total of at least one of 113, 122, 123 and 1122. Additional compounds may be present in the composition comprising 1316mxx used in step (d) as recited hereinabove.

[0100] In one embodiment, the composition comprising 1316mxx used in step (d) comprises 113, 122, 123 and 1122. In one embodiment, the composition comprising 1316mxx used in step (d) comprises 113, 122, and 123. In one embodiment, the composition comprising 1316mxx used in step (d) comprises 113, 122, and 1122. In one embodiment, the composition comprising 1316mxx used in step (d) comprises 122, 123 and 1122. In one embodiment, the composition comprising 1316mxx used in step (d) comprises 113 and 122. In one embodiment, the composition comprising 1316mxx used in step (d) comprises 113 and 123. In one embodiment, the composition comprising 1316mxx used in step (d) comprises 113 and 1122. In one embodiment, the composition comprising 1316mxx used in step (d) comprises 122 and 123. In one embodiment, the composition comprising 1316mxx used in step (d) comprises 122 and 1122. In one embodiment, the composition comprising 1316mxx used in step (d) comprises 123 and 1122. In one embodiment, the composition comprising 1316mxx used in step (d) comprises 113. In one embodiment, the composition comprising 1316mxx used in step (d) comprises 122. In one embodiment, the composition comprising 1316mxx used in step (d) comprises 123, In one embodiment, the composition comprising 1316mxx used in step (d) comprises 1122.

[0101] Step (d) is generally performed at a temperature in the range of 150°C to 250°C and a pressure of 80 to 300 psig (0.55 to 2.07 MPa). The contact time is typically in the range of 50 to 200 seconds.

[0102] The second product mixture comprising 1326mxz produced in step (d) may comprise more than 0.5% total of one or more of 113, 122, 123 and 1122 or more than 0.2% total of one or more of 113, 122, 123 and 1122 or more than 0.1% total of one or more of 113, 122, 123 and 1122.

[0103] The process further comprises a step (e) of purifying the second product mixture comprising 1326mxz by fractional distillation using a reflux ratio of no no more than 1 :1 or 2:1 or 3:1 to provide a composition comprising 1326mxz and no more than 0.5% (by weight or mole percent) total of at least one of 113, 122, 123 and 1122.

[0104] The second product mixture may comprise more than 0.5% or more than 0.2% or more than 0.1% or more than 0.05% or more than 0.01% total of 113, 122,123 and 1122. By purifying the second product mixture, there is provided a composition comprising 1326mxz and 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% total of 113, 122, 123 and 1122.

[0105] 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.

[0106] In one embodiment of step (e) for purifying the second product mixture comprising 1326mxz and at least one of 113, 122, 123 and 1122, by fractional distillation using a reflux ratio of no no more than 1:1, the second product mixture comprises more than 0.1% total of 113, 122, 123 and 1122. In one embodiment of step (e) for purifying the second product mixture comprising 1326mxz and at least one of 113, 122, 123 and 1122, by fractional distillation using a reflux ratio of no no more than 2:1 , the second product mixture comprises more than 0.1% total of 113, 122, 123 and 1122. In one embodiment of step (e) for purifying the second product mixture comprising 1326mxz and at least one of 113, 122, 123 and 1122, by fractional distillation using a reflux ratio of no no more than 3:1 , the second product mixture comprises more than 0.1% total of 113, 122, 123 and 1122.

[0107] The conditions for step (e) are the same as those for step (c). That is, step(e) is generally performed at a pressure of 200 psig or less, or 150 psig (1.03 MPa) or less or 80 psig (0.55 MPa) or less, that is a range of ambient pressure up to 200 psig (1.38 MPa).

[0108] The process further comprises a step (f) of contacting a composition comprising 1326mxz and no more than 0.5% total of 113, 122, 123 and 1122 with an alkali metal hydroxide in an aqueous basic 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 no more than 0.2% total of 113, 122, 123 and 1122. The composition comprising 1326mxz used in step (f) may comprise no more than 0.1% total of 113, 122, 123 and 1122. The composition comprising 1326mxz used in step (f) may comprise no more than 0.05% total of 113, 122, 123 and 1122. The composition comprising 1326mxz used in step(f) may comprise no more than 0.01% total of 113, 122, 123 and 1122. Additionalcompounds may be present in the composition comprising 1326mxz used in step (d) as recited hereinabove.

[0109] In one embodiment, the composition comprising 1326mxz used in step (f) comprises 113, 122, 123 and 1122. In one embodiment, the composition comprising 1326mxz used in step (f) comprises 113, 122, and 123. In one embodiment, the composition comprising 1326mxz used in step (f) comprises 113, 122, and 1122. In one embodiment, the composition comprising 1326mxz used in step (f) comprises 122, 123 and 1122. In one embodiment, the composition comprising 1326mxz used in step (f) comprises 113 and 122. In one embodiment, the composition comprising 1326mxz used in step (f) comprises 113 and 123. In one embodiment, the composition comprising 1326mxz used in step (f) comprises 113 and 1122. In one embodiment, the composition comprising 1326mxz used in step (f) comprises 122 and 123. In one embodiment, the composition comprising 1326mxz used in step (f) comprises 122 and 1122. In one embodiment, the composition comprising 1326mxz used in step (f) comprises 123 and 1122. In one embodiment, the composition comprising 1326mxz used in step (f) comprises 113. In one embodiment, the composition comprising 1326mxz used in step (f) comprises 122. In one embodiment, the composition comprising 1326mxz used in step (f) comprises 123, In one embodiment, the composition comprising 1326mxz used in step (f) comprises 1122.

[0110] Typical reaction conditions for step (f) are as follows. Temperature is from 150°C to 250°C, pressure is in the range fo 80 to 300 psig (0.55 to 2.07 MPa). The contact time is in the range of 50 to 200 seconds.

[0111] The process further comprises a step (g) of purifying the third product mixture comprising hexafluoro-2-butyne (PFBY) by fractional distillation using a reflux ratio of no no more than 1:1 or 2:1 or 3:1 to provide a composition comprising PFBY and 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% total of 113, 122, 123 and 1122.

[0112] The third product mixture may comprise more than 0.5% or more than 0.2% or more than 0.1% or more than 0.05% or more than 0.01 % total of 113, 122, 123 and 1122. By purifying the third product mixture, there is provided a composition comprising PFBY and no more than 0.5% or no more than 0.2% or no more than0.1% or no more than 0.05% or no more than 0.01% total of 113, 122, 123 and 1122.

[0113] 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.

[0114] In one embodiment of step (g) for purifying the third product mixture comprising PFBY and at least one of 113, 122, 123 and 1122, by fractional distillation using a reflux ratio of no no more than 1:1, the third product mixture comprises more than 0.5% or more than 0.2% or more than 0.1% or more than 0.05% or more than 0.01% total of 113, 122, 123 and 1122. In one embodiment of step (g) for purifying the third product mixture comprising PFBY and at least one of 113, 122, 123 and 1122, by fractional distillation using a reflux ratio of no no more than 2:1, the third product mixture comprises more than 0.5% or more than 0.2% or more than 0.1% or more than 0.05% or more than 0.01% total of 113, 122, 123 and 1122. In one embodiment for purifying the third product mixture comprising PFBY and at least one of 113, 122, 123 and 1122, by fractional distillation using a reflux ratio of no no more than 3:1 , the third product mixture comprises more than 0.5% or more than 0.2% or more than 0.1% or more than 0.05% or more than 0.01% total of 113, 122, 123 and 1122.

[0115] The conditions for step (g) are the same as those for step (c). That is, step (g) is generally performed at a pressure of 200 psig or less, or 150 psig (1.03 MPa) or less or 80 psig (0.55 MPa) or less, that is a range of ambient pressure up to 200 psig (1.38 MPa).

[0116] The process further comprises a step (h) of contacting a composition comprising hexafluoro-2-butyne and 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% total of 113, 122, 123 and 1122 with Lindlar’s catalyst, or a palladium catalyst further comprising a lanthanide element or silver in the presence of hydrogen to produce a fourth product mixture comprising 1336mzzZ.

[0117] The composition comprising PFBY used in step (h) may comprise no more than 0.2% total of 113, 122, 123 and 1122. The composition comprising 1326mxz used in step (f) may comprise no more than 0.2% total of 113, 122, 123 and 1122. The composition comprising PFBY used in step (h) may comprise no more than0.1% total of 113, 122, 123 and 1122. The composition comprising PFBY used in step (h) may comprise no more than 0.05% total of 113, 122, 123 and 1122. The composition comprising PFBY used in step (h) may comprise no more than 0.01 % total of 113, 122, 123 and 1122.

[0118] In one embodiment, the composition comprising PFBY used in step (h) comprises 113, 122, 123 and 1122. In one embodiment, the composition comprising PFBY used in step (h) comprises 113, 122, and 123. In one embodiment, the composition comprising PFBY used in step (h) comprises 113, 122, and 1122. In one embodiment, the composition comprising PFBY used in step (h) comprises 122, 123 and 1122. In one embodiment, the composition comprising PFBY used in step (h) comprises 113 and 122. In one embodiment, the composition comprising PFBY used in step (h) comprises 113 and 123. In one embodiment, the composition comprising PFBY used in step (h) comprises 113 and 1122. In one embodiment, the composition comprising PFBY used in step (h) comprises 122 and 123. In one embodiment, the composition comprising PFBY used in step (h) comprises 122 and 1122. In one embodiment, the composition comprising 1326mxz used in step (f) comprises 123 and 1122. In one embodiment, the composition comprising PFBY used in step (h) comprises 113. In one embodiment, the composition comprising PFBY used in step (h) comprises 122. In one embodiment, the composition comprising PFBY used in step (h) comprises 123, In one embodiment, the composition comprising PFBY used in step (h) comprises 1122.

[0119] Typical reaction conditions for step (h) are as follows. Temperature is in the range of 30°C to 60°C and pressure is in the range of atmospheric to 50 psig (atmospheric to 0.34 MPa). The residence time is in the range of 0.5 hour to 5 hours.

[0120] By using the process steps (a) through (h) as disclosed herein, the fourth product comprising 1336mzzZ produced in step (h) can be produced in high purity, with fewer byproducts and less product yield loss. Thus, purification of the fourth product comprising 1336mzzZ is simplified.

[0121] Without further elaboration, it is believed that one skilled in the art can, using the description herein, utilize the present invention to its fullest extent. After reading this specification, skilled artisans appreciate that other aspects andembodiments are possible without departing from the scope of the invention. The following specific embodiments are, therefore, to be construed as merely illustrative, and do not constrain the remainder of the disclosure in any way whatsoever.EXAMPLES

[0122] Materials. The materials used to prepare the Examples are commercially available or may be prepared by known methods.Example 1. Preparation of 1316mxx from 113a

[0123] An inconel tube (1 / 2 inch OD) is filled with 2 cc (1.07 gm) of 1% Ru / SiC 1 / 8” pellets. The temperature of the catalyst bed was raised to 120°C and purged with hydrogen (50 seem) for 60 minutes and then at 250°C for 180 minutes. The temperature was then lowered to 175°C for 120 minutes while maintaining a hydrogen flow of 20 seem. The temperature was lowered to 160°C and the flow of CFC-113a free of 122 is set to 2.31 ml / hour and the hydrogen to 32 seem. The reactor effluent is analyzed every hour for 113a, 1316mxx and 122via online GCMS. Conversion is 80% and selectivity is 80% to 1316mxx which contains 100 ppm of 122.Example 2. Preparation of 1326mxz

[0124] An Inconel tube® (0.5 inch OD, 15 inch length, 0.34 in wall thickness) was filled with 3 cc (1.2 gm) of Pd / Cu on acid washed carbon (12-20 mesh). The temperature of the reactor was raised to 100°C for 30 minutes under N2 flow (30 seem). The temperature was then increased to 200°C under H2 flow for one hour. A mixture of Z- and E-isomers of 1316mxx containing 50 ppm 122 (0.87 g / mL) was fed with 12 seem H2 at 175°C and 145 psig. The contact time is 90 s. The effluent of the reactor is analyzed online periodically for 1316mxx, 1326mxz and 1122 using an Agilent® 6890 GC / 5973 MS and a Restek® PC2618 5% Krytox® CBK-D / 60 / 80 6 meter x 2mm ID 1 / 8” OD packed column purged with helium at 30 seem. The product mixture contains 10-25 ppm 1122 (CHCI=CF2) and 10-15% 1326mxz (mixture of Z- and E-isomers of 1326mxz).Comparative example 2. Preparation of 1326mxz

[0125] An Inconel tube® (0.5 inch OD, 15 inch length, 0.34 in wall thickness) was filled with 3 cc (1 .2 gm) of Pd / Cu on acid washed carbon (12-20 mesh). The temperature of the reactor was raised to 100°C for 30 minutes under N2 flow (30 seem). The temperature was then increased to 200°C under H2 flow for one hour. 1316mxx containing 100 ppm 122 (0.87 g / mL) was fed with 12 seem H2 at 175°C and 145 psig. The contact time is 90 s. The effluent of the reactor is analyzed online periodically for 1316mxx, 1326mxz and 1122 using an Agilent® 6890 GC / 5973 MS and a 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. 20- 50 ppm 1122 (CHCI=CF2) formation was observed along with 10-15% formation of 1326mxz (mixture of Z- and E-isomers of 1326mxz).Example 3. Preparation of pfby

[0126] NaOH aqueous solution (12 mL, 0.12 mol) is added to the mixture of Z / E- 1326mxz containing 100 ppm 1122 (20 g, 0.1 mol) and water (18 mL) in the presence of Aliquat® 336 (0.53 g, 0.001325 mol) at 35°C. The reaction temperature was raised to 70°C after the addition, and gas chromatography was used to monitor the reaction for 1326mxz, PFBY and 1122. The reaction is completed after 2.5 hour and 15.0 product (conversion: 100%; yield: 92% PFBY containing 100 ppm 1122) was collected in a dry ice trap.Example 4. Preparation of 1336mzzz

[0127] An Inconel tube® (0.5 inch OD, 15 inch length, 0.34 in wall thickness) was filled with 2.6 cc (3.2 gm) of 200 ppm Pd on AI2O3 (12-20 mesh). The temperature of the reactor was raised to 100°C for 30 minutes under N2 flow (30 seem). The temperature was then increased to 200°C under H2 flow for one hour. PFBY containing 500 ppm 1122 (2 seem) was fed with 25.9 seem H2 in N2 (5% H2 in N2) at 95°C and 50 psig. The contact time was 20 s. The effluent of the reactor was analyzed online for PFBY, 1326mxz(Z), 1326mxz(E) and 1336mzz(Z) using an Agilent® 6890 GC / 5973 MS and a Restek® PC2618 5% Krytox® CBK-D / 60 / 80 6 meter x 2mm ID 1 / 8” OD packed column purged with helium at 30 seem. 10 ppm 1326mxz(Z) and 1 ppm 1326mxz(E) formation was observed along with 26%formation of 1336mzz(Z).Comparative example 4. Preparation of 1336mzzz

[0128] An Inconel tube® (0.5 inch OD, 15 inch length, 0.34 in wall thickness) was filled with 2.6 cc (3.2 gm) of 200 ppm Pd on AI2O3 (12-20 mesh). The temperature of the reactor was raised to 100°C for 30 minutes under N2 flow (30 seem). The temperature was then increased to 200°C under H2 flow for one hour. PFBY containing 1000 ppm 1122 (2 seem) was fed with 25.9 seem H2 in N2 (5% H2 in N2) at 95°C and 50 psig. The contact time was 20 s. The effluent of the reactor was analyzed online for PFBY, 1326mxz(Z), 1326mxz(E) and 1336mzz(Z) using an Agilent® 6890 GC / 5973 MS and a Restek® PC2618 5% Krytox® CBK-D / 60 / 80 6 meter x 2mm ID 1 / 8” OD packed column purged with helium at 30 seem. 25 ppm 1326mxz(Z) and 2 ppm 1326mxz(E) formation was observed along with 26% formation of 1336mzzZ.

[0129] While not wishing to be bound by theory, it is suggested that during PFBY hydrogenation to 1336mzz(Z), 1122 that is present in the PFBY is hydrogenated to form 152a plus HCI. HCI addition to PFBY forms 1326mxzZ and 1326mxzE, which have boiling points of 35°C and 42°C, respectively. Since the boiling point of 1336mzzZ is 33°C, 1326mxz formation may negatively impact the product purity due separation difficulty (close boiling points). In addition, HCI formation in PFBY hydrogenation in combination with inadvertent moisture that may be present may cause equipment corrosion. For these reasons, there is particular benefit to understand the concentration of 1122 and 1122 precursors in starting materials and intermediates that are used in producing 1336mzzZ.

Claims

CLAIMSWhat is claimed is:

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 no more than 0.5% total of at least one of 113, 122, 123 and 1122.

2. The composition of claim 1 wherein the composition comprises 113a.

3. The composition of claim 2 wherien the composition comprises no more than 0.2% total of at least one of 113, 122, 123 and 1122.

4. The composition of claim 2 wherien the composition comprises no more than 0.1 % total of at least one of 113, 122, 123 and 1122.

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

6. The composition of claim 2 wherien the composition comprises no more than 0.01% total of at least one of 113, 122, 123 and 1122.

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

8. The composition of claim 7 comprising 112, 112a, 113, 114, 114a, and 123a.

9. The composition of claim 7 further comprising no more than 0.5% total 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 no more than 0.5% total of one or more of 112, 112a, 114, 114a, 115, 215ba, 216, 316, 318, and PCE.11 . The composition of claim 10 comprising no more than 0.5% total of at least one of 111 , 214cb, CHCI2CCI3 and CCI3CCI3.

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 wherien the composition comprises no more than 0.2% total of at least one of 113, 122, 123 and 1122.

15. The composition of claim 13 wherien the composition comprises no more than 0.1% of 113, 122, 123 and 1122.

16. The composition of claim 13 wherien the composition comprises no more than 0.05% total of at least one of 113, 122, 123 and 1122.

17. The composition of claim 13 wherein the composition comprises Z- 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 no more than 0.5% total of one or more of 113a and 1336mzzZ.

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

20. The composition of claim 1 comprising 1326mxz.

21. The composition of claim 20 wherien the composition comprises no more than 0.2% total of at least one of 113, 122, 123 and 1122.

22. The composition of claim 20 wherien the composition comprises no more than 0.1% total of at least one of 113, 122, 123 and 1122.

23. The composition of claim 20 wherien the composition comprises no more than 0.05% total of at least one of 113, 122, 123 and 1122.

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

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

27. A process to prepare 1336mzzZ comprising (a) providing a composition comprising 113a and no more than 0.5% total of at least one of 113, 122, 123 and 1122; (b) contacting the composition comprising 113a and no more than0.5% 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; (c) purifying the first product mixture comprising 1316mxx by fractional distillation at a reflux ratio of no no more than 1 :1 to produce a composition comprising 1316mxx and no more than 0.5% total of at least one of 113, 122, 123 and 1122; (d) contacting the composition comprising 1316mxx from step (c) and no more than 0.5% total of at least one of 113, 122, 123 and 1122 with hydrogen in the presence of a catalyst selected from the group consisting of copper on carbon, nickel on carbon, copper and nickel on carbon and copper and palladium on carbon, to produce a second product mixture comprising 1326mxz; (e) purifying the second product mixture comprising 1326mxz by fractional distillation at a reflux ratio of no no more than 1 :1 to produce a composition comprising 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122; (f) contacting the composition comprising 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 from step (e) with an alkali metal hydroxide in an aqueous basic solution in the presence of a phase transfer catalyst to produce a third product mixture comprising hexafluoro-2-butyne; (g) purifying the third product mixture comprising hexafl uoro-2-butyne (PFBY) by fractional distillation using a reflux ratio of no no more than 1:1 to produce a composition comprising hexafl uoro-2- butyne (PFBY) and no more than 0.5% total of at least one of 113, 122, 123 and 1122; and (h) contacting the composition comprising hexafluoro-2-butyne and no more than 0.5% total of at least one of 113, 122, 123 and 1122 from step (g) with Lindlar’s catalyst, or a palladium catalyst further comprising a lanthanide element or silver in the presence of hydrogen to produce a fourth product mixture comprising 1336mzzZ.

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