Synthesis of 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene

Abstract

The present application relates to processes of preparing 1,1,1,2,2,5,5,6,6,6decafluoro-3-hexene, particularly E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene.

Description

TITLE OF INVENTIONSYNTHESIS OF 1 ,1 ,1 ,2,2,5,5,6,6,6-DECAFLUORO-3-HEXENEFIELD OF THE INVENTION

[0001] The present application relates to processes of preparing 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene.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 potential (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] Certain hydrofluoroolefins, such as E-1 , 1 , 1 ,2,2,5,5,6,6,6-decafluoro-3- hexene (E-C2FsCH=CHC2F5, E-HFO-153-10mczz), are believed to meet both goals. In particular, 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene may be useful in heat transfer fluid applications (e.g., immersion cooling systems, data-center cooling systems or thermal management solution for EV batteries). Accordingly, the present application provides new processes for preparing E-1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene.SUMMARY OF THE INVENTION

[0004] Any of the embodiments of the invention discussed herein can be used alone or in combination with each other. It will be understood by those skilled in the art that different embodiments discussed herein can be combined and form part of the invention. It will also be understood by those skilled in the art that certain aspects of different embodiments discussed herein can be combined and form part of the invention.

[0005] Embodiment 1 : In some embodiments, the present application provides a process of preparing 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene, the process comprising steps of: reacting (ia) vinyl chloride (CH2=CHCI, VC) or (ib) vinyl fluoride (CH2=CHF, VF) with CFC-113a (CF3CCI3) in the presence of a metal-containing compound and an organic initiator to make HCFC-343maf (CF3CCI2CH2CHCI2) or HCFC-344maf (CF3CCI2CH2CHCIF), respectively; (iia) fluorinating HCFC-343maf with a fluorinating agent to make a product mixture comprising HFO-1336ze (CHFCHCF2CF3, 1 ,3,3, 4,4,4-hexafluoro-1-butene), HFO-1336myf (CF3CF=CHCHF2, 1 ,1 ,1 ,2,4,4-hexafluoro-2-butene) or a mixture thereof; or (iib) fluorinating HCFC-344maf with a fluorinating agent make a product mixture comprising HFO-1336ze, HFO-1336myf or a mixture thereof; and (iii) reacting the product mixture comprising HFO-1336ze, HFO-1336myf or a mixture thereof with tetrafluoroethylene in the presence of a Lewis acid catalyst to produce1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene, HFO-153-1 Omczz (CF3CF2CH=CHCF2CF3).

[0006] Embodiment 2: In some embodiments, the present application is directed to a process of preparing 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene, the process comprising steps of: reacting (ia) vinyl chloride (CH2=CHCI, VC) with CFC-113a (CF3CCI3) in the presence of a metal-containing compound and an organic initiator to make HCFC-343maf (CF3CCI2CH2CHCI2); (iia) fluorinating HCFC-343maf with a fluorinating agent to make a product mixture comprising HFO-1336ze (CHF=CHCF2CF3, 1 ,3,3, 4,4,4-hexafluoro-l-butene), HFO-1336myf (CF3CF=CHCHF2, 1 ,1 ,1 ,2,4,4-hexafluoro-2-butene) or a mixture thereof; and (iii) reacting the product mixture comprising HFO-1336ze, HFO-1336myf or a mixture thereof with tetrafluoroethylene in the presence of a Lewis acid catalyst to produce 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene, HFO-153-1 Omczz (CF3CF2CH=CHCF2CF3).

[0007] Embodiment 3: In some embodiments, the present application provides a process of preparing 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene, the process comprising steps of: reacting (ib) vinyl fluoride (CH2=CHF, VF) with CFC-113a (CF3CCI3) in the presence of a metal-containing compound and an organic initiator to make HCFC-344maf (CF3CCI2CH2CHCIF; (iib) fluorinating HCFC-344maf with a fluorinating agent to make a product mixture comprising HFO-1336ze, HFO-1336myf or a mixture thereof; and (iii) reacting the product mixture comprising HFO-1336ze, HFO-1336myf or a mixture thereof with tetrafluoroethylene in the presence of aLewis acid catalyst to produce 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene, HFO-153- 10mczz (CF3CF2CH=CHCF2CF3).

[0008] Embodiment 4: In some embodiments, the present application provides a process of preparing 1 ,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene, the process comprising reacting a composition comprising HFO-1336ze, HFO-1336myf or a mixture thereof with tetrafluoroethylene in the presence of a Lewis acid catalyst to produce 1,1,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene (CF3CF2CH=CHCF2CF3).

[0009] Embodiment 5: The process of embodiments 1 , 2, 3 or 4, wherein the Lewis acid catalyst is a strong Lewis acid catalyst.

[0010] Embodiment 6: The process of embodiments 1 , 2, 3 or 4, wherein the Lewis acid catalyst is selected from SbFs, aluminum chlorofluoride (“ACF”, AICIxFy, wherein x = 0.1- 0.3, and y = 2.7-2.9), and aluminum chloride.

[0011] Embodiment 7: The process of embodiment 1 , wherein the metalcontaining compound of step (ia) or step (ib) comprises an iron-containing compound.

[0012] Embodiment 8: The process of embodiment 1 , wherein the organic initiator is selected from the group consisting of phosphines, phosphites, phosphates, phosphine oxides, amines, nitrites, amides, thiolates, thioethers, thiamides, and dithiocarbamates.

[0013] Embodiment 9: The process of embodiment 1 , wherein the organic initiator of step (ia) or step (ib) comprises a phosphine, phosphite, phosphate, or phosphine oxide.

[0014] Embodiment 10: The process of embodiment 1, wherein the organic initiator of step (ia) or step (ib) comprises a phosphine, phosphite, phosphate, or phosphine oxide or combinations of two of more thereof.

[0015] Embodiment 11: The process of embodiment 1 or 10, wherein the organic initiator of step (ia) or step (ib) comprises a phosphine, preferably triphenyl phosphine or tributyl phosphine.

[0016] Embodiment 12: The process of embodiment 1 , wherein the organic initiator of step (ia) or step (ib) comprises an amine, a nitrite, an amide, a thiolate, a thioether, a thiamide, or a dithiocarbamate.

[0017] Embodiment 13: The process of embodiment 1 , 9, or 10, wherein the wherein the organic initiator of step (ia) or step (ib) comprises a phosphine.

[0018] Embodiment 14: The process of embodiment 1 , 9, 10, or 13, wherein the wherein the phosphine comprises triphenyl phosphine.

[0019] Embodiment 15: A process of preparing a product mixture comprising HFO-1336ze (CH HCF2CF3. 1,3,3,4,4,4-hexafluoro-1-butene), HFO-1336myf (CF3CF=CHCHF2, 1 ,1 ,1 ,2,4,4-hexafluoro-2-butene) or a combination thereof, the process comprising fluorinating HCFC-343maf with a fluorinating agent to make a product mixture comprising HFO-1336ze (CHF—CHCF2CF3, 1 ,3, 3,4,4, -hexafluoro1- butene), HFO-1336myf (CF3CF=CHCHF2, 1 ,1 ,1 ,2,4,4-hexafluoro-2-butene) or a combination thereof.

[0020] Embodiment 16: A process of preparing a product mixture comprising HFO-1336ze (CH HCF2CF3. 1,3,3,4,4,4-hexafluoro-1-butene), HFO-1336myf (CF3CF=CHCHF2, 1 ,1 ,1 ,2,4,4-hexafluoro-2-butene) or a combination thereof, the process comprising fluorinating HCFC-344maf with a fluorinating agent to make a product mixture comprising HFO-1336ze (CHF—CHCF2CF3, 1 ,3, 3,4,4, -hexafluoro1- butene), HFO-1336myf (CF3CF=CHCHF2, 1 ,1 ,1 ,2,4,4-hexafluoro-2-butene) or a combination thereof.

[0021] Embodiment 17: The process of any one of embodiments 1 , 2, 15, or 16 wherein the fluorinating agent is hydrogen fluoride.

[0022] Embodiment 18: The process of any one of embodiments 1 , 2, or 7 to 17, wherein the fluorination reaction (iia) or (iib) is performed at a temperature of from about 150°C to about 350°C, preferably about 250°C to about 325°C, and more preferably about 275°C to about 310°C.

[0023] Embodiment 19: The process any one of embodiments 1 , 2 or 7 to 18, wherein the fluorination reaction (iia) or (iib) is performed at a pressure of from about 1 atm to about 20 atm, preferably about 2 atm to about 15atm, and more preferably about 3 atm to about 10atm.

[0024] Embodiment 20: The process of any one of embodiments 1 to 3, wherein the HFO-153-10mczz comprises a mixture of E-153-10mczz and Z-153-10mczz, and further comprising isomerizing Z-1,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene to E- 1 ,1,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene.

[0025] Embodiment 21: The process of any one of embodiments 1 to 18, wherein the reacting of the HFO-1336ze and the HFO-1336myf is performed as a liquid phase reaction.

[0026] Embodiment 22: The process of any one of embodiments 1 to 18, wherein the Lewis acid catalyst is SbFs, ACF or aluminum chloride, and wherein the reacting of the HFO-1336ze and the HFO-1336myf is performed at a temperature of from about 0°C to about 75°C, preferably about 5°C to about 50°C, and more preferably about 10°C to about 30°C.

[0027] Embodiment 23: The process of any one of embodiments 1 to 18, wherein the Lewis acid catalyst is SbFs, ACF or aluminum chloride, and wherein the reacting of the HFO-1336ze and the HFO-1336myf is performed at a pressure of from about 1 atm to about 20 atm, preferably about 1 atm to about 15atm, and more preferably about 1 atm to about 10 atm.

[0028] Embodiment 24: The process of any one of embodiments 1 to 2 and 4 to 17, wherein a ratio of the number of moles of the fluorinating agent to moles of HCFC-343maf is about 6: 1 to about 30: 1.

[0029] Embodiment 25: The process of any one of embodiments 1 and 3 to 17, wherein a ratio of the number of moles of the fluorinating agent to moles of HCFC- 344maf is about 6: 1 to about 30: 1.

[0030] Embodiment 26: The process of any one of embodiments 1 to 21 , wherein a ratio of the number of moles of HFO-1336ze to the number of moles of HFO1336myf is about 0% to about 99%.

[0031] Embodiment 26: The process of any one of embodiments 1 to 22, wherein a ratio of the number of moles of HFO-1336ze to the number of moles of tetrafluoroethylene in is about 0.1 to 1.

[0032] Embodiment 28: The process of any one of embodiments 1 to 23, wherein a ratio of the number of moles of HFO-1336myf to the number of moles of tetrafluoroethylene is about 0.1 to 1.

[0033] Embodiment 29: The process of any one of embodiments 1 to 23, wherein a ratio of the number of moles of HFO-1336ze and HFO-1336myf to the number of moles of the Lewis acid catalyst is about 0.01 to 20.

[0034] Embodiment 30: The process of any one of embodiments 1 to 25, wherein a ratio of the number of moles of tetrafluoroethylene to the number of moles of the Embodiment 31 : A composition comprising E-1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3- hexene and one or more additional compounds selected from Z-1, 1,1 , 2, 2, 5, 5, 6,6,6- decafluoro-3-hexene, E- and Z- isomers of CF3CF=CHCH(C2Fs)2, and E- and Z- isomers of dimers of C4F6H2 hydrofluoroolefin, wherein the composition is prepared according to the process of any one of embodiments 1 to 24. In one embodiment, there is a composition comprising E-1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene and 1 ,1,1 ,2,2,5,5,6,6,7,7,8,8,8-tetradecafluoro-3-octene.

[0035] Embodiment 32: The process of any one of embodiments 1 to 10 and 15 to 28, wherein the 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene comprises E- 1 ,1,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene.

[0036] Embodiment 33: The process of any one of embodiments 1 to 9 and 11 to 26, wherein the 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene is E- 1 ,1,1 ,2,2,5,5,6,6,6decafluoro-3-hexene.

[0037] Embodiment 34: The composition produced according to any one of embodiments 1-29, wherein the 1 ,1 ,1,2,2,5,5,6,6,6-decafluoro-3-hexene comprises E-1 , 1 , 1 ,2,2,5,5,6,6,6-decafluoro-3-hexene.

[0038] Embodiment 35: The composition of any one of embodiments 1-29, wherein the 1,1,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene is E- 1 ,1,1 ,2,2,5,5,6,6,6decafluoro-3-hexene.

[0039] Embodiment 36: In some embodiments, the present application provides a process of preparing 1 ,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene, the process comprising steps of: reacting (ia) vinyl chloride (CH2=CHCI, VC) or (ib) vinyl fluoride (CH2=CHF, VF) with CFC-113a (CF3CCI3) in the presence of a metal-containingcompound and an organic initiator to make HCFC-343maf (CF3CCI2CH2CHCI2) or HCFC-344maf (CF3CCI2CH2CHCIF), respectively; (iia’) dehydrochlorinating HCFC- 343maf in the presence of a catalyst to make a product mixture comprising HCFO- 1333maz (CF3-CCl2-CH=CHCI, 1,3,3-trichloro-4,4,4-trifluoro-1-butene), HCFO- 1333mxz (CF3-CCI=CH-CHCl2, 1,1,3-trichloro-4,4,4"trifluoro-2"butene), or a mixture thereof; or (iib’) dehydrochlorinating HCFC-344maf in the presence of a catalyst to make a product mixture comprising HCFO-1334maz (CF3-CCl2-CH=CHF, 3,3- dichloro-1,4,4,4-tetrafluoro-1-butene), HCFO-1334mxz (CF3-CCI=CH-CHCIF, 1,3- dichloro-1,4,4,4-tetrafluora-2-butene) or a mixture thereof; (iia”) fluorinating the product mixture comprising HCFO-1333maz, HCFO-1333mxz, or a mixture thereof, with a fluorinating agent to make a product mixture comprising HFO-1336ze, HFO- 1336myf or a mixture thereof; or (iib”) fluorinating the product mixture comprising HCFO-1334maz, HCFO-1334mxz, or a mixture thereof, with a fluorinating agent to make a product mixture comprising HFO-1336ze, HFO-1336myf or a mixture thereof; and (iii) reacting the product mixture comprising HFO-1336ze, HFO- 1336myf or a mixture thereof with tetrafluoroethylene in the presence of a Lewis acid catalyst to produce HFO-153-10mczz.

[0040] Embodiment 37: In some embodiments, the present application provides a process of preparing 1 ,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene, the process comprising steps of: reacting (ia) vinyl chloride with CFC-113a in the presence of a metal-containing compound and an organic initiator to make HCFC-343maf; (iia’) dehydrochlorinating HCFC-343maf in the presence of a catalyst to make a product mixture comprising HCFO-1333maz, HCFO-1333mxz, or a mixture thereof; (iia”) fluorinating the product mixture comprising HCFO-1333maz, HCFO-1333mxz, or a mixture thereof, with a fluorinating agent to make a product mixture comprising HFO- 1336ze, HFO-1336myf or a mixture thereof; and (iii) reacting the product mixture comprising HFO-1336ze, HFO-1336myf or a mixture thereof with tetrafluoroethylene in the presence of a Lewis acid catalyst to produce HFO-153-10mczz.

[0041] Embodiment 38: In some embodiments, the present application provides a process of preparing 1 ,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene, the process comprising steps of: reacting (ib) vinyl fluoride with CFC-113a in the presence of a metal-containing compound and an organic initiator to make HCFC-344maf; (iib’) dehydrochlorinating HCFC-344maf in the presence of a catalyst to make a productmixture comprising HCFO-1334maz, HCFO-1334mxz or a mixture thereof; (iib”) fluorinating the product mixture comprising HCFO-1334maz, HCFO-1334mxz, or a mixture thereof, with a fluorinating agent to make a product mixture comprising HFO- 1336ze, HFO-1336myf or a mixture thereof; and (iii) reacting the product mixture comprising HFO-1336ze, HFO-1336myf or a mixture thereof with tetrafluoroethylene in the presence of a Lewis acid catalyst to produce 1,1,1 ,2,2,5,5,6,6,6-decafluoro-3- hexene, HFO-153-10mczz (CF3CF2CH=CHCF2CF3).BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Fig. 1 illustrates the processes to produce E-1 ,1 ,1,2,2,5,5,6,6,6decafluoro- 3-hexene as disclosed herein.

[0043] Figs. 2A-2C depict individual processes according to embodiments of the present invention, and Fig. 2D depicts an integrated process comprising the individual processes according to embodiments of the present invention.

[0044] Figs. 3A-3C depict individual processes according to embodiments of the present invention, and Fig. 3D depicts an integrated process comprising the individual processes according to embodiments of the present invention.DETAILED DESCRIPTION OF THE INVENTION

[0045] The present invention relates broadly to processes of preparing 1 ,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (C2F5CH=CHC2F5, HFO-153-10mczz).

[0046] 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).

[0047] 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.

[0048] 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”.

[0049] 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.”

[0050] 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.

[0051] 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. It is not intended that the scope of the invention be limited to the specific values recited when defining a range. Moreover, all ranges set forth herein are intended to include not only the particular ranges specifically described, but also any combination of values therein, including the minimum and maximum values recited.

[0052] 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.

[0053] 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.

[0054] 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.

[0055] As used herein the term “about” in certain embodiments can be quantified to mean ± 1%, ± 2%, ± 3% up to and including ±10% of the stated value, and all whole numbers and fractions therebetween.

[0056] In some embodiments, the present disclosure describes processes for production of a mixture or composition comprising, consisting of, or consisting essentially of HFO-1336myf, HFO-1336ze, or a combination thereof from HCFC- 343maf.

[0057] In some embodiments, the present disclosure describes processes for production of a mixture or composition comprising, consisting of, or consisting essentially of HFO-1336myf, HFO-1336ze, or a combination thereof from HCFC- 344 maf.In some embodiments, the present disclosure describes processes for production of a mixture or composition comprising, consisting of, or consisting essentially of HFO- 1336myf (CF3CF=CHCHF2, 1,1 ,1 ,2,4,4-hexafluoro-2-butene), HFO-1336ze (CHF—CHCF2CF3, 1,3,3, , 4, 4-hexafluoro-1 -butene), or a combination thereof from HCFC-344maf (CF3CCI2CH2CHCIF).

[0058] In some embodiments, the present disclosure describes a process for production of 1,1 ,1,2,2,5,5,6,6,6-decafluoro-3-hexene from HFO-1336myf.

[0059] In some embodiments, the present disclosure describes a process for production of 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene from a mixture or composition comprising, consisting of, or consisting essentially of HFO-1336ze and HFO- 1336myf.

[0060] In some embodiments, the present disclosure describes an integrated process for production of 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene (C2FsCH=CHC2F5, HFO-153-10mczz) by way of a multi-step process route. In some embodiments, the present disclosure describes an integrated process for production of E-1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene and Z-1 , 1 , 1 ,2,2,5,5,6,6,6-decafluoro-3- hexene by way of a multi-step process route, with the E-isomer being the primary or main product of the integrated process.

[0061] In one embodiment, the multi-step processes of the present invention are carried out in a reactor comprising a series of reaction zones in fluid communication with each other. In another embodiment, the multi-step processes of the present invention are carried out in a series of reactors, each of which comprises a reaction zone, in fluid communication with each other. In certain embodiments, each reactor is a cylindrical tube or pipe, which may be straight or coiled.

[0062] In addition to the reactors disclosed herein, heaters, effluent lines, units associated with mass transfer, contacting vessels (pre-mixers), distillation columns, and feed and material transfer lines associated with reactors, heaters, vessels, columns, and units that are used in the processes of embodiments disclosed herein should be constructed of materials resistant to corrosion, such as those recited herein with respect to the reactors.

[0063] According to embodiments of the present invention, there is provided a step or process of producing HFO-153-10mczz from HFO-1336myf (CF3CF=CHCHF2). Preferably, the HFO-1336myf includes both the Z- and E-isomers. The process comprises reacting HFO-1336myf with tetrafluoroethylene (TFE), preferably in the liquid phase, in the presence of an acid catalyst in an amount sufficient to produce a composition comprising HFO-153-10mczz, which includes both the Z- and E- isomers.

[0064] According to embodiments of the present invention, there is provided a step or process of producing HFO-153-10mczz from a composition or mixture comprising,consisting essentially of, or consisting of HFO-1336ze (CF3CF2CH=CHF) and HFO- 1336myf (CF3CF=CHCHF2). Preferably, the HFO-1336ze includes both the Z- and E- isomers. Preferably, the HFO-1336myf includes both the Z- and E- isomers. In some embodiments, the composition comprises, consists essentially of, or consists of about 1 mol% to about 99 mol% HFO-1336ze and about 1 mol% to about 99 mol% HFO-1336myf. For the sake of brevity, the composition is sometimes referred to herein as “composition of HFO-1336ze and HFO-1336myf.” The process comprises reacting the composition of HFO-1336ze and HFO-1336myf with TFE, preferably in the liquid phase, in the presence of an acid catalyst in an amount sufficient to produce a composition comprising HFO-153-10mczz, which includes both the Z- and E- isomers.

[0065] In some embodiments of the processes of the present invention, either (i) HFO-1336myf or (ii) the composition of HFO-1336ze and HFO-1336myf is charged to a reactor, heated and contacted, in the presence of an acid catalyst, with TFE to make a reaction mixture comprising 1 ,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (i.e., HFO-153-10mczz) (E- and Z- isomers) at a conversion rate of about 10% to about 100%.

[0066] In some embodiments, a ratio of the number of moles of HFO-1336ze to the number of moles of HFO-1336myf is about 0% to about 99%.

[0067] In some embodiments, a ratio of the number of moles of HFO-1336ze to the number of moles of tetrafluoroethylene in is about 0.1 to 1.

[0068] In some embodiments, a ratio of the number of moles of HFO-1336myf to the number of moles of tetrafluoroethylene is about 0.1 to 1.

[0069] In some embodiments, a ratio of the number of moles of HFO-1336ze and HFO-1336myf to the number of moles of the Lewis acid catalyst is about 0.01 to 20.

[0070] In some embodiments, a ratio of the number of moles of tetrafluoroethylene to the number of moles of the Lewis acid catalyst in step (iii) is about 0.01 to 20.

[0071] As used herein, the term “Lewis acid catalyst” is a compound (e.g., a metal based compound) that acts as an electron pair acceptor to increase the reactivity of a substrate. Exemplary Lewis acid catalysts include, but are not limited to, transition metal compounds, e.g., compounds containing titanium, zinc, iron, copper, and zinc,and main group metal compounds, e.g., compounds containing aluminum, boron, silicon, tin, and antimony. In some embodiments, the Lewis acid catalyst is a strong Lewis acid catalyst. Additional examples of Lewis acid catalysts can be found, for example, in International Publication Nos. WO 2008 / 057513 and WO 2018 / 022500, the disclosure of each of which is incorporated herein by reference in its entirety.

[0072] In some embodiments, the Lewis acid catalyst is selected from SbFs, aluminum chlorofluoride (ACF), and aluminum chloride (AlCh). In some embodiments, the Lewis acid catalyst is SbFs. In some embodiments, the Lewis acid catalyst is ACF. In some embodiments, the Lewis acid catalyst is AICI3. ACF may be AICIxFy, wherein x = 0.1- 0.3, and y = 2.7-2.9.

[0073] In some embodiments, this reaction is carried out, for example, in accordance with the processes described in International Publication Nos. WO 2008 / 057513 and WO 2020 / 214912, the disclosure of each of which is incorporated herein by reference in its entirety.

[0074] The temperature and pressure of the reactor are maintained at levels sufficient to effect, in the presence of the acid catalyst, the formation of a composition comprising HFO-153-10mczz.

[0075] In some embodiments, the Lewis acid catalyst is AICI3, and the process comprises reacting HFO-1336myf or the composition of HFO-1336ze and HFO1336myf with TFE, in the presence of AICI3, at a temperature of from about 0°C to about 75°C, preferably about 5°C to about 50°C, and more preferably about 10°C to about 30°C. In some embodiments, the Lewis acid catalyst is AICI3, and the reacting of HFO-1336myf or the composition of HFO-1336ze and HFO-1336myf with TFE is performed in the presence of AICI3 at a pressure of from about 1 atm to about 20 atm, preferably about 1 atm to about 15atm, and more preferably about 1 atm to about 10 atm.

[0076] In some embodiments, the Lewis acid catalyst is SbFs, and the process comprises reacting HFO-1336myf or the composition of HFO-1336ze and HFO1336myf with TFE, in the presence of SbFs, at a temperature of from about 0°C to about 75°C, preferably about 5°C to about 50°C, and more preferably about 10°C to about 30°C. In some embodiments, the Lewis acid catalyst is SbFs, and the reacting of HFO-1336myf or the composition of HFO-1336ze and HFO-1336myf withTFE is performed in the presence of SbFsat a pressure of from about 1 atm to about 20 atm, preferably about 1 atm to about 15atm, and more preferably about 1 atm to about 10 atm.

[0077] In some embodiments, the Lewis acid catalyst is ACF, and the process comprises reacting HFO-1336myf or HFO- the composition of HFO-1336ze and HFO-1336myf with TFE, in the presence of ACF, at a temperature of from about 0°C to about 75°C, preferably about 5°C to about 50°C, and more preferably about 10°C to about 30°C. In some embodiments, the Lewis acid catalyst is ACF, and the reacting of HFO-1336myf or the composition of HFO-1336ze and HFO-1336myf with TFE is performed in the presence of ACF at a pressure of from about 1 atm to about 20 atm, preferably about 1 atm to about 15atm, and more preferably about 1 atm to about 10 atm.

[0078] In one embodiment, the reaction may be performed by introducing the HFO-1336myf or the composition of HFO-1336ze and HFO-1336myf, the TFE and the catalyst into a reaction vessel or zone, and then heating the mixture with agitation. In one embodiment, the catalyst is introduced into the reactor before introduction of the HFO-1336myf or the composition of HFO-1336ze and HFO1336myf. Preferably, the reaction is carried out in an inert environment which is devoid of water and oxygen.

[0079] In some embodiments, the reacting of HFO-1336myf or of the composition of HFO-1336ze and HFO-1336myf with TFE is performed as a liquid phase reaction. However, it will be understood by those skilled in the art that the reaction may alternatively be carried out in the vapor phase.

[0080] In one embodiment, the reacting of HFO-1336myf or of the composition of HFO-1336ze and HFO-1336myf with TFE may take place in the presence of a solvent capable of dissolving at least a portion of each reactant. An example of such a solvent includes, but is not limited to, HFO-153-10mczz.

[0081] In some embodiments, this reaction may be conducted in a reactor which is operating in batch, semi-batch, semi-continuous, or continuous modes, to produce a reaction mixture comprising HFO-153-10mczz. An effluent stream of the reactor comprises the composition comprising HFO-153-10mczz.

[0082] In some embodiments, the composition of the effluent stream comprises E1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene and one or more additional compounds selected from Z- 1 ,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene, E- and Z- isomers of CF3CF=CHCH(C2F5)2, and E- and Z- Isomers of dimers of C4F6H2 hydrofluoroolefins. Any byproducts, additional components of the reaction mixture aside from HFO-153mczz, and any of the unreacted, excess starting material may be, optionally purified and then, recycled for further reaction.

[0083] The composition produced from the reaction thus comprises both the E- and Z- isomers of HFO-153-mczz. E-HFO-153-mczz is the primary product of embodiments of the processes of the present invention. Thus, optionally, all or some of the Z-isomer of HFO-153-mczz contained in the reaction product may be isomerized to the E isomer.

[0084] In some embodiments, either HFO-1336myf or the composition of HFO- 1336ze and HFO-1336myf may be pre-mixed with TFE, and optionally also with the acid catalyst, and then introduced into the reactor for reaction at a temperature of from about 0°C to about 75°C, preferably about 5°C to about 50°C, and more preferably about 10°C to about 30°C, and a pressure of from about 1 atm to about 20 atm, preferably about 1 atm to about 15atm, and more preferably about 1 atm to about 10 atm.

[0085] In one embodiment, the composition of HFO-1336ze and HFO-1336myf may be pre-mixed with TFE to form a starting mixture. In some embodiments, the reaction comprises pre-mixing the composition of HFO-1336ze and HFO-1336myf with TFE to form a mixture, charging the mixture to the reactor containing an acid catalyst, and reacting the mixture in the presence of the acid catalyst to form a reaction product comprising HFO-153-10mczz. In other embodiments, the acid catalyst may be pre-mixed with the composition of HFO-1336ze and HFO-1336myf and / or the TFE, and charged to the reactor as part of the mixture, for reaction at a temperature of from about 0°C to about 75°C, preferably about 5°C to about 50°C, and more preferably about 10°C to about 30°C, and a pressure of from about 1 atm to about 20 atm, preferably about 1 atm to about 15atm, and more preferably about 1 atm to about 10 atm.

[0086] In one embodiment, HFO-1336myf and TFE may be pre-mixed with each other to form a starting mixture. In some embodiments, the reaction comprises premixing the HFO-1336myf and TFE to form a mixture, charging the mixture to the reactor containing an acid catalyst, and reacting the mixture in the presence of the acid catalyst to form a reaction product comprising HFO-153-10mczz. In other embodiments, the Lewis acid catalyst may be pre-mixed with the HFO-1336myf and / or the TFE, and charged to the reactor as part of the mixture, for reaction at a temperature of from about 0°C to about 75°C, preferably about 5°C to about 50°C, and more preferably about 10°C to about 30°C, and a pressure of from about 1 atm to about 20 atm, preferably about 1 atm to about 15atm, and more preferably about 1 atm to about 10 atm.

[0087] In some embodiments, the aforementioned pre-mixing is performed in the liquid phase. In some embodiments, the pre-mixed mixture is a liquid.

[0088] The Lewis acid catalyst for this reaction can be readily regenerated by any means known in the art if they become deactivated. One suitable method of regenerating the catalyst involves recycling of the catalyst, particularly the ACF or aluminum chloride catalyst, after filtration.

[0089] Also disclosed herein, in one embodiment, is a composition comprising the compound 1,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene (C2F5CH=CHC2F5, HFO-153- 10mczz) produced by the above-described reaction of HFO-1336myf or the composition of HFO-1336ze and HFO-1336myf with TFE, in the presence of an acid catalyst. In certain embodiments, C2FsCH=CHC2F5 is the E- isomer, Z- isomer or a combination thereof.

[0090] Also disclosed herein, in one embodiment, is a composition comprising E- 1 ,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene and one or more additional compounds selected from Z- 1,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene, E- and Z- isomers of CF3CF=CHCH(C2FS)2, and E- and Z- Isomers of dimers of C4F6H2 hydrofluoroolefins.

[0091] According to embodiments of the present invention, there is further provided a step or process of producing a product mixture comprising HFO-1336myf (CF3CF=CHCHF2), HFO-1336ze (CF3CF2CH=CHF), or a mixture thereof from HCFC-343maf or HCFC-344maf. The composition preferably comprises, consistsessentially of, or consists of about 1 mol% to about 99 mol% HFO-1336ze and 1 mol% to about 99 mol% HFO-1336myf.

[0092] In one embodiment, the HFO-1336myf or the composition of HFO- 1336ze and HFO-1336myf is produced in one step by catalytic fluorination of HCFC- 343maf. More particularly, the process comprises fluorination of HCFC-343maf by reaction with a fluorinating agent, such as HF, in the presence of a catalyst, preferably a fluorinated catalyst, to make a product comprising HFO-1336ze, HFO- 1336myf or a mixture thereof. The product preferably comprises both the E- and Z- isomers of HFO-1336ze and HFO-1336myf. The product comprises, consists of, or consists essentially of HFO-1336ze and HFO-1336myf which is or can be used in the above-described reaction to produce HFO-153-10mczz. Alternatively, if desired, HFO-1336myf may be separated from the reaction mixture and utilized in the abovedescribed reaction to produce HFO-153-10mczz.

[0093] Useful catalysts for the fluorinating of HCFC-343maf include chromium- based catalysts, such as chromium (III) oxide or fluorinated chromium (III) oxide, which catalyst may either be unsupported, or supported on a support such as activated carbon, graphite, fluoride graphite, or alumina fluoride. The chromium catalyst may either be used alone, or in the presence of a co-catalyst selected from nickel, cobalt, manganese or zinc salt. In one embodiment, a chromium catalyst is high surface area chromium oxide, or chromium / nickel on alumina fluoride (Cr / Ni / AIFs), the preparation of which is reported in European Patent EP486333. In another embodiment, the catalyst is fluorinated Guignet’s green catalyst. Additional suitable catalysts include, but are not limited to, JM 62-2 (chrome catalyst available from Johnson Matthey), LV (chrome catalyst available from Chemours), JM-62-3 (chrome catalyst available from Johnson Matthey), and Newport Chrome (chrome catalyst available from Chemours). The chromium catalysts are preferably activated before use, typically by a procedure whereby the catalyst is heated to from 350°C to 400°C under a flow of nitrogen for a period of time, after which the catalyst is heated under a flow of HF and nitrogen or air for an additional period of time.

[0094] In one embodiment, the Guignet’s Green of the fluoride-activated Guignet’s Green catalyst used in the present invention is made by reacting (fusing) boric acid with alkali metal dichromate at 500°C to 800°C, followed by hydrolysis of the reactionproduct, whereby said Guignet’s Green contains boron, alkali metal, and water of hydration. The usual alkali metal dichromates are the Na and / or K dichromates. The reaction is typically followed by the steps of cooling the reaction product in air, crushing this solid to produce a powder, followed by hydrolysis, filtering, drying, milling and screening. The Guignet’s Green is bluish green, but is known primarily as a green pigment, whereby the pigment is commonly referred to as Guignet’s Green. When used as a catalyst, it is also referred to as Guignet’s Green as disclosed in U.S. Pat. No. 3,413,363. In U.S. Pat. No. 6,034,289, Cr20s catalysts are disclosed as preferably being in the alpha form, and Guignet’s Green is also disclosed as a commercially available green pigment having the composition: O2O379-83 %, H2O 16-18 %, B2O51.5 to 2.7 % (sentence bridging cols. 2 and 3) that can be converted to the alpha form (col. 3, I. 3). U.S. Pat. No. 7,985,884 acknowledges the presence of alkali metal in the Guignet’s Green in the composition of Guignet’s Green disclosed in Example 1: 54.5% Cr, 1.43% B, 3,400 ppm Na, and 120 ppm K.

[0095] The physical shape of the catalyst is not critical and may, for example, include pellets, extrudates, powders, or granules. The fluoride activation of the catalyst is preferably carried out on the final shape of the catalyst.

[0096] The catalyst for this reaction can be readily regenerated by any means known in the art if they become deactivated.

[0097] In some embodiments, HCFC-343maf is dehydrochlorinated to make a product mixture comprising HCFO-1333maz, HCFO-1333mxz, or a mixture thereof. This product mixture may be fluorinating using the fluorinating agents disclosed herein in the presence of a catalyst. Useful catalysts for the fluorinating of HCFO- 1333maz, HCFO-1333mxz, or a mixture thereof are the same as recited for fluorinating HCFC-343maf.

[0098] In some embodiments, HCFC-344maf is dehydrochlorinated to make a product mixture comprising HCFO-1334maz, HCFO-1334mxz, or a mixture thereof. This product mixture may be fluorinating using the fluorinating agents disclosed herein in the presence of a catalyst. Useful catalysts for the fluorinating of HCFO- 1334maz, HCFO-1334mxz, or a mixture thereof are the same as recited for fluorinating HCFC-343maf and HCFC-344maf.

[0099] In some embodiments, the fluorinating agent is selected from hydrogen fluoride, antimony trifluoride, antimony tetrafluoride, antimony pentafluoride, antimony trichloride / hydrogen fluoride, antimony tetrachloride / hydrogen fluoride, or any mixture thereof. In some embodiments, the fluorinating agent is hydrogen fluoride.

[0100] In some embodiments, the molar ratio of fluorinating agent (e.g., HF) to HCFC-343maf or HCFC-344maf is, from about 6:1 to about 30:1, preferably from about 10:1 to about 25:1. In some embodiments, the molar ratio of fluorinating agent (e.g., HF) to HCFC-343maf is, from about 100:1 to about 25:1 , preferably about 40:1. In practice, however, an excess of HCFC-343maf or HCFC-344maf and / or fluorinating agent may be used as desired.

[0101] In one embodiment, contact time for the fluorination reaction of HCFC- 343maf or HCFC-344maf may be from about 2 seconds to about 80 seconds. In another embodiment, contact time for the fluorination reaction of HCFC-343maf or HCFC-344maf may be from about 10 seconds to about 60 seconds. In another embodiment, contact time for the fluorination reaction of HCFC-343maf or HCFC- 344maf may be from about 20 seconds to about 50 seconds.

[0102] In one embodiment, suitable temperatures for the reactor for the fluorination reaction of HCFC-343maf or HCFC-344maf are from about 120°C to about 200°C, preferably from about 150°C to about 180°C. In one embodiment, the pressure in the reactor for the fluorination reaction of HCFC-343maf or HCFC- 344maf may be from about 0 to 200 psig, preferably from about 30 to 180 psig.

[0103] In one embodiment, the fluorination reactions disclosed herein are performed at a temperature of from about 150°C to about 350°C, preferably about 250°C to about 325°C, and more preferably about 275°C to about 310°C.

[0104] In one embodiment, the fluorination reactions disclosed herein are performed at a pressure of from about 1 atm to about 20 atm, preferably about 2 atm to about 15atm, and more preferably about 3 atm to about 10 atm.

[0105] In one embodiment, the fluorination reaction may be performed by introducing -344maf, the fluorinating agent, and the catalyst into a reaction vessel or zone, and then heating the mixture with agitation.

[0106] Preferably, the fluorination reactions as disclosed herein are carried out in the vapor phase. However, it will be understood by those skilled in the art that the fluorination of HCFC-344maf may, alternatively, be performed in the liquid phase.

[0107] A one-step fluorination reaction of HCFC-344maf comprises contacting HCFC-344maf with hydrogen fluoride (HF), in the presence of the catalyst, to produce a reaction mixture of compounds comprising HFO-1336ze and HFO- 1336myf. The fluorination reaction is preferably carried out in an environment which is devoid of water. In some embodiments, an amount of oxygen may optionally be co-fed to the reactor with the HCFC-344maf. For example, about 0.05 vol.% to about 5 vol% of oxygen may be co-fed to the reactor.

[0108] In one embodiment, the HCFC-344maf starting material may be pre-mixed with the HF, and then introduced into the reactor to form a reaction product comprising HFO-1336ze and HFO-1336myf. In some embodiments, the catalyst may optionally also be pre-mixed with the HCFC-344maf and HF. Preferably, the premixing is performed at a temperature of from about 25°C to about 175°C and a pressure of from about 0 psig to about 10 psig. In another embodiment, the HF may not be contacted with the HCFC-344maf until the components have been introduced into the reactor.

[0109] In some embodiments, the fluorination reaction of HCFC-344maf produces an effluent stream comprising a reaction product, composition or mixture comprising HFO-1336ze and HFO-1336myf. The fluorination reaction selectively produces HFO- 1336ze (E and Z isomers) and HFO-1336myf (E and Z isomers) from HCFC-344maf at a conversion rate of about 20% to about 100%. The composition produced from the fluorination of HCFC-344maf comprises, consists essentially of, or consists of about 1 mol% to about 99 mol% HFO-1336ze and about 1 mol% to about 99 mol% HFO-1336myf.

[0110] In some embodiments, this step may be conducted in a reactor or reaction zone which is operating in batch, semi-batch, semi-continuous, or continuous modes, to produce a reaction mixture comprising HFO-1336ze and HFO-1336myf. An effluent stream of the reactor or reaction zone comprises the reaction mixture comprising HFO-1336ze and HFO-1336myf.

[0111] For the fluorination reaction of HCFC-343maf or HCFC-344maf, the reactor effluent may further contain excess HF and HCI, as well as the reaction products HFO-1336ze (CF3CF2CH=CHF) and HFO-1336myf (CF3CF=CHCHF2). It is also possible that some of the starting material, HCFC-343maf or HCFC-344maf, will also be in the effluent stream. Any byproducts, additional components of the reaction mixture aside from HFO-1336ze and HFO-1336myf, and any of the unreacted starting material may be, optionally purified and recycled for further reaction.

[0112] In another embodiment, the composition of HFO-1336ze and HFO-1336myf is produced in two steps by dehydrochlorination of HCFC-343maf to produce a reaction mixture comprising HFO-1333maz and HFO-1333mxz (step (iia’), followed by fluorination of the reaction mixture comprising HFO-1333maz and HFO-1333mxz to produce the composition comprising HFO-1336ze and HFO-1336myf (step iia”).

[0113] In another embodiment, the composition of HFO-1336ze and HFO-1336myf is produced in two steps by dehydrochlorination of HCFC-344maf to produce a reaction mixture comprising HFO-1334maz and HFO-1334mxz (step (iib’), followed by fluorination of the reaction mixture comprising HFO-1333maz and HFO-1333mxz to produce the composition comprising HFO-1336ze and HFO-1336myf (step iib”).

[0114] In one embodiment, the dehydrochlorination of the HCFC-343maf or HCFC-344maf is performed in the presence of a catalyst, such as FeCI3. In one embodiment, the catalyzed dehydrochlorination is carried out at a temperature from about 25°C to 250°C, preferably 50°C to 175°C. In one embodiment, the reaction pressure is from about 0 psig to 300 psig, preferably from about 0 to 150 psig. In one embodiment, the catalyst to reactant molar ratio is between about 0.001:0.2, preferably about 0.05:0.1.

[0115] In another embodiment, the dehydrochlorination of the HCFC-343maf or HCFC-344maf is performed by contacting the HCFC-343maf or HCFC-344maf with a basic substance. Suitable basic substances include alkali metal hydroxides (e.g., sodium hydroxide or potassium hydroxide), alkali metal oxide (for example, sodium oxide), alkaline earth metal hydroxides (e.g., calcium hydroxide), alkaline earth metal oxides (e.g., calcium oxide), alkali metal alkoxides (e.g., sodium methoxide or sodium ethoxide), aqueous ammonia, sodium amide, or mixtures of basicsubstances such as soda lime. Preferred basic substances are sodium hydroxide and potassium hydroxide, most preferably potassium hydroxide.

[0116] The contacting of the HCFC-343maf or HCFC-344maf with a basic substance may take place in the liquid phase preferably in the presence of a solvent capable of dissolving at least a portion of the reactants. Solvents suitable for the dehydrochlorination step include one or more polar organic solvents such as alcohols (e.g., methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and tertiary butanol), nitriles (e.g., acetonitrile, propionitrile, butyronitrile, benzonitrile, or adiponitrile), dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, or sulfolane. The choice of solvent may depend on the boiling point product and the ease of separation of traces of the solvent from the product during purification. In one embodiment, preferred solvent for the reaction is methanol.

[0117] In one embodiment, the base-catalyzed dehydrochlorination is carried out at a temperature from about 20°C to 150°C, preferably 20°C to 50°C. In one embodiment, the reagent to base molar ratio is between about 0.2 to 3, preferably between about 1 to 1.2 moles. In one embodiment, the reagent to solvent ratio by volume is about 1 to 100, preferably about 1 to 10.

[0118] In one embodiment, the HFO-1336myf, HFO-1336ze, or a composition comprising HFO-1336ze and HFO-1336myf is produced in one step by dehydrochlorination / fluorination of HCFC-343maf. More particularly, the process comprises dehydrochlorination of HCFC-343maf in the presence of a catalyst in the vapor phase or liquid phase to produce a product comprising HFO-1336ze, HFO- 1336myf, or a mixture thereof. The mixture preferably comprises both the E- and Z- isomers of HFO-1336ze and HFO-1336myf. The reaction mixture comprises the composition comprising, consisting of, or consisting essentially of HFO-1336ze and HFO-1336myf which is or can be used in the above-described reaction to produce HFO-153-10mczz. Alternatively, if desired, HFO-1336myf may be separated from the reaction mixture and utilized in the above-described reaction to produce HFO- 153-10mczz.

[0119] In one embodiment, the HFO-1336myf, HFO-1336ze, or a composition comprising HFO-1336ze and HFO-1336myf is produced in one step by dehydrochlorination / fluorination of HCFC-344maf. More particularly, the processcomprises dehydrochlorination of HCFC-344maf in the presence of a catalyst in the vapor phase or liquid phase to produce a product comprising HFO-1336ze, HFO- 1336myf, or a mixture thereof. The mixture preferably comprises both the E- and Z- isomers of HFO-1336ze and HFO-1336myf. The reaction mixture comprises the composition comprising, consisting of, or consisting essentially of HFO-1336ze and HFO-1336myf which is or can be used in the above-described reaction to produce HFO-153-10mczz. Alternatively, if desired, HFO-1336myf may be separated from the reaction mixture and utilized in the above-described reaction to produce HFO- 153-10mczz.

[0120] In one embodiment, the dehydrochlorination / fluorination is carried out in the vapor phase using a dehydrochlorination catalyst. Dehydrochlorination catalysts include but are not limited to alumina, aluminum fluoride, fluorided alumina, metal compounds on aluminum fluoride, metal compounds on fluorided alumina; oxides, fluorides, and oxyfluorides of magnesium, zinc and mixtures of magnesium and zinc and / or aluminum; lanthanum oxide and fluorided lanthanum oxide; chromium oxides, fluorided chromium oxides, and cubic chromium trifluoride; carbon, acid washed carbon, activated carbon, three dimensional matrix carbonaceous materials; and metal compounds supported on carbon. The metal compounds may be oxides, fluorides, and oxyfluorides of at least one metal selected from the group consisting of sodium, potassium, rubidium, cesium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, chromium, iron, cobalt, rhodium, nickel, copper, zinc, and mixtures thereof.

[0121] In one embodiment, the catalytic vapor phase dehydrochlorination of HCFC-343maf or HCFC-344maf is carried out using fluorided alumina, aluminum fluoride or mixtures thereof as catalysts. Fluorided alumina and aluminum fluoride can be prepared as described in U.S. Patent No. 4,902,838, or by treatment of alumina with a vaporizable fluorine containing compound such as CF2CI2, CF2HCI, and CHF3.

[0122] In other embodiments, the dehydrochlorination of HCFC-343maf or HCFC- 344maf is carried out using carbon, activated carbon, or three-dimensional matrix carbonaceous materials; or using metals such as sodium, potassium, rubidium, cesium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium,chromium, iron, cobalt, rhodium, nickel, copper, zinc, and mixtures thereof, supported on carbon as catalysts. Carbon from any of the following sources are useful for the dehydrochlorination; wood, peat, coal, coconut shells, bones, lignite, petroleum-based residues and sugar. Such carbons are commercially available. Carbon includes acid-washed carbon (e.g., carbon that has been treated with hydrochloric acid or hydrochloric acid followed by hydrofluoric acid).

[0123] In a further embodiment, the catalytic dehydrochlorination of HCFC-343maf or HCFC-344maf is carried out using chromium oxides, fluorided chromium oxides, and cubic chromium trifluoride as catalysts. Cubic chromium trifluoride may be prepared from CrFsX W, where X is 3 to 9, preferably 4, by heating in air or an inert atmosphere (e.g., nitrogen or argon) at a temperature of about 350°C to about 400°C for 3 to 12 hours, preferably 3 to 6 hours.

[0124] The physical shape of the catalyst is not critical and may, for example, include pellets, powders or granules. Additionally, for catalysts supported on carbon, the carbon may be in the form of powder, granules, or pellets, or the like. Although not essential, catalysts may be treated with HF before use. It is thought that this converts some of the surface oxides to oxyfluorides. This pretreatment can be accomplished by placing the catalyst in a suitable container (which can be the reactor to be used to perform the reaction) and thereafter, passing HF over the dried catalyst so as to partially saturate the catalyst with HF. This is conveniently carried out by passing HF over the catalyst for a period of time (e.g., about 15 to 300 minutes) at a temperature of, for example, about 200°C to about 450°C.

[0125] The catalytic dehydrochlorination may be suitably conducted at a temperature in the range of from about 200°C to about 500°C, and is preferably conducted at a temperature in the range of from about 300°C to about 450°C. The contact time is typically from about 1 to about 450 seconds, preferably from about 10 to about 120 seconds.

[0126] The reaction pressure can be subatmospheric, atmospheric or superatmospheric. Generally, near atmospheric pressures are preferred. However, the dehydrochlorination can be beneficially run under reduced pressure (i.e. , pressures less than one atmosphere).

[0127] The catalytic dehydrochlorination can optionally be carried out in the presence of an inert gas such as nitrogen, helium, or argon. The addition of an inert gas can be used to increase the extent of dehydrochlorination. Of note are processes where the mole ratio of inert gas to hydrofluorocarbon undergoing dehydrochlorination is from about 5:1 to about 0.5:1. Nitrogen is the preferred inert gas.

[0128] In one embodiment, the dehydrochlorination of HCFC-344maf to produce a product mixture comprising HFO-1336ze, HFO-1336myf or a mixture thereof may be carried out by the pyrolysis of HCFC-344maf.

[0129] Pyrolysis, as the term is used herein, means chemical change produced by heating in the absence of catalyst. Pyrolysis reactors generally comprise three zones: a) a preheat zone, in which reactants are brought close to the reaction temperature; b) a reaction zone, in which reactants reach reaction temperature and are at least partially pyrolyzed, and products and any byproducts form; c) a quench zone, in which the stream exiting the reaction zone is cooled to stop the pyrolysis reaction. Laboratory-scale reactors have a reaction zone, but the preheating and quenching zones may be omitted.

[0130] The reactor for carrying out the pyrolysis may be of any shape consistent with the process but is preferably a cylindrical tube, either straight or coiled. Although not critical, such reactors typically have an inner diameter of from about 1.3 to about 5.1 cm (about 0.5 to about 2 inches). Heat is applied to the outside of the tube, the chemical reaction taking place on the inside of the tube. The reactor and its associated feed lines, effluent lines and associated units should be constructed, at least as regards the surfaces exposed to the reactants and products, of materials resistant to hydrogen fluoride. Typical materials of construction include stainless steels, in particular of the austenitic type, the well-known high nickel alloys, such as nickel-copper alloys commercially available from Special Metals Corp. (New Hartford, New York) under the trademark Monel®, nickel-based alloys commercially available from Haynes International (Kokomo, Indiana) under the trademark Hastelloy® (hereinafter referred to as “Hastelloy®”)and nickel-chromium alloys commercially available from Special Metals Corp, under the trademark Inconel®, and copper-clad steel.

[0131] Where the reactor is exposed to high temperature the reactor may be constructed of more than one material. For example, the outer surface layer of the reactor should be chosen for ability to maintain structural integrity and resist corrosion at the pyrolysis temperature, the inner surface layer of the reactor should be chosen of materials resistant to attack by, that is, inert to, the reactant and products. In the case of the present process, the product hydrogen fluoride is corrosive to certain materials. Thus, the reactor may be constructed of an outer material chosen for physical strength at high temperature and an inner material chosen for resistance to corrosion by the reactants and products under the temperature of the pyrolysis.

[0132] In one embodiment, the reactor outer surface layer is resistant to oxidation or other corrosion and maintains sufficient strength at the reaction temperatures to keep the reaction vessel from failing of distorting. In one embodiment, this layer is a nickel, iron, chromium alloy sold by Special Metals Corp. (New Hartford, New York) under the trademark Inconel®. In another embodiment, this layer is another nickel, iron, chromium alloy sold by Special Metals Corp, under the trademark Inconel® 600.

[0133] The pyrolysis of HCFC-344maf to a product mixture comprising HFO- 1336ze, HFO-1336myf or a mixture thereof is carried out in the absence of catalyst in a substantially empty reactor. By absence of catalyst is meant that no material or treatment is added to the pyrolysis reactor that increases the reaction rate by reducing the activation energy of the pyrolysis process. It is understood that although surfaces that are unavoidably present in any containment vessel, such as a pyrolysis reactor, may have incidental catalytic or anticatalytic effects on the pyrolysis process, the effect makes an insignificant contribution, if any, to the pyrolysis rate. More specifically, absence of catalyst means absence of conventional catalysts in a particulate, pellet, fibrous or supported form that are useful in promoting the elimination of hydrogen fluoride from a hydrofluorocarbon (i.e. , dehydrochlorination). Examples of such dehydrochlorination catalysts include: fluorided alumina, aluminum fluoride, chromium oxide, optionally containing other metals, metal oxides or metal halides; chromium fluoride, and activated carbon, optionally containing other metals, metal oxides or metal halides, and others as listed previously herein.

[0134] In one embodiment, substantially empty reactors useful for carrying out the dehydrochlorination are tubes comprising the aforementioned materials of construction. Substantially empty reactors include those wherein the flow of gases through the reactor is partially obstructed to cause back-mixing, i.e. , turbulence, and thereby promote mixing of gases and good heat transfer. This partial obstruction can be conveniently obtained by placing packing within the interior of the reactor, filling its cross-section or by using perforated baffles. The reactor packing can be particulate or fibrillar, preferably in cartridge disposition for ease of insertion and removal, has an open structure like that of Raschig rings (ceramic or metal pieces of tube that are approximately equal in length and diameter) or other packings with a high free volume, to avoid the accumulation of coke and to minimize pressure drop, and permits the free flow of gas. Preferably the exterior surface of such reactor packing comprises materials identical to those of the reactor inner surface layer; materials that do not catalyze dehydrochlorination of hydrofluorocarbons and are resistant to hydrogen fluoride. The free volume of the reaction zone is at least about 80%, preferably at least about 90%, and more preferably about 95%. The free volume is the volume of the reaction zone minus the volume of the material that makes up the reactor packing.

[0135] In this embodiment, 343maf or 344maf can be converted to a mixture comprising 1336ze and 1336yf.

[0136] In one embodiment, the residence time of gases in the reaction zone is from about 0.5 to about 60 seconds. In another embodiment, the residence time is from about 2 seconds to about 20 seconds.

[0137] In one embodiment, the pyrolysis can be conducted in the presence of one or more unreactive diluent gases, that is diluent gases that do not react under the pyrolysis conditions. Such unreactive diluent gases include the inert gases nitrogen, argon, and helium. Fluorocarbons that are stable under the pyrolysis conditions, for example, trifluoromethane and perfluorocarbons, may also be used as unreactive diluent gases. Of note are processes where the mole ratio of inert gas to HCFC- 344maf fed to the pyrolysis reactor is from about 5:1 to 1 :1. Nitrogen is a preferred inert gas because of its comparatively low cost.

[0138] In one embodiment, the pyrolysis reaction is conducted at subatmospheric total pressure. In another embodiment, the pyrolysis reaction can be beneficially run under reduced total pressure (i.e. , total pressure less than one atmosphere). In another embodiment, the pyrolysis reaction is carried out at or near atmospheric total pressure.

[0139] In one embodiment, the dehydrochlorination of HCFC-344maf is accomplished using an aqueous alkaline solution. In one embodiment, the reaction is carried out in the presence of a non-aqueous solvent in which the HCFC-344maf (incorrect structure! CF3CCI2CH2CHCIF) is at least partially miscible. In another embodiment, the reaction is carried out with no non-aqueous solvent. In another embodiment, the reaction is carried out in the presence of a phase transfer catalyst. In yet another embodiment, the reaction is carried out with no phase transfer catalyst.

[0140] In one embodiment, the base in the aqueous alkaline solution is selected from the group consisting of hydroxide, oxide, carbonate, or phosphate salts of alkali metals, alkaline earth metals, and mixtures thereof. In one embodiment, bases which may be used include without limitation lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium carbonate, sodium phosphate, potassium phosphate, or the like and mixtures thereof.

[0141] As used herein, the aqueous alkaline solution is a liquid (whether a solution, dispersion, emulsion, or suspension and the like) that is primarily an aqueous liquid having a pH of over 7. In some embodiments the basic aqueous solution has a pH of over 8. In some embodiments, the basic aqueous solution has a pH of over 10. In some embodiments, the basic aqueous solution has a pH of IQ- 13. In some embodiments, the basic aqueous solution contains small amounts of organic liquids which may be miscible or immiscible with water. In some embodiments, the liquid medium in the aqueous alkaline solution is at least 90% water. In one embodiment the water is tap water; in other embodiments the water is deionized or distilled water.

[0142] In one embodiment, it may desirable (e.g., to increase reaction rate) to employ a ratio of base to HCFC-344maf of greater than one. In some embodiments,large excesses of base (in the basic aqueous solution) are to be avoided as further reaction of the desired hydrochlorofluoroolefin may occur. Thus, in some embodiments, it may be necessary to employ an amount of base (in the basic aqueous solution) that is slightly below the stoichiometric amount so as to minimize secondary reactions. Thus, in one embodiment, the molar ratio of base (in the basic aqueous solution) to HCFC-344maf is from about 0.75:1 to about 10:1. In another embodiment, the molar ratio of base (in the basic aqueous solution) to HCFC- 344maf is from about 0.9:1 to about 5:1. In yet another embodiment, the molar ratio of base to HCFC-344maf is from about 1 :1 to about 4:1.

[0143] In certain embodiments, the non-aqueous solvent is selected from the group consisting of alkyl and aryl nitriles, alkyl and aryl ethers, alcohols, amides, ketones, sulfoxides, phosphate esters and mixtures thereof.

[0144] In one embodiment, a solid base (e.g., KOH, NaOH, LiOH or mixtures thereof) is dissolved in water, or alternatively, a concentrated solution of a base (e.g., 50% by weight aqueous potassium hydroxide) is diluted to the desired concentration with water. The non-aqueous solvent for the method is then added with agitation under otherwise ambient conditions. In one embodiment, a solvent for the reaction can be a nitrile, ether, alcohol, amide, ketone, sulfoxide, phosphate ester, or mixtures thereof. In another embodiment, the solvent is selected from the group consisting of acetonitrile, propionitrile, butyronitrile, methyl glutaronitrile, adiponitrile, benzonitrile, ethylene carbonate, propylene carbonate, ethanol, methanol, propanol, isopropanol, butanol, methyl ethyl ketone, methyl isoamyl ketone, diisobutyl ketone, anisole, 2- methyltetrahydrofuran, tetra hydrofuran, dioxane, diglyme, triglyme, tetraglyme, N,N- dimethyl formamide, N,N-dimethyl acetamide, N-methyl pyrrolidinone, sulfolane, dimethyl sulfoxide, perfluoro-N-methyl morpholine, perfluorotetrahydrofuran, and mixtures thereof. Preferred solvents include acetonitrile, adiponitrile, 2-methyl tetrahydrofuran, tetrahydrofuran, dioxane, diglyme, and tetraglyme.

[0145] As used herein, phase transfer catalyst is intended to mean a substance that facilitates the transfer of ionic compounds into an organic phase from an aqueous phase or from a solid phase. The phase transfer catalyst facilitates the reaction of these dissimilar and incompatible components. While various phase transfer catalysts may function in different ways, their mechanism of action is notdeterminative of their utility in the reaction provided that the phase transfer catalyst facilitates the dehydrochlorination reaction.

[0146] The phase transfer catalyst is selected from the group consisting of crown ethers, onium salts, cryptands, polyalkylene glycols, and mixture thereof.

[0147] In one embodiment, the base need not be highly soluble in the solvent. An amount of a phase transfer catalyst may be added to the solvent for the reaction in quantities that improve the solubility of the base therein. In one embodiment, the amount of phase transfer catalyst used will be from about 0.001 to about 10 mole percent based on the total amount of base present. In another embodiment, the amount of phase transfer catalyst used will be from about 0.01 to about 5 mole percent based on the total amount of base present. In yet another embodiment, the amount of phase transfer catalyst used will be from about 0.05 to about 5 mole percent based on the total amount of base present. In one embodiment of the invention, an aqueous or inorganic phase is present as a consequence of the base and an organic phase is present.

[0148] In some embodiments, the phase transfer catalyst can be ionic or neutral. In one embodiment, the phase transfer catalyst is selected from the group consisting of crown ethers, onium salts, cryptands and polyalkylene glycols and mixtures and derivatives thereof.

[0149] Crown ethers are cyclic molecules in which ether groups are connected by dimethylene linkages; the compounds form a molecular structure that is believed to be capable of "receiving" or holding the alkali metal ion of the hydroxide and to thereby facilitate the reaction. In some embodiments, it is preferred to match certain crown ether phase transfer catalysts with certain bases used in the basic aqueous solutions. In one embodiment, crown ethers include 18-crown-6, is used in combination with potassium hydroxide basic aqueous solution; 15-crown-5, is used in combination with sodium hydroxide basic aqueous solution; 12-crown-4, is used in combination with lithium hydroxide basic aqueous solution. Derivatives of the above crown ethers are also useful, e.g., dibenzo-18-crown-6, dicyclohexano-18-crown-6, and dibenzo-24-crown-8 as well as 12-crown-4. Other polyethers particularly useful in combination with basic aqueous solution made from alkali metal compounds, and especially for lithium, are described in U.S. Patent No. 4,560,759 the disclosure ofwhich is herein incorporated by reference. Other compounds analogous to the crown ethers and useful for the same purpose are compounds which differ by the replacement of one or more of the oxygen atoms by other kinds of donor atoms, particularly N or S.

[0150] In some embodiments, onium salts include quaternary phosphonium salts and quaternary ammonium salts that may be used as the phase transfer catalyst in the process of the present invention; such compounds can be represented by the following formulas: R1R2R3R4P(+)X’(')and R1R2R3R4N(+)X’(_).wherein each of R1, R2, R3and R4, which may be the same or different, is an alkyl group, an aryl group or an aralkyl group, and X' is selected from the group consisting of F, Cl, Br, I, OH, CO3, HCO3, SO4, HSO4, H2PO4, HPO4 and PO4. Specific examples of these compounds include tetramethylammonium chloride, tetramethylammonium bromide, benzyltriethylammonium chloride, methyltrioctylammonium chloride (a quaternary ammonium salt sold under the trademark Aliquat™ 336), tetra-n-butylammonium chloride, tetra-n-butylammonium bromide, tetra-n-butylammonium hydrogen sulfate, tetra-n-butylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium chloride, triphenylmethylphosphonium bromide and triphenylmethylphosphonium chloride. In one embodiment, benzyltriethylammonium chloride is used under strongly basic conditions. Other useful compounds within this class of compounds include those exhibiting high temperature stabilities (e.g., up to about 200°C.) including 4-dialkylaminopyridinium salts, tetraphenylarsonium chloride, bis[tris(dimethylamino)phosphine]iminium chloride, and tetratris[tris(dimethylamino)phosphinimino]phosphonium chloride; the latter two compounds are also reported to be stable in the presence of hot, concentrated sodium hydroxide and, therefore, can be particularly useful.

[0151] In other embodiments, cryptands are another class of compounds useful in the reaction as phase transfer catalysts. These are three-dimensional polymacrocyclic chelating agents that are formed by joining bridgehead structures with chains that contain properly spaced donor atoms. For example, bicyclic molecules that result from joining nitrogen bridgeheads with chains of (-OCH2CH2-) groups as in 2.2.2-cryptand (4,7,13,16,21 ,24-hexaoxa-1 ,10- diazabicyclo(8.8.8)hexacosane; available under the brand name Cryptand™ 222 and the trademark Kryptofix® 222). The donor atoms of the bridges may all be O, N, or S,or the compounds may be mixed donor macrocycles in which the bridge strands contain combinations of such donor atoms.

[0152] In some embodiments, polyalkylene glycol ethers are useful as phase transfer catalysts. In some embodiments, the polyalkylene glycol ethers can be represented by the formula: R6O (R5O)t R7, wherein R5is an alkylene group containing two or more carbon atoms, each of R6and R7, which may be the same or different, is a hydrogen atom, an alkyl group, an aryl group or, an aralkyl group, and t is an integer of at least 2. Such compounds include, for example glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, diisopropylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol and tetramethylene glycol, and monoalkyl ethers such as monomethyl, monoethyl, monopropyl and monobutyl ethers of such glycols, dialkyl ethers such as tetraethylene glycol dimethyl ether and pentaethylene glycol dimethyl ether, phenyl ethers, benzyl ethers, and polyalkylene glycols such as polyethylene glycol (average molecular weight about 300) dimethyl ether, polyethylene glycol (average molecular weight about 300) dibutyl ether, and polyethylene glycol (average molecular weight about 400) dimethyl ether, and ethoxylated furfurylalcohol. Among them, compounds wherein both R6and R7are alkyl groups, aryl groups or aralkyl groups are preferred.

[0153] Combinations and mixtures of the above-described phase transfer catalysts from within one of the groups may also be useful as well as combinations or mixtures of two or more phase transfer catalysts selected from more than one group, for example, crown ethers and oniums, or from more than two of the groups, e.g., quaternary phosphonium salts and quaternary ammonium salts, and crown ethers and polyalkylene glycol ethers.

[0154] In one embodiment, the dehydrochlorination of HCFC-343maf is conducted within a temperature range at which the HCFC-343maf will dehydrochlorinate. In one embodiment, such temperatures can be from about 5°C to about 150°C. In another embodiment, the reaction is conducted in the range of from about 10°C to about 110°C. In yet another embodiment, the reaction is carried out in the range of from about 15°C to about 90°C. The reaction pressure is not critical. The reaction can be conducted at atmospheric pressure, super-atmosphericpressure, or under reduced pressure. In one embodiment, the reaction is carried out at atmospheric pressure.

[0155] The dehydrochlorination reaction of this invention may be carried out in either a batch or a continuous mode.

[0156] The composition produced from the fluorination process or the dehydrochlorination process comprises, consists essentially of, or consists of 1-99 mol% HFO-1333maz and 1-99 mol% HFO-1333mxz.

[0157] Also disclosed herein, in one embodiment, is a composition comprising HFO-1336myf produced from HCFC-343maf by either of the above-described reactions (i.e. , fluorination of HCFC-343maf, or dehydrochlorination of HCFC-343maf to produce a reaction mixture comprising HFO-1333maz and HFO-1333mxz followed by fluorination of the reaction mixture). In certain embodiments, HFO-1336myf is the E- isomer, Z- isomer or a combination thereof.

[0158] Also disclosed herein, in one embodiment, is a composition comprising HFO-1336ze and HFO-1336myf produced from HCFC-343maf or from HCFC- 344maf by any of the above-described reactions. In certain embodiments, HFO- 1336ze is the E- isomer, Z- isomer or a combination thereof. In certain embodiments, HFO-1336myf is the E- isomer, Z- isomer or a combination thereof. The composition comprises, consists essentially of, or consists of about 1 mol% to about 99 mol% HFO-1336ze and about 1 mol% to about 99 mol% HFO-1336myf.INTEGRATED PROCESSES

[0159] As illustrated in Fig. 1, in some embodiments, the present invention provides an integrated process for producing HFO-153-10mczz from HCFC-343maf. In one embodiment, the integrated process comprises fluorination by reaction of HCFC-343maf (CF3CCI2CH2CHCI2) with a fluorinating agent in the presence of a catalyst to make a composition comprising HFO-1336ze (CHF-CHCF2CF3, 1,3,3,4,4,4-hexafluoro-l-butene) and HFO-1336myf (CF3CF=CHCHF2, 1 ,1,1,2,4,4hexafluoro-2-butene) (Step ia), and reaction of either HFO-1336myf or the composition comprising HFO-1336ze and HFO-1336myf with TFE in the presence of an acid catalyst to produce HFO-153-10mczz (CF3CF2CH=CHCF2CF3, 1 ,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene) (Step iia).

[0160] In an alternative, HCFC-343maf is dehydrochlorinated to produce a reaction mixture comprising HFO-1333maz and HFO1333mxz (Step iia’), followed by fluorination of the reaction mixture comprising HFO-1333maz and HFO-1333mxz to produce the composition comprising HFO-1336ze and HFO-1336myf (Step iia”), and reaction of either HFO-1336myf or the composition comprising HFO-1336ze and HFO-1336myf with CF2=CF2 (TFE) in the presence of an acid catalyst to produce HFO-153-10mczz (Step iii).

[0161] In an alternative embodiment, the present invention provides an integrated process for producing HFO-153-10mczz from HCFC-344maf. In this alternative embodiment, the alternative integrated process comprises dehydrochlorination of HCFC-344maf (CF3CCI2CH2CHCIF) to make a product mixture comprising HFO- 1336ze (CHF-CHCF2CF3) and HFO-1336myf (CF3CF=CHCHF2), and reaction of either HFO-1336myf or HFO-1336ze or a mixture of HFO-1336ze and HFO-1336myf with TFE in the presence of an acid catalyst to produce HFO-153-10mczz (CF3CF2CH=CHCF2CF3, 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene). These steps are illustrated in steps iib, iib’, and iii.

[0162] In some embodiments, the HCFC-343maf or the HCFC-344maf is produced by an insertion reaction of vinyl chloride (CH2=CHCI, VC) or vinyl fluoride (CH2=CHF, VF) and CFC-113a (CF3CCI3) in the presence of a metal-containing compound and an organic initiator. A detailed example and explanation of a metal catalyzed olefin insertion process to produce HCFC-343maf may be found in International Application Publication No. WO 2018 / 022500 A1 and / or International Application Publication No. WO 2012 / 067865 A1 , the disclosures of which are incorporated herein by reference in their entireties. International Application Publication No. WO 2018 / 022500 A1 also discloses metal catalyzed olefin insertion process to produce HCFC-344maf from vinyl fluoride.

[0163] Preferably, in one embodiment, the insertion process comprises the insertion of vinyl chloride or vinyl fluoride into 1,1,1-trichloro-2,2,2-trifluoroethane (CFC-113a, CF3CCI3) in the presence of a metal-containing compound that comprises, consists essentially of, or consists of metallic iron and an organic initiator, to produce a product comprising HCFC-343maf (CF3CCI2CH2CHCI2) or HCFC- 344maf (CF3CCI2CH2CHCIF), preferably for use as a reactive intermediate for thesubsequent reaction (i.e., fluorination of HCFC-343maf to produce a product comprising HFO-1336ze,HFO-1336myf or a mixture thereof, or dehydrochlorination of HCFC-343maf to produce a reaction mixture comprising HFO-1333maz and HFO- 1333mxz followed by fluorination of the reaction mixture to produce a product comprising HFO-1336ze,HFO-1336myf or a mixture thereof, or dehydrochlorination of HCFC-344maf to produce a product comprising HFO-1336ze,HFO-1336myf or a mixture thereof.

[0164] The insertion reaction involving 1 ,1 ,1-trichloro-2,2,2-trifluoroethane (CFC- 113a) and vinyl chloride or vinyl fluoride is preferably based on a stoichiometry of 1 mole of CFC-113a per mole of vinyl chloride or vinyl fluoride. In practice, however, an excess of CFC-113a may be used as desired. Typically, the mole ratio of CFC113a to vinyl chloride or vinyl fluoride is about 1 :1 to about 20:1.

[0165] In one embodiment, the olefin insertion process utilizes a metal-containing compound comprising, consisting essentially of or consisting of an iron-containing compound, preferably iron, and an organic initiator, preferably, a phosphorous- containing compound, preferably phosphine and more preferably triphenyl phosphine, for the vinyl chloride or vinyl fluoride insertion of 1 , 1 , 1-trichloro-2,2,2- trifluoroethane (CFC113a) with a high rate of conversion and selectivity. In one embodiment, the catalyst is unsupported.

[0166] In some embodiments, a ratio of the number of moles of CFC-113a reactant to moles of vinyl chloride or vinyl fluoride is from about 3:1 to 1 :1. In another embodiment, the molar ratio of CFC-113a reactant to moles of vinyl chloride or vinyl fluoride is from about 2.25:1 to 1 :1. In another embodiment, the molar ratio of CFC113a reactant to moles of vinyl chloride or vinyl fluoride is from about 2:1 to 1 :1.

[0167] In one embodiment, a ratio of the number of moles of iron-containing compound to the number of moles of vinyl chloride or vinyl fluoride is from about 0.01 :1 to 0.1 :1. In another embodiment, the molar ratio of iron-containing compound to vinyl chloride or vinyl fluoride is from about 0.03:1 to 0.06:1. In another embodiment, the ratio of iron-containing compound to vinyl chloride or vinyl fluoride is from about 0.07:1 to 0.1 :1. For example, the molar ratio of iron-containing compound, such as iron powder, to vinyl chloride may be from 0.03-0.06 moles of iron-containing compound to every one mole of vinyl chloride or vinyl fluoride, whilein another example, the molar ratio is from 0.07-0.1 moles of iron-containing compound to every mole of vinyl chloride or vinyl fluoride. In yet another example, a ratio of iron-containing compound to vinyl chloride or vinyl fluoride may be 0.03:1 to 0.05:1 , while in a further example, the ratio of iron-containing compound to vinyl chloride or vinyl fluoride may be 0.08: 1 to 0.1 : 1.

[0168] In one aspect of the disclosure, a number of moles of organic initiator may be measured in relation to a number of moles of vinyl chloride or vinyl fluoride present in the reaction system (step (i). For example, in one embodiment, a molar ratio of organic initiator to vinyl chloride or vinyl fluoride may be from about 0.01:1 to 0.04:1. In another embodiment, the molar ratio of organic initiator to vinyl chloride or vinyl fluoride may be from about 0.02:1 to 0.06:1. For example, the molar ratio of organic initiator to vinyl chloride or vinyl fluoride may be 0.02:1 to 0.03:1, while in another example, the molar ratio of organic initiator to vinyl chloride or vinyl fluoride may be 0.04:1 to 0.05:1.

[0169] In one embodiment, the organic initiator is a phosphorus-containing compound selected from the group consisting of phosphine oxide, phosphine, phosphite, phosphate or combinations of two or more thereof. In one aspect of the invention, the organic initiator is a phosphorus-containing compound, which is a phosphine. In one aspect of the invention, the phosphine is triphenylphosphine. In one aspect of the invention, the molar ratio of triphenyl phosphine to vinyl chloride or vinyl fluoride is 0.02:1 to 0.03:1 , while in another example, the molar ratio of triphenyl phosphine to vinyl chloride or vinyl fluoride is 0.04: 1 to 0.05: 1.

[0170] In one embodiment, the insertion reaction may be carried out at an elevated temperature. In another embodiment, the insertion reaction may be carried out at a temperature between about 50°C and 250°C, between about 100°C and 200°C, between about 120°C and 180°C, and in some cases between about 130°C and 170°C.

[0171] In one embodiment, the insertion reaction may be carried out at a pressure of about 1 atm to about 50 atm.

[0172] In one embodiment, the insertion reaction may be performed by introducing the CFC-113a and vinyl chloride or vinyl fluoride starting materials and the metalcontaining compound and organic initiator into a reaction vessel or zone, and thenheating the mixture with agitation. In one embodiment, the insertion reaction is carried out in an environment which is devoid of oxygen.

[0173] In some embodiments, the insertion process is performed in the liquid phase.

[0174] In some embodiments, the insertion reaction may be conducted in a reactor or reaction zone which is operating in batch, semi-batch, semi-continuous, or continuous modes, to produce a reaction mixture comprising HCFC-343maf or HCFC-344maf. An effluent stream of the reactor or reaction zone comprises the reaction mixture comprising HCFC-343maf or HCFC-344maf.

[0175] For the formation of HCFC-343maf, the reactor effluent may further contain butyl chloride, organic initiator, such as triphenylphosphine, tributyl phosphate and iron salts, as well as the reaction product HCFC-343maf. It is also possible that some of the starting materials will also be in the effluent stream. Any byproducts, additional components of the reaction mixture aside from HCFC-343maf, and any of the unreacted starting material may be, optionally purified and recycled for further reaction.

[0176] For the formation of HCFC-344maf, the reactor effluent may further contain butyl chloride, organic initiator and iron salts, as well as the reaction product HCFC- 344maf. It is also possible that some of the starting materials will also be in the effluent stream. Any byproducts, additional components of the reaction mixture aside from HCFC-344maf, and any of the unreacted starting material may be, optionally purified and recycled for further reaction.

[0177] In one embodiment, the CFC-113a and vinyl chloride or vinyl fluoride starting materials may be pre-mixed with each other, and optionally also with or without the catalyst, and then introduced into the reactor. In one embodiment, only one of the CFC-113a and vinyl chloride or vinyl fluoride starting materials may be pre-mixed with the catalyst and then introduced into the reactor. In one embodiment, the premixing is performed at the same temperature and pressure as the insertion reaction.

[0178] In some embodiments, the aforementioned pre-mixing is performed in the liquid phase. In some embodiments, the pre-mixed mixture is a liquid.

[0179] In certain embodiments, the iron-containing compound of the catalyst may be from any source (including a combination of sources) of an iron component and may be, for example, iron powder, iron wire, iron screen or iron turnings.

[0180] In some embodiments, the organic initiator may be a phosphorus- containing ligand, such as an alkylphosphine or arylphosphine or an alkyl or aryl phosphate, including but not limited to triphenyl phosphine, tributyl phosphine, tributylphosphate and the like. In one embodiment, the organic initiator comprises, consists essentially of or consists of triphenyl phosphine. In one embodiment, the organic initiator comprises, consists essentially of or consists of tributyl phosphate.

[0181] The insertion process of the insertion reaction produces an effluent stream comprising a reaction product or mixture comprising HCFC-343maf or HCFC344maf. The insertion process selectively produces HCFC-343maf or HCFC-344maf at a conversion rate of about 10% to about 100%.

[0182] Also disclosed herein, in one embodiment, is a composition comprising the compound CF3CCI2CH2CHCI2 (HCFC-343maf) produced by the insertion of vinyl chloride into CFC-113a.

[0183] Also disclosed herein, in one embodiment, is a composition comprising the compound CF3CCI2CH2CHCIF (HCFC-344maf) produced by the insertion of vinyl fluoride into CFC-113a.

[0184] In some embodiments, the reactions described above are integrated to provide integrated processes for producing HFO-153-10mczz from vinyl chloride and CFC-113a. In one embodiment, the integrated process comprises an insertion reaction of vinyl chloride and CFC-113a in the presence of a metal-containing compound, such as an iron-containing compound, and an organic initiator, wherein the organic initiator is preferably a phosphate or a phosphine, to make HCFC- 343maf (Step ia), fluorination by reaction of HCFC-343maf with a fluorinating agent such as HF, in the presence of a catalyst to make a product comprising HFO- 1336ze, HFO-1336myf or a mixture thereof (Step iia), and reaction of either HFO- 1336myf or HFO-1336ze or a mixture of HFO-1336ze and HFO-1336myf with TFE in the presence of an acid catalyst, such as SbFs or ACF, to produce HFO-153-10mczz (Step iii). In one embodiment, the integrated process comprises an insertion reaction of vinyl chloride and CFC-113a in the presence of a metal-containingcompound and an organic initiator to make HCFC-343maf (Step ia), dehydrochlorination of HCFC-343maf to produce a reaction mixture comprising HFO-1333maz and HFO-1333mxz (Step iia’), followed by fluorination of the reaction mixture comprising HFO-1333maz and HFO-1333mxz to produce the composition comprising HFO-1336ze and HFO-1336myf (Step iia”), and reaction of either HFO- 1336myf or the composition comprising HFO-1336ze and HFO-1336myf with TFE in the presence of an acid catalyst to produce HFO-153-10mczz (Step iii). These integrated processes are reflected in the reactions shown below:

[0185] In an alternative process, Step ia is replaced by an insertion reaction of vinyl fluoride and CFC-113a in the presence of a metal-containing compound and an organic initiator, preferably a phosphine, to make HCFC-344maf (Step ib), dehydrochlorination by reaction of HCFC-344maf to make a product comprising HFO-1336ze, HFO-1336myf or a mixture thereof (Step iib), and reaction of either HFO-1336myf or HFO-1336ze or a mixture of HFO-1336ze and HFO-1336myf with TFE in the presence of an acid catalyst to produce HFO-153-10mczz (Step iii).

[0186] Also disclosed herein, in some embodiments, is a composition comprising HFO-153-10mczz produced by any of the integrated processes described herein. In certain embodiments, HFO-153-10mczz is the E isomer, Z isomer or a combination thereof.

[0187] Each of the reactions or processes of the present invention preferably comprises reactions carried out in the liquid phase. However, it will be understood by those skilled in the art that the reactions or processes could alternatively be carried out as vapor phase reactions.

[0188] In the integrated processes of embodiments of the present invention, including alternatives, each step, aside from the last step, produces one or more reactive intermediates which is / are used in subsequent steps of the integrated processes. However, it will be understood by those skilled in the art that the products of these steps may instead be utilized for other purposes, such as a refrigerant or refrigerant components or heat transfer fluids.

[0189] Each of the reactions or processes of the present invention may be conducted in a reaction zone which constitutes a portion of a reaction vessel, and which is of appropriate size for the scale for the respective reaction. In oneembodiment, each of the reactions or process of the present invention may be conducted in a reactor comprising a reaction vessel of appropriate size for the scale for the respective reaction. In one embodiment, the reaction vessel is comprised of materials which are resistant to corrosion. In one embodiment, suitable reaction vessels include those fabricated from well-known alloys, such as nickel-based alloys such as Hastelloy®, nickel-chromium alloys commercially available from Special Metals Corp, under the trademark Inconel® (hereinafter "Inconel®") or nickel-copper alloys commercially available from Special Metals Corp. (New Hartford, New York) under the trademark Monel®, or vessels having fluoropolymers linings. In another embodiment, the reaction vessel may be made of other materials of construction including stainless steels, in particular of the austenitic type, and copper-clad steel.

[0190] In one embodiment, a single reactor may be used for any of the integrated processes of the present invention, wherein the reactor comprises a plurality of serially-connected reaction zones and each step of the integrated process is carried out in a sequential manner in a respective zone. In such an embodiment, the first step is carried out in the first reaction zone of the reactor to produce the first effluent stream comprising a first reaction mixture comprising a first reactive intermediate; the first reactive intermediate is isolated and recovered from the first reaction mixture and optionally purified; the first reactive intermediate is then fed to a second reaction zone of the reactor, downstream of the first reaction zone, to produce the second effluent stream comprising a second reaction mixture of compounds comprising a second reactive intermediate; the second reactive intermediate is isolated and recovered from the second reaction mixture and optionally purified; and so forth. Additional components such as catalysts and fluorinating agents utilized for the reactions may be introduced to the appropriate zones and / or pre-mixed with the starting materials for each reaction step before introduction into the reaction zone. In one embodiment, reaction zones (e.g., first, second, third, fourth reaction zones) of the reactor may be separated from each other, for example by partitions, with flow communication between certain zones being selectively permitted or prevented by the use of valves.

[0191] In another embodiment, a single reactor may be used for any of the integrated processes of the present invention, wherein between each step of theintegrated process, the operating conditions of the reactor are adjusted to those suitable for the specific reaction step to be carried out.

[0192] In another embodiment, any of the integrated processes of the present invention is carried out in a plurality of serially-connected reactors which are in flow communication with each other. In such an embodiment, the first step is performed in a first reactor to produce the first effluent stream comprising a first reaction mixture comprising a first reactive intermediate; the first reactive intermediate is isolated and recovered from the first reaction mixture and optionally purified; the first reactive intermediate is then introduced, for example via a conduit, to a second reactor (downstream of the first reactor) to produce the second effluent stream comprising a second reaction mixture of compounds comprising a second reactive intermediate; and so forth. Additional components such as catalysts and fluorinating agents utilized for the reactions may be introduced to the appropriate reactors and / or premixed with the starting materials for each reaction step before introduction into the reactors. Flow communication between the reactors may be selectively permitted or prevented by the use of valves.

[0193] According to the embodiments of any of the integrated processes, including alternatives, each the desired products to be used as a reactive intermediate, such as HCFC-343maf, HCFC-344maf, HFO-1336ze and HFO-1336myf, may be separated and recovered from the reaction mixture by any conventional method known in the art. For example, in one embodiment, reactive intermediates may be isolated from the respective reaction mixtures via fractionation distillation, and any undesired impurities may be removed via distillation or scrubbing as needed; or the solid residues may be removed by decantation or filtration and the intermediate product may be isolated and recovered by distillation of the resulting first liquid product mixture. Additional products comprised within the reaction mixture or any additional products in the form of unreacted starting materials and / or byproducts may be recycled back to the first reaction zone or first reactor for further processing.

[0194] Certain Embodiments of the processes of the present invention is described in further detail below with reference to Figs. 2A-2D and 3A-3D.

[0195] As shown in Figs. 2A and 3A, a composition comprising HFO-1336myf or a composition comprising HFO-1336ze and HFO-1336myf is co-fed into a reactor 100through line 102, along with TFA which is fed into the reactor 100 through line 104, where the feed components contact a Lewis acid catalyst 106 and, as a result, a product mixture comprising HFO-153-10mczz (CF3CF2CH=CHCF2CF3, 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene) as the main or major component is discharged through effluent line 108. The reaction mixture within effluent line 108 is routed for isolation of the desired product, namely HFO-153-10mczz, for example via fractionation distillation. Further, the isolated HFO-153-10mczz may be routed to treatment devices (not shown) for purification. For example, any undesired impurities, such as excess acids, may be removed via distillation or scrubbing as needed. Any byproducts and other components of the reaction mixture of effluent line 108 may be, optionally purified and then, recycled for further reaction.

[0196] The HFO-153-10mczz recovered from effluent line 108 includes both the Z and E isomers. E-HFO-153-mczz is the primary product of the integrated process of the present invention. Thus, optionally, all or some of the Z-HFO-153-mczz may be isomerized to E-HFO-153-10mczz.

[0197] Referring to Fig. 2B, in one embodiment, the composition comprising HFO- 1336myf or comprising HFO-1336ze and HFO-1336myf is produced in a reactor 200. HCFC-343maf and a fluorinating agent are fed into the reactor 200 via lines 202 and 204, and the HCFC-343maf is fluorinated in the reactor 200 to make a product mixture comprising HFO-1336ze (CHF DHCF2CF3, 1 ,3,3,4,4,4-hexafluoro-1-butene) and HFO-1336myf (CF3CF=CHCHF2, 1 ,1 ,1 ,2,4,4-hexafluoro-2-butene), which is discharged through effluent line 206.

[0198] Referring to Fig. 3B, in one embodiment, the composition comprising HFO- 1336myf or comprising HFO-1336ze and HFO-1336myf is produced in a series of reactors 250, 260. HCFC-343maf is introduced into the first reactor 250 via line 252 and is dehydrochlorinated therein to make an intermediate product mixture comprising HFO-1333maz and HFO-1333mxz. The intermediate product mixture comprising HFO-1333maz and HFO-1333mxz is withdrawn from the first reactor 250 via a first effluent line 254, which is then routed to the second reactor 260. A fluorinating agent is also provided to the second reactor 260 via line 262. The HFO- 1333maz and HFO-1333mxz are fluorinated in the second reactor 260 to make a product mixture comprising HFO-1336ze (CHF=CHCF2CF3, 1,3,3,4,4,4-hexafluorol-butene) and HFO-1336myf (CF3CF=CHCHF2, 1,1,1,2,4,4-hexafluoro-2-butene), which is discharged from the second reactor 260 through a second effluent line 264.

[0199] The reaction mixture within effluent lines 206, 264 is routed for isolation of the desired product, namely HFO-1336myf or a mixture comprising HFO-1336ze and HFO-1336myf, for example via fractionation distillation. Further, the isolated products may be routed to treatment devices (not shown) for purification. For example, any undesired impurities, such as excess acids, may be removed via adsorption, distillation or scrubbing as needed. Any byproducts and other components of the reaction mixture of effluent lines 206, 264 may be, optionally purified and then, recycled for further reaction. In one embodiment, the isolated product is a composition comprising 1-99 mol% HFO-1336ze and 1-99 mol% HFO1336myf.

[0200] Referring to Figs. 2C and 3C, in one embodiment, the HCFC-343maf feed material for producing the HFO-1336ze and HFO-1336myf is produced in a reactor 300. Vinyl chloride and CFC-113a are introduced into the reactor 300 via lines 302, 304 and are contacted with an iron metal and triphenyl phosphine 306 to make a product mixture comprising HCFC-343maf (CF3CCI2CH2CHCI2). The product mixture is withdrawn from reactor 300 via an effluent line 308.

[0201] The reaction mixture within effluent line 308 is routed for isolation of the desired product, namely HCFC-343maf, for example via fractionation distillation. Further, the isolated product may be routed to treatment devices (not shown) for purification. For example, any undesired impurities, such as excess acids, may be removed via adsorption, distillation or scrubbing as needed. Any byproducts and other components of the reaction mixture of effluent line 308 may be, optionally purified and then, recycled for further reaction.

[0202] As shown in Figs. 2D and 3D, the above-discussed processes and systems of Figs. 2A-2C and Figs. 3A-3C may be integrated together in integrated systems and processes to form HFO-153-10mczz.

[0203] As shown in Figs. 2D and 3D, the HCFC-343maf produced in reactor 300 is an intermediate product withdrawn from the reactor 300 via effluent line 308, and is utilized as the starting material for subsequent steps of the integrated process to produce a composition comprising HFO-1336ze and HFO-1336myf. Moreparticularly, the HCFC-343maf produced by the insertion process in reactor 300 is a reactive intermediate which, after undergoing any necessary separation and / or purification processes, is provided from the reactor 300 (e.g., a first reactor or first reaction zone of the integrated processes) to the reactor 200 (Fig. 2D) via line 308 along with a fluorinating agent via line 204, or to the reactor 250 (Fig. 3D). A composition comprising HFO-1336ze and HFO-1336myf is produced in reactor 200 or reactor 260, as described above, and is a reactive intermediate which, after undergoing any necessary separation and / or purification processes, is provided from the reactor 200 to the reactor 100 via line 206 along with TFE via line 104, or from the reactor series 250, 260 (e.g., a second reactor or second reaction zone of the integrated processes) to the reactor 100 via line 264 along with TFE via line 104, to produce a composition comprising HFO-153-10mczz in reactor 100. The composition comprising HFO-153-10mczz is then withdrawn from the reactor 100 via line 108.

[0204] In some embodiments, the present application provides a process of preparing HFO-153-10mczz (CF3CF2CH=CHCF2CF3, 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro- 3-hexene). The process comprises reacting HFO-1336myf with tetrafluoroethylene in the presence of a Lewis acid catalyst to produce HFO-153-10mczz (CF3CF2CH=CHCF2CF3, 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene).

[0205] In some embodiments, the present application provides a process of preparing HFO-153-10mczz (CF3CF2CH=CHCF2CF3, 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro- 3-hexene). The process comprises reacting HFO-1336ze and HFO-1336myf with tetrafluoroethylene in the presence of a Lewis acid catalyst to produce HFO-153- 10mczz (CF3CF2CH=CHCF2CF3, 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene).

[0206] In some embodiments, the present application provides a process of preparing a composition comprising HFO-1336ze (CHF=CHCF2CF3, 1 ,3,3, ,4, 4hexafluoro-1-butene), HFO-1336myf (CF3CF=CHCHF2, 1 , 1 ,1 , 2,4,4- hexafluoro-2butene) or a mixture thereof The process comprises fluorinating HCFC- 343maf with a fluorinating agent in the presence of a catalyst to make the composition comprising HFO-1336ze (CHF=CHCF2CF3, 1 ,3,3,4,4,4-hexafluoro-l- butene), HFO-1336myf (CF3CF=CHCHF2, 1 ,1 ,1 ,2,4,4-hexafluoro-2-butene) or a mixture thereof.

[0207] In some embodiments, the present application provides a process of preparing a composition comprising HFO-1336ze (CHF—CHCFsCFs,1 ,3, 3,4,4, 4hexafluoro-1-butene), HFO-1336myf (CF3CF=CHCHF2, 1 , 1 ,1 , 2,4,4- hexafluoro-2butene) or a mixture thereof. The process comprises dehydrochlorinating HCFC-344maf to make the composition comprising HFO- 1336ze (CHF-CHCF2CF3, 1.3, 3, 4,4,4-hexafluoro-l -butene), HFO-1336myf(CF3CF=CHCHF2, 1 ,1 ,1 ,2,4,4hexafluoro-2-butene) or a mixture thereof.

[0208] In some embodiments, the present application provides a process of preparing HFO-1336ze (CHF-CHCF2CF3. 1,3.3,4,4,4-hexafluoro-1-butene), HFO- 1336myf (CF3CF=CHCHF2, 1 ,1 ,1 ,2,4,4-hexafluoro-2-butene) or a mixture thereof. The process comprises (i) dehydrochlorinating HCFC-343maf in the presence of a catalyst to make HFO-1333maz and HFO-1333mxz, and (ii) fluorinating the HFO- 1333maz and HFO-1333mxz with a fluorinating agent in the presence of a catalyst to make the composition comprising HFO-1336ze (CHF^CHCFsCFs,1 ,3,3,4,4,4hexafluoro-1-butene), HFO-1336myf (CF3CF=CHCHF2, 1 ,1 ,1 ,2,4,4- hexafluoro-2butene) or a mixture thereof.

[0209] In some embodiments, the present application provides a process of preparing HFO-153-10mczz (CF3CF2CH=CHCF2CF3, 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro- 3-hexene). The process comprises:(i) fluorinating HCFC-343maf with a fluorinating agent in the presence of a catalyst to make a composition comprising HFO-1336ze (CHF^CHCFiCFs,1.3.3. .4.4-hexafluoro-l -butene), HFO-1336myf (CF3CF=CHCHF2,1.1.1.2.4.4-hexafluoro-2-butene) or a mixture thereof; and(ii) reacting the composition comprising HFO-1336ze, HFO-1336myf or a mixture thereof with tetrafluoroethylene in the presence of a Lewis acid catalyst to produce HFO-153-10mczz (CF3CF2CH=CHCF2CF3,1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene).

[0210] In some embodiments, the present application provides a process of preparing HFO-153-10mczz (CF3CF2CH=CHCF2CF3, 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro- 3-hexene). The process comprises:(i) dehydrochlorinating HCFC-344maf to make a composition comprising HFO- 1336ze (CHF=CHCF2CF3i1 , 3,3,4, ,4-hexafluoro-1-butene), HFO-1336myf (CF3CF=CHCHF2, 1 ,1 ,1 ,2,4,4-hexafluoro-2-butene) or a mixture thereof; and(ii) reacting the composition comprising HFO-1336ze, HFO-1336myf or a mixture thereof with tetrafluoroethylene in the presence of a Lewis acid catalyst to produce HFO-153-10mczz (CF3CF2CH=CHCF2CF3,1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene).

[0211] In some embodiments, the present application provides a process of preparing HFO-153-10mczz (CF3CF2CH=CHCF2CF3, 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro- 3-hexene). The process comprises:(i) fluorinating HCFC-343maf with a fluorinating agent in the presence of a catalyst to make HFO-1336myf (CF3CF=CHCHF2, 1 ,1 , 1 ,2,4, 4-hexafluoro-2- butene); and(ii) reacting the HFO-1336myf with tetrafluoroethylene in the presence of a Lewis acid catalyst to produce HFO-153-10mczz (CF3CF2CH=CHCF2CF3, 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene).

[0212] In some embodiments, the present application provides a process of preparing HFO-153-10mczz (CF3CF2CH=CHCF2CF3, 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro- 3-hexene). The process comprises:(i) dehydrochlorinating HCFC-343maf in the presence of a catalyst to make HFO-1333maz and HFO-1333mxz;(ii) fluorinating the HFO-1333maz and HFO-1333mxz with a fluorinating agent in the presence of a catalyst to make HFO-1336ze (CHF=CHCF2CF3, 1,3,3(4,4,4-hexafluoro-1-butene) and HFO-1336myf (CF3CF=CHCHF2, 1 ,1 ,1 ,2,4,4-hexafluoro-2-butene) ; and(iii) reacting the HFO-1336ze and the HFO-1336myf with tetrafluoroethylene in the presence of a Lewis acid catalyst to produce HFO-153-10mczz (CF3CF2CH=CHCF2CF3, 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene).

[0213] In some embodiments, the present application provides a process of preparing HFO-153-10mczz (CF3CF2CH=CHCF2CF3, 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro- 3-hexene). The process comprises:(i) dehydrochlorinating HCFC-343maf in the presence of a catalyst to make HFO-1333maz and HFO-1333mxz;(ii) fluorinating the HFO-1333maz and HFO-1333mxz with a fluorinating agent in the presence of a catalyst to make HFO-1336myf (CF3CF=CHCHF2,1.1.1.2.4.4-hexafluoro-2-butene); and(iii) reacting the HFO-1336myf with tetrafluoroethylene in the presence of a Lewis acid catalyst to produce HFO-153-10mczz (CF3CF2CH=CHCF2CF3, 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene).

[0214] In some embodiments, the present application provides a process of preparing HFO-153-10mczz (CF3CF2CH=CHCF2CF3, 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro- 3-hexene). The process comprises:(i) reacting vinyl chloride (CH2=CHCI, VC) or vinyl fluoride (CH2=CHF, VF) and CFC-113a (CF3CCI3) in the presence of a a metal-containing compound and an organic initiator to make HCFC-343maf (CF3CCI2CH2CHCI2) or HCFC- 344maf (CF3CCI2CH2CHCIF);(ii) fluorinating the HCFC-343maf with a fluorinating agent in the presence of a catalyst to make a composition comprising HFO-1336ze (CHF=;CHCF2CF3,1.3.3.4.4.4-hexafluoro-lbutene), HFO-1336myf (CF3CF=CHCHF2,1.1.1.2.4.4-hexafluoro-2-butene) or a mixture thereof; and(iii) reacting the composition comprising HFO-1336ze HFO-1336myf or a mixture thereof with tetrafluoroethylene in the presence of a Lewis acid catalyst to produce HFO-153-10mczz (CF3CF2CH=CHCF2CF3,1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene).

[0215] In some embodiments, the present application provides a process of preparing HFO-153-10mczz (CF3CF2CH=CHCF2CF3, 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro- 3-hexene). The process comprises:(i) reacting vinyl chloride (CH2=CHCI, VC) or vinyl fluoride (CH2=CHF, VF) and CFC-113a (CF3CCI3) in the presence of a metal-containing compound and a phosphorous-containing or nitrogen-containing compound to make HCFC-343maf (CF3CCI2CH2CHCI2) or HCFC-344maf (CF3CCI2CH2CHCIF), respectively;(ii) converting HCFC-343maf into HFO-1336myf or converting HCFC-344maf to HFO-1336myf;(iii) (CF3CF=CHCHF2, 1 ,1 ,1 ,2,4,4-hexafluoro-2-butene) using fluorinating agent in the presence of a catalyst; and(iv) reacting the HFO-1336myf with tetrafluoroethylene in the presence of a Lewis acid catalyst to produce HFO-153-10mczz (CF3CF2CH=CHCF2CF3, 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene).

[0216] In some embodiments, the present application provides a process of preparing HFO-153-10mczz (CF3CF2CH=CHCF2CF3, 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro- 3-hexene). The process comprises:(i) reacting vinyl chloride (CH2=CHCI, VC) and CFC-113a (CF3CCI3) in the presence of a metal-containing compound and organic initiator comprising a phosphorous-containing compound, in a first reaction zone to form a first effluent comprising HCFC-343maf (CF3CCI2CH2CHCI2);(ii) providing the HCFC-343maf (CF3CCI2CH2CHCI2) from the first effluent of the first reaction zone to a second reaction zone and fluorinating the HCFC- 343maf with a fluorinating agent in the presence of a catalyst in the second reaction zone to form a second effluent comprising HFO-1336ze (CHF^CHCFsCF , 1,3,3, 4,4, 4-hexafluoro-1 -butene) and HFO-1336myf(CF3CF=CHCHF2, 1 ,1 , 1 ,2,4,4-hexafluoro-2-butene); and(iii) providing the HFO-1336ze (CHF™CHCF2CF3, 1 ,3, 3,4,4, 4-hexafluoro-1- butene) and HFO-1336myf (CF3CF=CHCHF2, 1 ,1 , 1 ,2,4, 4-hexafluoro-2- butene) from the second effluent of the second reaction zone to a third reaction zone and reacting the HFO-1336ze and the HFO-1336myf with tetrafluoroethylene in the presence of a Lewis acid catalyst in the third reaction zone to produce HFO-153-10mczz (CF3CF2CH=CHCF2CF3,1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene).

[0217] In some embodiments, the present application provides a process of preparing HFO-153-10mczz (CF3CF2CH=CHCF2CF3, 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro- 3-hexene). The process comprises:(i) reacting vinyl chloride (CH2=CHCI, VC) and CFC-113a (CF3CCI3) in the presence of a metal-containing compound and a phosphorous-containing compound in a first reaction zone to form a first effluent comprising HCFC- 343maf (CF3CCI2CH2CHCI2);(ii) providing the HCFC-343maf (CF3CCI2CH2CHCI2) from the first effluent of the first reaction zone to a second reaction zone and fluorinating the HCFC-343maf with a fluorinating agent in the presence of a catalyst in the second reaction zone to form a second effluent comprising HFO-1336myf (CF3CF=CHCHF2, 1 ,1 ,1 ,2,4,4-hexafluoro-2-butene); and(iii) providing the HFO-1336myf (CF3CF=CHCHF2, 1 ,1 , 1 ,2,4, 4-hexafluoro-2- butene) from the second effluent of the second reaction zone to a third reaction zone and reacting the HFO-1336myf with tetrafluoroethylene in the presence of a Lewis acid catalyst in the third reaction zone to produce HFO- 153-10mczz (CF3CF2CH=CHCF2CF3, 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3- hexene).

[0218] In some embodiments, the present application provides a process of preparing HFO-153-10mczz (CF3CF2CH=CHCF2CF3, 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro- 3-hexene). The process comprises:(i) reacting vinyl chloride (CH2=CHCI, VC) and CFC-113a (CF3CCI3) in the presence of a metal-containing compound and an organic initiator comprising a phosphorous-containing compound to make HCFC-343maf (CF3CCI2CH2CHCI2);(ii) dehydrochlorinating the HCFC-343maf in the presence of a catalyst to make HFO-1333maz and HFO-1333mxz;(iii) fluorinating the HFO-1333maz and HFO-1333mxz with a fluorinating agent in the presence of a Lewis acid catalyst to make HFO-1336ze (CHF=CHCF2CF3, 1 , 3,3, .4, -hexafluoro-1 -butene) and HFO-1336myf (CF3CF=CHCHF2, 1 ,1 ,1 ,2,4,4-hexafluoro-2-butene); and(iv) reacting the HFO-1336ze and the HFO-1336myf with tetrafluoroethylene in the presence of a Lewis acid catalyst to produce HFO-153-10mczz (CF3CF2CH=CHCF2CF3, 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene).

[0219] In some embodiments, the present application provides a process of preparing HFO-153-10mczz (CF3CF2CH=CHCF2CF3, 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro- 3-hexene). The process comprises:(i) reacting vinyl chloride (CH2=CHCI, VC) and CFC-113a (CF3CCI3) in the presence of a catalyst system comprising a metal-containing compound and a phosphorous-containing compound to make HCFC-343maf(CF3CCI2CH2CHCI2);(ii) dehydrochlorinating the HCFC-343maf in the presence of a catalyst to make HFO-1333maz and HFO-1333mxz;(iii) fluorinating the HFO-1333maz and HFO-1333mxz with a fluorinating agent in the presence of a catalyst to make HFO-1336myf (CF3CF=CHCHF2,1 ,1 ,1 ,2,4,4-hexafluoro-2-butene) ; and(iv) reacting the HFO-1336myf with tetrafluoroethylene in the presence of a Lewis acid catalyst to produce HFO-153-10mczz (CF3CF2CH=CHCF2CF3, 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene).

[0220] In some embodiments, the present application provides a process of preparing HFO-153-10mczz (CF3CF2CH=CHCF2CF3, 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro- 3-hexene). The process comprises:(i) reacting vinyl chloride (CH2=CHCI, VC) and CFC-113a (CF3CCI3) in the presence of a catalyst system comprising a metal-containing compound and a phosphorous-containing compound in a first reaction zone to form a first effluent comprising HCFC-343maf (CF3CCI2CH2CHCI2);(ii) providing the HCFC-343maf (CF3CCI2CH2CHCI2) from the first effluent of the first reaction zone to a second reaction zone and dehydrochlorinating the HCFC-343maf in the presence of a catalyst in the second reaction zone to form a second effluent comprising HCFO-1333maz and HCFO-1333mxz;(iii) providing the HCFO-1333maz and HCFO-1333mxz from the second effluent of the second reaction zone to a third reaction zone and fluorinating the HCFO-1333maz and HCFO-1333mxz with a fluorinating agent in the presence of a catalyst in the third reaction zone to form a third effluent comprising HFO-1336ze (CHF=CHCF2CF3, 1,3, 3, 4,4,4- hexafluoro-1-butene) and HFO-1336myf (CF3CF=CHCHF2, 1 ,1 , 1 ,2, 4, 4- hexafluoro-2-butene); and(iv) providing the HFO-1336ze (CHF-CHCF2CF3, 1 ,3, 3,4,4, 4-hexafluoro-1- butene) and HFO-1336myf (CF3CF=CHCHF2, 1 ,1 , 1 ,2,4, 4-hexafluoro-2- butene) from the third effluent of the third reaction zone to a fourth reaction zone and reacting the HFO-1336ze and the H FO-1336 myf with tetrafluoroethylene in the presence of a Lewis acid catalyst in the fourth reaction zone to produce HFO-153-10mczz (CF3CF2CH=CHCF2CF3,1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene).

[0221] In some embodiments, the present application provides a process of preparing HFO-153-10mczz (CF3CF2CH=CHCF2CF3, 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro- 3-hexene). The process comprises:(i) reacting vinyl chloride (CH2=CHCI, VC) and CFC-113a (CF3CCI3) in the presence of a catalyst system comprising a metal-containing compound and a phosphorous-containing compound in a first reaction zone to form a first effluent comprising HCFC-343maf (CF3CCI2CH2CHCI2);(ii) providing the HCFC-343maf (CF3CCI2CH2CHCI2) from the first effluent of the first reaction zone to a second reaction zone and dehydrochlorinating the HCFC-343maf in the presence of a catalyst in the second reaction zone to form a second effluent comprising HcFO-1333maz and HCFO-1333mxz;(iii) providing the HCFO-1333maz and HCFO-1333mxz from the second effluent of the second reaction zone to a third reaction zone and fluorinating the HFO1333maz and HFO-1333mxz with a fluorinating agent in the presence of a catalyst in the third reaction zone to form a third effluent comprising HFO-1336myf (CF3CF=CHCHF2, 1 ,1 ,1 ,2,4,4-hexafluoro-2-butene); and(iv) providing the HFO-1336myf (CF3CF=CHCHF2, 1 ,1 , 1 ,2,4, 4-hexafluoro-2- butene) from the third effluent of the third reaction zone to a fourth reaction zone and reacting the HFO-1336myf with tetrafluoroethylene in the presence of a Lewis acid catalyst in the fourth reaction zone to produce HFO- 153-1 Omczz (CF3CF2CH=CHCF2CF3, 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3- hexene).

[0222] In any of the embodiments disclosed herein, the Lewis acid catalyst may be selected from SbFs, ACF and AlCh.

[0223] In any of the process embodiments disclosed herein, the reactants and / or catalysts and / or fluorinating agents may be pre-mixed in any of the manners discussed herein for carrying out the integrated processes of the present invention.

[0224] In any of the process embodiments disclosed herein, components generated by a process step which are not needed for a subsequent reaction of the integrated processes may be recycled back to the reaction system.

[0225] In any of the process embodiments disclosed herein, any conventional separation, isolation and recovery mechanisms known in the art may be utilized for isolating a desired compound or compounds from a reaction effluent, such that the isolated compound or compounds can then be utilized as a reactive intermediate for subsequent reaction(s).

[0226] In any of the process embodiments disclosed herein, any conventional purification mechanisms known in the art may be utilized for purifying a reaction effluent or a compound thereof.

[0227] In any of the process embodiments disclosed herein, any conventional regeneration mechanisms known in the art may be utilized for regenerating the catalyst utilized in any step of the integrated processes of the present invention.

[0228] In some embodiments, the present application further provides compositions comprising HFO-153-1 Omczz in combination with one or more additional compounds ( / .e., minor components), the compositions being prepared according to one or more of the processes described herein. In such compositions, the HFO-153-10mczz constitutes a major component while the one or more additional compounds constitute minor components.

[0229] In one embodiment, the present application provides a composition comprising E-1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene and one or more additional compounds selected from Z- 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene, E- and Z- isomers of CF3CF=CHCH(C2F5)2, and E- and Z- Isomers of dimers of C4F6H2 hydrofluoroolefins, wherein the composition is prepared according to any of the processes described herein.

[0230] In a further embodiment, the compositions disclosed herein may be used in combination with at least one lubricant selected from polyalkylene glycols, polyol esters, polyvinylethers, mineral oils, alkylbenzenes, synthetic paraffins, synthetic napthenes, and poly(alpha)olefins.

[0231] In one embodiment, lubricants may comprise those suitable for use with refrigeration or air-conditioning apparatus. Among these lubricants are those conventionally used in vapor compression refrigeration apparatus utilizing chlorofluorocarbon refrigerants. In one embodiment, lubricants comprise those commonly known as “mineral oils” in the field of compression refrigeration lubrication. Mineral oils comprise paraffins (i.e. , straight-chain and branched- carbon chain, saturated hydrocarbons), naphthenes (i.e., cyclic paraffins) and aromatics (i.e., unsaturated, cyclic hydrocarbons containing one or more rings characterized by alternating double bonds). In one embodiment, lubricants comprise those commonly known as “synthetic oils” in the field of compression refrigeration lubrication.Synthetic oils comprise alkylaryls (i.e., linear and branched alkyl alkylbenzenes), synthetic paraffins and naphthenes, and poly(alphaolefins). Representative conventional lubricants are the commercially available BVM 100 N (paraffinic mineral oil sold by BVA Oils), napthenic mineral oil commercially available from Crompton Co. under the trademarks Suniso® 3GS and Suniso® 5GS, naphthenic mineral oil commercially available from Pennzoil under the trademark Sontex® 372LT, napthenic mineral oil commercially available from Calumet Lubricants under the trademark Calumet® RO-30, linear alkylbenzenes commercially available from Shrieve Chemicals under the trademarks Zerol® 75, Zerol® 150 and Zerol® 500, and HAB 22 (branched alkylbenzene sold by Nippon Oil).

[0232] In another embodiment, lubricants may also comprise those, which have been designed for use with hydrofluorocarbon refrigerants and are miscible withrefrigerants of the present invention under compression refrigeration and air conditioning apparatus’ operating conditions. Such lubricants include, but are not limited to, polyol esters (POEs) such as Castrol® 100 (Castrol, United Kingdom), polyalkylene glycols (PAGs) such as RL-488A from Dow (Dow Chemical, Midland, Michigan), polyvinyl ethers (PVEs), and polycarbonates (PCs).

[0233] Lubricants used with the compositions disclosed herein are selected by considering a given compressor’s requirements and the environment to which the lubricant will be exposed.

[0234] In one embodiment, the compositions disclosed herein may further comprise an additive selected from the group consisting of compatibilizers, UV dyes, solubilizing agents, tracers, stabilizers, perfluoropolyethers (PFPE), and functionalized perfluoropolyethers.

[0235] In one embodiment, the compositions may be used with about 0.01 weight percent to about 5 weight percent of a stabilizer, free radical scavenger or antioxidant. Such other additives include but are not limited to, nitromethane, hindered phenols, hydroxylamines, thiols, phosphites, or lactones. Single additives or combinations may be used.

[0236] Applications and uses of the compositions include, for example, but not limited to, heat transfer fluids for semiconductor manufacturing, dielectric fluids, immersion cooling fluids, carrier fluids, foam blowing agents, fire-extinguishing agents, precision cleaning solvents and the like.

[0237] In one embodiment, the composition of this invention can be used as a working fluid in an immersion cooling unit including an immersion cell, defining an internal cavity, is provided, wherein an electronic or electrical component is positioned in the internal cavity. In this embodiment, the working fluid partially fills the internal cavity and at least partially immerses the heat generating electronic or electrical device. A condensing coil is positioned inside the cavity above the working fluid.

[0238] In one embodiment of this invention, an immersion cooling unit comprises: an immersion cell, defining an internal cavity; i) an electrical component in the internal cavity; ii) a working fluid partially filling the internal cavity; iii) a condensingcoil, positioned in the internal cavity above the electrical component; wherein the working fluid at least partially immerses the electrical component; and wherein the working fluid comprises, consists essentially of, or consists of a composition comprising E-1 ,1 ,1,2,2,5,5,6,6,6-decafluoro-3-hexene and one or more additional compounds selected from Z- 1 ,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene, E- and Z- isomers of CF3CF=CHCH(C2F5)2, and E- and Z- Isomers of dimers of C4F6H2 hydrofluoroolefins.

[0239] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, suitable methods and materials are described below. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.

[0240] The invention will be described in greater detail by way of specific examples. The following examples are offered for illustrative purposes and are not intended to limit the invention in any manner. Those of skill in the art will readily recognize a variety of non-critical parameters which can be changed or modified to yield essentially the same results.EXAMPLES

[0241] It will be understood by those skilled in the art that the reactions and processes described in the Examples may be integrated together.Example 1. Preparation of HFO-1336ze (CHF=CHCF2CF3, 1,3,3,4,4,4-hexafluoro- 1-butene) and HFO-1336myf (CF3CF=CHCHF2, 1,1,1,2,4,4-hexafluoro-2-butene) from HCFC-343maf (Fluorination of 1,1,3,3-tetrachloro-4,4,4-trifluorobutane)

[0242] 4 cc of chromium oxide catalyst (12 / 20 mesh) is loaded into an Inconel (0.5-inch OD) tube reactor. The reaction is run by feeding liquid HCFC-343maf into a heated chamber where it vaporized and mixed with HF and N2. The reaction mixture is then allowed to pass through the reactor heated at 275°C to 350°C. Part of the reactor effluent passed through a series of valves and analyzed by GCMS. Part ofthe reactor effluent can also be passed through a caustic scrubber, dried over a desiccant and trapped in a dry ice acetone trap. The trapped material was then analyzed by GCMS. Results will show formation of 1 ,3,3,4,4,4-hexafluorobut-1-ene (HFO-1336ze) and 1,1,3,4,4,4-hexafluorobut-2-ene (HFO-1336myf) as a 1 to 4 mixture.Example 2. Preparation of 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (HFO-153- 10mczz) from HFO-1336ze and HFO-1336myf

[0243] A dry 100 mL Hastelloy shaker tube is loaded with 2 grams of antimony pentafluoride. The tube is evacuated and chilled in a dry ice / acetone bath. Then, 20 grams (0.122moles) of 1 ,3,3,4,4,4-hexafluorobut-1-ene (HFO-1336ze) 1 1 , 1 ,3, 4,4,4- hexafluorobut-2-ene (HFO-1336myf) as a 1 :4 (wt% / wt%) mixture and 12.2 grams (0.122 moles) of tetrafluoroethylene is added to the tube. The tube is then allowed to warm up while shaking for 24 hours. After 24 hours, the tube is analyzed by GCMS and will be found to produce a mixture comprising 93 wt% HFO-153-10mczz, 3 wt% 1 ,1,1,2,2,5,5,6,6,7,7,8,8,8-tetradecafluoro-3-octene, and 3 wt% starting material mixture.Example 3. Preparation of 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (HFO- 15310mczz) from HFO-1336ze and HFO-1336myf

[0244] A Hastelloy shaker tube (400 ml) is loaded with 150 g of dry HFO- 15310mczz. The shaker tube is flashed with dry nitrogen and 3.4 g of aluminum chlorofluoride (ACF) is added to it. The reactor is closed, cooled down with dry ice and evacuated. Then, 59 grams (0.36 mol) of a mixture of HFO 1336ze and HFO1336myf is added to the evacuated vessel, followed by 36 grams (0.36 mol) of tetrafluoroethylene (TFE). The agitated shaker tube is allowed to warm up and is kept at ambient temperature for about 24 hours. Substantial pressure drop is observed in the first 3 hours. The next morning, the reaction vessel is vented off and unloaded. The resulting crude reaction mixture is analyzed by GC to show formation of E-HFO-153-10mczz - 96.0 gc area %, Z-HFO-153-10mczz - 0.5 gc area %, and others - 3.5 gc area %.Example 4. Preparation of 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (HFO-153- 10mczz) from HFO-1336ze

[0245] Hastelloy shaker tube (400 ml) was loaded with 100 g of dry HFO-153- 10mczz. Shaker tube was flashed with dry nitrogen and 2.9 g of aluminumchlorofluoride (ACF) was added to it. The reactor was closed, cooled down with dry ice and evacuated. HFO-1336ze (41g, 0.25 mol) was added to the evacuated vessel, followed by 25 g (0.25 mol) of tetrafluoroethylene (TFE). The agitated shaker tube was allowed to warm up and was kept at ambient temperature (20°C) for 16 hours. A substantial pressure drop was observed in the first 3 hours. The next morning, the reaction vessel was vented off and unloaded. The resulting crude reaction mixture (160 g) was analyzed by GC and NMR and it was found to have the following composition: E-isomer of HFO-153-10mczz - 98.2 wt. %; Z-isomer of HFO- 15310mczz - 0.3 wt. %; others - 1.5%. Yield of HFO-153-10mczz (E- and Z- isomers) calculated based on weight gain and purity of crude material was found to be 91 %.

[0246] Use of AlCh or ACF as the catalyst may be advantageous because both materials are not soluble in the reaction mixture and can be removed by filtration or decantation.Example 5. Preparation of 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (HFO-153- 10mczz) from HFO-1336myf

[0247] A Hastelloy shaker tube (400 ml) is loaded with 3 grams of antimony pentafluoride (SbFs) and 100 g of dry HFO-153-10mczz. The reactor is closed, cooled down with dry ice and evacuated. HFO-1336myf (50 g, 0.305 mol) is added to the evacuated vessel, followed by 25 g (0.25 mol) of tetrafluoroethylene (TFE). Agitated shaker tube is allowed to warm up and is kept at ambient temperature (20°C) for 16 hours. The next morning, the reaction vessel is vented off and unloaded. The crude reaction mixture analyzed by GC will have the following composition: 95.5. wt. % E-isomer of HFO-153-10mczz, 0.5 wt. % Z-isomer of HFO- 153-10mczz, and 4 wt.% others.Example 6. Formation of HFO-1333mxz from HCFC-343maf using FeCh

[0248] 0.7 grams of anhydrous FeC and 17.34 grams of HCFC-343maf are added into a 25 ml dry 3-neck round bottom flask, equipped with stirring bar, Deanstark apparatus and condenser. The flask is slowly heated to 147°C while stirring.

[0249] The condensate is collected into the Dean-Stark receiver. Analysis of product by NMR will show 35% formation HFO-1333mxz.Example 1. Formation of HFO-1333mxz from HCFC-343maf using KOH

[0250] Into a 25 ml flask is added 3.74 grams of HCFC-343maf into 3 ml of MeOH. A KOH / MeOH solution is prepared by dissolving 3.5 grams of KOH in 10 ml MeOH. 3 ml of KOH / MeOH solution is added dropwise. The solution is washed with H2O, dried and analyzed by GO using thermal detector. Analysis will show conversion of HCFC-343maf at 86.8% and selectivity for HFO-1333mxz at 84.26%.

[0251] It is to be understood that while the invention has been described in conjunction with the detailed description thereof, the foregoing description is intended to illustrate and not limit the scope of the invention, which is defined by the scope of the appended claims. Other aspects, advantages, and modifications are within the scope of the following claims. It should be appreciated by those persons having ordinary skill in the art(s) to which the present invention relates that any of the features described herein in respect of any particular aspect and / or embodiment of the present invention can be combined with one or more of any of the other features of any other aspects and / or embodiments of the present invention described herein, with modifications as appropriate to ensure compatibility of the combinations. Such combinations are considered to be part of the present invention contemplated by this disclosure.

Claims

CLAIMSWhat is claimed is:1 . A process of preparing 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene, the process comprising steps of:(i) reacting vinyl chloride (CH2=CHCI, VC) or vinyl fluoride (VF, CH2=CHF) and CFC-113a (CF3CCI3) in the presence of a metal-containing compound and an organic initiator to make HCFC-343maf (CF3CCI2CH2CHCI2) or HCFC-344maf (CF3CCI2CH2CHCIF), respectively;(ii) fluorinating the HCFC-343maf or HCFC-344maf produced in step (i) with a fluorinating agent and catalyst to make a product comprising HFO- 1336ze (CHF=CHCF2CF3, 1 ,3,3,4,4,4-hexafluoro-1-butene), HFO- 1336myf (CF3CF=CHCHF2, 1 ,1 ,1 ,2,4,4-hexafluoro-2-butene) or a mixture thereof; and(iii) reacting the product comprising HFO-1336ze (CHF DHCF2CF3,1.3.3.4.4.4-hexafluoro-1-butene), HFO-1336myf (CF3CF=CHCHF2,1.1.1.2.4.4-hexafluoro-2-butene) or a mixture thereof with tetrafluoroethylene in the presence of a Lewis acid catalyst to produce 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene (CF3CF2CH=CHCF2CF3).

2. A process of preparing 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene, the process comprising steps of:(ia) fluorinating HCFC-343maf with a fluorinating agent to make a composition comprising HFO-1336ze (CHROHCF2CF3, 1 ,3, 3, 4,4,4- hexafluoro-1 -butene), HFO-1336myf (CF3CF=CHCHF2, 1 , 1 , 1 , 2,4,4- hexafluoro-2-butene) or a mixture thereof; or(ib) dehydrochlorinating HCFC-344maf (CF3CCI2CH2CHCIF) to make a composition comprising HFO-1336ze (CHF=CHCF2CF3, 1 ,3,3,4,4,4hexafluoro-1-butene), HFO-1336myf (CF3CF=CHCHF2, 1 ,1 ,1 ,2,4,4hexafluoro-2-butene) or a mixture thereof; and(ii) reacting the composition comprising HFO-1336ze (CHF^CHCF CFs,1.3.3.4.4.4-hexafluoro-l-butene), HFO-1336myf (CF3CF=CHCHF2,1 ,1 ,1 ,2,4,4-hexafluoro-2-butene) or a mixture thereof with tetrafluoroethylene in the presence of a Lewis acid catalyst to produce 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene (CF3CF2CH=CHCF2CF3).

3. A process of preparing 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene, the process comprising reacting a composition comprising HFO-1336ze (CHF—CHCFzCFs, 1 ,3,3, 4.4, 4-hexafluoro-1-butene), HFO-1336myf (CF3CF=CHCHF2, 1 , 1 ,1 , 2,4,4- hexafluoro-2-butene) or a mixture thereof with tetrafluoroethylene in the presence of an acid catalyst to produce HFO-153-10mczz , 1 , 1 ,1 , 2, 2, 5, 5, 6,6,6- decafluoro-3-hexene (CF3CF2CH=CHCF2CF3).

4. The process of any of claims 1-3, wherein the Lewis acid catalyst is a strong Lewis acid catalyst.

5. The process of any of claims 1-3, wherein the Lewis acid catalyst is selected from the group consisting of SbFs, aluminum chlorofluoride, and aluminum chloride.

6. The process of claim 1 , wherein the metal-containing compound of the initiator system of step (i) comprises an iron-containing compound.

7. The process of claim 1 , wherein the organic initiator of the catalyst system comprises a phosphine, phosphine oxide, phosphite or phosphate, preferably triphenyl phosphine, tributyl phosphine or tributylphosphate.

8. The process of claim 8, wherein the organic initiator of the catalyst system comprises a phosphine and the phosphine comprises triphenyl phosphine.

9. A process of preparing HFO-1336ze (CHF^CHC JCFS, 1,3, 3,4,4, 4-hexafluoro- 1-butene) and HFO-1336myf (CF3CF=CHCHF2, 1 ,1 , 1 ,2,4, 4-hexafluoro-2- butene), the process comprising fluorinating HCFC-343maf with a fluorinating agent and catalyst to make HFO-1336ze (CHF~CHCF2CF3, 1 , 3, 3, 4,4,4- hexafluoro- 1 -butene) and HFO-1336myf (CF3CF=CHCHF2, 1 , 1 , 1 , 2,4,4- hexafluoro-2-butene).

10. The process of any of claims 1 , 2, or 9, wherein the fluorinating agent is hydrogen fluoride.11 . The process of any of claims 1 , 2 or 9, wherein the fluorination reaction is performed at a temperature of from about 150°C to about 350°C, preferably about 250°C to about 325°C, and more preferably about 275°C to about 31 C C.

12. The process of any of claims 1 , 2 or 9, wherein the fluorination reaction is performed at a pressure of from about 1 atm to about 20 atm, preferably about 2 atm to about 15atm, and more preferably about 3 atm to about 10atm.

13. The process of any of claims 1-3, further comprising isomerizing Z-1 , 1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene to E-1 , 1 , 1 ,2,2,5,5,6,6,6-decafluoro-3- hexene.

14. The process of any of claims 1-3, wherein reacting the composition comprising HFO-1336ze HFO-1336myf or a mixture thereof is performed as a liquid phase reaction.

15. The process of any of claims 1-3, wherein the Lewis acid catalyst is SbFs and wherein reacting the composition comprising HFO-1336ze HFO-1336myf or a mixture thereof is performed at a temperature of from about 0°C to about 75°C, preferably about 5°C to about 50°C, and more preferably about 10°C to about 30°C.

16. The process of any of claims 1-3, wherein the Lewis acid catalyst is SbFs and wherein reacting the composition comprising HFO-1336ze HFO-1336myf or a mixture thereof is performed at a pressure of from about 1 atm to about 20 atm, preferably about 1 atm to about 15atm, and more preferably about 1 atm to about 10 atm.

17. The process of any of claims 1 -3, wherein the Lewis acid catalyst is ACF and wherein reacting the composition comprising HFO-1336ze HFO-1336myf or a mixture thereof is performed at a temperature of from about 0°C to about 75°C, preferably about 5°C to about 50°C, and more preferably about 10°C to about 30°C.

18. The process of any of claims 1 -3, wherein the Lewis acid catalyst is ACF and wherein the reacting the composition comprising HFO-1336ze HFO-1336myf or a mixture thereof is performed at a pressure of from about 1 atm to about 20 atm, preferably about 1 atm to about 15atm, and more preferably about 1 atm to about 10 atm.

19. The process of any of claims 1 -3, wherein the Lewis acid catalyst is AlCh and wherein reacting the composition comprising HFO-1336ze HFO-1336myf or a mixture thereof is performed at a temperature of from about 0°C to about 75°C, preferably about 5°C to about 50°C, and more preferably about 10°C to about 30°C.

20. The process of any of claims 1-3, wherein the Lewis acid catalyst is AICI3 and wherein reacting the composition comprising HFO-1336ze HFO-1336myf or a mixture thereof is performed at a pressure of from about 1 atm to about 20 atm, preferably about 1 atm to about 15atm, and more preferably about 1 atm to about 10 atm.21 . The process of any of claims 1 , 2 or 10, wherein a ratio of the number of moles of the fluorinating agent to moles of HCFC-343myf in step (ii) is about 6: 1 to about 30:1.

22. The process of any of claims 1-3, wherein a ratio of the number of moles of HFO-1336ze to the number of moles of HFO-1336myf is about 0% to about 99%.

23. The process of any of claims 1-3, wherein a ratio of the number of moles of HFO-1336ze to the number of moles of tetrafluoroethylene is about 0.1 to 1.

24. The process of any of claims 1-3, wherein a ratio of the number of moles of HFO-1336myf to the number of moles of tetrafluoroethylene is about 0.1 to 1.

25. The process of any of claims 1-3, wherein a ratio of the number of moles of HFO-1336ze and HFO-1336myf to the number of moles of the Lewis acid catalyst is about 0.01 to 20.

26. The process of any of claims 1-3, wherein a ratio of the number of moles of tetrafluoroethylene to the number of moles of the Lewis acid catalyst is about 0.01 to 20.

27. A composition comprising E-1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene and one or more additional compounds selected from Z-1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro- 3-hexene, E- and Z- isomers of CF3CF=CHCH(C2Fs)2, and E- and Z- isomers of dimers of C4F6H2 hydrofluoroolefins.

28. The composition of claim 27, wherein the composition comprises Z- 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene.

29. The composition of claim 27 or 28, wherein the composition comprises 1 , 1 ,1 ,2,2,5,5,6,6,7,7,8,8,8-tetradecafluoro-3-octene.

30. A composition prepared according to the process of any of claims 1-3.

31. An immersion cooling unit comprising an immersion cell, defining an internal cavity, a heat generating electronic or electrical component positioned in the internal cavity, a working fluid which partially fills the internal cavity and at least partially immerses the heat generating electronic or electrical device, and a condensing coil positioned inside the cavity above the working fluid, wherein the working fluid is a composition comprising E-1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene and one or more additional compounds selected from Z-1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3- hexene, E- and Z- isomers of CF3CF=CHCH(C2Fs)2, and E- and Z- isomers of dimers of C4F6H2 hydrofluoroolefins.

32. The immersion cooling unit of claim 32, wherein the working fluid comprises Z- 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene.

33. The immersion cooling unit of claim 31 or 32, wherein the working fluid comprises 1 ,1 ,1 ,2,2,5,5,6,6,7,7,8,8,8-tetradecafluoro-3-octene.

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